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Re-entrant spin glass behaviour and magneto-dielectric

effect in insulating Sm2NiMnO6 double perovskite†
Cite this: J. Mater. Chem. C, 2013, 1,
6565
P. Neenu Lekshmi,a G. R. Raji,a M. Vasundhara,a Manoj Raama Varma,*a
S. Savitha Pillaib and M. Valantcd

Received 21st June 2013
Accepted 29th July 2013
DOI: 10.1039/c3tc31203h
www.rsc.org/MaterialsC
The structure and magneto-dielectric properties of Sm2NiMnO6 double perovskite have been investigated.
The pure monoclinic bulk phase of Sm2NiMnO6 is an intrinsic B-site disordered ferromagnet showing a
second order magnetic phase transition
157 K, along with a low temperature re-entrant spin glass-like
transition (
20 K) due to the inherent coupling of Ni–Mn network with Sm3+ ion. Moreover, it is an
insulator with room temperature dc resistivity
108 U cm. Furthermore, the high dielectric permittivity
(
103) coupled with a shift in dielectric maxima towards higher temperature with frequency, analysis of
the phenomenological parameters (Tm, TB, g, DTrelax), and the validity of non-linear Vogel–Fulcher
relation, we define this ferromagnetic insulator as a relaxor-type dielectric material. Importantly, it
exhibits a positive intrinsic magneto-dielectric (MD) response
2% at 100 kHz under a low magnetic
field of 0.5 T close to 150 K. The intrinsic MD effect indicates a correlation between spin orientations on
the two magnetic sublattices (Ni and Mn) and the magneto-dielectric coupling in the ferromagnetic
regime. The insulating ferromagnetic behaviour coupled with MD effect make Sm2NiMnO6 an attractive
spintronic material.

I Introduction
Double perovskite oxides, A2B0 B00 O6, (A – alkaline earth metals
such as Ca, Ba, Sr, etc., or rare earth ions of larger ionic radii, B0
and B00 – transition metal cations or lanthanides with smaller
ionic radii) have received much interest since they provide a
unique opportunity to induce and control the multiferroic
behaviours in oxide systems. They display interesting proper-
ties, such as metallic/half-metallic ferromagnetic and magne-
toresistive properties as observed in Sr2FeMoO6 (ref. 1) (half-
metallic ferromagnet), Sr2FeReO6 (ref. 2) (half-metallic ferri-
magnet) and Sr2FeWO6 (ref. 3) (antiferromagnetic insulator),
together with a number of interesting phenomena, including
room temperature magnetoresistance, magneto-capacitance
and magnetostriction. The presence of mutually coupled
magnetic and dielectric properties, the so-called magneto-
dielectric (MD) or magneto-capacitance (MC) effect, are current
a
Materials Science and Technology Division, National Institute for Interdisciplinary
Science and Technology, CSIR, Trivandrum-695 019, India. E-mail:
manojraamavarma@yahoo.co.uk
b
Institute for Intensive Research in Basic Sciences, Mahatma Gandhi University,
Kottayam-686 560, India
c
Materials Research Laboratory, University of Nova Gorica, Nova Gorica-5000,
Slovenia
d
Center of Excellence for Biosensors, Instrumentation and Process Control, 5250
Solkan, Slovenia
† CCDC reference number 957848. For crystallographic data in CIF or other
electronic format see DOI: 10.1039/c3tc31203h
focuses of interest since they provide vast scientic and novel
technological impact.4–6 The rare earth based double perovskite
La2NiMnO6, is a single material platform with multiple func-
tions such as ferromagnetic semiconductivity, spin–phonon
and magneto-electric coupling near ambient temperature, and
is expected to have unprecedented device applications.7 These
complex physical properties arise from competing interactions
between magnetic (spins), structural (phonons) and polariza-
tion (charges) order parameters. While most transition metals
involved in single perovskites are antiferromagnetic insulators
due to the negative super exchange interaction between the
transition metal ions,8 distorted double perovskite La2NiMnO6
is a ferromagnetic insulator due to the positive super exchange
interaction between Ni and Mn cations.9–13 Such behaviour is
signicant for exploring spintronic materials since it allows MD
properties to be achieved. Furthermore, the B-site metal ion
ordering in the crystallographic lattice greatly modies the
magnetic, transport and MD properties of the material. The
reported large negative MD of 16%, near the ferromagnetic
transition (
280 K) in bulk ordered La2NiMnO6 was assigned to
the intrinsic spin–lattice coupling.4 Recently Choudhury et al.
reported a large MD coupling (8–20%) in the ferromagnetic
region in a partially disordered La2NiMnO6 polycrystalline
sample attributed to asymmetric hopping across the transition
metal cations.13 However, extrinsic effects like particle size,
grain boundaries, spin disorder, Maxwell–Wagner (MW) inter-
facial effect etc., can also inuence the dielectric response under
magnetic eld.14,15

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It has been reported that, depending on the type, charge and
size of the cation present in the B-site, some of the double
perovskites show interesting spin glass behaviour also. Spin
glasses are magnetic systems which exhibit a “freezing transi-
tion” to a state of a new kind of order in which spins are aligned
in random directions.16 The re-entrant spin glass (RSG) transi-
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tion is a well-known phenomenon of spin glasses emerging
from either long-range ferromagnetic (FM) or anti-ferromag-
netic (AFM) ordering above the spin glass transition tempera-
ture. Moreover, a few reports are available for the critical
exponents at the phase transition between the intermediate
ordered state and the high-temperature paramagnetic state of
the re-entrant systems. However, until now, the exact nature of
the re-entrant transition is still unclear and highly controversial
due to complex experimental data of RSG.17–21
It has been observed that the properties of La2NiMnO6 will
generally change noticeably with the substitution of La ion by
Rare-Earth (RE) elements with smaller ionic radius. Moreover,
the entire series of these oxides (RE2NiMnO6) have been
reported to be ferromagnetic with a decrease in TC, or JNi–Mn,
due to the larger deviation of the Ni–O–Mn bond angle from
180 with the substitution of heavier RE element. But the
investigation of RE2NiMnO6 (ref. 22–24) ceramics is relatively
sparse as compared to La2NiMnO6. Sm2NiMnO6 is reported to
be ferromagnetic with a double transition in the temperature
dependence of its magnetisation curve,23,25 however, its MD
studies have not been reported until now. The present investi-
gation focuses on the in-depth analysis of ac as well as dc
magnetisation measurements and here in this report, for the
rst time, we show the MD effect of Sm2NiMnO6. We also notice
that the present compound exhibits a higher resistivity value at
room temperature and an intrinsic MD effect which may orig-
inate from the weak spin–lattice interaction. Thus the observed
insulating ferromagnetic behaviour with MD coupling makes
Sm2NiMnO6 an attractive spintronics material.
II Experiment
Single-phase polycrystalline Sm2NiMnO6 samples were prepared
from polymeric precursors by the Pechini method. The analytical
grade metal nitrate solution was mixed with a stoichiometric
amount of citric acid and the resulting emerald-green chelated
solution was stirred for about 1 hour on a hot plate at 70  C.
Ethylene glycol was added to this solution and then heated to
approximately 150  C to allow the chelates to undergo poly-
esterication as well as to remove excess water. The resulting
yellowish-green-brown gel was slowly decomposed in air at
320  C. The product underwent a subsequent treatment in air at
800  C for 2 h in order to eliminate all the organic materials and
nitrates. The precursor powder was then grinded and calcined at
various temperatures, ranging from 900 to 1200  C with inter-
mediate grinding, with a nal sintering at 1300  C. The powder
X-ray diffraction pattern is obtained with a PANalytical X'pert
Pro diffractometer in Bragg–Brentano geometry with Cu-Ka
radiation in the 2q range of 10 to 90 with a step size of
0.008 . Reitveld renement of the diffraction pattern was carried
out using the GSAS soware. Temperature dependent ac
6566 | J. Mater. Chem. C, 2013, 1, 6565–6574
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susceptibility measurements, c(T), temperature dependent dc
magnetic measurements under eld cooled and zero eld cooled,
M(T) and magnetic isotherms, M(H), were performed in a SQUID
VSM magnetometer from Quantum Design. The electron trans-
port (resistivity) measurements were carried out by constant
voltage method in the temperature range of 10–300 K using a
known resistor. In this method, a constant voltage source (4 V)
and a known resistor was placed in series with the sample. Then
the voltage drop across the known resistor was measured using a
Kiethley nanovoltmeter (2182 A) and from that the unknown
resistance of the sample was calculated. For dielectric charac-
terisation disk samples with a diameter of 10 mm and height of 2
mm have been plated with silver paste and inserted into the cold
head of the closed cycle cryo cooler (ARS-2HV). The measure-
ments have been performed with a LCR meter (Agilent E4980A)
that has been compensated for the coaxial cable length and open
and short circuit calibrated. The magnetic eld has been applied
to the samples by inserting them into the center of a hollow
cylindrical NdFeB magnet.
III Results and analysis
A Structural characterisation
The X-ray diffraction pattern of the polycrystalline Sm2NiMnO6
conrmed the presence of a single phase monoclinic structure
with P21/n space group. The Reitveld renement result conrms
the monoclinic (P21/n) phase of Sm2NiMnO6. Since P21/n is a
maximal nonisomorphic sub group of Pbnm, it is difficult to
distinguish between P21/n and Pbnm space groups simply by the
X-ray diffraction technique especially if the ordering is incom-
plete and b is very close to 90 . However, renement using
orthorhombic Pbnm space group led to unsatisfactory results.
Further, the obtained lattice parameters and volume obtained
from renement using monoclinic P21/n are found similar to
the reported value of monoclinic Sm2NiMnO6 double perov-
skites.23,25 But, the lack of superstructure peak below 20
suggests that the ordering is not strong enough in the current
sample. Bond valence sum (BVS) formalism was done to
calculate the valence state of Ni and Mn ions. The effective
valence Vij between the ith and jth atoms is dened as
X
Vij ¼ eððd0 dij Þ=0:37Þ , where dij is the bond length between i and
j
j atoms and d0 is the bond valence parameter that has been
empirically determined for the i–j pair.26 Furthermore, the bond
valence sum calculated from Ni–O and Mn–O bond lengths,
using the soware SPuDs indicate valence uctuations between
Ni2+/Ni3+ and Mn4+/Mn3+. But the values are found to be more
close to Ni3+/Mn3+ that is consistent with the reported oxidation
state of high temperature sintered La2NiMnO6.11 Details of the
lattice parameters extracted along with renement parameters
and BVS are listed in Table 1.
B Magnetic characterisation
dc magnetisation. The M(T) measurements of zero eld-
cooled (ZFC) and eld-cooled (FC) cycles under the elds of
100 Oe, 2 T and 5 T in the temperature range 5 to 300 K are
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Table 1 Lattice parameters, structural refinement parameters and bond valence phase along with minor AFM phase. This coexistence of FM–
sum for Sm2NiMnO6 at room temperature AFM causing the spin uctuations may lead to the freezing of
spins at the lower temperatures, thereby causing the formation
Sm2NiMnO6
of the second transition at Tf, which is in turn understood in
Space group P21/n terms of glassy systems.27,28 The existence of the glassy state in
the vicinity of the FM transition gives rise to two possible types
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Lattice parameters of SG behaviour: Re-entrant Spin Glass (RSG) or Cluster-Glass

a (Å) 5.3469(2)
b (Å) 5.5076(2)
(CG). Furthermore, the irreversibility observed in ZFC and FC
c (Å) 7.6040(3) below TC and the remarkable shi in TC to higher tempera-
b (deg.) 90.042(9) tures with the application of elds, 156 K for 100 Oe, 162 K
Volume (Å3) 223.93(2) for 2 T and 172 K for 5 T, clearly suggest the presence of a
Rwp 0.0467 spin disorder and competing interactions due to the coexis-
Rp 0.0364
tence of FM–AFM phases in the supposed ferromagnetic
Bond valence sum region, Tf # T # TC, whereas the appearance of a sharp drop in
Ni2+ 2.58 magnetisation below Tf and the deviation from CW behaviour
Ni3+ 3.34 are indicative of RSG behaviour.29–33 Therefore the M–T data
Mn4+ 3.47 shows a possible frustrated state below the Curie temperature
Mn3+ 3.45
in Sm2NiMnO6, which needs further evidence.
Magnetic isotherms. In the inset of Fig. 2(a) and (b), we
present the magnetisation (M) vs. applied eld (H) curves of
Sm2NiMnO6 at 300 K in the range of 60 000 Oe to +60 000 Oe
and at 65 K in the range of 20 000 Oe to +20 000 Oe, respectively.
The M–H loop at 300 K is completely a straight line as in the case of
PM state. The M–H loop at 65 K has an ‘S’ like appearance, i.e. a
rapid increase in magnetisation value at lower magnetic elds but
does not saturate even at applied magnetic elds of 20 000 Oe,
with a small hysteresis at lower elds, indicating the co-existence
of frustrated and FM states. In order to characterise the magnetic

Fig. 1 Temperature dependence of field-cooled (FC) and zero-field-cooled (ZFC)

dc magnetisation measured at 100 Oe, 2 T and 5 T and inverse susceptibilities with
linear fit to Curie–Weiss law in the high temperature region for 100 Oe.

shown in Fig. 1. The M(T) curve clearly indicates a double

transition under 100 Oe eld; the rst one is a very sharp
transition at higher temperatures around 156 K, resembling a
paramagnetic (PM) to ferromagnetic (FM) transition, TC, and
the other one is at lower temperatures around 20 K, resem-
bling a spin glass/glassy behaviour, Tf. This double transition
and the irreversibility between FC and ZFC curves vanishes at
higher applied elds (H ¼ 2 T and 5 T) and both ZFC and FC
curves collapse into a single broad PM to FM like transition.
The inverse magnetic susceptibility of ZFC at 100 Oe in the
higher temperature range was tted to classical Curie–Weiss
(CW) law and is shown in Fig. 1. A deviation of the t to CW
law can be clearly seen for temperatures that are signicantly
above TC. The effective paramagnetic moment calculated from
the CW analysis is meff
5.76 mB F.U.1 [F.U. – Formula Units].
Moreover, the Curie constant (C) and the Weiss temperature
(Q) were determined to be 4.15 emu mol1 K1 and 172.51 K,
respectively. The positive value of Q calculated from the t
suggests the presence of predominantly ferromagnetic
Fig. 2 (a) Low field hysteresis loop measured at different temperatures in the
exchange interactions. The disappearance of the double tran- range 200 Oe to +200 Oe. Inset: M vs. H curves measured up to 6 T at 300 K, (b)
sitions with the application of higher elds and eld depen- low field hysteresis loop measured at 65 K and 150 K in the range 200 Oe to
dence on TC are a clear indication of the coexistence of FM +200 Oe. Inset: M vs. H curves measured up to 2 T at 65 K.

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ordering below TC, M(H) isotherms in the low eld regime
(200 Oe # H # +200 Oe) were also studied at different temper-
atures (5, 20, 30, 65, 75 and 150 K) and are shown in Fig. 2a. The
low eld ZFC hysteresis experiment was carried out in such a way
that the sample was cooled from 300 K to the required low
temperature and aer taking the M–H loop the sample was again
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heated to 300 K. This process was repeated for each temperature in
order to avoid the thermal remanence effect that might be present
in the sample below TC. At low applied elds, the M(H) curve
exhibits a typical FM-like hysteresis loop. At 150 K (Fig. 2b), the
hysteresis loop shows a lower remanent magnetisation, MR, (0.03
mB F.U.1) and coercive eld, HC, (10 Oe), moreover, the virgin
branch crosses the M(H) loop reecting either frustrated interac-
tion, or eld induced growth of the FM phase.34 On lowering the
temperature to 75 K the magnitudes of MR (0.17 mB F.U.1) and HC
(50 Oe) slightly increase, at 65 K the magnitude of HC is found to
be the same but MR (0.14 mB F.U.1) is decreased. Moreover, the
virgin branch crosses the hysteresis loop at 65 K also (Fig. 2b).
However at 30 K, the M(H) loop is similar to 75 K. At 20 K (
Tf),
there is a noticeable increase in MR (around 0.21 mB F.U.1) and
the vertex of the loop is found to be pointing to a much higher
magnetisation value. Interestingly, below Tf at 5 K, the hysteresis
loop shows a further decrease in MR. In a conventional spin glass
system the magnitude of MR and HC increases with decreasing
temperature,29 but here an anomaly is observed and it is signi-
cant with the development of spin canting effects below TC.29,35,36
Moreover, these features are in corroboration with those reported
in general for systems classied as RSG where the ferromagnetic
phase itself develops in the presence of competing
interactions.29,32,35
Fig. 3 (a) M vs. H around TC, (b) Arrott plots, M2 vs. H/M, (c) MAPs, M1/g vs. (H/M)1/b using critical exponents b ¼ 0.475 and g ¼ 0.98489. Inset: critical isotherm on a
log–log scale at TC ¼ 158 K along with the fitting curve to eqn (3), (d) Kouvel–Fisher plots for spontaneous magnetization Ms(0) and inverse initial susceptibility c01, (e)
temperature dependence of Ms(0) and c01 along with the fitting curves to eqn (1) and (2), respectively.
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In order to further understand the critical behaviour,
we have carried out isothermal magnetisation measurements
near TC. Fig. 3a shows a series of M(H) curves in the
immediate vicinity (152 K # T # 162 K) of the Curie temper-
ature at an interval of 1 K. The gradual change of the
M(H) curves and the curvature at low elds due to the co-
existence of frustrated state and FM state make it difficult to
extract an accurate value of TC. Fig. 3b shows Arrott plots, M2
vs. H/M, for the compound and it clearly indicates a positive
slope with non-linear curves showing curvature even at
higher elds. However, the straight line extrapolated to the
curve at a temperature of 152 K shows a positive intercept at
the M2 axis whereas the 162 K shows an intercept on the H/M
axis, indicating a second order phase transition between 152 K
and 162 K. The critical behaviour of magnetic systems with a
second order magnetic phase transition near the Curie
temperature is characterised by a set of interrelated
critical exponents, b, associated with the spontaneous mag-
netisation (Ms), g which is associated with initial magnetic
susceptibility (c0) and d, which is related to the critical
magnetisation isotherm at TC. They are mathematically
related as:
Ms(0) ¼ m0|s|b, s < 0, T < TC (1)
 
h0 g
c0 1 ¼ s ; s . 0; T . TC (2)
m0
H ¼ A0Md, s ¼ 0, T ¼ TC (3)
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where Ms(0) is the spontaneous magnetisation; c01 is the Table 2 The critical exponents obtained in this work from several methods and
inverse of the susceptibility; s is the reduced temperature comparison of critical parameters predicted by different theoretical models
  
T
s¼  1 ; TC is the Curie temperature and m0, h0 and A0 TC b g d Ref.
TC
are the critical amplitudes. For rst order ferromagnetic phase Sm2NiMnO6
transitions, the critical exponents are impossibly dened MAP 158.8 0.475 0.9849 This work
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because the applied magnetic eld can shi the transition Kouvel–Fischer method 158.42 0.4537 This work
158.35 0.9501 This work
which results in a eld dependent phase boundary TC(H).37,38 Power law 158.34 0.4319 This work
The analysis of static critical phenomenology near the Curie 158.38 0.9279 This work
temperature is capable of giving further evidence for re-entrant 158 3.0465 This work
behaviour.39–41 The TC and critical exponents can be easily Wisdom scaling relation 3.0735 This work
determined from several methods which include the modied Mean-eld model 0.5 1.0 3.0 45
3D Heisenberg model 0.365 1.336 4.80 45
Arrott plots (MAP) technique,42 the Kouvel–Fisher method43 and 3D Ising model 0.325 1.24 4.82 45
the Widom scaling relation.44 The MAP technique is based on Tricritical model 0.25 1 5 45
Arrott–Noakes equation of state, Spin glass 1 2.2 3.1 40

 1
H g 1
¼ as þ bM b ðHÞ (4)
M
from several models are summarized in Table 2 for comparison.
where a and b are material dependent parameters. The regular In earlier studies the critical exponents of the re-entrant systems
Arrott plot shows that the M2 vs. H/M relationship is based on are reported to have values in between the classical three
the mean-eld model of critical exponent of b ¼ 0.5 and g ¼ 1.0. dimensional ferromagnetic materials and those characterising
In the case of MAP, different values of b and g are taken as trial a spin glass transition.40,41 We have got an analogous behaviour,
exponents from various models for the construction of MAP which further supports the presence of RSG behaviour.
[(H/M)(1/g)  M(1/b)] and then are tted into the data of the linear ac susceptibility. To further characterise the RSG behaviour,
part or directly tted into the initial Arrott plot.45 The Ms(0) is c(T) measurements were done in an applied eld Hac ¼ 1 Oe in
determined from the intersection of the linear extrapolation of the temperature range 5 to 300 K at various frequencies ranging
1
the straight line in the modied Arrott plots with the M b axis, from 29 Hz to 999 Hz, shown in Fig. 4a. From the real, c0 (T) and
while the c01 corresponds to the intersection of these lines imaginary c00 (T) parts of susceptibility, a high temperature
 1
H g
with the axis. An initial value of TC is determined from
M
the isotherm that passes through the origin. These data are
tted to the exponential behaviour of eqn (1) and (2) to obtain
new values of b and g, respectively. These new values are then
used to obtain the new MAPs. This procedure is continued until
they converge to a stable value. Finally, we obtained the best
tted values as: b ¼ 0.475, g ¼ 0.9849 and TC ¼ 158.8 K and the
1
 1
H g
M b vs. is shown in Fig. 3c. The corresponding value of
M
d, obtained from the Widom scaling relation is
 
g
d¼ 1þ ¼ 3:0735. Thus the calculated d value is close to
b
the estimated, d ¼ 3.0465 value from the critical isotherm at
158 K (inset Fig. 3c), which is near to TC.
In addition, we also determined the critical exponents b and
g along with TC by the Kouvel–Fisher method,43
Ms ðTÞ T  TC
¼ (5)
dMs ðTÞ=dT b

c0 1 ðTÞ T  TC
¼ (6)
dc0 1 ðTÞ=dT g
and also directly from the power-law predictions of eqn (1) and
(2) which are given in Fig. 3d and e, respectively. The values of
Fig. 4 (a) Temperature dependence of ac susceptibility at various frequencies
TC and the critical exponents of Sm2NiMnO6 are obtained under Hac ¼ 1 Oe, (b) ln(s) vs. ln(t) [where reduced temperature, t ¼ (Tf  TSG)/TSG]
through different methods and the theoretical values derived with linear fit. Inset: ln(n) vs. Tf with the fit to Vogel–Fulcher law.

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maxima was observed at Tp around 150 K, which shows no effect

on frequency dependence, whereas a low temperature maxima
at Tf around 20 K exhibits a clear shi towards high temperature
with increasing applied frequency. Between the two maxima
(Tf # T # Tp) in c0 (T) a systematic plateau-like behaviour is
observed whereas in the case of c00 (T) broad shoulders are
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observed. The TC was obtained at 157 K by extrapolating the

1
linear part of CW t from 0 ðTÞ (not shown).
c
From the c(T) frequency variation measurements, both c0 (T)
and c00 (T) show strong frequency dependence at Tf, on the other
hand, the frequency dependence of the peak at Tp is found to be Fig. 5 Temperature dependence of ac magnetic susceptibility at various dc bias
fields under fixed Hac ¼ 1 Oe and f ¼ 88 Hz.
quite negligible. Thus it is apparent that the observed maxima
at Tf indicates the presence of a frustrated magnetic state, the
existence of spin glass-like nature, however, the maxima at Tp
suggest the presence of a strong ferromagnetic interaction. is the characteristic frequency of the clusters, Tf the freezing
Again, the double maxima observed in c(T) and the M(T) temperature and T0 is the Vogel–Fulcher temperature, which is
measurements are found to be similar, which further corrobo- the measure of inter-cluster interaction strength. The excellent
rates RSG behaviour.29–33 agreement of this t (inset Fig. 4b), with the rened parameters
For further clarication, analysis of the susceptibility data at Tf n0 ¼ 2  103, Ea/kB ¼ 2.16 and T0 ¼ 14.6, is a clear indication of
was performed. The maximum change in the freezing tempera- RSG behaviour.46
ture, DTf is denoted as DTf (u) ¼ DTf (u) ¼ T 999 Hz
 T 29 Hz
¼ 2.3 K. To further probe the RSG behaviour, ac susceptibility
f f
DTf measurements were proceeded with super imposed dc elds
The relative shi in freezing temperature,
½Tf DlogðuÞ
, can be (Hdc ¼ 0, 0.255, 4.53, 19.75, 49.95, 80.16 and 110.29 Oe) under
used to describe the magnetic order of the system. This value Hac 1 Oe and frequency 88 Hz in the temperature range 5 to 300
typically lies between 0.005 and 0.08 for a spin glass (SG) and is 2 K (Fig. 5). c0 (T) and c00 (T) show a shi in Tf towards lower
for non-interacting super paramagnetic materials. The obtained temperatures with a slight change in the magnitude while a
value 0.098  0.004 characterises our system to be more likely a drastic decrease in the magnitude for the Tp comes with
cluster glass type. Dynamical scaling analysis was performed increasing eld. The intensity of the peak at around TC in c00 (T)
 zn0 diminishes with increasing eld indicating the FM nature of the
s ðTf  TSG Þ
using the critical slowing down relation,17 ¼ , compound. Moreover, we observe an anomaly in the interme-
s0 TSG
diate temperature region, Tf # T # Tp, in c00 (T) whose magni-
where s is the relaxation time corresponding to the measured
 tude depends on the applied dc eld which yet again indicates
1
frequency s ¼ . Fig. 4b shows the dependence of s with the presence of frustration. This interpretation is supported by
n   
ðTf  TSG Þ the decrease in MR and the behaviour of virgin curve in the low
reduced temperature, t t ¼ . From the analysis, eld hysteresis loop at 65 K. This is a clear signature of RSG
TSG
TSG, the critical spin glass ordering temperature as frequency behaviour in the studied compound.31,35
tends to zero, s0, the characteristic relaxation time of single spin
ip, and the dynamic critical exponent, zn0 are determined as 14.9 C dc transport properties
K, 3.1  105 and 1.98, respectively, n0 is the critical exponent of
"  n0 # Fig. 6 shows the temperature dependence of dc resistivity (rdc)
Tf measured in the temperature range 50–300 K. The dc transport
correlation length, x ¼ 1 . For a spin-glass system,
TSG property shows high resistance of the compounds which
s0 ¼ 1013 and zn0 are typically found to lie between 4 and 12, the
higher value of s0 and lower value of zn0 implies slower spin ip-
ping, attributed to the presence of randomly oriented ferromag-
netic clusters. Such higher s0 values have also been observed in a
variety of magnetic systems including metallic alloys and oxides
showing RSG behaviour.31–33 Furthermore, the failure of Arrhenius

Ea

relation n ¼ n0 e kB Tf (not shown) implies that the dynamics are
not simply associated with the single-spin ips, but rather reect a
cooperative character, which is cluster glass like. To investigate
the interaction among RSG clusters, the Vogel–Fulcher law17 is

Ea

proposed, n ¼ n0 e kB ðTf T0 Þ . Here Ea is the activation energy or
the potential barrier that separates two adjacent clusters where n0 Fig. 6 Temperature dependence of dc resistivity. Inset: linear fit for Mott VRH in
the low temperature region.

6570 | J. Mater. Chem. C, 2013, 1, 6565–6574 This journal is ª The Royal Society of Chemistry 2013
 View Article Online

Paper Journal of Materials Chemistry C

precluded the resistivity measurements below 50 K. For oxide D Dielectric and magneto-dielectric behaviour
systems, different models have been proposed to describe the
Fig. 7a shows the temperature dependence of the real part, 30 , of
temperature dependent charge transport behaviour which is
dielectric permittivity, 30 (T), at several frequencies, which
dened by lnr f 1/n, where n ¼ 1, 2 and 4 corresponds to a
exhibits two dominant frequency-dependent dielectric relaxa-
simple thermal activation model, Efros–Shklovskii type
tions which saturate and become relatively frequency inde-
hopping, and Mott's variable range hopping (VRH), respec-
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pendent at lower temperatures. The presence of strong

tively.47 Among these the resistivity data is aptly following the
dielectric relaxations is also seen in the corresponding loss
VRH mechanism in the low temperature region (T < 180 K) as data, tan d(T) Fig. 7b. The peak temperature (Tm) at which
shown in the inset of Fig. 6. In Mott's VRH, the hopping maximum dielectric constant occurs is found to be frequency-
dynamics are controlled by collective excitation of the charge
dependent and shis to higher temperatures with an increase
carriers and the mechanism is given by,
in the measuring frequency. Relaxor like dielectric behaviour is
2 3
 1 well manifested from the frequency dependent peak in 30 (T) and
T 4
r ¼ r0 exp4 5
0
(7) from the frequency dependent tan d(T). Also, the maximum
T 0
value 3m of the dielectric constant decreases with increase in
24 frequency. A deviation from Curie–Weiss law can be clearly seen
where r0 and T0 are constants; T0 ¼ , where N(EF)
pkB NðEF Þx3 in the reciprocal of the dielectric constant (1/30 ) versus temper-
is the density of localized states at the Fermi level and x is the ature, at 10 kHz as shown in Fig. 7c. The reciprocal dielectric
decay length of the localized wave function and kB is the constant starts to follow the Curie–Weiss law above 250 K which
Boltzmann constant. The value of T0 is obtained as
1.7  108 is dened as the burn temperature (TB). The difference between
K, which is of a similar magnitude as observed in transition TB and Tm, (250 K  228 K ¼ 22 K) shows a characteristic diffuse
metal oxides.48 By taking x as 3.95 Å (the average distance transition. The evaluation of relaxor behaviour using a modied
between two neighboring Ni or Mn ions obtained from struc- Curie–Weiss law is shown in the inset of Fig. 7c. The value of g
tural renement), N(EF) is obtained as 8.5  1024 eV1 m1. The
1.98 obviously indicates that the material has an almost
hopping energy has been estimated from T0 using the formula completely diffused phase transition. Furthermore, the degree
kB of relaxation behaviour, where Tm(1000 kHz) and Tm(10 kHz) are the
Ea ¼ T0 1=4 T 3=4 . It varies from 0.05 to 0.13 eV in the
4 temperatures corresponding to the maximum dielectric
temperature range of 50–180 K. constant at 1000 kHz and 10 kHz, respectively, obtained at 99 K
suggests strong frequency dispersion. Like many relaxors, the

Fig. 7 (a) 30 vs. T curves at different frequencies. Inset: expanded view of low temperature relaxation, (b) tan d vs. T curves at different frequencies, (c) 1/30 vs. T at 500
kHz with CW fit. Inset: modified CW fit [log(1/30  1/3m 0
) vs. log(T  Tm)] at 500 kHz, (d) non-linear Vogel–Fulcher fitting.

This journal is ª The Royal Society of Chemistry 2013 J. Mater. Chem. C, 2013, 1, 6565–6574 | 6571

Journal of Materials Chemistry C
frequency dependence of the maximum in the loss tangent can
be well tted to the non-linear Vogel–Fulcher (VF) law,26
 
E
s ¼ s0 exp  a  (8)
kB Tm  Tf
which is used to characterize the frequency dispersion behaviour
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in relaxors, where s0 is the pre exponential factor; Ea is the acti-
vation energy; kB is the Boltzmann constant; Tm is the tempera-
ture at which maximum of 30 occurs at the angular frequency u ¼
2pn; s ¼ u1 and Tf is the static freezing temperature at which the
relaxation time s tends to innity. The best t of VF law (Fig. 7d)
to the experimental data shows a glassy behaviour analogous to
the spin glass state in magnetic materials with polarisation
uctuations above Tf. The glassy behaviour is attributed to the
interaction arising from B-site cation disorder and valence uc-
tuations.13,26 The parameters obtained from the non-linear t are
Ea ¼ 0.15 eV, s0 ¼ 2.65 ns and Tf ¼ 15.9 K.
The temperature dependent 30 measured both in the presence
and in the absence of a low external magnetic eld (0.5 T) at
different frequencies and similarly tan d are shown in Fig. 8a and
b, respectively. The % MD [dened by MD (%) ¼ 100(D3MD/30)]
and the % Magneto-Dielectric Loss [MDL (%) ¼ 100(Dtan dMD/
tan d0)] are shown in the inset of Fig. 8a and b, respectively. The
MD effect demonstrates a positive MD effect below 150 K and
which further decreases to give a colossal negative MD effect
above the transition temperature. Moreover, both MD effect and
MDL increase with eld for all temperatures below the FM
Fig. 8 (a) The temperature dependent 30 measured at 0 T (closed symbols) and
0.5 T (open symbols). Inset: % MD effect with temperature. (b) The temperature
dependent dielectric loss measured at 0 T (closed symbols) and 0.5 T (open
symbols). Inset: temperature dependence of % MDL effect.
6572 | J. Mater. Chem. C, 2013, 1, 6565–6574
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Paper
Table 3 Calculated effective magnetic moment, meff for the possible spin-state
configurations in Sm2NiMnO6
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Spin states meff ¼ ð2mSm Þ2 þ mNi 2 þ mMn 2
Mn3+ (S ¼ 2), Ni3+ (S ¼ 3/2) 6.47
(S ¼ 2), Ni3+ (S ¼ 1/2)
Mn3+ 5.46
Mn4+ (S ¼ 3/2), Ni2+ (S ¼ 1) 5.08
Mn2+ (S ¼ 2), Ni4+ (S ¼ 2) 7.86
Mn2+ (S ¼ 2), Ni4+ (S ¼ 1) 6.77
Mn2+ (S ¼ 2), Ni4+ (S ¼ 0) 6.15

1 SðS þ 1Þ  LðL þ 1Þ
mSm ¼ gSm 2 JðJ þ 1Þ 2 ¼ 0:8452 gSm ¼ 3 þ

2 2JðJ þ 1Þ
¼ 0:2857 ;
1
mNi =mMn ðspin-onlyÞ ¼ ½4SðS þ 1Þ2 :
transition but they show different signs above the FM transition,
which suggests that the observed MD effect may be an intrinsic
effect.49 However, the observed colossal negative MD effect above
the transition temperature clearly indicates the presence of
extrinsic contribution also. The intrinsic contribution originates
from the asymmetric hopping of charge carriers (between Ni and
Mn sites), whereas the extrinsic contributions may arise due to
particle size, spin disorder or Maxwell–Wagner relaxations, i.e.
from accumulated charge carriers near the grain boundaries.13,49,57
IV Discussions
The double magnetic transition observed in dc and ac mag-
netisations and the presence of large bifurcation in ZFC/FC
magnetisation below TC, with a sharp drop in magnetisation
below Tf, indicates the occurrence of re-entrant behaviour.
Deviation of the t to CW law for temperatures signicantly
above TC attributes to spin uctuations associated with glassy
systems.33 The various possible spin-state combinations for Ni
and Mn ions and the calculated total effective moment of
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Sm2NiMnO6, meff ¼ ð2mSm Þ2 þ mNi 2 þ mMn 2 are shown in
Table 3. The experimental meff (5.76 mB F.U.1) value is found to
lie in between that theoretically predicted for high spin (HS)
Mn3+ (t2g3, eg1), HS Ni3+ (t2g5, eg2) and HS Mn3+ (t2g3, eg1), low
spin (LS) Ni3+ (t2g6, eg1), which is likely to be due to the presence
of mixed spin states in Ni3+ (3d7 system). Ni3+ systems are close
to HS–LS transition point due to the increased covalency.
Moreover, the increased charge transfer will further increase the
effects of 3d spin–orbit coupling.58
The dc magnetisation also indicates the co-existence of FM–
AFM interactions in the supposed ferromagnetic region Tf # T #
TC, which is supported by the low eld hysteresis behaviour in the
temperature range Tf # T # TC. Thus the thermomagnetic anal-
ysis of ZFC and FC indicates the presence of competing FM–AFM
exchange interactions in the system, which may arise due to the
combination of intrinsic disorder50 along with inherent magneto
crystalline anisotropy.23 The intrinsic disorder might be attrib-
uted due to the presence of antiferromagnetic pairs such as
Mn3+–O–Mn3+, Ni3+–O–Ni3+, which have been introduced due to
the intrinsic antisite boundary in Ni/Mn network so that the
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Paper
ferromagnetic interaction is weakened.9,13 The inherent contri-
bution arises from the spin–orbit coupling between Mn–Ni
network and Sm3+ ion.23–25 It is proven from the past studies that
Sm3+ spin order at low temperatures and the 4f Sm spins might
cause an AFM interaction23–25,51,52 with the FM Ni3+–O–Mn3+ that
may be causing the sharp down turn at 20 K in the ZFC–M(T)
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curve with the eld of 100 Oe and the presence of a small peak in
c(T) around 20 K. However, the appearance of hysteresis in the
low eld M(H) below Tf (T ¼ 5 K) suggests the presence of a
competing AFM–FM interaction. Moreover, the observed low
temperature peak in the dc magnetisation depends largely on the
magnitude of applied elds which further supports the
competing AFM–FM interactions51–54 resulting in RSG behaviour
in Sm2NiMnO6. Moreover, rigorous critical analysis near the
Curie temperature shows the values of the exponents (b, g, d)
slightly deviate from the mean eld values, which in turn could be
due to the presence of competing magnetic interactions, and
thereby establishes the RSG behaviour. Moreover, the detailed
analysis of ac susceptibility near Tf along with ac superimposed
dc measurements strongly supports the RSG behaviour.
Resistivity shows an insulating type dependence on tempera-
ture, being rdc
108 U cm at 300 K. The three classes of models
for resistivity in oxides do not t the experimental data in the
whole measured temperature range (50–300 K). Among them
resistivity evolution in the low temperature region (T < 180 K)
follows the VRH model. This type of hopping conduction is typical
of phase separated systems (FM and AFM clusters) where the
charge carriers move by hopping between two localized electronic
states.55 Thus the overall resistivity behaviour is consistent with
the hopping motion of the charge carriers through such localized
states, as observed in many disordered systems.47
The dielectric transport studies clearly show the presence of
double dielectric relaxations. The deviation from Curie–Weiss
law, the parameter g
2 obtained from modied Curie–Weiss
t, the degree of relaxation, DTrelax
99 K, and the validity of
non-linear Vogel–Fulcher relationship indicate a glassy like
characteristic and provide direct evidence for a relaxor dielectric
behaviour. This particular nature indicates that the system
freezes to a glassy state below a certain temperature and thereby
takes much longer to respond to the small external ac signal.
The low temperature dielectric relaxation may arise from the
asymmetric hopping of charge carriers between Ni and Mn ions
which can be attributed to the presence of polarized nano-
regions (PNRs) creating a defect related hopping mecha-
nism.26,56 The PNRs are characteristics in the double perovskite
structure arising from structural disorder in the lattice, due to
the inhomogeneous distribution of the B-site cations (due to the
coexistence of two different B-site cations Ni and Mn) with
valence uctuations. The obtained activation energy from the
VF t for the dielectric relaxation (
0.15 eV) is close to the
hopping energy obtained from the VRH mechanism (0.13 eV for
180 K) from the dc resistivity which further gives an evidence for
the presence of hopping mechanism. Again, the observed
colossal dielectric response above 150 K which may arise from
the extrinsic Maxwell–Wagner kind relaxation, which emerges
from the different conductivities near the grain boundaries due
to the presence of accumulated charges.13,57 Furthermore, the
This journal is ª The Royal Society of Chemistry 2013
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Journal of Materials Chemistry C
appearance of a spin glass like transition and dipolar freezing
character around the same low temperature regime (below 20 K)
support the possibility of a multiglass state at lower tempera-
tures.13,59 Interestingly a notable intrinsic positive and an
extrinsic colossal negative MD response are observed below and
above the FM transition temperature, respectively. The intrinsic
effect may arise from the connection between the spin orien-
tations on the two magnetic sublattices (Ni and Mn) and the
magneto-dielectric coupling below the ferromagnetic transition
temperature. Moreover, in the presence of even a low magnetic
eld, the spin–spin correlation is signicantly enhanced,
leading to an increasing MD effect up to somewhere near the
ferromagnetic transition temperature. However, the MD effect
further decreases even in the presence of the magnetic eld due
to thermal disordering of the spin orientation.13
V Conclusions
The present investigation reports polycrystalline Sm2NiMnO6
double perovskite oxide crystallises into a single phase mono-
clinic structure with a phase group P21/n having intrinsic B-site
disordered Ni3+/Mn3+ ion pairs with the characteristic features of
an insulating RSG behaviour along with relaxor dielectric prop-
erties. Furthermore, the magneto-capacitance measurements
even under a low magnetic eld of 0.5 T at 10 kHz show a positive
intrinsic MD response (
2%) below the FM–PM transition
temperature (
150 K) and a negative extrinsic colossal MD effect
above the transition temperature. From the experimental
evidences, we suggest the RSG behaviour in the compound arises
due to the presence of competing magnetic exchange interactions
induced by intrinsic disorder along with inherent coupling of Ni–
Mn network with Sm3+ ion. Moreover, the observed colossal
dielectric response and the dielectric relaxation dynamics may
arise due to the existence of PNRs in a disordered surrounding
which in turn is due to the presence of intrinsic antisite disorder.
Furthermore, the observed positive MD effect indicates a corre-
lation between spin orientations on the two magnetic sublattices
(Ni and Mn) and the magneto-dielectric coupling in the ferro-
magnetic regime. These observations suggest Sm2NiMnO6 is an
attractive spintronics material since the insulating ferromagnetic
nature along with magneto-dielectric properties are of capital
importance for exploring spintronic materials.
Acknowledgements
P. Neenu Lekshmi is thankful to Council of Scientic and
Industrial Research (CSIR), India for granting the Senior Research
Fellowship. M. Vasundhara and M. R. Varma acknowledge
Department of Science and Technology (DST), and CSIR, India
granted Project SURE (No. CSC0132) for the nancial support.
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