Journal of Physics: Condensed Matter

PAPER Related content

- Spin glass behaviour and extrinsic origin of
The extrinsic origin of the magnetodielectric effect magnetodielectric effect in non-multiferroic
La2NiMnO6 nanoparticles
in the double perovskite La2NiMnO6 K Devi Chandrasekhar, A K Das and A
Venimadhav

- A comparative study of structural,

magnetic, dielectric behaviors and
To cite this article: K Devi Chandrasekhar et al 2012 J. Phys.: Condens. Matter 24 495901
impedance spectroscopy for bulk and
nanometric double perovskite
Sm2CoMnO6
P R Mandal, R C Sahoo and T K Nath

View the article online for updates and enhancements. - Observation of relaxor ferroelectricity and
multiferroic behaviour in nanoparticles of
the ferromagnetic semiconductor
La2NiMnO6
Md G Masud, Arijit Ghosh, J Sannigrahi et
al.

Recent citations
- Unusual magnetodielectric effects in La 2
CuMnO 6 induced by a dynamic crossover
in dielectric relaxation at TC
Jasnamol Pezhumkattil Palakkal et al

- Influence of compositional variation on

structural, electrical and magnetic
characteristics of (Ba1x Gd) (Ti1x Fe x ) O3
(0.2 x 0.5)
Sushrisangita Sahoo et al

- Importance of frequency dependent

magnetoresistance measurements in
analysing the intrinsicality of
magnetodielectric effect: A case study
Hari Mohan Rai et al

This content was downloaded from IP address 118.185.236.192 on 26/03/2018 at 16:14

IOP PUBLISHING JOURNAL OF PHYSICS: CONDENSED MATTER
J. Phys.: Condens. Matter 24 (2012) 495901 (9pp) doi:10.1088/0953-8984/24/49/495901

The extrinsic origin of the

magnetodielectric effect in the double
perovskite La2NiMnO6
K Devi Chandrasekhar1,2 , A K Das1 , C Mitra3 and A Venimadhav2
1
Department of Physics and Meteorology, Indian Institute of Technology, Kharagpur-721302, India
2
Cryogenic Engineering Centre, Indian Institute of Technology, Kharagpur-721302, India
3
Indian Institute of Science Education and Research, Kolkata-741252, India

E-mail: venimadhav@hijli.iitkgp.ernet.in

Received 30 August 2012, in final form 18 October 2012

Published 16 November 2012
Online at stacks.iop.org/JPhysCM/24/495901
Abstract
A La2 NiMnO6 polycrystalline sample prepared by the sol–gel method showed monoclinic
crystal structure with the P21 /n space group and a saturation magnetization of 4.63 µB /f.u. at
5 K. Impedance spectroscopy results in the temperature range of 10 K < T < 300 K have
revealed a distinct conduction process at grains and grain boundaries, where the grains
followed the variable range hopping mechanism and the grain boundaries obeyed Arrhenius
thermal activation. A negative magnetoresistance of 2.5% was observed at the paramagnetic to
ferromagnetic transition, and this became temperature independent below the magnetic
ordering. A marginal positive magnetodielectric (MD) effect that followed the dielectric
relaxation was observed and its magnitude was found to decrease with increase of the
frequency. A systematic study on the magnetic field induced dielectric properties, dc transport
and dc bias effect on the dielectric permittivity has revealed the extrinsic origin of the MD
effect in the bulk sample of La2 NiMnO6 .

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

1. Introduction 9]. Also, recent theoretical studies on two-dimensional

Magnetic field induced change in the dielectric permittivity
(ε 0 ), namely the MD effect, has been studied routinely to
understand the magnetoelectric coupling in multiferroics [1,
2]. Recently, the observation of significant MD response
in nonmultiferroic but insulating magnetic oxide systems
has found to be intriguing (e.g. Mn3 O4 , SeCuO3 and
TeCuO3 systems) [3, 4]. Several mechanisms have been
proposed to account for the intrinsic MD effect; examples are
spin-lattice coupling, magnetostriction, exchange striction,
charge ordering, etc [3, 5–7]. However, redundant extrinsic
effects also contribute to the MD. It has been noticed
that the combined effect of magnetoresistance (MR) and
Maxwell–Wagner (MW) interfacial polarization accounts for
the MD in both multiferroic and nonmultiferroic systems [8,
nonmagnetic and strongly inhomogeneous media have
suggested an occurrence of the MD effect through the
generation of Hall voltage in the presence of external
magnetic fields [10]. Even though an extrinsic MD itself is
adequate for many device applications, it hinders the apparent
understanding of the effect and sometimes leads to improper
conclusions about the system. A thorough dielectric study
under a magnetic field is necessary to distinguish the extrinsic
and intrinsic contributions to the MD effect.
The double perovskite La2 NiMnO6 (LNMO) has
attracted considerable attention in this field due to its high
temperature ferromagnetic ordering, insulating characteristics
and MD effect [9]. In an ideal case, rock salt ordering
of Ni2+ and Mn4+ octahedra follow a 180◦ ferromagnetic
superexchange interaction [11, 12]. Based on the synthesis

0953-8984/12/495901+09$33.00 1 c 2012 IOP Publishing Ltd Printed in the UK & the USA


J. Phys.: Condens. Matter 24 (2012) 495901
conditions, multiple crystallographic and magnetic phases
have been reported [12]. The research attention on this
family of materials has significantly increased since the
exploration of multifunctional properties such as large MD
phenomena (LNMO, La2 CoMnO6 (LCMO)), spin–phonon
coupling and the multiferroic effect (Bi2 NiMnO6 ) [11,
13–15]. The ordering of the two transition metal cations
in the crystallographic lattice plays a crucial role in the
magnetic and transport properties of the system [12]. In
fact, the MD behavior seems to be affected greatly by
the ordering of B-site cations. For example, Rogado et al
have reported a negative MD of 16% in the highly ordered
LNMO polycrystalline system, and this was assigned to the
spin-lattice coupling in the system [11]. Debraj et al have
reported multiglass behavior with a colossal MD (−16% at
300 K) in partially disordered LNMO polycrystalline samples,
and they suggested an asymmetric hopping of electrons
between the transition metal ions (Ni(2+δ)+ –Mn(4−δ)+ ) as
the cause of the MD effect [16]. The LNMO epitaxial thin
film showed a positive MD (50% at 130 K), but much
below its ferromagnetic transition (270 K) temperature, and
it was related to the change in the relaxation dynamics of the
electrical dipoles under the magnetic field [17]. On the other
hand, a minute positive extrinsic MD (∼4% at 105 K) has
been reported in LNMO nanoparticles where the long range
ferromagnetic ordering was completely broken [18].
The MD behavior of LNMO and its isostructural
(LCMO) materials has been found to display variations in
both magnitude and sign; figure 1 shows the MD behavior of
various systems taken from the literature for a 1 T magnetic
field and a 10 kHz frequency (except for the symbols ‘◦’
measured at 2 T and ‘?’ taken at 1 MHz) [11, 13, 16–20].
Except for bulk samples of LNMO, other systems including
LNMO film have shown a positive MD [11, 13, 15–20].
However, we believe that there is no systematic dielectric
study available to date to exclude the extrinsic contribution
of MD in the LNMO bulk system. In this report, we have
prepared an LNMO bulk sample with a high saturation
magnetization (4.63 µB /f.u.) and found a small (2.5%) but
positive MD. Systematic study of the impedance as a function
of temperature and frequency, the dielectric permittivity with
varying magnetic field and dc bias along with dc transport
and MR has revealed an extrinsic origin of the observed MD
effect.
2. Experimental details
A polycrystalline sample of LNMO was prepared by
the sol–gel method. In this method, high purity La2 O3 ,
Mn(CH3 COO)2 ·4H2 O and Ni(NO3 )2 ·6H2 O were taken as the
raw materials. Firstly, the La2 O3 was converted to lanthanum
nitrate by dissolving in HNO3 . The Mn(CH3 COO)2 ·4H2 O
and Ni(NO3 )2 .6H2 O were dissolved in water. All three
solutions were mixed in a beaker and ethylene glycol was
added to this solution with continuous stirring while heating
the mixture at 70 ◦ C for 1 h followed by 150 ◦ C until gel
formation. After combustion of the gel, a black fluffy powder
2
K Devi Chandrasekhar et al
Figure 1. The literature values of maximum MD for 1 T and
10 kHz frequency are plotted (except for the symbols ‘◦’ (2 T) and
‘?’ (1 MHz)). Here T, B and N indicate thin films, bulk and
nanoparticles, respectively. The corresponding references are
indicated by the numbers beside each legend.
was collected. The final powder was calcinated at 1300 ◦ C
for 24 h. The final sintering of the pellets was carried out at
1300 ◦ C for 24 h and then they were slowly cooled to room
temperature with a cooling rate of 1 ◦ C min−1 .
High resolution x-ray diffraction (HRXRD) from a
Panalytical instrument with Cu Kα radiation was used
to determine the structure of the polycrystalline samples.
The detailed structural analysis was carried out with
Rietveld refinement using FullProf suite software. Field
emission scanning electron microscopy (FESEM) was used
to characterize the surface morphology of the polycrystalline
samples. The dc electrical transport property was measured
on the pellet samples with the standard four probe technique.
To avoid the Joule heating effect, transport measurements
were performed with a 1 µA current (using a Keithley-6221
current source and a Keithley-2182 nanovoltmeter). The
static magnetization measurements were performed using
a Quantum Design VSM-SQUID magnetometer. Dielectric
measurements were carried out in the temperature range of
10–300 K using an Agilent HP4294A impedance analyzer
from 40 Hz to 1 MHz. High purity silver paste contacts
were applied to both faces of the pellet to form a parallel
capacitance geometry. As known from the literature [16, 17,
25], LNMO shows a colossal dielectric permittivity and a
large change of dε 0 /dT near the dielectric relaxation. Proper
care was taken to keep the temperature uniform in the entire
sample chamber during MD measurements (as a variation of
0.25 K was found to give ∼20% MD). Also, the obtained
MD was verified using ε 0 versus magnetic field (H) sweeps at
different temperatures. A low ac excitation voltage (500 mV)
was employed to conduct the measurement in the linear
capacitance voltage region. The temperature and magnetic
field dependent dielectric properties were investigated in
a cryogen free superconducting system with closed cycle
helium refrigeration.
J. Phys.: Condens. Matter 24 (2012) 495901 K Devi Chandrasekhar et al

Table 1. A list of the structural parameter from the Rietveld fit with a reliability factor of Rp = 9 and χ 2 = 2.1.
Lattice parameters
a (Å) b (Å) c (Å) α(deg) β(deg) γ (deg)
5.514 5.460 7.74 90 89.93 90
Atomic positions
2
x y z U (Å )
La −0.001 26 0.018 55 0.2552 0.0066
Ni 0 0.5 0 0.0055
Mn 0.5 0 0 0.03
O1 0.044 03 0.4948 0.2449 0.0061
O2 0.742 0.281 0.0113 0.238
O3 0.295 0.7 0.53 0.152
Bond distances and bond angles
Mn–O1 (Å) Mn–O2 (Å) Mn–O3 (Å) Ni–O1 (Å) Ni–O2 (Å) Ni–O3 (Å)
1.9115 1.8549 2.0058 1.9896 2.0410 1.9888
Mn–O1 –Ni (deg) Mn–O2 –Ni (deg) Mn–O3 –Ni (deg)
165.5 169.7 152.50

Figure 2. The experimental HRXRD data of the samples (dots)

with the fitted curve (black line) and the difference (grey line) on
Rietveld refinement. The inset shows an FESEM micrograph of the
LNMO polycrystals.

3. Results and discussion Figure 3. The field cooled magnetization for a 1 T applied field; the
insets show (I) isothermal M–H at 5 K and (II) the Curie–Weiss fit.
3.1. Structural analysis

The room temperature HRXRD and the corresponding
Rietveld refinement shown in figure 2 confirmed that the
sample was single phase with no detectable secondary
phase. Rietveld refinement of the data results in a B-site
ordered monoclinic structure with the P21 /n space group. The
obtained lattice parameters, atomic positions, bond lengths
and bond angles are shown in table 1 and the values are
consistent with the reported literature [11]. The inset of
figure 2 shows an FESEM micrograph that demonstrates
uniform grains (size distribution of 1–5 µm) separated by
grain boundaries.
3.2. Magnetization measurements
The temperature dependent magnetization measured in the
field cooling (FC) mode under a magnetic field of 1 T is
shown in figure 3. A single magnetic transition at 272 K
was obtained similarly to Rogado et al [11]. The inset of
figure 3(a) shows the magnetization versus the applied field
at 5 K, where a saturation magnetization of ∼4.63 µB /f.u. is
observed. The observed saturation magnetization is slightly
smaller than the spin only magnetization of 5 µB /f.u. for
the Ni2+ –Mn4+ couple, and this indicates the presence of
∼4% antisite defects in the system. The Curie–Weiss fit to
the inverse of susceptibility (1/χ ) versus temperature (T) plot
is shown in the inset of figure 3(b); the obtained parameters
like the Curie constant (Cm ) and Curie temperature (θ ) are
4.5865 emu K−1 mol−1 Oe−1 and 294 K respectively, and
the values are in agreement with previous reports [11, 12].
An estimation of the effective q paramagnetic susceptibility
from the Curie constant (µeff = 3kcm
N ) is ∼6.05 µB , which

3
J. Phys.: Condens. Matter 24 (2012) 495901 K Devi Chandrasekhar et al

is slightly higher than the theoretically predicted value of

5.97 µB . A small difference in the paramagnetic susceptibility
values hints at the formation of short range ferromagnetic
clusters above the transition temperature [21].

3.3. Dielectric measurements

The real and imaginary parts of the dielectric permittivity

(ε 0 and ε 00 ) as a function of temperature in the range of
10–300 K are shown in figure 4. At room temperature,
the low frequency ε 0 exhibits a colossal value of 2200 at
10 kHz. A large variation in ε 0 with respect to frequency
near room temperature indicates the extrinsic polarization due
to the MW effect [22–24]. With decrease of temperature,
ε 0 decreases following a sharp drop; this drop is associated
with a relaxation peak in ε 00 and the peak position shifts
to higher temperature with increase of frequency. At low
temperatures ε 0 exhibits a saturation value of ∼10 irrespective
of the applied frequency, and this can be regarded as the
intrinsic ε 0 of the LNMO system. This value is much smaller
than the theoretically predicted value of ε 0 (42) from the
phonon and electronic contribution [16]. Lin et al have
described the dielectric property of LNMO as a relaxor like
phenomenon [25]. In general, relaxors contain permanent
electrical dipoles in nanoscale regions, where the peak
position of ε 00 coincides with the loss tangent (tan δ) peak as
well as the maximum dε0 /dT value [26, 27]. In figure 4(b)
we have plotted the tan δ and ε 00 of the LNMO bulk sample
for 10 kHz; a large temperature separation between tan δ and
ε 00 peaks rules out the existence of permanent dipoles in our
LNMO bulk sample. In fact, the appearance of relaxor like
behavior in an electrically heterogeneous system can also
occur due to the crossover in the relaxation time associated
with the grains and grain boundaries [24, 28]. We have
analyzed the relaxation mechanism by the thermally activated
Arrhenius behavior given by Figure 4. Temperature variation of (a) the real part of ε, (b) ε 00 and
tan δ and (c) ε00 ; the inset in (c) shows a plot of ln τ versus 1/T and
the solid line indicates the fit to equation (1).
 
−Ea
τε = τε0 exp , (1)
KB T
where Ea is the activation energy required for the relaxation mechanisms [31]. Figure 5(a) shows the imaginary part of
process and τε0 is the pre-exponential factor. The plot of Z 00 as a function of the frequency for different temperatures
ln τ versus 1/T is shown in figure 4(c), where the solid (100–300 K). The impedance data have been normalized by
lines indicate the fit to equation (1). The obtained activation taking the geometric correction factor g = A/2d, where A is
energy and relaxation time are 0.22 eV and 4.5 × 10−10 s, the electrode area and d is the thickness of the pellet [32].
respectively. As shown in figure 5(a), the impedance at low temperature
is dominated by a single relaxation peak; however, with
3.4. Impedance studies increase of temperature a second relaxation emerges at much
lower frequencies and both the peaks are systematically
Impedance spectroscopy is a powerful tool to investigate the shifted to higher frequency with increase of temperature.
electric properties of materials in a wide range of frequency Similarly, the imaginarily part of M 00 (figure 5(b)) exhibits
and temperature [29, 30]. This technique is employed to two relaxation peaks, one at high frequencies and the other
study the intra and inter grain inhomogeneities. Since different at low frequencies. It can be noticed that the high frequency
dielectric functions have different relaxation times, it is often relaxation in both the dielectric functions exhibits much
better to represent the data in different dielectric functions in stronger dispersion compared to the low frequency relaxation.
the frequency plots to capture the essential physical process Figure 5(c) shows a combined plot of M 00 and Z 00 versus
of the system. Combined plots of the imaginary part of frequency for 180 K, where the impedance plot is dominated
the impedance (Z 00 ) and the electrical modulus (M 00 ) can by the highest resistive component and, on the other hand, the
distinguish between the long range and localized conduction M 00 plot is dominated by the lowest capacitance component

4
J. Phys.: Condens. Matter 24 (2012) 495901 K Devi Chandrasekhar et al

Figure 5. The frequency variation of (a) the imaginary part of the impedance (Z 00 ) and (b) the imaginary part of the electrical modulus (M 00 )
for different temperatures. (c) Combined plots of Z 00 and M 00 versus frequency for 180 K and (d) plots of ln τ versus 1/T for the Z 00 and M 00
peaks. The solid lines indicate the fit to equation (1).

with high frequency inclination [24]. The relaxation with high Table 2. Grain and grain boundary activation energies and
R and C leads to a large relaxation time and it will appear at relaxation times for Z 00 and M 00 .
the lower frequency side of the frequency spectrum, which Grain Grain boundary
can be assigned to the grain boundary contribution. The high Z 00
Ea (eV) 0.14 0.119
frequency relaxation with low R and C can be assigned to τ (s) 2.4 × 10−10 5.6 × 10−6
the grain contribution. It can be noticed that both the grain M 00 Ea (eV) 0.155 0.127
and grain boundary peaks in M 00 and Z 00 appear close in τ (s) 2.2 × 10−10 6.02 × 10−6
the frequency spectrum, which indicates that the transport
at grains and grain boundaries is the combined effect of
localized and long range conduction mechanisms [31]. To The shape and the width of the arc indicate the type of
get further information about the relaxation mechanism at relaxation mechanism for the system. In the case of a single
the grains and grain boundaries, we have analyzed the data relaxation process, a perfect semicircular arc describing a
using the thermally activated Arrhenius mechanism, and the Debye function can be obtained with its center on the real
respective plots are shown in figure 5(d). The grain relaxation axis. In real systems, depressed semicircles are common, and
deviates from Arrhenius behavior at low temperatures (below they indicate the distribution of the relaxation time. This can
130 K). However, the grain boundary shows a satisfactory fit. be estimated from the angle between the real axis and the line
The obtained fitting parameters for both the impedance and to the center of the circle at the high frequency intercept. In
modulus functions are shown in table 2. It can be noted that such cases an ideal capacitor C is replaced by a constant phase
the range of activation energy in both the cases is comparable element (CPE) Q; this is defined as [30]
to the polaronic relaxation [33]. However, the relaxation time
associated with the grain boundary is almost 4 orders higher 1
ZQ∗ = , (2)
than that of the grain; this implies that charge carriers at grain (iω)n C
boundaries have lower mobility than that in grains. where n is the empirical exponent and its value varies from
The complex impedance plots of Z 0 versus Z 00 (Nyquist) 0 to 1; for an ideal capacitor n = 1 and for an ideal resistor
at different temperatures are shown in figure 6(a). The it is 0. The capacitance values obtained from the CPE can
complex impedance plots are characterized by successive be corrected to units of Faraday cm−1 (F cm−1 ) using the
semicircular arcs of grain, grain boundary and electrode standard conversion [32].
contributions, and each arc is represented by a parallel As shown in figure 6(a), the complex impedance
combination of two RQ elements, where R and Q are the plots exhibit single semicircular arcs at high temperatures.
resistance and the constant phase element of the circuit. With decrease of temperature, the impedance shows two

5
J. Phys.: Condens. Matter 24 (2012) 495901
Figure 6. (a) Nyquist plots for different temperatures; the inset
shows the plot of Z 0 versus Z 00 /f . (b) The temperature variation of
the grain and grain boundary resistivities, where the solid lines
indicate the fit to equation equation (3). The inset shows the grain
resistivity variation and the solid line indicates the fit to equation
equation (4). (c) Variation of the dc resistivity with respect to T −0.25 .
semicircular arcs and these can be assigned to the grain and
grain boundary contributions. The complex impedance data
have been analyzed by considering the electrical equivalent
circuit of two RQ elements connected in series, as shown in
6
K Devi Chandrasekhar et al
the inset of figure 6(a); the data have been fitted using ZSIMP
WIN version 2 and the solid lines indicate the best fit with
the experimental data points. The obtained fitting parameters
are shown in table 3. The resistivity values increase with
decrease of temperature, indicating the semiconducting nature
in both the grain and grain boundary regions. It is well
known that close relaxation times of different contributions
(corresponding to the grain boundary and the electrode, etc)
cannot be resolved from the usual Nyquist plot and show up
as a single semicircular arc. In order to validate the above
circuit model and clarify the low frequency semicircular arc
we have presented the impedance data in a Z 0 versus Z 00 /f
plot, as suggested by Abrantes et al and shown in the inset of
figure 6(a) [34]. As shown in the figure, the impedance data
clearly reveal two regions with different slopes corresponding
to grains and grain boundaries, and the interfacial relaxation
between the sample and the electrode is absent within our
frequency window. This confirms that the MW interfacial
polarization in LNMO originates from the blocking of charge
carriers at the grain and grain boundary interface.
To explore the conduction mechanism at the grains and
grain boundaries, the obtained resistivity from the Nyquist fit
has been analyzed using different conduction mechanisms.
According to the Arrhenius law, the thermal activation
mechanism can be expressed as [30]
 
E0
ρ = ρ10 exp , (3)
KB T
where ρ10 is constant and E0 is the required activation energy
for the conduction process. Figure 6(b) shows the fitting of the
Arrhenius law to the experimental data. The grain boundary
shows good agreement in the entire measured temperature
range with an activation energy of 0.14 eV.
At grains, the Arrhenius behavior fails below 200 K (as
shown in figure 6(b)), but Mott variable range hopping (VRH)
fits well in the entire temperature range, as shown in the inset
of figure 6(b). The VRH mechanism is given by
"  1 #
T0 4
ρ = ρ0 exp , (4)
T
where ρ0 and T0 are constants; T0 is given by T0 =
24/[π kB N(EF )ξ 3 ], where N(EF ) is the density of localized
states at the Fermi level and ξ is the decay length of the
localized wave function. The T0 value is ∼5.18 × 108 K
and is close to the reported value for LNMO [25]. The
density of the localized state, N(EF ), is of the order of
3.37 × 1018 eV−1 cm−3 (by taking ξ = 0.37 nm, which
is the average distance between two neighboring Ni or Mn
ions obtained from the structural refinement). The hopping
energy has been estimated from the T0 using the formula
W = 0.25kB T00.25 T 0.75 ; it is varies from 0.13 to 0.22 eV in the
temperature range of 140–290 K. Also, the resistivity from dc
transport follows the VRH, as shown in figure 6(c). In fact, the
dc conduction mechanism in other double perovskite systems
has been explained using the VRH mechanism [25]. The
obtained hopping energy from the dc resistivity (0.16–0.24 eV
for 170–290 K) is very close to the dielectric relaxation
J. Phys.: Condens. Matter 24 (2012) 495901 K Devi Chandrasekhar et al

Figure 7. (a) The temperature dependent real part of ε for a magnetic field of 0 and 5 T and the MD (%) for 100 kHz. (b) The frequency
dependent MD variation for different temperatures. (c) The temperature dependent M; the isothermal MR at 220 K is shown in the inset. (d)
The isothermal MD behavior for different temperatures, where the inset shows the dc bias effect on capacitance at different frequencies and
temperatures.

Table 3. Variation of the grain and grain boundary electrical parameters with respect to temperature.
T (K) CG (pF cm−1 ) ρG (×106  cm) nG CGB (pF cm−1 ) ρGB (×106  cm) nGB
160 3.735 0.7741 0.8366 1004 27.86 0.7921
170 3.873 0.4136 0.8133 831.19 11.84 0.8224
180 4.034 0.2405 0.785 730.26 6.048 0.8636
190 4.1407 0.1341 0.7505 704.4 3.536 0.8826
200 4.212 0.081 65 0.7091 694.3 2.328 0.8946
210 4.2582 0.050 09 0.6432 688.64 1.561 0.9057
220 4.2499 0.031 75 0.5799 689.17 1.107 0.9131
230 4.313 0.020 62 0.5116 695.1 0.807 0.9196
240 4.2014 0.013 66 0.4725 722.35 0.6012 0.9242
250 3.967 0.008 96 0.4304 738.24 0.4432 0.9259
260 3.478 0.006 05 0.4304 752.3 0.349 0.9254
270 2.785 0.004 16 0.3938 773.3 0.2734 0.9253
280 1.8486 0.003 02 0.3181 781.5 0.2175 0.9262
290 0.930 11 0.002 46 0.2075 808.7 0.1882 0.935

and grain hopping energy obtained from the impedance; this
indicates that the observed dielectric relaxation mechanism is
dominated by the grain conduction.
3.5. Magnetodielectric study
Figure 7(a) shows the temperature dependent ε 0 for 100 kHz
with and without an external magnetic field. At low
temperature the MD value is close to zero and it increases
with increase of temperature and attains a maximum value
of 2.5% close to the dielectric step and decreases at high
temperatures. The sign and magnitude of the MD observed
here is very different from the reported MD values on LNMO
bulk [11, 16]. However, the sign of the MD is similar
to that of other double perovskites [13, 15, 20]. Although
the appearance of an MD peak (250 K) near the magnetic
transition hints at a correlation between ε 0 and the magnetic
ordering, a close examination of the MD behavior for different
frequencies indicates that MDmax appears at the dielectric
relaxation maxima (at the measured frequency), implicating
that the MD follows the relaxation phenomena (relaxation
time τ = RG CGB ) rather than the magnetic ordering. The
frequency dependent MD (%) for different temperatures is
shown in figure 7(b), where the MD peak position moves to
the high frequency side with increase of temperature and a
strong suppression of the MD peak is noticed above 260 K.

7
J. Phys.: Condens. Matter 24 (2012) 495901
The decrease in magnitude of the MD at higher frequencies
signifies MW induced MD behavior. The field dependent MD
(100 kHz) behavior for different temperatures is shown in
figure 7(d). The MD shows path independent linear variation
with the applied magnetic field, which rules out the thermal
effects in the MD measurements. The observed MD variation
does not obey M 2 dependence (figure not shown here), which
rules out the spin–lattice coupling as a possible origin for the
observed MD behavior.
3.6. Magnetoresistance and dielectric permittivity with dc
bias
The temperature dependent MR with the application of
a magnetic field of 5 T is shown in figure 7(c). An
MR of −0.2% has been observed near 300 K and the
negative MR increases with decrease of temperature across
the paramagnetic to ferromagnetic transition and attains a
saturation value of −2.5% below the magnetic ordering.
Although the sign of the MR is similar to that of the
isostructural La2 CoMnO6 system, the nature of the MR is
different. In La2 CoMnO6 , the MR shows a linear variation
with temperature without any anomaly near the magnetic
ordering [20]. The appearance of the MR across the magnetic
transition and its saturation suggests a correlation between
the magnetism and the transport mechanism in LNMO. In
the La2 NiMnO6 system, the hopping of polarons between
the transition metal sites depends on their relative spin
orientations, such that parallel spin alignment favors the
hopping mechanism [16]. The observation of a drastic change
in the MR near the magnetic transition can be attributed to
the enhanced spin-pair correlations across the paramagnetic
to ferromagnetic transition. The isothermal MR measured
at 220 K is shown in the inset of figure 7(c). A linear
variation of the MR with the applied magnetic field rules
out the spin polarization transport near the grain boundaries
as a possible origin for the MR [35]. The nature of the MD
around the magnetic transition is the same as that of the MR,
where a suppression of the MD is observed above 260 K
(figure 7(b)). However, below the magnetic ordering, although
the MR shows a temperature independent behavior, the MD
shows a strong frequency dependence following the dielectric
relaxation suggesting a large contribution from the MW effect.
Simulations on electrically heterogeneous systems by
Catalan et al have revealed the extrinsic MD effect due to the
combined effect of MR and MW interfacial polarization [8].
In the present case different transport mechanism at the
grains and grain boundaries with a large variation in
their resistivity results in band bending at the interface
which can lead to the formation of internal barrier layer
capacitor (IBLC) structure between the grains and the
grain boundaries. This is the source of the MW interfacial
polarization, and such an IBLC structure behaves like a
Schottky barrier and shows nonlinear C–V characteristics
in the MW region [36]. The dc bias dependent capacitance
(C–V) close to the MD peaks (at the respective frequencies)
was measured and is shown in the inset of figure 7(d); a
nonlinear nature of the C–V characteristics can be noticed.
8
K Devi Chandrasekhar et al
In an electrically inhomogeneous system, the space charge
region gives rise to a dielectric relaxation that is related to
the resistivity of the grains [37, 38]. In fact, the similar
relaxation energies obtained from dielectric (0.22 eV) and
dc transport (0.16–0.24 eV for 170–290 K) measurements
and the comparable magnitude of MR and MD suggests
that an enhanced polaron transport under a magnetic field
within the grain changes the relaxation time of the carriers
at the interface. We note, moreover, that the origin of the
observed MD in LNMO bulk is consistent with Catalan’s
explanation; it is driven by the combined effect of MR
and the MW interfacial polarization [8]. Such an extrinsic
origin is even validated in many well known multiferroic and
nonmultiferroic systems [9, 38, 39].
4. Conclusions
We have carried out detailed experiments on the impedance,
magnetic field induced dielectric properties, dc transport
and dc bias effects on the dielectric permittivity of LNMO
bulk samples. The temperature dependent dielectric properties
preclude the previous description of relaxor behavior of the
system. The impedance measurements revealed an electrically
inhomogeneous system with different transport properties
at the grains and grain boundaries. A small but positive
MD behavior found in our study is in contrast with the
recent literature [11, 16]. The observation of the comparable
magnitude of the MD and MR, the frequency dependence of
the MD and the nonlinear C–V suggests an extrinsic origin of
the MD due to MW interfacial polarization and MR.
Acknowledgments
This work was supported by the DST fast track project.
The authors also acknowledge the use of the SQUID VSM
facility at the CRF of IIT Kharagpur. Dr Rawat, UGC-DAE
Consortium for Scientific Research, Indore is acknowledged
for providing the data shown in figure 7(c).
References
[1] Kitagawa Y, Hiraoka Y, Honda T, Ishikura T,
Nakamura H and Kimura T 2010 Nature Mater. 9 797
[2] Manfred F 2005 J. Phys. D: Appl. Phys. 38 R123
[3] Tackett R, Lawes G, Melot B C, Grossman M,
Toberer E S and Seshadri R 2007 Phys. Rev. B 76 024409
[4] Lawes G, Ramirez A P, Varma C M and
Subramanian M A 2003 Phys. Rev. Lett. 91 257208
[5] Song K M, Park Y A, Lee K D, Yun B K, Jung M H, Cho J,
Jung J H and Hur N 2011 Phys. Rev. B 83 012404
[6] Adem U, Nénert G, Arramel A, Mufti N, Blake G R and
Palstra T T M 2009 Eur. Phys. J. B 71 393
[7] Jeroen van den B and Daniel I K 2008 J. Phys.: Condens.
Matter 20 434217
[8] Catalan G 2006 Appl. Phys. Lett. 88 102902
[9] Schmidt R, Ventura J, Langenberg E, Nemes N M,
Munuera C, Varela M, Garcia-Hernandez M, Leon C and
Santamaria J 2012 Phys. Rev. B 86 035113
[10] Parish M M and Littlewood P B 2008 Phys. Rev. Lett.
101 166602
J. Phys.: Condens. Matter 24 (2012) 495901
[11] Rogado N S, Li J, Sleight A W and Subramanian M A 2005
Adv. Mater. 17 2225
[12] Dass R I, Yan J Q and Goodenough J B 2003 Phys. Rev. B
68 064415
[13] Singh M P, Truong K D and Fournier P 2007 Appl. Phys. Lett.
91 042504
[14] Iliev M N, Guo H and Gupta A 2007 Appl. Phys. Lett.
90 151914
[15] Azuma M, Takata K, Saito T, Ishiwata S, Shimakawa Y and
Takano M 2005 J. Am. Chem. Soc. 127 8889
[16] Choudhury D et al 2012 Phys. Rev. Lett. 108 127201
[17] Padhan P, Guo H Z, LeClair P and Gupta A 2008 Appl. Phys.
Lett. 92 022909
[18] Chandrasekhar K D, Das A K and Venimadhav A 2012
J. Phys.: Condens. Matter 24 376003
[19] Lin Y Q and Chen X M 2011 J. Am. Ceram. Soc. 94 782
[20] Murthy J K and Venimadhav A 2012 J. Appl. Phys.
111 024102
[21] Zhou S, Shi L, Yang H and Zhao J 2007 Appl. Phys. Lett.
91 172505
[22] Lunkenheimer P, Fichtl R, Ebbinghaus S G and Loidl A 2004
Phys. Rev. B 70 172102
[23] Lunkenheimer P, Krohns S, Riegg S, Ebbinghaus S G,
Reller A and Loidl A 2009 Eur. Phys. J. Special Topics
180 61
[24] Li M, Feteira A and Sinclair D C 2009 J. Appl. Phys.
105 114109
K Devi Chandrasekhar et al
[25] Lin Y Q, Chen X M and Liu X Q 2009 Solid State Commun.
149 784
[26] Neupane K P, Cohn J L, Terashita H and Neumeier J J 2006
Phys. Rev. B 74 144428
[27] Grubbs R K, Venturini E L, Clem P G, Richardson J J,
Tuttle B A and Samara G A 2005 Phys. Rev. B 72 104111
[28] Wang C-C, Zhang M-N, Xu K-B and Wang G-J 2012 J. Appl.
Phys. 112 034109
[29] Kremer F and Schönhals A 2003 Broadband Dielectric
Spectroscopy (Berlin: Springer)
[30] Jonscher A K 1983 Dielectric Relaxation in Solids (London:
Chelsea Dielectrics)
[31] Gerhardt R 1994 J. Phys. Chem. Solids 55 1491
[32] Schmidt R, Eerenstein W and Midgley P A 2009 Phys. Rev. B
79 214107
[33] Bidault O, Maglione M, Actis M, Kchikech M and
Salce B 1995 Phys. Rev. B 52 4191
[34] Abrantes J C C, Labrincha J A and Frade J R 2000 Mater. Res.
Bull. 35 727
[35] Siwach P K, Singh H K and Srivastava O N 2008 J. Phys.:
Condens. Matter 20 273201
[36] Biškup N, Andrés A D, Martinez J L and Perca C 2005 Phys.
Rev. B 72 024115
[37] Coehlo R 1978 Physics of Dielectrics (Amsterdam: Elsevier)
[38] Mario M 2008 J. Phys.: Condens. Matter 20 322202
[39] Kamba S, Nuzhnyy D, Savinov M, Šebek J, Petzelt J,
Prokleška J, Haumont R and Kreisel J 2007 Phys. Rev. B
75 024403