Journal of Magnetism and Magnetic Materials 563 (2022) 169950

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Journal of Magnetism and Magnetic Materials

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

Effect of reentrant spinglass-like states on Schottky Anomaly and exchange

bias in polycrystalline Sm0.5Y0.5Fe0.58Mn0.42O3
S. Raut a, *, S. Chakravarty b, H.S. Mohanty c, S. Mahapatra a, S. Bhardwaj d, A.M. Awasthi d,
B. Kar a, K. Singh h, M. Chandra d, A. Lakhani d, V. Ganesan d, i, M. Mishra Patidar d, j,
R.K. Sharma e, Velaga Srihari f, H.K. Poswal f, S. Mukherjee g, S. Giri g, S. Panigrahi a, *
a
Department of Physics and Astronomy, NIT Rourkela, Sundargarh 769008, Rourkela, Odisha, India
b
UGC-DAE Consortium for Scienti c Research, Kalapakkam Node, Kokilamedu 603104, Tamil Nadu, India
c
Department of Physics, GIET University, Gunupur, Odisha 765022, India
d
UGC-DAE Consortium for Scienti c Research, University Campus, Khandwa Road, Indore 452001, Madhya Pradesh, India
e
Indus 2 Synchrotron Facility, Raja Ramanna Centre for Advanced Technology (RRCAT), Indore 452013, Madhya Pradesh, India
f
High Pressure and Synchrotron Radiation Physics Division, Bhabha Atomic Research Centre, 400085 Mumbai, Maharashtra, India
g
School of Physical Sciences, Indian Association for the Cultivation of Science, 2A&2B Raja SC Mullick Road, Jadavpur, Kolkata 32 (WB), India
h
National Institute of Technology, Jalandhar, G.T. Road, Amritsar Bypass, Jalandhar (Punjab, 144011), India
i
Medi-Caps University, Indore, A.B. Rd, Pigdamber, Rau, Indore, Madhya Pradesh 453331, India
j
Emerald Heights International School, A.B. Road, Rau, Opposite Akashwani, Indore (MP) 453331, India

A R T I C L E I N F O A B S T R A C T

Keywords: The speci c-heat and exchange bias effects in polycrystalline Sm0.5Y0.5Fe0.58Mn0.42O3 [SYFM (58–42)] have been
Speci c heat investigated within the temperature interval of 2–300 K. Speci c-heat measurements as a function of temper-
Weak ferromagnetism ature have revealed a sizable linear contribution at low temperature that may be associated with the glassy
Exchange bias effect
magnetic ordering, alongwith a diffused Schottky peak over a wide temperature range between 2 and 20 K. The
observed distribution of Schottky levels is explained by the inhomogeneity of the molecular eld in the spinglass
(SG) state that leads to variable splitting of the Kramer’s ground-state doublets in Sm3 + ions. A nite zero eld
exchange bias (EB) effect have been observed at low temperatures for T < 70 K. The eld dependency of the
exchange bias showed the tuning of the sign of EB that can be attributed to the competition of the interfacial
exchange bias and atomic EB arising from the cooling eld induced anisotropy of the weak ferromagnetic mo-
ments of the constituent ions of Fe3+/Mn3+.
.

1. Introduction
For more than half a century, group of perovskites RMO3 with rare
earth cations (R3+) in the A site and rst row transition metal cations
(M3+) in the B site has been investigated thoroughly owing to the
exhibited wide varieties of physical properties and exotic ground states
that are not only interesting in device applications but also fundamen-
tally important in condensed matter physics [1–4]. RFeO3 and RMnO3
compounds has been widely studied in the context of spin induced
magnetoelectricity and multiferroicity [5–8]. These family of perov-
skites exhibit an exotic magnetic ground states and correlated properties
that arises from the complex interaction of the 3d-4f moments. For
example the temperature induced spin reorientation (SR) below their
Neel temperature TN in orthoferrites is primarily caused by the aniso-
tropic super-exchange R3+-Fe3+ interaction [9,10]. So in orthoferrites
with diamagnetic ions such as Y3+, Yb3+, Lu3+ the SR transition doesn’t
occur [11,12]. RFeO3 has a very high paramagnetic-antiferromagnetic
transition temperatures (TN = 640–740 K) [11,12] arising from the
strong Fe3+-Fe3+ near neighbour symmetric superexchange interactions.
However, due to antisymmetric Dzyaloshinskii-Moriya Interaction (DM)
[13,14] causes the near neighbour Fe spins to get slightly canted giving
rise to weak ferromagnetism in the materials below their TN.
On the other hand, RMnO3 has TN at very low temperatures [7,8]
owing to the as compared weaker Mn3+-Mn3+ superexchange

* Corresponding author.
E-mail address: subhajitrut@gmail.com (S. Raut).

https://doi.org/10.1016/j.jmmm.2022.169950
Received 17 March 2022; Received in revised form 2 September 2022; Accepted 8 September 2022
Available online 18 September 2022
0304-8853/© 2022 Elsevier B.V. All rights reserved.
S. Raut et al.
interaction. It has been previously observed that substitution of Mn3+ in
Fe3+ lattice in compounds such as YFeO3 invoke the temperature
induced SR transition which is of First order in nature. This is similar to
Morin transition observed in α-Fe2O3 (Hematite) near 260 K [15]. With
increase of x in YFe1-xMnxO3, TN decreases while TSR increases and these
two transitions occur close to 330 K for x = 0.45 [16]. YFe0.6Mn0.4O3 is
found to exhibit magnetodielectric effect adjunct to TSR ~ 317 K [17].
Such magnetodielectric materials can also have potential applications in
spin-charge transducers, microwave tunable lters, miniaturization of
antenna and magnetic sensors [18]. Earlier literatures also reported in
heavily doped systems such as YFe0.6Mn0.4O3 [16,17] and YFe0.5Cr0.5O3
[19,20] about the occurrence of magnetization reversal or negative
magnetization (NM) at temperatures below TSR and TN respectively.
NM, different from superconducting states, is described as a phe-
nomena of switching overall magnetization from positive to negative
(negative to positive) values when measured under positive (negative)
magnetic elds. It is usually observed in systems having two or more
magnetic moments, under the in uence of strong magnetocrystalline
anisotropy. It is usually observed in ferrimagnets (FIM) [21,22] with
different magnetic ions or same magnetic ion at different crystallo-
graphic sites, having different temperature dependency of the up (M↑)
and down (M↓) sublattice magnetizations. The up (M↑) and down (M↓)
magnetizations being antiferromagnetically coupled causes neutraliza-
tion of each other moments, leading the net magnetization (M) to be
zero. The point of null magnetization is termed as the compensation
temperature (Tcomp) and upon decreasing temperature below Tcomp,
(M↓) thermal variation dominates causing net M to become negative.
However in mixed systems of RMO 3 like.
YFe0.5Cr0.5O3 [19,20], LuFe0.5Cr0.5O3 [24], YFe0.6Mn0.4O3 [16], the
NM below TN / TSR have been attributed to the eld cooled induced
anisotropy of the weak ferromagnetic moments originating from anti-
symmetric DM interaction between various magnetic species. Previously
mean eld approximation and Monte Carlo simulations showed that the
DM interaction between various pairs of magnetic ions in YFe0.5Cr0.5O3
[19,25], LuFe0.5Cr0.5O3 [25] are of the form of D Fe-Fe || D Cr-Cr || - D Fe-Cr.
Thus the NM below Tcomp arises from the ferrimagnetic spin structure
comprised by the weak ferromagnetic moments of different magnetic
species under FC condition. In analogy with this conclusion the NM state
in YFe1-xMnxO3 (x = 0.40, 0.45) is attributed to the ferrimagnetic
ground state resulting from antiferromagnetic coupling of the canted
moments of Fe–O–Fe and Mn–O–Mn with that of collinear Fe–O–Mn
moments [17].
Another potentially applicable phenomena exhibited by magnetic
materials in single phase [20–27] or heterostructure [28–36] is the ex-
change bias effect. EB is a phenomena where the hysteresis M-H loops of
a magnetic material measured at certain temperatures are found to be
shifted horizontally (along the H axes) and vertically (along the M axes),
when the system is driven through zero eld cooled (ZFC) [37] / or eld
cooled conditions [35–38]. Exchange bias since its discovery by Mei-
klejohn and Bean [38], have been a signi cant topic of research in
magnetism. Initially foccussed in antiferromagnetic (AFM) /ferromag-
netic (FM) bilayers [38], EB effect have been discovered in several
materials with coexisting magnetic phases such as spinglasses (SG), FM,
AFM, canted AFM, FIM, that have been reviewed by several research
groups [39–42]. Both the NM and EB have been observed in monophasic
metal oxides such as Co2VO4, GdBaMn 2O5, core–shell La0.2Ce0.8CrO3,
Sr2YbRuO6, multiferroic Co(Cr0.95Fe0.05)2O4, intermetallic compounds
YbFe4Al8, hexacyanide SmxGd1-x Cr(CN)6⋅4H2O, orthoferrites and
orthochromates [20–24,26,29,43] and so on. This renders them to be
useful in constructing thermomagnetic switches, tunable magneto-
caloric devices, magnetic recording devices, and magnetoresistive
random access memory (MRRAM).
Several of the mixed perovskite systems such as YFe0.5Cr0.5O3 [20],
LuFe0.5Cr0.5O3 [24], also exhibits both NM and EB at considerably
higher temperatures. Although the origin of the NM is in both YFe0.5-
Cr0.5O3 and LuFe0.5Cr0.5O3 are found same [19], yet the EB effects
Journal of Magnetism and Magnetic Materials 563 (2022) 169950
especially under varying eld cooled conditions differ largely. The
origin of the hysteresis loop is found shifted from the (+H, ¡M) to (−H,
þM) coordinates under varying eld cooled conditions i.e. when the
applied cooling eld changes from low to high values [20,24]. It has
been concluded that the FC induced anisotropy of the weak ferromag-
netic components viz. D Fe-Fe || D Cr-Cr || - D Fe-Cr are mainly responsible
for the observed eld dependency of the EB in these half Cr doped
compounds. However no EB effect studies have been made for the Mn
doped compounds so far that can shed light to the proposed new
mechanism of EB anisotropy in these mixed perovskite compounds.
In this work we report about speci c heat and exchange bias effect
studies of a Mn and Sm co-doped system Sm0.5Y0.5Fe 0.58Mn0.42O3. In Cp
(T) measurement between 2 and 300 K and in zero eld, a smeared out
feature of Schottky anomaly can be observed for T < 20 K. It occurs from
the splitting of the lowest Kramer’s doublet (by internal molecular eld
of the Fe/Mn sublattice) obtained from splitting of the ground state 6H5/
3+
2 of free Sm ion by crystal eld [44,45]. Interestingly, EB measure-
ments at different temperatures shows the compound also exhibited a
zero eld exchange bias effect at cryogenic temperatures. These
observed features strongly ascertain the pronounced effects of phase
coexistence, due to the re-entrant spinglass like phase formation for T <
70 K [46] in the present material.
2. Experimental techniques
The details of the sample preparation and other characterization
results viz. X-ray photoemission spectroscopy, magnetic, dielectric,
magnetodielectric, Raman spectroscopy, pyroelectric current measure-
ments and temperature dependent synchrotron X-ray diffraction are
reported elsewhere [46]. Temperature dependence of heat capacity (Cp)
was recorded under zero magnetic eld using a commercial PPMS sys-
tem (14 T/2 K) installed in UGC DAE CSR, Indore, between 2 and 300 K.
The ac magnetic susceptibility and exchange bias measurements were
performed in a SQUID-VSM magnetometer (Model: MPMS 3, Quantum
Design make). For EB, the system was slowly zero- eld-cooled (ZFC)
from temperature above TN (i.e 400 K) down to T = 5 K, followed by a
10 min wait time, to guarantee the thermal stabilization. From one
measurement to another, the sample was warmed up again above TN and
the superconducting magnet was demagnetized in the oscillating mode,
in order to prevent the presence of trapped current on the magnet and
ensure a reliable ZFC / FC process.
3. Results and discussions
3.1. Speci c heat measurements
The zero and in eld speci c heat measurements are prominent
techniques to investigate the magnetic transitions in orthoferrites
especially at low temperatures [47–49], however the zero eld heat
capacity measurements on the specimen were only done in order to
delineate the effect of sublattice magnetization on the Sm3+ ions. Fig. 1
(A)-(E) displays the results of the zero eld Cp (T) measurement of SYFM
(58–42) between 1.8 and 300 K. The Cp (T) vs T plot of SYFM (58–42) as
displayed in Fig. 1(A) displays no signature of SR transitions as the
measured thermal interval lies below the rst order magnetic transition
(FOMT) [46]. However, a notable incomplete bump-like feature
appeared within the temperature interval of 1.8–12.2 K, whose low
temperature tail seems to be complete for T < 1.5 K. This low temper-
ature bump in Cp (T) is a characteristic feature of the Schottky anomaly,
exhibited by several other perovskite materials with magnetic R3+ ions
in the lattice [44,49]. The solid line in Fig. 1(A) displays the Debye-
speci c heat of scaled LaGaO3, a non-magnetic, isostructural analogue
of the concerned perovskite, calculated using the Debye temperature θD
= 545 K [50] in the expression: