Journal of Magnetism and Magnetic Materials 529 (2021) 167887

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Journal of Magnetism and Magnetic Materials

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Spin–phonon interaction and magnetoelastic coupling associated with

unusual cluster-glass states in YFe0.9Cr0.1O3
Subhajit Raut *, Somnath Mahapatra, Simanchalo Panigrahi
Thin Film Lab., Department of Physics and Astronomy, National Institute of Technology, Rourkela, Sundergarh 769008, Odisha, India

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

Keywords: The magnetic, optical phonon behavior of the polycrystalline YFe0.9Cr0.1O3 (YFC-10), prepared by solid-state
Spin–phonon interaction reaction route, had been studied via static and ac magnetization measurements and Raman spectroscopic
Cluster glass techniques respectively. The results indicated that YFe0.9Cr0.1O3 undergoes unusual cluster-glass transitions at
Weak ferromagnetism
low temperatures viz. Tf1 (SG1) = 108 K (Freez.1) and Tf2 (SG2) = 30 K (Freez.2) coexisting with the long-range
Raman Effect
weak ferromagnetic (WFM) state. Raman spectroscopic (RS) measurements revealed 12 distinct modes of vi­
brations at all temperatures with 83–433 K. Interestingly, the freezing transition at Tf1 is found to be accom­
panied by significant phonon renormalization. From the detailed analysis of the line-shape function of the Raman
modes, the anomalous T-variation of the peak position and the linewidths suggests the existence of spin-phonon
interaction in the present solid solution. Moreover the temperature dependent synchrotron X-ray diffraction
studies between 10 and 300 K revealed the anomalous thermal variation of the lattice parameters and micro­
scopic structural parameters such as super-exchange angles and (Fe/Cr)O6 octahedral bond lengths and bond
angles at both the freezing transitions. Overall, the system exhibits the strong magnetoelastic and spin phonon
coupling over a broad thermal regime viz. from Liquid. N2 to temperatures above room temperature (RT = 300
K) which makes YFe0.9Cr0.1O3 reliable for application purpose.

1. Introduction role in the observance of phenomena such as superconductivity arising

Magnetic materials exhibiting strong inter-correlations between
spin, charge, lattice and electronic degrees of freedom has found enor­
mous importance in the field of material science research. Such coupling
between the different degrees of freedom enables multifunctional
behavior in the materials thereby rendering technologically important
properties in materials such as colossal magnetoresistance (CMR) and
giant magnetoresistance (GMR) phenomena [1–3], giant magneto-
caloric effects (GMCE) [4–6] and multiferroicity [7,8]. Likewise, the
materials with magnetically ordered states, the spin glasses (SG’s) also
find importance in technology especially to the artificial neural net­
works in computational science [9]. It has been established that disorder
and magnetic frustration attributed to the competing inter-actions are
primarily required for the frozen SG state. The deeper exploration of
these interactions are inevitable also in order to understand the under­
lying mechanism for occurrences of the SG states. Moreover, in the
above mentioned functional materials, the interaction between lattice
vibrations (phonons) and different degrees of freedom plays a crucial
from electron-phonon interactions and magneto-electric effects in mul­
tiferroic materials arising from spin–phonon interactions. Nevertheless,
materials exhibiting more than single novel functionality are being
preferential explored [14]
Members of the mixed rare earth orthoferrites and orthochromates
has gained considerable attention in the last few decades owing the
intriguing properties such as magnetization reversal (MR) [17,14]. Spin
reorientation (SR) transitions, negative thermal expansion (NTE) [14],
diverse magneto electric effects [62–64]. In RFeO3 materials, the tran­
sition metal sublattice usually orders magnetically at TN1 between 620
and 740 K and between 120 and 250 K for RCrO3 (depending on the rare
earth ion) into a slightly canted antiferromagnetic structure with a very
weak ferromagnetic component [9–11]. The interaction between the
R3+ and M3+ ions usually causes the phenomenon of SR and MR in the
RMO3 series [12]. Hence, for the nonmagnetic R3+ ions, both the phe­
nomena of MR and SR are found to be absent [13]. However, these
phenomenal features can be found in the perovskite solid solutions with
two different transition metal ions even with nonmagnetic R3+ ion. For

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

https://doi.org/10.1016/j.jmmm.2021.167887
Received 2 September 2020; Received in revised form 10 January 2021; Accepted 22 February 2021
Available online 6 March 2021
0304-8853/© 2021 Elsevier B.V. All rights reserved.
S. Raut et al.
instance, Pomiro et al. [14] examined the three members of the perov­
skite family RFe0.5Cr0.5O3 (R = Lu, Tm and Yb) through combined
neutron powder diffraction and magnetization measurements and re­
ported that R = Tm and Yb systems exhibited spin reorientation tran­
sition (TSR) below their Néel temperature TN, which are close to room
temperature. But no such SR occurs in the Lu-based system, instead a
magnetization reversal can be observed with a high compensation
temperature Tcomp.≈ 225 K. Mandal et al. [61] reported composition
dependent first order spin reorientation transition and weak ferromag­
netic transition (second order) in YFe(1-x)MnxO3 (x ≤ 0.45) solid solu­
tions. In YFe(1-x)MnxO3 solid solutions, TN decreases whereas TSR
increases with increasing ‘x’ content and at the intermediate value of x
= 0.40, both the TN and TSR occur around room temperatures. In this
regards, the solid solutions YFe0.5Cr0.5O3 (YFC-50) have gained
considerable attention from several researchers owing to the high value
of Tcomp. ~ 240 K, exchange bias, magnetocaloric effects [17] and
magnetoelectricity [16]. Using molecular field approximation (MFA), it
had been established that the magnetization in the entire temperature
within the ordered state for all the compositions in YFe(1− x)CrxO3 (0 ≤ x
≤ 1) (YFC) is governed by the competition between the Dzyaloshinskii-
Moriya (DM) interaction from all the possible pairs of the transition
metal ions namely DFe-Fe, DFe-Cr and DCr-Cr interactions [15]. Later Bil­
loni et al. through monte-carlo simulations [18] confirmed the proposed
mechanism of MR stated in Dasari et al.[15] for the intermediate com­
positions viz. x = 0.4, 0.5 in YFC series.
From the above discussions, it is apparent that considerable atten­
tions had been given from past decades to YFC-50, both experimentally
and theoretically owing to its peculiar MR phenomenon above liquid
nitrogen temperature, with diamagnetic Y3+ ion in it. This system is a
prototype of a single-phase material with complex magnetic interactions
and magnetoelectric correlations. Unlike YFC-50, the physical proper­
ties of the lower Cr percentage doped materials haven not gained
considerable attention owing to their weak ferroelectricity [15] and
absence of MR effect. In our previous work on YFe0.9Cr0.1O3 (YFC-10)
[19], we studied the dielectric and ferroelectric properties of it has been
shown that the YFC-10 exhibits strong magnetoelastic coupling which
are manifested as abrupt changes in the unit cell volume and lattice
parameters at the magnetic transition temperatures. This system also
exhibited an isostructural transition below TN and in a narrow temper­
ature interval of 400–500 K, arising due to the competition between the
in-plane and out-of-plane (symmetric super-exchange and antisym­
metric DM) interactions. Also, the inequivalent DM interactions be­
tween the various cations randomly distributed at the same
crystallographic site is found to be responsible for the weak ferroelec­
tricity (~0.005µC/cm2) in this system [15,19].
In this article, the Ac and Dc magnetic susceptibility measurements
below room temperatures (RT) have been used in order to examine the
magnetic properties of the prepared YFC-10 ceramics upto low tem­
peratures. Magnetic susceptibility measurements revealed unusual
cluster-glass like states at low temperatures in the ordered magnetic
state. Moreover, the optical phonon behavior at the freezing transition
temperatures Tf1 and Tf2 and at the isostructural distortion region have
also been studied via Raman spectroscopy in a broad temperature
regime from 80 to 450 K. The temperature dependent Raman spectro­
scopic measurements revealed the existence of the strong spin–phonon
(spin–lattice) coupling and magneto-elastic effects which are manifested
as abrupt thermal variation of the Raman line width and Raman shift at
the glass transition temperatures and at the isostructural distortion re­
gion as well. The phenomenon of magnetoelastic or spin lattice coupling
associated with both freezing transitions in YFC-10 is directly revealed
through SXRD measurements. These results suggest the intrinsic
coupling between the spin, charge and lattice degrees of freedom in YFC-
10, which makes it a promising magneto-dielectric material.
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Journal of Magnetism and Magnetic Materials 529 (2021) 167887
2. Experimental techniques
The polycrystalline samples of YFe0.9Cr0.1O3 are prepared via con­
ventional solid state reaction route using high purity oxides of Y2O3
(99.9%, Sigma-Aldrich), Cr2O3 (Alfa Aesar, 99.99%) and Fe2O3 (Alfa
Aesar, 99.99%). The details of the sample preparation are mentioned
elsewhere [19]. The single phase formation of the material has been
confirmed via X-ray diffraction technique using laboratory sources (Co-
kα) which is further confirmed through synchrotron x-ray diffraction
(SXRD) at room temperature. The XPS of our prepared material were
recorded in ESCA spectrometer SPECS Surface Nano Analysis GmbH,
Germany make installed in UGC-DAE, Indore Center, used for the highly
insulating materials. The data has been recorded using Al-Kα (1486.61
eV) X-rays. 13 KV, 100 W. The obtained XPS spectra have been analyzed
using XPSPEAK 41 software. The Dc and Ac magnetic susceptibility
measurements were performed in an MPMS 3 -SQUID VSM (Super­
conducting Quantum Interference Device-vibrating sample magnetom­
eter, Quantum Design) installed in Institute of Physics, Bhubaneshwar,
India. The Raman spectra were recorded in a confocal micro Raman
spectrometer, ALPHA 300R (WiTec, Germany). The temperature
dependent Raman spectroscopy were done in Linkam THMS600 stage
using the liquid nitrogen as coolant. During measurement, the sample is
warmed at the rate of 20 ◦ C per min. from the lowest attained temper­
ature (83 K) and halted for 5 min at the desired temperatures before the
data acquisition. The data acquisition time was maintained for 30secs at
each temperatures during the entire measurements. The synchrotron X-
ray diffraction (SXRD) data were collected using a He closed cycle
refrigerator (CCR) installed at BL12 Indus-II synchrotron source, Raja
Ramanna Centre for Advanced Technology (RRCAT), India. The wave­
length used was 0.801280 Å.
3. Results and discussions
3.1. X-ray photoelectron spectroscopy studies
In order to determine the possible valance states of the elements
present in the prepared specimen, XPS measurement was conducted on
the prepared sample. Fig. 1(a)-(f) displays the XPS core-level spectra of
the elements in YFC-10. Fig. 1(a) displays the C-1s spectra used as a
reference for assigning the spectra of the other elements and for
charging effect correction. It shows three reference spectra (taken dur­
ing the measurement) with slightly varying peak positions with binding
energies at 288.8 eV, 289.0 eV and 288.9 eV designated as Ref.1, Ref.2
and Ref.3 respectively in Fig. 1(a). For charging corrections the mean
value of the peak position was subtracted from the 284.6 eV (actual
carbon reference peak). The calculated difference of ~4.33 eV gives the
peak shift due to charging and is subtracted from the binding energy
values of the spectra of all other elements to give the charging correction
to the binding energy values in the spectra for each species. The peak
deconvolutions is proceeded thereafter for data analysis. The mixed
Gaussian-Lorentzian line shape function superimposed on a Shirley
background is used for the peak synthesis (deconvolution) procedure.
Fig. 1(b) shows the peak synthesis of the O1s core-level spectrum.
Peak deconvolutions yielded three synthetic peaks with their maxima at
binding energies 528.76 eV, 529.87 eV and 531.09 eV. The peak at
528.76 eV, usually designated as the low binding energy component
(LBEC) in literatures [20] corresponds to the oxygen from Mt.-O (Mt =
Y, Fe/Cr) bonds in stoichiometric units. The medium binding energy
component (MBEC) at 529.87 eV appears from the increasing oxygen
losses from the lattice that accounts for the chemical non-stoichiometry
in the specimen. The high binding energy component (HBEC) at 531.09
eV corresponds to the oxygen from surface adsorbed OH− radical [20].
Fig. 1(c) shows the Fe 2p core-level XPS spectrum in the specimen,
with the Fe- 2p3/2 and Fe-2p1/2 doublets at the maximum binding en­
ergies of 710.37 eV and 724.17 eV marked as broken red and blue lines
in the figure respectively. Peak deconvolution of the Fe- 2p3/2 spectrum
S. Raut et al. Journal of Magnetism and Magnetic Materials 529 (2021) 167887

Fig. 1. XPS core-level spectra for the specimen: (a) C1s peaks used as reference for peak assignment of various elements in YFC-10. (b) O1s spectrum deconvoluted in
three component peaks. (c) Fe 2p spectra with the Fe 2p3/2 peak deconvoluted into two components. (d) Cr 2p spectra of which the Cr 2p3/2 spectra is deconvoluted
in to two components. (e) Y 3d spectra deconvoluted into Y 3d5/2 and Y 3d3/2 component peaks. (f) The Y 3p spectra showing single synthetic peaks each for Y 3p3/2
and Y 3p1/2 of Y3+ ions as shown by the broken curves in figure (f).

results into two synthetic peaks with maxima centered at 709.8 eV and
711.97 eV. The higher binding energy peak accounts for the Fe3+ ions
while the lower ones at 709.8 eV corresponds to the Fe2+ ions [21]. The
peak positions of the Fe- 2p3/2 synthetic peaks are similar to that
observed in YFeO3 single crystals reported in cheng et al. [23]. Usually,
the Fe3+ 2p3/2 line is associated with a satellite peak ~ 8 eV above this
principal peak [22] which is also indicated in Fig. 1(c). The occurrence
of these two peaks in the recorded XPS spectrum of Fe 2p3/2 angular
momenta further indicates the presence of the mixed valance ions of Fe
in the prepared specimen of YFC-10. Such occurrences of Fe2+ and Fe3+
ionic states has also been found earlier in several ceramic systems con­
taining Fe and Cr such as in double perovskite YFeCrO6 [24] and mixed
perovskites RFe0.5Cr0.5O3 systems [26]. The estimated value of the ratio
of the two valence states calculated from the area under the synthetic
curves as [Fe2+]/[Fe3+] as 0.47.
Fig. 1 (d) shows the peak deconvolutions of the Cr-2p core-level
spectra in the sample. The spectra shows two peaks with maxima at
binding energies 575.97 eV and 586.27 eV corresponding to Cr-2p3/2
and Cr-2p1/2 total angular momenta respectively. Peak deconvolution of
the Cr-2p3/2 peak yielded two synthetic peaks at 575.33 eV and 576.44
eV. The lower binding energy peak at 575.33 eV corresponds to Cr2+
ions while the higher binding energy curve correspond to the Cr3+ ions
[23,24]. Since the satellite peak of Cr-2p3/2 is superimposed on Cr-2p1/2
peak [25], the relative concentration of the ions in different valance
states of Cr in YFC-10 is determined only from the deconvoluted peaks of
Cr-2p3/2, as the ratio of the relative area [Cr2+]/[Cr3+], which came out
to be 0.32. Fig. 2(e) shows the peak synthesis of Y 3d core-level spectra
in the specimen, yielding Y-3d5/2 and Y-3d3/2 overlapped curves at
maximum binding energies 156.67 eV and 158.77 eV respectively cor­
responding to Y3+ ions. Similarly for the Y 3p core-level spectra in YFC-
10, peak deconvolution of the Y-3p3/2 and Y-3p1/2 yielded single peak
for each (shown as broken curves), corresponding to Y3+ ions in the
specimen.
The presence of the oxygen vacancies can be due to the high calci­
nation and sintering temperatures used in the preparation method for
the bulk YFC-10 and are usually found in numerous ceramic oxides [23].

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S. Raut et al. Journal of Magnetism and Magnetic Materials 529 (2021) 167887

Fig. 2. (a)-(c) The DC magnetization measurement of YFC-10 in ZFC and FC protocols under H = 100Oe under 100Oe, 1kOe and 30kOe field respectively. The point
of inflections are indicated as broken lines, black and red respectively at high (T1) and at low (T2) temperatures. (d) Isothermal hysteresis curve M(H) at 5 K dis­
playing the weak ferromagnetic behavior.

In the bulk oxides, the release of oxygen from the lattice creates trapped 4. Temperature dependent DC and AC magnetization studies
charges. The ionization of the oxygen vacancies liberates these trapped
charges and as the released charges are absorbed by the Fe3+/Cr3+ ions, 4.1. Dc magnetization studies [M(T) vs. T and hysteresis]
charge transformations into Fe2+ /Cr2+ ions respectively takes place in
the specimen as explained with the KrÖgner-Vink notations [26,27] The temperature dependent dc magnetization of YFC-10 measured
through the relations under Zero field cooled warming (ZFC) and Field cooled warming (FCW)
protocols within the temperature interval of 5–300 K at various applied
Oo ⇔ Vo + ½O2 (1a) fields are illustrated in Fig. 2(a)-(c). For applied fields of 100 Oe and
Vo ⇔ V0o −
+ 2e (1b) 1kOe, the ZFC and FCW curves exhibited a wide irreversibility from 300
K downwards upto the lowest measured temperature. As shown in Fig. 2
Cr3+ + e− ⇔ Cr2+ (1d) (a) in 100 Oe field, the ZFC magnetization exhibited a continuous
downturn below temperature ~270 K followed by a sharp rise for T
Fe 3+ −
+ e ⇔ Fe 2+
(1c)
below 30 K. In contrast to ZFC, the FCW magnetization continues to
Here Oo, Vo and V0o 2−
represents the lattice O ions, oxygen vacancies have nearly constant values until 250 K below which, it continuously
and ionized oxygen vacancies respectively. Cations with different va­ decreases similar to ZFC magnetization. The FC curve also exhibits a
lance and oxygen vacancies have found to be responsible for diverse clear bump-like feature centered around 45 K and again rises below 30 K
physical properties in these materials such as anomalous dielectric re­ similar to the ZFC curve. At intermediate applied fields of 1kOe [Fig. 2
laxations below room temperatures [28], extrinsic origin of the pyro­ (b)], the thermomagnetic irreversibility persists below 300 K with a
current in YFC-50 [29], high electrical conductivity at elevated sharp rise of the magnetization below 30 K. However both the ZFC and
temperatures in ferroelectric oxides [30] etc. Another important con­ FC magnetization exhibited a sharp fall around 190 K, followed by a
sequenses of the mixed valence of the magnetic ions in that single phase gradual decrease upto 70 K above which both the ZFC and FC magne­
materials is that the magnetic interactions can be greatly biased from the tization slowly increases first upto 28 K and the rises sharply with
Fe2+-Fe3+, Cr2+-Cr3+ interacting pairs with the usual Fe3+-Fe3+, Fe3+- decreasing temperature upto 5 K. However, in contrast to the ZFC curve
Cr3+ and Cr3+-Cr3+ symmetric and antisymmetric exchange interactions shown in Fig. 2(a), the ZFC magnetization under 1kOe exhibits a bump
in YFC-10. around 40 K. Fig. 2(c) shows the ZFC-FC curves measured with 30kOe

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S. Raut et al. Journal of Magnetism and Magnetic Materials 529 (2021) 167887

magnetic field. It can be observed that although the ZFC and FC
magnetization overlapped significantly between 300 and 200 K, yet a
wide thermomagnetic irreversibility exist for T < 200 K. A prominent
broad hump occurred in the ZFC-FC magnetization around 160 K after
decreasing from 250 K down to 190 K, but unlike shown in Fig. 2(a) and
(b), both the ZFC and FC magnetization exhibits the bump centered
around 50 K. As obtained for lower and intermediate fields, both the ZFC
and FC magnetization measured in the 30kOe field also exhibited sharp
increase below 30 K. Such features like thermomagnetic irreversibility
of the ZFC-FCW magnetization at all applied fields from temperatures
much above Tf1 and the increase of the FCW magnetization above it
indicates the formation of spin-glass like or more precisely cluster-glass
states at low temperatures in the prepared specimen of YFC-10. Similar
features in ZFC-FCW magnetization have been previously reported in
various metallic systems (amorphous DyNi) [31], reentrant spin-glass
insulating systems (La0.5Sr0.5CoO3) [32], the electron-doped manga­
nite Ca1− xSmxMnO3 [33] and in Heusler alloys (Ni2Mn1.36Sn0.64) [34].
Although the bifurcation between the ZFC-FCW magnetization is a
signature of spin-glass like magnetic transition, it is also exhibited by
highly anisotropic ferromagnets, compounds with canted magnetic
structure arising from competing antiferromagnetic (AFM) and ferro­
magnetic (FM) exchange interactions and also in high-anisotropic anti­
ferromagnets with random orientations of crystallites [35–38]. The
Isothermal hysteresis loop of the prepared YFC-10 ceramics measured at
5 K as shown in Fig. 2(d), demonstrates the weak ferromagnetic
behavior as that observed above RT [19]. Such hysteresis loops are
composed of a low field ferromagnetic component (FM) superimposed
by a high field antiferromagnetic component (AFM) and is described as
(H) = σS +χ AFM H . Here σS is the low field saturation magnetization
value of the FM component and χAFM is the antiferromagnetic
susceptibility.
4.2. AC magnetization studies
The temperature dependent ac magnetic susceptibility measure­
ments have been employed in order to gain further insight into the

Fig. 3. (a) & (b) Displays the thermal variation of real (M′ ) and imaginary part (M”) of the AC magnetic susceptibility respectively. The arrows in figure (c) indicates
the direction of variation of the frequency dependent features in M′ spectra.(e) & (f) shows the variation of the relaxation times with the reduced temperature
‘t’[=(Tf-TSG)/TSG] for the Freez.1 and Freez.2 transitions respectively. The solid lines (red) shows the power law fit, representing the critical slow dynamics of the
freezing processes as described in text. The inset of figures (c) & (d) describes the T variation of the relaxation times in Vogel-Fulcher (VF) shown as the red line in the
insets and are described in the text. (e) Relaxation dynamics studied under the FC protocol at 20 K (circle, blue) and 115 K (square, black).

5
S. Raut et al.
possible magnetic states at low temperatures in the prepared ceramics.
Since the thermomagnetic irreversibility drastically increases below
250 K, the ac susceptibility measurements at different frequencies
spanned between 5 and 300 K. The real part (M′ ) and imaginary part
(M′′ ) of the ac susceptibility are displayed in Fig. 3(a) and 3(b) respec­
tively. Astonishingly, both M′ and M′′ exhibited frequency dependent
features at Tf1 and Tf2 respectively, thereby ruling out the possibility of
the spin reorientation transitions which have been reported to be absent
for lower percentage Cr- doped compositions in the YFe(1− x)CrxO3 series
[15] and also confirms the re-entrance of glass-like magnetic states at
low temperatures in YFC-10. The M′ vs. T showed a monotonous
decrease in the magnetization values below 180 K with a slightly
increasing tail below 30 K at 3 Hz. On increasing the frequency, both of
these features shifted towards the higher temperatures. However, the
frequency dependent tail at low temperatures and at low frequency
appears as a complete weak bump in M′ vs T datas at higher applied
frequencies. In the Fig. 3 (b), the two sets of broad peaks are observed in
the M′′ vs. T plots within the temperature of 5–300 K and are designated
as Freez. 1 and Freez. 2 processes in Fig. 3(b). The Freez.1 peaks co­
incides with the monotonously decreasing slopes in M′ vs. T plots above
150 K [marked by black arrow in Fig. 3(a)] and the peak temperature
exhibited frequency dependency displaying an increasing trend with
applied ac frequency enhancement. The Freez. 2 peaks coincided with
the bumps at the low temperatures [marked by purple arrow in Fig. 3
(a)] and similar to the Freez. 1 peaks, the peak temperature of Freez. 2
peaks also exhibited frequency dependency. The peak amplitude de­
creases for Freez.1 whereas it increases for Freez. 2 peaks. Similar fea­
tures in the ac magnetization spectra [M′ (T, f) and M′′ (T, f)] within the
long ranged magnetically ordered state has previously been observed in
several re-entrant cluster glass systems [39,40,34]. For example, Chat­
terjee et al. [Ref. [34]] has found similar loss peaks within the
martensitic state in Ni2Mn1.36Sn0.64 Heusler alloys as obtained during
Freez.1 process in YFC-10, and were coincident with the frequency
dependent step-like features in the real part (χ′ ) of the ac susceptibility.
The frequency sensitivity of both the sets of the peaks in M′′ spectra have
been estimated by calculating the Mydosh parameter (K) =
ΔTf /Tf (ΔLog10 f)and are obtained as 0.147 and 0.477 for Freez.1 and
Freez.2 processes respectively. The typical values of K for the canonical
spin glasses are very less ~0.005–0.08, while for non-interacting super
paramagnetic state K assumes high values ~2. The obtained values of K
for the freezing processes in YFC-10 suggest the formation of cluster-
glass like characteristic frozen states in the prepared specimen at low
temperatures.
The dynamical scaling behavior [41] has also been studied for the
observed freezing processes using the critical slowing down relationship
[( )/ ]− zν
= τ0 Tf − TSG TSG . Here τ0 is microscopic spin flipping time, Tf
(K) is frequency dependent freezing temperature at which the maximum
relaxation time (τ = 1/2πf) of the system occurs and it corresponds to the
measured frequency, TSG is the glassy freezing temperature in the limit f
→ 0 Hz, Hdc → 0 and zν is the critical exponent. Fig. 3(c) & (d) displays
the excellent power law fit (dynamical scaling) for the Freez.1and
Freez.2 processes respectively in the Log10 τ vs. Log10 t plots, where t =
(Tf − TSG )/TSG is the reduced temperature. For this linear fitting process,
a series of values of the TSG below 150 K for Freez. 1 and 50 K for Freez. 2
in the steps of 0.2 K were taken as trials for the best fit. After numerous
trials, the best fit (as observed from the maximum adj.R2 of the fitted
curve) to the experimental datas were obtained for TSG1 = 108 K and
TSG2 = 30 K for Freez.1 and Freez.2 processes respectively. The extracted
values of the parameters from the fits for both the relaxation processes
are listed in Table 1. The spin flipping times τ0 (Freez.1) = (1.387 ±
0.232) × 10− 4 s and τ0 (Freez.2) = (2.298 ± 0.247) × 10− 3 s are much
larger than the typical values ~ 10− 13 s for single spin flips [42,43]. Also
for the canonical spin glasses, zν values spans between 5 and 12, but the
obtained values of 6.76 ± 0.29 (Freez.1) and 4.11 ± 0.22 (Freez.2) are
lower and resembles a slow spin flipping process and can be associated
6
Journal of Magnetism and Magnetic Materials 529 (2021) 167887
Table 1
Parameters obtained from the AC-susceptibility data analysis: (TSG) glass-like
phase transition temperature according to the power law fit, (zν) the critical
exponent, (τ0) the shortest microscopic flipping time according to the power law
fit, (T0) a measure of interaction strength between the magnetic entities esti­
mated from the VF law fit, (τ*) the shortest microscopic flipping time according
to the VF law fit and (Ea/kB) average activation energy barrier.
Process TSG zν τ0 (s) T0 (K) τ* (s) Ea/kB (K)
(K)
Freez.1 108 6.76 (1.387 ± 104.24 5.927 445 ± 5.9
± 0.29 0.232) ± 0.63 × 10− 6
×
10− 4
Freez.2 30.0 4.11 (2.298 ± 14.72 ± 2.083 228 ± 16.6
± 0.22 0.247) × 2.14 × 10− 5
10− 3
with randomly oriented ferromagnetic clusters instead of interacting
atomic spins [39].
Another plausible mechanism for the freezing process assumes that
the frequency dependency of the freezing temperature Tf can be inter­
preted in terms of thermally activated process of interacting magnetic
entities. In that case Tf (τ) dependence can be well described by the
Vogel–Fulcher law (VF) [44].
( ( ))
τ = τ* exp Ea /kB Tf − T0 (1)
where τ* is the characteristic time constant for the clusters, Ea is the
energy barrier separating two clusters and T0 is the Vogel-Fulcher
temperature which measures the inter-cluster interaction strength.
The time constants of both the freezing processes exhibited excellent
agreement with VF law [Eq. (1)] and are displayed in the insets of the
Fig. 3(c) and (d) respectively for Freez.1 and Freez.2 and the fitted pa­
rameters are also listed in Table 1. It can be seen from Table 1 that the
values of τ* are much larger than that obtained for the dilute spin glass
systems (~10-8) [45] and also resembles re-entrant cluster glass or
reentrant spin-glass systems such as Nd2NiMnO6 [39] and Heusler alloys
[34]. Also the values of T0 (104.24 ± 0.63 K for Freez.1 and 14.72 ±
2.14 K for Freez.2) are much smaller than the Ea/kB = (445 ± 5.9) K for
Freez.1 and (228 ± 16.6) K for Freez.2. Recalling the physical signifi­
cance of T0 and Ea/kB, it can be suggested that T0 ≫ (Ea/kB) indicates the
strong coupling whereas T0 ≪ (Ea/kB) indicates weak coupling between
the magnetic entities. Hence the interaction between the magnetic
clusters are either extremely feeble or does not exist at all.
4.2.1. Aging effects
We further investigated the spin-glass like relaxation dynamics in the
present system by recording the thermo-remnant magnetization against
time. In this protocol, the sample was cooled under 100Oe-applied field
from 300 K upto the desired temperatures for relaxation studies each
time. The field is switched off at the measuring temperatures and the
decay of the sample’s magnetization was recorded for t = 5000 s.
The Fig. 3(e) shows the M (t)/M (0) versus t curves recorded at 115 K
and 20 K. The M (t) data are fitted with the modified stretch exponential
function
( t )β
M(t) = M0 − Mg exp[− ] (2)
τ
The M0 and Mg are the ferromagnetic (FM) and exponential components
of M (t) respectively. β is an exponent which lies in the range 0 < β ≤ 1.
In the above expression, β < 1 indicates the relaxation mechanism
involving activation against multiple anisotropy barriers as proposed for
SGs. Although the above expression for the spin dynamics relaxation
have satisfactorily described the M (t) variation at 20 K, yet it failed to
reproduce the decay process at 115 K. However, by modifying the above
expression with another glassy component in the form,
S. Raut et al.
[ ( )β1 ] [ ( )β2 ]
t t
M(t) = M0 − Mg1 exp − − Mg2 exp − ⋯.. (3)
τ1 τ2
the fitting of the 115 K data becomes satisfactory as displayed in Fig. 3
(e), by the continuous curves. The values of the fitted parameters Mg/
M0, τ and β obtained from M (t)/M (0) curve fit with Eq. (2) at T = 20 K
are 0.497%, (828.72 ± 11.225) s and 0.83 ± 0.008 respectively, while
the values of the fitted parameters obtained from fitting of the M (t)/M
(0) curve at T = 115 K with Eq. (3) yielded Mg1/M(0) and Mg2/M(0) as
6.324% and 5.758% respectively. The values of the time constants τ1
and τ2 for the relaxations are obtained as (1145 ± 119) s and (1052 ±
119) s with β1 and β2 as 0.840 ± 0.0375 and 0.856 ± 0.0371
respectively.
All the above Dc and Ac magnetic susceptibility experiments on YFC-
10 clearly shows the spin-glass like states appearing below 200 K which
is unusual to find in these mixed perovskite systems due to the absence
of frustration in their magnetic sublattices with Fe3+ and Cr3+ ions. In
our previous work on YFC-10 [19], the existence of the ferromagnetic
clusters have been found from high temperature dc magnetization
measurements where 1/χm vs. T obeyed Curie-Weiss law at tempera­
tures far above TN (~553 K). Formation of such magnetic clusters can
results from the ferromagnetic interactions between magnetic cations
with multiple valance states in YFe0.9Cr0.1O3. Our XPS results have
indicated the presence of the mixed species of magnetic cations namely
Fe3+-Fe2+ and Cr2+-Cr3+ pairs. Hence in the present specimen of YFC-10
there are Cr2+/Cr3+ and Fe2+/Fe3+ interactions other than the usual
Fe3+/Fe3+, Cr2+/Cr3+ and Fe3+/Cr3+ magnetic interactions. The in­
teractions between Cr2+/Cr3+ or Fe2+/Fe3+ pairs give rise to super-
exchange interactions via the intervening O2− ions. Due to antiparallel
alignment of the spins there will be a non-zero spin moment generated
giving rise to FM behavior. According to the Goodenough rule [46], the
interaction between Fe3+-O2− -Fe3+, Cr3+-O2− -Fe3+ and Cr3+-O2− -Cr3+
are however antiferromagnetic in nature with super-exchange angles Φ
≪ 180◦ giving rise to the antiparallel alignment between the concerned
spins. Also the interaction between the Cr2+/Cr2+ ion pairs which rep­
resents the d4 - d4 case can also be ferromagnetic/antiferromagnetic
between some pairs [46]. The SXRD results in this work has also showed
that the magnetic cations are randomly distributed at the 4c site of the
Pnma unit cell. Such randomness in the Fe/Cr distribution at the same
crystallographic site can lead to the frustration through bond randomness
among the ferromagnetic/antiferromagnetic bonds, forming of the
ferromagnetic clusters within the ‘sea’ of the antiferromagnetic matrix.
Moreover, different clusters can be formed in the material with different
cationic species coupled ferromagnetically. Such FM and AFM clusters
can sequentially undergo freezing processes at two separate tempera­
tures below RT, giving rise to the frequency dependent anomalous fea­
tures in the ac magnetic susceptibility spectrum and magnetization
relaxations below the freezing temperatures. The formation of the glassy
phases is evident in the present system at low temperatures, yet the
coexistence of the long range and spin-glass like phases is strongly
anticipated in this system. The isothermal hysteresis loop measured at 5
K (Fig. 2(d)) exhibits a weak ferromagnetic behavior similar to that
observed at 300 K and also at temperatures just below TN [19].
Occurrence of two spin glass transitions have been reported earlier
for several multiferroic and non multi ferroic systems [67–71]. Indeed it
has been theoretically grounded for the concentrated Heisenberg and
Ising spin systems that the spin glass (SG) state arising from freezing of
either of the longitudinal or transverse components of the spins in the
long range ordered (LRO) phase, can coexist with the LRO phase on the
same magnetic sublattices [71–75]. It has also been much more inter­
esting about another situation where two successive SG’s transitions
have been predicted on theoretical grounds for concentrated Heisenberg
systems with small single ion magnetic anisotropy (SIMA) as compared
to the magnetic exchange interactions (J), where both the longitudinal
and transverse components of the spins can freeze successively leading
to the two SG transitions below the Almeida-Thouless (AT) and Gabay
7
Journal of Magnetism and Magnetic Materials 529 (2021) 167887
–Toulouse (GT) lines respectively. Although these theories have been
developed for concentrated ferromagnetic systems (FM), still they have
been applied to the disordered antiferromagnetic (AFM) systems as well
[76].
It has been concluded in earlier studies on YFC series that although
the spin cantation and the weak ferromagnetism in the end members of
the series viz YFeO3 and YCrO3 is invoked mainly by DM interactions
between the Fe3+-Fe3+ and Cr3+-Cr3+ pairs respectively, the contribu­
tions from SIMA had been found to be significant for compositions x >
0.5 which presumably affects the thermal variation of the net magne­
tization of the materials [15]. The SIMA contribution is small compared
to the super-exchange and DM interactions for x ≤ 0.3. Hence in pres­
ence of high degree of chemical and bond disorderness and frustration as
explained earlier for the present system, together with the small SIMA
contribution in contrast to the strength of the superexchange in­
teractions between the magnetic spins, two SG transitions below RT,
corresponding to the longitudinal and transverse freezing of the spins in
the Fe/Cr sublattices can occur, and also coexist with the LRO (WFM)
state in the present specimen.
Although the theoretical predictions for the occurrences of the two
SG states coexisting with the LRO have been verified using the macro­
scopic measurements (Ac and Dc magnetic susceptibility measurements)
[77–80], yet the results are rather controversial as it is not clear that the
LRO and the SG phases are formed on the same or separate magnetic
sublattices. Such controversies can be resolved using other microscopic
tools such as neutron scattering, Mossbauer spectroscopic studies, etc.,
that have been used to verify the longitudinal and transverse spinglass
model in the various Ising and Heisenberg systems [76,81–85]. Likewise
the SG transitions in the present system have been verified also through
detailed temperature dependent Raman spectroscopy and X-ray
diffraction studies as shown in the preceding sections
4.3. Temperature dependent Raman spectroscopic measurements
Raman spectroscopy is a versatile experimental tool to probe the
local structural changes such as lattice distortions [66] and octahedral
rotations through lattice excitations and it can also probe magnetic ex­
citations i.e magnons and even their interactions as well i.e. magnon-
phonon coupling. Hence it is an ideal tool to investigate the spin–pho­
non (spin–lattice coupling) in a crystal [47–49,65]. Lattice dynamical
calculations with crystal symmetry Pnma, predicted 60 Γ-point phonon
modes, out of which, 24 normal modes (7Ag + 5B1g + 7B 2g + 5B3g) are
Raman active. The unpolarised Raman spectra of YFC-10 recorded
within the spectral range of 100–800 cm− 1 and between the temperature
range of 83–433 K are shown in Fig. 4(a). In order to get better identi­
fication of the modes, the spectra recorded at 83 K was analyzed, as the
thermal broadening effects are subtle at low temperatures. No evolution
of the extra peaks in the entire measured temperature range have been
observed, which rules out the possibility of any structural phase tran­
sition in the present specimen. The lorentzian peak deconvolution of the
observed spectra at 83 K yielded 12 distinct normal modes of vibrations.
The remaining predicted modes are either masked by band overlap or
their intensity is below the detection limit. The mode assignment has
been made with comparison with the ref. [50,51]. The peak position of
the bands along with their symmetry assignments and respective full
width half maxima (FWHM) and associated atomic motions are listed in
Table 2. The vibration modes below 200 cm− 1 are mainly characterized
by displacements of the heavy rare-earth ions. Above 300 cm− 1, motions
of the light oxygen ions dominate, and in the intermediate frequency
range vibration patterns involve both ions.
The higher frequency modes mainly involve the various FeO6 octa­
hedral motions [51]. Fig. 4(c)-(j) displays the thermal variations of the
peak shift (right panel) and FWHM (left panel) of some of the observed
Raman modes.
Usually the thermal variation of the band center of a particular
phonon mode can be described taking into account the various contri
S. Raut et al. Journal of Magnetism and Magnetic Materials 529 (2021) 167887

Fig. 4. (a) Temperature dependent Raman spectra of YFC-10 at selected temperatures between 83 and 433 K. (b) peak deconvolution with Lorentzian line shape
function at 83 K. (c)-(h) Thermal variation of the line shape parameters, Raman Shift (Right panel) and FWHM (left Panel) of Ag(4), B2g(3), B2g(7), B3g(3), B3g(5) and
Ag(7) modes respectively. The dashed red and blue lines represents the usual anharmonic T variation of the RS and FWHM respectively.

butions according to the relation [52]: [ ]

( ) ( ) ( ) ( ) 2
ωj (T) = ωj (0) + Δωj anh (T)+ Δωj qh (T)+ Δωj el.− (T)+ Δωj (T) ωj (T) = ωj (0) − Aj 1 + ( ( ) )
ph. sp.− ph. exp ℏωj (0)/2kB T − 1
(4) [
3
th − Bj 1 + ( ( ) )
where ωj(T) and ωj(0) are the phonon frequencies of the j mode at any exp ℏωj (0)/2kB T − 1 (5)
temperature T and at 0 K respectively. All other terms in the Eq. (4) are
]
described as: 3
+( ( ) )2
exp ℏωj (0)/2kB T − 1
(i) (Δωj)anh describes the change in the mode frequency due to the
intrinsic anharmonic effects arising from the thermal variation where ωj(0) is the mode frequency at 0 K in the harmonic approximation
and is given as: while Aj and Bj are the cubic and quartic anharmonic coefficients
respectively giving their respective strengths.

8
S. Raut et al. Journal of Magnetism and Magnetic Materials 529 (2021) 167887

Table 2 presence of structural defects while Cj and Dj are parameters for cubic
The observed band positions, the corresponding symmetry assignment, FWHM and quartic anharmonic processes, respectively.
and main atomic motions of the observed Raman modes in YFe0.9Cr0.1O3.
Sl. Symmetry Band center Line width Associated Atomic (ii) (Δωj)qh describes the contributions from quasi-harmonic effects
No. Assignment (cm− 1) (cm− 1) motions which arises from the magnetostriction. For a particular mode, it
1 Ag(2) 144.72 2.07 Y(z), out-of-phase is approximated as (Δωj/ωj)qh = γj(ΔV/V) (γj is the Grüneisen
2 Ag(3) 263.588 7.195 [010]pc FeO6 rotation, parameter for the normal mode j and ΔV/V is the fractional unit
in-phase cell volume change due to thermal expansion). This factor is
3 Ag(4) 337.849 3.408 O(1) x-z plane
applicable for cubic crystals or for isotropically expanded lattices.
4 Ag(7) 497.998 10.519 O(1)-Fe-O(2) scissor-
like bending This effect can contribute in the system studied here in the
5 B1g(1) 149.65 1.84 Y(y) in-phase in x-z, freezing transition regions [see Fig. 5(c)-(f)] as the magneto-
out-of-phase in y volume effects is clearly revealed from the SXRD measurements
6 B2g(2) 214.499 2.720 Y(x), out-of-phase and one should also consider the possibility of phonon frequency
7 B2g(3) 273.356 3.769 [101]pc FeO6 rotation,
in-phase
shift due to anisotropic lattice anomalies especially around
8 B2g(6) 532.217 57.114 O(2)-Fe-O(2) scissor- Freez.1 transitions.
like bending, in-phase (iii) (Δωj)el.-ph. describes the effects of the electron–phonon coupling
9 B2g(7) 663.896 22.085 Fe-O(2) stretching, in- on the jth phonon frequency which can be neglected when the
phase
carrier concentration is low.
10 B3g(1) 177.16 2.598 Y(y) out-of-phase in x-z,
y (iv) (Δωj)sp-ph describes the change in phonon frequency due to
11 B3g(3) 428.79 12.132 octahedra squeezing in spin–lattice (spin–phonon) coupling which is caused by the
y phonon modulation of the spin-exchange integral [52]. A quan­
12 B3g(5) 631.64 22.461 FeO6 breathing titative approach to the measurement of spin phonon coupling
strength was put forward in Granando et al. [52]. In the Molec­
Similarly, the line widths of the Raman mode has the following ular Field Approximation (MFA), the phonon renormalization
temperature dependency due to the nearest neighbor spin–spin correlation is given as:
[ ] → →
2 (Δω)sp.− ph = η < S i. S j > (7)
Γj (T) = Γj (0) − Cj 1 + ( ( ) )
exp ℏωj (0)/2kB T − 1 Here the spin–spin correlation function is given as
[ 〈 〉
→→
− Dj 1 + ( (
3
) ) S i, S j = 4{M(T)/Ms }2 . (8)where M (T) is the magnetization of
exp ℏωj (0)/2kB T − 1
] YFC-10 per Fe/Cr site, Ms is the saturation magnetization and η is the
3 spin–phonon coupling strength. The factor of 4 on the right hand site
+( ( ) )2 (6)
exp ℏωj (0)/2kB T − 1 stands for the four nearest neighbor canted Fe/Cr spins in the ac-plane.
From all the aforementioned effects on the mode frequency at a
where Γj(0) is intrinsic broadening of the jth mode arising from factors particular temperature, we can neglect the contributions from the
other than phonon decay from anharmonic processes such as the electron–phonon coupling as the material exhibits insulating behavior in
the concerned temperature range of the Raman spectroscopic

Fig. 5. Plot of Δω(T) versus {M(T)/Ms}2 for mode (a)B2g(3), (b) B3g(3) and (c) Ag(7). The dashed and solid lines in figures (a)-(b) and (c) respectively represents the
linear least square fits to the datas. Shaded regions in figures (a) and (b) denotes the isostructural distortion regions (Ref. [19]) in YFC-10 and the arrows mark the
temperatures at which an abrupt change of slope (m) occurs.

9
S. Raut et al.
measurements [33]. Fig. 4(c) illustrates the thermal variation of the
band center and line width of the Ag(4) mode that are solely described
by Eqs. (5) and (6) respectively with single set of the parameters.
However, the thermal variation of the band centers as well as the line­
widths of several Raman active modes such as B2g(3), B2g(7), B3g(3),
B3g(5) and Ag(7) could not be described by a single set of fitting pa­
rameters in Eqs. (5) and (6) within the entire temperature interval as
displayed in Fig. 4(d)-(h). As evident from Fig. 4(d), the peak shift of the
B2g(3) mode deviates significantly from the anharmonicity above 323 K
and further the peak shift increases in the frequency with increasing
temperature (thereby countering the anharmonic model) above 383 K.
Thus a significant renormalization occurs for temperatures above 383 K
for the B2g(3) Raman active mode. The line width of the B2g(3) Raman
mode is found to obey the anharmonic variation (Eq. (6)) below 300 K
while it becomes independent of temperature above it. The B2g(3) line
width also exhibited critical T-behavior above 383 K. Similar T variation
of the band peak frequency and linewidths have also been exhibited by
the B2g(7) and B3g(3) Raman active modes. The peak frequencies of the
B2g(7) mode deviated from the anharmonic T behavior above 343 K and
becomes temperature independent with further increasing tempera­
tures. The B2g(7) phonon linewidth also clearly deviates from that pre­
dicted by Eq. (6) above 343 K and remained apparently invariant above
it. The B3g(3) band center frequency and linewidths as shown in Fig. 4(f)
deviates significantly above 353 K from the anharmonic model while the
linewidth upon increasing satisfactorily according to the anharmonic
interaction becomes largely T independent above 323 K. However for T
≥ 353 K, it exhibits a critical behavior similar to that exhibited by
FWHM of B2g(3) mode.
In our previous work [Ref. [19]] on YFC-10, the presence of signif­
icant magnetoelastic coupling at TN ≈ 550 K and in the isostructural
distortion region which prevails about a wide range of temperatures
~400–500 K has been inferred. The temperature range chosen here for
the Raman spectroscopic measurements covers the Freez.1 transition
temperatures upto some temperatures within the isostructural distortion
region also. Significant lattice distortion prevails in the thermal region ≈
400–500 K in the prepared material [19], which arises from the
competition between the interlayer and intralayer symmetric and anti­
symmetric exchange interactions. Hence the deviations from the
anharmonicity of the phonon line widths and peak frequencies for T >
353 K indicates a strong spin–phonon coupling is also associated with
the isostructural transition region.
A remarkable feature have been noticed in the T variation of the peak
frequency of the B3g (5) mode as shown in Fig. 4(g). The band center
frequency shows a satisfactory T variation according to Eq. (5) between
243 and 363 K, while a significant phonon softening is noticed for T <
243 K as well as hardening of the phonon mode is evident for T > 363 K
similar to the B2g(7) mode. However, the linewidth of the B3g (5) mode
exhibits a satisfactory fitting with Eq. (6) between 83 and 363 K and
upon further increasing the temperature it exhibits a rapid increase with
temperature so that for T > 363 K a significant deviation from the fitting
line occurred. At last coming to Fig. 4(h), the band center frequency of
the Ag(7) mode cannot be described solely using the single fitting pa­
rameters in the usual anharmonic model within the entire temperature
interval. The best fit [with Eq. (5)] of the T variation of the peak fre­
quency of the Ag(7) bending mode has been done within 293 K ≤ T ≤ 433
K. The fitting result shows a significant phonon renormalization for T <
293 K causing hardening of the phonon mode in the Freez. 1 transition
region. Also the linewidth of the Ag (7) mode satisfactorily matches the
anharmonic model below Freez.1 transition region, above which it be­
comes apparently T invariant upto 433 K. This indicates the existence of
spin phonon coupling which is also associated with the spin glass tran­
sition (Tf1) in the prepared ceramics.
Bhadram et al. [50] showed that the existence of the spin–phonon
interaction around a magnetic transition is truly revealed from the
changes in the thermal variation of the phonon line widths (FWHM) as
the phonon decay lifetimes are not affected by the presence of
10
Journal of Magnetism and Magnetic Materials 529 (2021) 167887
magnetostriction/magnetovolume effects. The line width of a particular
phonon mode is affected from the usual anharmonicity only due to the
presence of spin–phonon (sp.-ph.) and (el.-ph.) interactions [50]. Hence
the changes observed in the thermal variation of the linewidths associ­
ated with the hardening of the B2g(3) and B3g(3) modes and softening of
the B2g(7) mode reveal the presence of sp.-ph. interaction in the iso­
structural distortion region in YFC-10. Similarly, the deviation from the
anharmonic modelling of the T variation of FWHM of the B3g (5) mode
above 363 K associated with the hardening of the phonon mode
apparently reveals the presence of spin phonon interaction in the iso­
structural transition regime. Interestingly, the thermal variation of the
linewidth for T < 250 K of B3g (5) is satisfactorily described by eqn. (6)
yet the frequency shift of the peak position exhibits a significant soft­
ening. Since no anomalous T variation of the B3g (5) LW is associated
with this mode softening, the magneto-strictive or quasi-harmonic effects
[described in Eq. (4)] is solely responsible for the observed mode soft­
ening. The apparent independency of the LW with temperature of the Ag
(7) mode is found to be similar to the GaFeO3 single crystals [53] and
indicates the phenomenon of the phonon modulation of the exchange
integral by Ag (7) bending mode across the freez. 1 transition region.
Since approaching the SG transitions from the long range ordered (LRO)
state, the spin–spin correlation function in the (LRO) state within the
material gets modified from the interaction between the spins in the
clustered regions with different spin–spin correlation functions itself.
→ →
Such modification in the < S i . S j > in the material on the same mag­
netic lattice affects the frequency of the mode causing it’s significant
renormalization with different coupling strength from the LRO state.
To quantify the spin–phonon coupling strength as given by the last
term in Eq. (4), we utilized the formalism proposed by Granado et al
[33] suggesting a mechanism for phonon renormalization due to
spin–phonon interactions. The sp.ph. coupling strength has been esti­
mated from the plots of change of the phonon frequency from anhar­
monicity versus squared normalized magnetization above RT for B2g(3)
and B3g(3) modes and are displayed in Fig. 5(a) & (b) respectively. As
evident from these figures, the linear variation of the data plotted as Δω
against [M (T)/M s] 2 satisfactorily holds but with severe changes in the
slopes above the isostructural distortion thermal regime (shaded re­
gion). For example, remarkable changes from negative towards positive
slope has occurred in the linear variation of the Δω versus [M (T)/M s] 2
plot above 373 K for the B2g(3) mode (Fig. 5(a)), while a similar and
sharp changes from the positive to negative slope has been observed in
the plot for the B3g(3) mode above 379 K (Fig. 5(b)). Such abrupt
changes in the slope of the Δω versus [M (T)/Ms] 2 plots strongly in­
dicates the changes in spin dynamics across the isostructural distortion
region in YFC-10. Similar slope changes within the ferromagnetic state
have been reported previously in GaFeO3 single crystals [53].
As significant phonon hardening was observed in the T variation of
the Ag (7) bending mode, the spin phonon coupling strength associated
with this mode is also estimated from similar plot shown in Fig. 5(c). The
linear fit of the datas of the plot of Δω vs. [M (T)/M s]2 for the Ag (7)
mode gives the value of the slope m = − 34.191 ± 6.193 cm− 1 from
which the spin–phonon coupling strength is calculated to be − 8.548 ±
1.548 cm− 1 [using Eq. (7) and Eq. (8)]. The sp.-ph. coupling strengths
associated with the B2g(3) mode within and below the isostructural
distortion region are λ1 ≈ − 7.05 ± 0.27 cm− 1 and λ2 ≈ 2.08 ± 0.18 cm− 1
respectively.
Similarly from the slopes obtained for the B3g(3) modes [Fig. 5(b)],
the values of the coupling strength are obtained as λ1 ≈ 4.02 ± 0.77
cm− 1 and λ2 ≈ − 6.91 ± 0.99 cm− 1 respectively within and below the
isostructural distortion regions. These obtained values of λ’s for YFC-10
are comparable to the earlier estimates reported for other systems using
Raman scattering. As such, for example Lockwood et al. [54] showed the
spin–phonon coupling strength for different modes in the range from 1.3
to − 0.4 cm− 1 for antiferromagnetic rutile structured MnF2 and FeF2, and
Gupta et al [55] found a very large spin–phonon coupling strength
S. Raut et al. Journal of Magnetism and Magnetic Materials 529 (2021) 167887

(~5.2 cm− 1) for Sr4Ru3O10. Table 3

Therefore the obtained values of the sp.-ph coupling strength in YFC- Refined Lattice Parameters, fractional atomic position, equivalent temperature
10 associated with various Raman active modes indicates strong factors and reliability factors obtained from Rietveld refinement of the SXRD
coupling between spin and lattice dynamics. In order to get direct evi­ patterns of YFC-10 at 300 K and 12 K with Fe/Cr randomly distributed at the
dence of the true nature of the spin–phonon interaction in YFC-10, Wyckoff position 4c (0, 0, 1/2).
analysis via inelastic neutron scattering experiments are required Temperature 300 K 12 K
further. Space group Pnma Pnma
a (Å) 5.59638(14) 5.59508(12)
b (Ǻ) 7.61265(17) 7.60260(14)
4.4. Temperature dependent X-ray diffraction measurements c (Ǻ) 5.28896(14) 5.28157(12)
V (Ǻ3) 225.327(10) 224.663(8)
In order to verify further the spin–lattice interactions which are Yx 0.0664(3) 0.0691(2)
y 0.2500 0.2500
associated with the cluster-glass like transitions in the present ortho­ z − 0.0175(4) − 0.0177(4)
ferrite –orthochromite system, the synchrotron X-ray diffraction mea­ Uiso. (Ǻ2) 0.006(14) 0.004(4)
surement have been employed further between temperatures 10–300 K. O1 x 0.4520(14) 0.4586(14)
Fig. 6(A) and (B) displays the Rietveld refinement of the X-ray dif­ y 0.2500 0.25000
z 0.1087(18) 0.1062(15)
fractogram of the prepared specimen at 300 K and 12 K respectively.
Uiso. (Ǻ2) 0.009(8) 0.000(2)
Similar to that obtained before in the high temperature X-ray diffraction O2 x 0.3066(9) 0.3040(11)
studies [19], the prepared specimen of YFC-10 contains <1% of the y 0.0568(9) 0.0580(7)
unreacted Y2O3 (cubic) phases that are indicated as purple coloured z − 0.3122(12) − 0.3054(11)
vertical lines in the diffractogram figures. All the diffractograms within Uiso. (Ǻ2) 0.008(6) 0.001(3)
RF (%) 4.90 1.70
the temperature range of 10–300 K were refined in the orthorhombic RBragg (%) 5.11 1.74
space group pnma and no evidence of structural phase transition was χ2 3.25 0.482
observed in YFC-10 down to the lowest measured temperature also. The
results of the Rietveld refinements of the X-ray diffraction patterns at 12
and 300 K are listed in the Table 3. K. Thereafter V(T) exhibited a sharp and continuous decrease with a dip
Fig. 6(C)-(F) displays the thermal (T) variation of the unit cell vol­ at 140 K with a subsequent change ΔV(T) ≈ 0.41 Å within 60 K of the
ume V(T) and lattice parameters a(T), b(T) and c(T) of YFC-10 between temperature interval. Below 130 K, V(T) decreases slowly upto T ≈ 22 K,
10 and 300 K. As shown in Fig. 6(C), the cell volume decreases slightly below which V(T) decreases abruptly with |ΔV(T)| ≈ 0.115 Å for the
below 300 K and then begins to increase in the similar manner upto 200 temperature decrease up to 12 K. Similar T variation have also been

Fig. 6. (A),(B) the Rietveld Refinement of the SXRD patterns of YFC-10 respectively at 300 and 12 K respectively. The Bragg’s reflections denoted by C and O
represents the minor cubic phases of Y2O3 and major phase of orthorhombic YFC-10 respectively. (C)-(F) displays the thermal variation of the cell volume and lattice
parameters of YFC-10 between 12 and 300 K. The shaded portions brown and pink in the figure represents the Spin-glass transition T- regions associated with Freez. 1
and Freez. 2 processes respectively. The Inset of figure (C) highlights the anomalous dip in the V(T) at Tf1. The broken lines black and blue indicates the inflection
points in the T variation of the cell parameters within Freez.1 and Freez.2 transition regions.

11
S. Raut et al.
observed for the lattice parameters b(T) and c(T) in the measured below
RT thermal domain as displayed in Fig. 6(E) and (F) respectively. Unlike
V(T), b(T) and c(T), the lattice parameter a(T) [shown in Fig. 6(D)]
increases monotonously with temperature decrement from 300 to 200 K
by Δa(T) ≈ 1.46 × 10− 3 Å. It decreases first rapidly and then slowly with
decreasing temperature, exhibiting a similar dip at 140 K as observed for
other lattice constants. a(T) also exhibited a sharp decrease of |Δa(T)| ≈
7.5 × 10− 4 between 22.3 and 12 K temperature interval similar to that
observed in V(T), b(T) and c(T) within the same thermal interval. The
anomalies in the T variation of the lattice constants and cell volume
below RT reveal strong magnetoelastic coupling near 22 K and 200 K
temperatures and hence suggests the presence of the magnetostriction/
magneto volume effects associated with the spin glass transition pro­
cesses in YFC-10 [86].
In order to gain further insight on the observed critical behavior of
the lattice parameters, the thermal variation of the microscopic
Fig. 7. Thermal variations of (A), (B) super-exchange angles ϕ1 and ϕ2 respectively; (C), (D) Fe-O1 and Fe-O2 octahedral bond lengths. The shaded regions indicates
the spin-freezing transition regimes in YFC-10. (E) The schematic representation of the various microscopic structural parameters in YFC-10 unit cell. (M = Fe/Cr).
12
Journal of Magnetism and Magnetic Materials 529 (2021) 167887
structural parameters such as super-exchange angles (Φ1 and Φ2),
octahedral bond lengths etc. have also been analyzed here in the similar
way as that has been done with the high temperature SXRD data in ref.
[19]. Fig. 7(A) and (B) illustrates the thermal variation of the super-
exchange angles Φ1 (along b-direction) and Φ2 within the ac plane of
the crystal. The schematic representations of these exchange angles are
illustrated in Fig. 7(E). As evident from the Fig. 7(A), Φ1 increases at first
slowly and then rapidly below 250 K with decreasing temperature upto
200 K, where Φ1 exhibits a maximum. Thereafter it decreases rapidly
with decreasing T, from 144.5 to 143.1◦ within the temperature interval
of 40 K. At the temperature of 160 K, Φ1 exhibits a minimum and with
decreasing T, it increases again attaining a value ~144.3◦ at 130 K.
Below 130 K, Φ1 again decreases upto T = 22.3 K, where it increases
abruptly upto the lowest measured temperature. Similar critical thermal
variation has also been demonstrated by Φ2 below RT as illustrated in
Fig. 7(B). Below RT Φ2 exhibits, a nearly linear and rapid increase upto
S. Raut et al. Journal of Magnetism and Magnetic Materials 529 (2021) 167887

200 K where a maxima of 144.98◦ is attained within the Freez.1 process

(shaded green portion in the Fig. 7). Thereafter it decreases steeply with
decreasing temperature upto 180 K. However unlike the Φ1, Φ2 in­
creases upto 160 K exhibiting a maxima of 144.6◦ in the Freez.1 tran­
sition region. As the temperature is decreased, the Φ2 increases for
temperatures below 150 K upto T = 22.3 K, below which it displays a
steep decrease.
Since the (Fe/Cr)O6 octahedra are the essential building blocks of the
Pnma structure in orthoferrites and orthochromates, the shift in the
oxygen ions O1 and O2 can be revealed by carefully analyzing the
octahedral bond lengths and bond angles. Fig. 7(C) and (D) describes the
T variation of the various octahedral bond lengths namely d(Fe/Cr-O1)
(along b direction) and d(Fe/Cr-O21), d(Fe/Cr-O22) (within the a-c plane)
respectively.
As the temperature is decreased below RT, all octahedral bond
lengths exhibited a gradual decrease with temperatures upto 200 K.
Below 200 K, as the temperature is decreased, d(Fe/Cr-O1) increases and
exhibits a maximum at 160 K and again decreasing further abruptly upto
130 K. Interestingly, an abrupt rise of 0.004 Å in d(Fe/Cr-O1) occurred
roughly between 130 K and 120 K. Since the Fe/Cr atoms in the Pnma
unit cell of YFC-10 have fixed fractional position coordinates, the
anomalous shift in the O1 oxygen ions in the ac plane, as revealed from
Fig. 7(c), increases the Fe/Cr-O1 bond distance and decreases the ex­
Fig. 8. Thermal variation of the octahedral bond angles α1, α2 and β repre­
change angle Φ1 upon decreasing the temperature from 130 to 120 K.
sented in (A)-(C). The insets of figures (A) & (C) highlights the anomalous bond
Similarly, the minimum of d(Fe-O1) at 200 K causes the maximum value
angle variation at the low T cluster-glass transition (Freez.2).
of angle Φ1 at same temperature. As the temperature is decreased further
below 120 K, d(Fe-O1) decreases and again shows anomalous thermal
small for β (~0.93◦ ) and α2 (~0.14◦ ). As the temperature is decreased
variations in the Freez2. region (shown by shaded purple region in the
further, α1 is nearly constant upto 200 K while α2 increases within the
Fig. 7) in a counter manner to that exhibited by Φ1. Lastly the steep
same thermal window. Thereafter as the temperature is decreased, α1
reduction in d(Fe-O1) below 22.3 K, causes a rapid increase in Φ1 also.
decreases upto 180 K, then increases exhibiting a maximum at 160 K. On
Fig. 7(d) shows the T variation of the two octahedral bond lengths in
the other hand α2 exhibits a maxima at 200 K, then decreases with
the a-c plane of the crystal namely d(Fe/Cr-O21) and d(Fe/Cr-O22). In the
decreasing temperature upto 160 K below which it increases further
whole temperature range, both these octahedral bond distances
with lowering temperature. Below 140 K, there is a nearly constant T
exhibited critical behaviors in the Freez.1 and Freez.2 process but in a
variation of both α1 and α2 upto 22.3 K, where α1 decreases while α2
mutually exclusive manner. Below 250 K, d(Fe/Cr-O21) decreases almost
increases rapidly with decreasing temperature.
linearly upto 200 K where it assumes nearly constant values upon
Similarly as bond angle α2, β also increases linearly below 250 K with
varying T to 180 K, whereas d(Fe/Cr-O22) increases linearly upto 180 K.
decreasing T as illustrated in Fig. 8(c). However in contrast to α1 and α2,
Hence, the super-exchange angle Φ2 decreases and exhibits a minimum
β increases further with decreasing temperature upto 180 K, thereafter it
at 180 K. As the temperature decreases below 180 K, d(Fe/Cr-O21) in­
decreases significantly with decreasing T exhibiting a minimum at 160
creases by 0.012 Å whereas the d(Fe/Cr-O22) decreases by 0.019 Å within
K. Within the temperature interval of 160–180 K (ΔT = 20 K), Δβ be­
δT = 20 K. As a result of this competitive changes with temperature of
comes ~ 0.5◦ . Below 130 K β remains nearly constant with temperature
d(Fe/Cr-O21) and d(Fe/Cr-O22), Φ2 also increases steeply upto 160 K.
variation and begins to increases slowly like α2 below 51 K which is
However, since d(Fe/Cr-O21) abruptly increases by 0.011 Å upto 140 K
marked as the onset of the Freez.2 process and exhibits a maximum at
while d(Fe/Cr-O22) change is negligible within the same thermal range,
22.3 K as shown in the inset of Fig. 8[C].
there is an overall increase in the O21-Fe/Cr-O22 bonds, which gives a
Thus, our SXRD analysis of the polycrystalline YFC-10 between 12
minima in the T variation of Φ2 at 150 K. Thus, the competitive nature of
and 300 K exhibited the intense critical T-variation of the lattice pa­
the thermal variation of the Fe/Cr-O22 and Fe/Cr-O21 octahedral bond
rameters within the freezing transition regions I and II. This critical
lengths together determines the critical behavior of the exchange angle
behavior of the lattice parameters a(T), b(T) and c(T) and cell volume V
Φ2 in the entire measured temperature range. It can be interestingly
(T) is accounted from the anomalous variation of the microscopic
noted that both Fe/Cr-O22 and Fe/Cr-O21 exhibited a drastic change in
structural parameters such as octahedral bond lengths and bond angles
slope below 22.3 K similar to that observed in d(Fe/Cr-O1) [Fig. 7(c),
over the same T windows, which clearly reveals the magnetoelastic
purple shaded region].
coupling associated with the spin-glass transitions at low temperatures.
Fig. 8(a)–(c) gives the thermal variation of the octahedral bond an­
In the spin glass transition regions the in-plane (Φ2) and out-of-plane
gles α1, α2 and β as depicted schematically in Fig. 7(E). It has been found
(Φ1) super exchange angles are also found to exhibit the critical be­
previously by Zhou and Goodenough [87], the MO6 octahedra (M = Fe,
haviors which are consequences of the anomalous shifts of the O2−
Mn, V, Ni, Cr, Ti,….,and Ga) in RMO3 (R = Rare earth or Y) series are
ligand connecting the octahedras in the a-c plane and along b-directions
nearly rigid with nearly equal bond distances d ≈ 2.00 Å and octahedral
respectively. These changes in the slope of the thermal variation of the
bond angle β deviating from 90◦ by small amount δ (≈ 0.3◦ ) for rare
lattice parameters have been reported previously in several oxides such
earth ionic radii (IR) ≤ 1.11 Å and becomes highly non-rigid i.e the
as in SmFeO3 nanoparticles [56] where nonlinear T-variation of the
octahedral bond angles deviates far from 90◦ by sufficiently larger
lattice constants were evidenced at the spin reorientation regions, in
values for rare earth ionic radii (IR) ≥ 1.11 Å. The observed bond angle
oxide and sulpho spinel chromates [57,58] at the ferroelectric and
β = 90.42 (16) Å at 300 K in YFC-10 is consistent with the results re­
magnetic transition temperatures, in Triangular lattice antiferromagnets
ported in Zhou et al. [87] for IR≈1.02 Å (Y3+) ions. Although α1 and β
(TLA’s) such as LiCrO2 [59] and its doped compounds [59,60]. These
are less deviated from 90◦ yet α2 differs from 90◦ by ~ 3◦ .
isostructural distortions at the magnetically ordering temperature are
As shown in Fig. 8, all the octahedral bond angles decreases first
found responsible for the observed ferroelectricity and magneto-electric
between 300 and 250 K, which is significantly large for α1 (~4.5◦ ) while

13
S. Raut et al.
coupling in the abovementioned improper multiferroic materials. Thus
the critical behavior in the thermal variation of the lattice parameters of
YFC-10 not only verifies the spin-glass freezing processes at low tem­
peratures, but also re-establishes the property of coupled spin and lattice
degrees of freedom in the material.
5. Conclusion
The polycrystalline samples of YFe0.9Cr0.1O3 were prepared via solid-
state reaction route. The rietveld refinement of the synchrotron x-ray
diffractogram revealed the disordered arrangement of the Fe/Cr atoms
at the 4b-site of the Orthorhombic crystal. The room temperature XPS
measurements suggests the presence of multiple valance states of the
transition metal ions viz. Fe2+ and Fe3+ as the iron cations whereas
chromium is present in Cr2+ and Cr3+ states, in the prepared specimen.
The Dc and Ac magnetic susceptibility study from 5 to 300 K showed the
existence of unusual cluster glass states SG1 and SG2 arising from the
quenched disorderness resulting in the randomly distributed clusters in
the AFM matrix corresponding to the longitudinal and transverse
freezing of the spins. The temperature dependent Raman spectroscopic
studies between 80 and 450 K revealed the existence of strong spin
phonon and magnetoelastic coupling in the present YFC-10 ceramics.
Above RT, abrupt and pronounced changes in the spin–phonon coupling
strength from negative → positive (positive → negative) associated with
B2g(3) [B3g(3)] mode was revealed across the isostructural distortion T
region. Nevertheless, the spin phonon coupling and the magnetoelastic
phenomenon renders it to be a potential candidate for magnetodielectric
(MD) materials as several MD materials exhibits strong spin phonon
coupling as well.
6. Author statement
The manuscript has been thoroughly revised taking of the reviewers
suggestions as much as possible. Where the references and text which
are needed to be modified have been done carefully. The reviewer
comments have also been addressed in separate files. Overall, we think
that our long hard work incorporated in the manuscript is now fit for the
esteemed journal for publication.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
S.R. and S.P. acknowledges Dr. D Samal and Dr. S.N. Sarangi IOP,
Bhubaneshwar, for assisting in SQUID-VSM measurements. The authors
are also grateful to Dr. Uday P Deshpande, UGC-DAE CSR Indore center
for XPS measurements and Dr. A.K. Sinha, BL-12, INDUS 2, RRCAT
Indore for the low temperature SXRD measurements. The Ministry of
Human Resource and Development (MHRD), India supported the whole
work, under the indigenous fellowship scheme. This work is also
partially funded by project approved under collaborative research
scheme (CRS) vide project no.: CSR-IC-255/2017-18/1336 dated 31-03-
2018.
References
[1] G.J. Liu, J.R. Sun, J.Z. Wang, B.G. Shen, Magnetic field-induced entropy change in
phase-separated manganites, Appl. Phys. Lett. 89 (22) (2006) 222503, https://doi.
org/10.1063/1.2397535.
[2] K.J.S. Sokhey, M.K. Chattopadhyay, A.K. Nigam, S.B. Roy, P. Chaddah, Signatures
of phase separation across the disorder broadened first order ferromagnetic to
antiferromagnetic transition in doped-CeFe2 alloys, Solid State Commun. 129
(2003) 19–23, https://doi.org/10.1016/j.ssc.2003.08.036.
14
Journal of Magnetism and Magnetic Materials 529 (2021) 167887
[3] P. Schiffer, A. Ramirez, O. Bao, S.W. Cheong, Low temperature magnetoresistance
and the magnetic phase diagram of La(1–x)CaxMnO3, Phys. Rev. Lett. 75 (1995)
3336, https://doi.org/10.1103/PhysRevLett.75.3336.
[4] P. Sande, L.E. Hueso, D.R. Miguéns, J. Rivas, F. Rivadulla, M.A. López-Quintela,
F. Rivadulla, M.A. Ĺopez-Quintela, Large magnetocaloric effect in manganites with
charge order, Appl. Phys. Lett. 79 (2001) 2040–2042, https://doi.org/10.1063/
1.1403317.
[5] R. Kainuma, Y. Imano, W. Ito, Y. Sutou, H. Morito, S. Okamoto, O. Kitakami,
K. Oikawa, A. Fujita, T. Kanomata, K. Ishida, Magnetic-field-induced shape
recovery by reverse phase transformation, Nature 439 (2006) 957–960, https://
doi.org/10.1038/nature04493.
[6] X. Si, Y. Liu, X. Lu, Y. Shen, W. Wang, W. Yu, T. Zhou, T. Gao, Near room
temperature magnetocaloric properties and the universal curve of MnCoGe1-xCux,
J. Appl. Phys. 121 (2017) 185103, https://doi.org/10.1063/1.4983075.
[7] H. Katsura, N. Nagaosa, A.V. Balatsky, Spin current and magnetoelectric effect in
noncollinear magnets, Phys. Rev. Lett. 95 (2005), 057205, https://doi.org/
10.1103/PhysRevLett.95.057205.
[8] W. Eerenstein, N.D. Mathur, J.F. Scott, Multiferroic and magnetoelectric materials,
Nature 442 (2006) 759–765, https://doi.org/10.1038/nature05023.
[9] D.J. Amit, H. Gutfreund, H. Sompolinsky, Spin-glass models of neural networks,
Phys. Rev. A 32 (1985) 1007–1018, https://doi.org/10.1103/PhysRevA.32.1007.
[10] L.T. Tsymbal, Y.B. Bazaliy, V.N. Derkachenko, V.I. Kamenev, G.N. Kakazei, F.
J. Palomares, P.E. Wigen, Magnetic and structural properties of spin-reorientation
transitions in orthoferrites, J. Appl. Phys. 101 (2007) 123919, https://doi.org/
10.1063/1.2749404.
[11] Y.B. Bazaliy, L.T. Tsymbal, G.N. Kakazei, A.I. Izotov, P.E. Wigen, Spin-
reorientation in ErFeO3: Zero-field transitions, three-dimensional phase diagram,
and anisotropy of erbium magnetism, Phys. Rev. B 69 (2004), 104429, https://doi.
org/10.1103/PhysRevB.69.104429.
[12] A. Bhattacharjee, K. Saito, M. Sorai, Heat capacity and magnetic phase transitions
of rare-earth orthoferrite HoFeO3, J. Phys. Chem. Solids 63 (2002) 569–574,
https://doi.org/10.1016/S0022-3697(01)00195-0.
[13] R.L. White, Review of recent work on the magnetic and spectroscopic properties of
the rare-earth orthoferrites, J. Appl. Phys. 40 (1969) 1061–1069, https://doi.org/
10.1063/1.1657530.
[14] F. Pomiro, R.D. Sánchez, G. Cuello, A. Maignan, C. Martin, R.E. Carbonio, Spin
reorientation, magnetization reversal, and negative thermal expansion observed
in RFe0.5Cr0.5O3 perovskites (R=Lu, Yb, Tm), Phys. Rev. B 94 (2016) 134402,
https://doi.org/10.1103/PhysRevB.94.134402.
[15] N. Dasari, P. Mandal, A. Sundaresan, and .N S. Vidhyadhiraja, Weak
ferromagnetism and magnetization reversal in YFe1-xCrxO3, Europhys. Lett. 99
(2012) 17008, doi: 10.1209/0295-5075/99/17008.
[16] B. Rajeswaran, P. Mandal, R. Saha, E. Suard, A. Sundaresan, C.N.R. Rao,
Ferroelectricity induced by cations of nonequivalent spins disordered in the weakly
ferromagnetic perovskites, YCr1–xMxO3 (M = Fe or Mn), Chem. Mater. 24 (2012)
3591–3595, https://doi.org/10.1021/cm301944s.
[17] M.K. Sharma, K. Singh, K. Mukherjee, Exchange bias in a mixed metal oxide based
magnetocaloric compound YFe0.5Cr0.5O3, J. Magn. Magn. Mater. 414 (2016)
116–121, https://doi.org/10.1016/j.jmmm.2016.04.047.
[18] O. V. Billoni, F. Pomiro, S. A. Cannas, C. Martin, A. Maignan and R. E. Carbonio
Magnetization reversal in mixed ferrite-chromite perovskites with non-magnetic
cation on the A-site, J. Phys. Condens. Matter 28 (2016) 476003, https://doi.org/
10.1088/0953-8984/28/47/476003.
[19] S. Raut, B. Kar, S. Velaga, H. K. Poswal and S. Panigrahi, Significance of
isostructural distortion and strong magnetoelastic coupling in the weak
ferromagnet YFe0.9Cr0.1O3, J. Appl. Phys. 126 (2019) 074103, https://doi.org/
10.1063/1.5098007.
[20] M. Naeem, S.K. Hasanain, M. Kobayashi, Y. Ishida, A. Fujimori, S. Buzby, S.I. Shah,
Effect of reducing atmosphere on the magnetism of Zn(1–x)Co(x)O (0≤x≤0.10)
nanoparticles, Nanotechnology 17 (2006) 2675–2680, https://doi.org/10.1088/
0957-4484/17/10/039.
[21] W.Y. Chen, J.S. Jeng, J.S. Chen, Improvement of mobility in ZnO thin film
transistor with an oxygen enriched MgO gate dielectric, ECS Solid State Lett. 1
(2012) N17–N19, https://doi.org/10.1149/2.003205ssl.
[22] M.A. Farid, H. Zhang, X. Lin, A. Yang, S. Yang, G. Li, F. Liao, J. Lin, Structural and
magnetic properties of tetragonal perovskite BaFe1− xBixO3− δ, RSC Adv. 5 (2015)
12866–12871, https://doi.org/10.1039/C4RA13540G.
[23] Z.X. Cheng, H. Shen, J.Y. Xu, P. Liu, S.J. Zhang, J.L. Wang, X.L. Wang, S.X. Dou,
Magnetocapacitance effect in nonmultiferroic YFeO3 single crystal, J. Appl. Phys.
111 (2012), 034103, https://doi.org/10.1063/1.3681294.
[24] R.P. Maiti, S. Dutta, M.K. Mitra, D. Chakravorty, Large magnetodielectric effect in
nanocrystalline double perovskite Y2FeCrO6, J. Phys. D: Appl. Phys. 46 (2013),
415303, https://doi.org/10.1088/0022-3727/46/41/415303.
[25] A.M. Salvi, J.E. Castle, J.F. Watts, E. Desimoni, Peak fitting of the chromium 2p
XPS spectrum, Appl. Surf. Sci. 90 (1995) 333–341, https://doi.org/10.1016/0169-
4332(95)00168-9.
[26] T. Patri, J. Ponnaiah, P. Kutty, A. Ghosh, Raman and dielectric spectroscopic
analysis of magnetic phase transition in Y(Fe0.5Cr0.5)O3 multiferroic ceramics,
Ceram. Int. 42 (2016) 13834–13840, https://doi.org/10.1016/j.
ceramint.2016.05.188.
[27] L. Zhuo and F. Huiqing, Relaxation associated with the synergetic oxygen
vacancies and electrons in (Ba1− xBix) 0.9 Sr0.1TiO3− δ ceramics, J. Appl. Phys.
108 (2010) 034103, https://doi.org/10.1063/1.3457232.
[28] Y. Ma, X.M. Chen, Y.Q. Lin, Relaxorlike dielectric behavior and weak
ferromagnetism in YFeO3 ceramics, J. Appl. Phys. 103 (2008) 124111, https://doi.
org/10.1063/1.2947601.
S. Raut et al.
[29] J.Y. Yang, X.D. Shen, V. Pomjakushin, L. Keller, E. Pomjakushina, Y.W. Long,
M. Kenzelmann, Characterization of magnetic symmetry and electric polarization
of YCr0.5Fe0.5O3, Phys. Rev. B 101 (2020) 014415, https://doi.org/10.1103/
PhysRevB.101.014415.
[30] A. Pelaiz-Barranco,
́ J.D.S. Guerra, R. Ĺopez-Noda, E.B. Aráujo, Ionized oxygen
vacancy-related electrical conductivity in (Pb1− xLax)(Zr0.90Ti0.10)1− x/
4O3 ceramics, J. Phys. D: Appl. Phys. 41 (2008) 215503 (5pp), https://doi.org/
10.1088/0022-3727/41/21/215503.
[31] B. Dieny, B. Barbara, Critical properties of a random-anisotropy system a-DyNi: A
new universality class in disordered systems? Phys. Rev. Lett. 57 (1986) 1169,
https://doi.org/10.1103/PhysRevLett.57.1169.
[32] S. Mukherjee, R. Ranganathan, P.S. Anilkumar, P.A. Joy, Static and dynamic
response of cluster glass in La0.5Sr0.5CoO3, Phys. Rev. B 54 (1996) 9267, https://
doi.org/10.1103/PhysRevB.54.9267.
[33] A. Maignan, C. Martin, F. Damay, B. Raveau, J. Hejtmanek, Transition from a
paramagnetic metallic to a cluster glass metallic state in electron-doped perovskite
manganites, Phys. Rev. B 58 (1998) 2758–2763, https://doi.org/10.1103/
PhysRevB.58.2758.
[34] S. Chatterjee, S. Giri, S. K. De, S. Majumdar, Reentrant-spin-glass state in
Ni2Mn1.36Sn0.64 shape-memory alloy, Phys. Rev. B 79 (2009) 092410, https://
doi.org/10.1103/PhysRevB.79.092410.
[35] N.V. Baranov, A.V. Proshkin, A.F. Gubkin, A. Cervellino, H. Michor, G. Hilscher, E.
G. Gerasimov, G. Ehlers, M. Frontzek, A. Podlesnyak, Enhanced survival of short-
range magnetic correlations and frustrated interactions in R3T intermetallics,
J. Magn. Magn. Mater. 324 (2012) 1907–1912, https://doi.org/10.1016/j.
jmmm.2012.01.021.
[36] J.L. Wang, Y.P. Shen, C.P. Yang, N. Tang, B. Fuquan, D. Yang, G.H. Wu, F.M. Yang,
Spin reorientation and magnetohistory of DyFe12-xNbx compounds, J. Phys.:
Condens. Matter 13 (2001) 1733–1741, https://doi.org/10.1088/0953-8984/13/
8/310.
[37] S. Baran, M. Hofmann, J. Leciejewicz, M. Slaski, A. Szytula, Antiferromagnetic
ordering in PrCuSn and NdCuSn, J. Phys.: Condens. Matter 10 (9) (1998)
2107–2114, https://doi.org/10.1088/0953-8984/10/9/014.
[38] E.A. Sherstobitova, A.F. Gubkin, P.B. Terent’ev, A.A. Sherstobitov, A.N. Pirogov, N.
V. Mushnikov, Structural and magnetic properties of ErFe2D3.1, J. Alloys
Compounds 538 538 (2012) 79–84, https://doi.org/10.1016/j.
jallcom.2012.05.107.
[39] R. Yadav, S. Elizabeth, Magnetic frustration and dielectric relaxation in insulating
Nd2NiMnO6 double perovskites, J. Appl. Phys. 117 (2015), 053902, https://doi.
org/10.1063/1.4906989.
[40] J.K. Murthy, A. Venimadhav, Reentrant cluster glass behavior in La2CoMnO6
nanoparticles, J. Appl. Phys. 113 (2013), 163906, https://doi.org/10.1063/
1.4802658.
[41] P.C. Hohenberg, B.I. Halperin, Theory of dynamic critical phenomena, Rev. Mod.
Phys. 49 (3) (1977) 435–479, https://doi.org/10.1103/RevModPhys.49.435.
[42] K. Gunnarsson, P. Svedlindh, P. Nordblad, L. Lundgren, H. Aruga, A. Ito, Dynamics
of an ising spin-glass in the vicinity of the spin-glass temperature, Phys. Rev. Lett.
61 (6) (1988) 754–757, https://doi.org/10.1103/PhysRevLett.61.754.
[43] R Laiho, E. L¨ahderanta, J. Salminen, K. G. Lisunov, V. S. Zakhvalinskii, Spin
dynamics and magnetic phase diagram of La1− xCaxMnO3 (0<~x<~0.15), Phys.
Rev. B 63 (2001) 094405, https://doi.org/10.1103/PhysRevB.63.094405.
[44] J.L. Tholence, On the frequency dependence of the transition temperature in spin
glasses, Solid State Commun. 35 (1980) 113–117, https://doi.org/10.1016/0038-
1098(80)90225-2.
[45] J. Souletie, J.L. Tholence, Critical slowing down in spin glasses and other glasses:
Fulcher versus power law, Phys. Rev. B 32 (1985) 516–519, https://doi.org/
10.1103/PhysRevB.32.516.
[46] J.B. Goodenough, Direct cation- -cation interactions in several oxides, Phys. Rev.
117 (1960) 1442–1451, https://doi.org/10.1103/PhysRev.117.1442.
[47] J. Laverdi‘ere, S. Jandl, A. A. Mukhin, V. Y. Ivanov, V. G. Ivanov, M. N. Iliev, Spin-
phonon coupling in orthorhombic RMnO3 (R=Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Y): A
Raman study, Phys. Rev. B 73 (2006) 214301, https://doi.org/10.1103/
PhysRevB.73.214301.
[48] W. S. Ferreira, J. Agostinho Moreira, A. Almeida, M. R. Chaves, J. P. Araújo, J. B.
Oliveira, J. M. Machado Da Silva, M. A. Sá, T. M. Mendonça, P. Simeão Carvalho, J.
Kreisel, J. L. Ribeiro, L. G. Vieira, P. B. Tavares, S. Mendonça, Spin-phonon
coupling and magnetoelectric properties: EuMnO3 versus GdMnO3, Phys. Rev. B
79 (2009) 054303, https://doi.org/10.1103/PhysRevB.79.054303.
[49] J. A. Moreira, A. Almeida, W. S. Ferreira, J. E. Araújo, A. M. Pereira, M. R. Chaves,
J. Kreisel, S. M. F. Vilela, P. B. Tavares, Coupling between phonons and magnetic
excitations in orthorhombic Eu1− xYxMnO3, Phys. Rev. B 81 (2010) 054447,
https://doi.org/10.1103/PhysRevB.81.054447.
[50] V. S. Bhadram, B. Rajeswaran, A. Sundaresan, C. Narayana, Spin-phonon coupling
in multiferroic RCrO3 (R-Y, Lu, Gd, Eu, Sm): A Raman study, Europhys. Lett. 101
(2013) 17008, https://doi.org/10.1209/0295-5075/101/17008.
[51] M. C.Weber, M. Guennou, H. J. Zhao, J. Ĩ́ niguez, R. Vilarinho, A. Almeida, J. A.
Moreira, J. Kreisel, Raman spectroscopy of rare-earth orthoferrites RFeO3 (R=La,
Sm, Eu, Gd, Tb, Dy), Phys. Rev. B 94 (2016) 214103, https://doi.org/10.1103/
PhysRevB.94.214103.
[52] E. Granado, A. García, J.A. Sanjurjo, C. Rettori, I. Torriani, F. Prado, R.D. Sánchez,
A. Caneiro, S.B. Oseroff, Magnetic ordering effects in the Raman spectra of
La1− xMn1− xO3, Phys. Rev. B 60 (1999) 11879, https://doi.org/10.1103/
PhysRevB.60.11879.
[53] S. Mukherjee, A. Garg and R. Gupta, Probing magnetoelastic coupling and
structural changes in magnetoelectric gallium ferrite, J. Phys.: Condens. Matter 23
(2011) 445403, https://doi.org/10.1088/0953-8984/23/44/445403.
15
Journal of Magnetism and Magnetic Materials 529 (2021) 167887
[54] D.J. Lockwood, M.G. Cottam, The spin-phonon interaction in FeF2 and MnF2
studied by Raman spectroscopy, J. Appl. Phys. 64 (1988) 5876–5878, https://doi.
org/10.1063/1.342186.
[55] R. Gupta, M. Kim, H. Barath, S.L. Cooper, G. Cao, Field- and pressure-induced
phases in Sr4Ru3O10: A spectroscopic investigation, Phys. Rev. Lett. 96 (2006),
067004, https://doi.org/10.1103/PhysRevLett.96.067004.
[56] S. Chaturvedi, P. Shyam, A. Apte, J. Kumar, A. Bhattacharyya, A.M. Awasthi,
S. Kulkarni, Dynamics of electron density, spin-phonon coupling, and dielectric
properties of SmFeO3 nanoparticles at the spin-reorientation temperature: Role of
exchange striction, Phys. Rev. B 93 (2016), 174117, https://doi.org/10.1103/
PhysRevB.93.174117.
[57] K. Dey, S. Majumdar, S. Giri, Ferroelectricity in spiral short-range-ordered
magnetic state of spinel MnCr2O4: Significance of topological frustration and
magnetoelastic coupling, Phys. Rev. B 90 (2014), 184424, https://doi.org/
10.1103/PhysRevB.90.18442.
[58] K. Dey, A. Karmakar, A. Indra, S. Majumdar, U. Rütt, O. Gutowski, M. v.
Zimmermann, S. Giri, Thermally assisted and magnetic field driven isostructural
distortion of spinel structure and occurrence of polar order in CoCr2S4, Phys. Rev.
B 92 (2015) 024401, https://doi.org/10.1103/PhysRevB.92.024401.
[59] K. Dey, A. Karmakar, S. Majumdar, S. Giri, Strong magnetoelastic coupling and
unconventional electric polarization in the triangular-lattice multiferroic
Li0.99Cu0.01CrO2, Phys. Rev. B 87 (2013) 094403, https://doi.org/10.1103/
PhysRevB.87.094403.
[60] K. Dey, A. Karmakar, S. Majumdar, S. Giri, Structural correlation to spontaneous
electric and magnetic order in multiferroic LiCr0.99Fe0.01O2, Scripta Mater. 75
(2014) 94–97, https://doi.org/10.1016/j.scriptamat.2013.11.032.
[61] P. Mandal, V.S. Bhadram, Y. Sundarayya, C. Narayana, A. Sundaresan, C.N.R. Rao,
137202, Spin-reorientation, ferroelectricity, and magnetodielectric effect in
YFe1− xMnxO3 (0.1≤x≤0.40), Phys. Rev. Lett. 107 (2011), https://doi.org/
10.1103/PhysRevLett.107.137202.
[62] L.H. Yin, J. Yang, P. Tong, X. Luo, C.B. Park, K.W. Shin, W.H. Song, J.M. Dai, K.
H. Kim, X.B. Zhu, Y.P. Sun, Role of rare earth ions in the magnetic, magnetocaloric
and magnetoelectric properties of RCrO3 (R = Dy, Nd, Tb, Er) crystals, J. Mater.
Chem. C 4 (2016) 11198, https://doi.org/10.1039/C6TC03989H.
[63] G. Kotnana, S.N. Jammalamadaka, Enhanced spin – Reorientation temperature and
origin of magnetocapacitance in HoFeO3, J. Magn. Magn. Mater. 418 (2016)
81–85, https://doi.org/10.1016/j.jmmm.2016.02.054.
[64] N. Ramu, R. Muralidharan, K. Meera, Y.H. Jeong, Tailoring the magnetic and
magnetoelectric properties of rare earth orthoferrites for room temperature
applications, RSC Adv. 6 (2016) 72295–72299, https://doi.org/10.1039/
C6RA15850A.
[65] P. Prakash, V. Sathe, C.L. Prajapat, A.K. Nigam, P.S.R. Krishna, A. Das, Spin phonon
coupling in Mn doped HoFeO3 compounds exhibiting spin reorientation behavior,
J. Phys.: Condens. Matter 32 (2020) 095801, https://doi.org/10.1088/1361-
648X/ab576d.
[66] A. Pal, S. Ghosh, A. G. Joshi, Shiv Kumar, S. Patil, P. K. Gupta, P. Singh, V. K.
Gangwar, P. Prakash, R. K. Singh, E. F. Schwier, M. Sawada, K. Shimada, A. K.
Ghosh, A. Das, S. Chatterjee, Investigation of multi-mode spin–phonon coupling
and local B-site disorder in Pr2CoFeO6 by Raman spectroscopy and correlation
with its electronic structure by XPS and XAS studies, J. Phys.: Condens. Matter 31
(2019) 275802, https://doi.org/10.1088/1361-648X/ab144f .
[67] M.K. Singh, W. Prellier, M.P. Singh, R.S. Katiyar, J.F. Scott, Spin-glass transition in
single-crystal BiFeO3, Phys. Rev. B 77 (2008), 144403.
[68] B. Ramachandran, M.S.R. Rao, Low temperature magnetocaloric effect in
polycrystalline BiFeO3 ceramics, Appl. Phys. Lett. 95 (2009) 142505, https://doi.
org/10.1063/1.3242411.
[69] W.-M. Zhu, H.-Y. Guo, Z.-G. Ye, Structural and magnetic characterization of
multiferroic (BiFeO3)1–x(PbTiO3)x solid solutions, Phys. Rev. B 78 (2008), 014401,
https://doi.org/10.1103/PhysRevB.78.014401.
[70] W. Kleemann, V.V. Shvartsman, P. Borisov, Coexistence of antiferromagnetic and
spin cluster glass order in the magnetoelectric relaxor multiferroic
PbFe0.5Nb0.5O3, Phys. Rev. Lett. 105 (2010) 257202, https://doi.org/10.1103/
PhysRevLett.105.257202 .
[71] D.M. Cragg, D. Sherrington, Spin-glass with local uniaxial anisotropy, Phys. Rev.
Lett. 49 (1982) 1190–1193, https://doi.org/10.1103/PhysRevLett.49.1190.
[72] D. Sherrington, S. Kirkpatrick, Solvable model of a spin-glass, Phys. Rev. Lett. 35
(1975) 1792–1796, https://doi.org/10.1103/PhysRevLett.35.1792.
[73] J.R.L.d. Almeida, D.J. Thouless, Stability of the Sherrington-Kirkpatrick solution of
a spin glass model, J. Phys. A: Math. Gen. 11 (1978) 983–990, https://doi.org/
10.1088/0305-4470/11/5/028.
[74] A.D. Beath, D.H. Ryan, Coexistence of spin-glass and ferromagnetic order in the ±J
Heisenberg spin-glass model, Phys. Rev. B 76 (2007), 064410, https://doi.org/
10.1103/PhysRevB.76.064410.
[75] M. Gabay, G. Toulouse, Coexistence of spin-glass and ferromagnetic orderings,
Phys. Rev. Lett. 47 (1981) 201–204, https://doi.org/10.1103/PhysRevLett.47.201.
[76] H. Yoshizawa, S. Mitsuda, H. Aruga, A. Ito, Mixed phase of spin-glass ordering and
antiferromagnetism in an Ising system, FexMn1− xTiO3, Phys. Rev. Lett. 59 (1987)
2364, https://doi.org/10.1103/PhysRevLett.59.2364.
[77] S. Murayama, K. Yokosawa, Y. Miyako, E.F. Wassermann, Two successive
transitions in uniaxially anisotropic spin-glasses, Phys. Rev. Lett. 57 (1986)
1785–1788, https://doi.org/10.1103/PhysRevLett.57.1785.
[78] Y. Yamaguchi, T. Nakano, Y. Nozue, T. Kimura, Magnetoelectric effect in an XY-
like spin glass system NixMn1− xTiO3, Phys. Rev. Lett. 108 (2012), 057203, https://
doi.org/10.1103/PhysRevLett.108.057203.
S. Raut et al.
[79] J.K. Srivastava, W. Treutmann, E. Untersteller, Anisotropic spin glass
pseudobrookite: Evidence for transverse freezing and possible implications, Phys.
Rev. B 68 (2003), 144404, https://doi.org/10.1103/PhysRevB.68.144404.
[80] S. Sharma, T. Basu, A. Shahee, K. Singh, N. P. Lalla, E. V. Sampathkumaran,
Multiglass properties and magnetoelectric coupling in the uniaxial anisotropic
spin-cluster-glass Fe2TiO5, https://doi.org/10.1103/PhysRevB.90.144426.
[81] S. von, Po-zen, Wong, T.T.M. Molnar, J.A. Palstra, H. Mydosh, S.M. Yoshizawa,
Shapiro, A. Ito, Coexistence of spin-glass and antiferromagnetic orders in the ising
system Fe0.55Mg0.45Cl2, Phys. Rev. Lett. 55 (1985), https://doi.org/10.1103/
PhysRevLett.55.2043.
[82] Po-zen Wong, H. Yoshizawa, S. M. Shapiro, Coexistence of antiferromagnetism and
spin-glass ordering in the Ising system Fe0.55Mg0.45Cl2, J. Appl. Phys. 57 (1985)
3462, https://doi.org/10.1063/1.335080.
[83] A. Ito, H. Aruga, E. Torikai, M. Kikuchi, Y. Syono, H. Takei, Time-dependent
phenomena in a short-range ising spin-glass, Fe0.5Mn0.5TiO3, Phys. Rev. Lett. 57
(1986) 483, https://doi.org/10.1103/PhysRevLett.57.483.
16
Journal of Magnetism and Magnetic Materials 529 (2021) 167887
[84] I.A. Campbell, S. Senoussi, F. Varret, J. Teillet, A. Hamzic, Competing
ferromagnetic and spin-glass order in a AuFe alloy, Phys. Rev. Lett. 50 (1983)
1615, https://doi.org/10.1103/PhysRevLett.50.1615.
[85] I. Mirebeau, G. Iancu, M. Hennion, G. Gavoille, J. Hubsch, Neutron study of the
frustrated spinel compound Mg1+tFe2− 2tTitO4 (t=0.55), Phys. Rev. B 54 (1996)
15928, https://doi.org/10.1103/PhysRevB.54.15928.
[86] A. Chatterjee, S. Majumdar, S. Chatterjee, A.-C. Dippel, O. Gutowski, M.
V. Zimmermann, S. Giri, Magnetoelastic coupling at spin-glass-like transition in
Sr3NiSb2O9, J. Alloy. Compd. 778 (2019) 30–36, https://doi.org/10.1016/j.
jallcom.2018.11.074.
[87] J.-S. Zhou, J.B. Goodenough, Universal octahedral-site distortion in orthorhombic
perovskite oxides, Phys. Rev. Lett 94 (2005), 065501, https://doi.org/10.1103/
PhysRevLett.94.065501.