Magnetoelectric (ME) materials with ferroelectric and magnetic transition temperatures near room temperature are of current interest in research due to their technological importance and potential applications. Herein, we report the coupled magnetic ordering and phonons in gallium ferrite (GaFeO3), a near room temperature ME perovskite, using magnetization and inelastic light scattering measurements as a function of temperature. Temperature-dependent magnetization behavior studied in a wide temperature range of 5–395 K at both field-cooled (FC) and zero-field-cooled (ZFC) conditions using different static magnetic fields confirms the magnetic transition temperature Tc at 220 K. On temperature dependent Raman spectroscopy, no significant changes in Raman spectra were observed at an elevated temperature that can be attributed to the absence of structural phase transition. Instead of expected anharmonic behavior, several librational (rigid rotation) and stretching modes of rigid BO6 units were found to be hardening below Tc, suggesting the significant magnetoelastic coupling contributions to phonon frequencies. The asymmetric stretching mode at 753 cm−1 is found to have larger spin-phonon coupling contribution (λ∼2.93), while the lattice mode at 153 cm−1 and external librational mode at 240 cm−1 had the lowest effect (λ∼0.88).

1.
M.
Fiebig
, “
Revival of the magnetoelectric effect
,”
J. Phys. D Appl. Phys.
38
,
R123
R152
(
2005
).
2.
Z. H.
Sun
,
B. L.
Cheng
,
S.
Dai
,
L. Z.
Cao
,
Y. L.
Zhou
,
K. J.
Jin
,
Z. H.
Chen
, and
G. Z.
Yang
, “
Dielectric property studies of multiferroic GaFeO3
,”
J. Phys. D Appl. Phys.
39
,
2481
2484
(
2006
).
3.
E.
Lage
,
C.
Kirchhof
,
V.
Hrkac
,
L.
Kienle
,
R.
Jahns
,
R.
Knöchel
,
E.
Quandt
, and
D.
Meyners
, “
Exchange biasing of magnetoelectric composites
,”
Nat. Mater.
11
,
523
529
(
2012
).
4.
C.
Israel
,
N. D.
Mathur
, and
J. F.
Scott
, “
A one-cent room-temperature magnetoelectric sensor
,”
Nat. Mater.
7
,
93
94
(
2008
).
5.
X.
Chen
,
A.
Hochstrat
,
P.
Borisov
, and
W.
Kleemann
, “
Magnetoelectric exchange bias systems in spintronics
,”
Appl. Phys. Lett.
89
,
202508
(
2006
).
6.
S. X.
Wang
and
A. M.
Taratorin
,
Magnetic Information Storage Technology
(
Academic Press
,
San Diego
,
California
,
1999
).
7.
J. F.
Scott
, “
Multiferroic memories
Nat. Mater.
6
,
256
257
(
2007
).
8.
A.
Roy
,
R.
Gupta
, and
A.
Garg
, “
Multiferroic memories
,”
Adv. Condens. Matter Phys.
2012
,
926290
(
2012
).
9.
M.
Gajek
,
M.
Bibes
,
S.
Fusil
,
K.
Bouzehouane
,
J.
Fontcuberta
,
A.
Barthélémy
, and
A.
Fert
, “
Tunnel junctions with multiferroic barriers
,”
Nat. Mater.
6
,
296
302
(
2007
).
10.
L. F.
Henrichs
,
O.
Cespedes
,
J.
Bennett
,
J.
Landers
,
S.
Salamon
,
C.
Heuser
,
T.
Hansen
,
T.
Helbig
,
O.
Gutfleisch
,
D. C.
Lupascu
,
H.
Wende
,
W.
Kleemann
, and
A. J.
Bell
, “
Multiferroic clusters: A new perspective for relaxor-type room-temperature multiferroics
,”
Adv. Funct. Mater.
26
,
2111
2121
(
2016
).
11.
N. A.
Hill
, “
Why are there so few magnetic ferroelectrics?
,”
J. Phys. Chem. B
104
,
6694
6709
(
2000
).
12.
G.
Catalan
and
J. F.
Scott
, “
Physics and applications of bismuth ferrite
,”
Adv. Mater.
21
,
2463
2485
(
2009
).
13.
B. W.
Lee
,
P. S.
Yoo
,
V. B.
Nam
,
K. R. N.
Toreh
, and
C. U.
Jung
, “
Magnetic and electric properties of stoichiometric BiMnO3 thin films
,”
Nanoscale Res. Lett.
10
,
47
(
2015
).
14.
S.
Quezel
,
F.
Tcheou
,
J.
Rossat-Mignod
,
G.
Quezel
, and
E.
Roudaut
, “
Magnetic structure of the perovskite-like compound TbMnO3
,”
Physica B + C
86–88
,
916
918
(
1977
).
15.
J. P.
Remeika
, “
GaFeO3: A ferromagnetic-piezoelectric compound
,”
J. Appl. Phys.
263
,
3
5
(
1960
).
16.
A.
Poole
,
B.
Roessli
,
O.
Zaharko
, and
K. W.
Krämer
, “
The magnetic structure of multiferroic BaMnF4
,”
J. Phys. Condens. Matter
23
,
266004
(
2011
).
17.
M.
Balli
,
B.
Roberge
,
P.
Fournier
, and
S.
Jandl
, “
Review of the magnetocaloric effect in RMnO3 and RMn2O5 multiferroic crystals
,”
Crystals
7
,
44
(
2017
).
18.
J.
Wang
,
J. B.
Neaton
,
H.
Zheng
,
V.
Nagarajan
,
S. B.
Ogale
,
B.
Liu
,
D.
Viehland
,
V.
Vaithyanathan
,
D. G.
Schlom
,
U. V.
Waghmare
,
N. A.
Spaldin
,
K. M.
Rabe
,
M.
Wuttig
, and
R.
Ramesh
, “
Epitaxial BiFeO3 multiferroic thin film heterostructures
,”
Science.
299
,
1719
1722
(
2003
).
19.
P.
Toulemonde
,
P.
Bordet
,
P.
Bouvier
, and
J.
Kreisel
, “
Single-crystalline BiMnO3 studied by temperature-dependent x-ray diffraction and Raman spectroscopy
,”
Phys. Rev. B Condens. Matter Mater. Phys.
89
,
22
(
2014
).
20.
X.
Fabrèges
,
I.
Mirebeau
,
P.
Bonville
,
S.
Petit
,
G.
Lebras-Jasmin
,
A.
Forget
,
G.
André
, and
S.
Pailhès
, “
Magnetic order in YbMnO3 studied by neutron diffraction and Mössbauer spectroscopy
,”
Phys. Rev. B
78
,
214422
(
2008
).
21.
J. M.
Moreau
,
C.
Michel
,
R.
Gerson
, and
W. J.
James
, “
Ferroelectric BiFeO3 X-Ray and neutron diffraction study
,”
J. Phys. Chem. C
32
,
1315
1320
(
1971
).
22.
R. B.
Frankel
,
N. A.
Blum
,
S.
Foner
,
A. J.
Freeman
, and
M.
Schierber
, “
Ferrimagnetic structure of magnetoelectric Ga2-xFexO3
,”
Phys. Rev. Lett.
15
,
958
960
(
1965
).
23.
T.
Arima
,
D.
Higashiyama
,
Y.
Kaneko
,
J. P.
He
,
T.
Goto
,
S.
Miyasaka
,
T.
Kimura
,
K.
Oikawa
,
T.
Kamiyama
,
R.
Kumai
, and
Y.
Tokura
, “
Structural and magnetoelectric properties of Ga2-xFexO3 single crystals grown by a floating-zone method
,”
Phys. Rev. B Condens. Matter Mater. Phys.
70
,
1
8
(
2004
).
24.
J. H.
Jung
,
M.
Matsubara
,
T.
Arima
,
J. P.
He
,
Y.
Kaneko
, and
Y.
Tokura
, “
Optical magnetoelectric effect in the polar GaFeO3 ferrimagnet
,”
Phys. Rev. Lett.
93
,
037403
1
(
2004
).
25.
Y.
Ogawa
,
Y.
Kaneko
,
J. P.
He
,
X. Z.
Yu
,
T.
Arima
, and
Y.
Tokura
, “
Magnetization-induced second harmonic generation in a polar ferromagnet
,”
Phys. Rev. Lett.
92
,
4
(
2004
).
26.
R.
Saha
,
A.
Shireen
,
S. N.
Shirodkar
,
U. V.
Waghmare
,
A.
Sundaresan
, and
C. N. R.
Rao
, “
Multiferroic and magnetoelectric nature of GaFeO3, AlFeO3 and related oxides
,”
Solid State Commun.
152
,
1964
1968
(
2012
).
27.
J. Y.
Kim
,
T. Y.
Koo
, and
J. H.
Park
, “
Orbital and bonding anisotropy in a half-filled GaFeO3 magnetoelectric ferrimagnet
,”
Phys. Rev. Lett.
96
,
047205
(
2006
).
28.
M. J.
Han
,
T.
Ozaki
, and
J.
Yu
, “
Magnetic ordering and exchange interactions in multiferroic GaFeO3
,”
Phys. Rev. B
75
,
060404
(
2007
).
29.
S.
Mukherjee
,
A.
Garg
, and
R.
Gupta
, “
Spin glass-like phase below ∼210 K in magnetoelectric gallium ferrite
,”
Appl. Phys. Lett.
100
,
112904
(
2012
).
30.
R.
Gupta
,
M.
Kim
,
H.
Barath
,
S. L.
Cooper
, and
G.
Cao
, “
Field- and pressure-induced phases in Sr4Ru3O10: A spectroscopic investigation
,”
Phys. Rev. Lett.
96
,
1
4
(
2006
).
31.
A.
Thomasson
,
J.
Kreisel
,
C.
Lefèvre
,
F.
Roulland
,
G.
Versini
,
S.
Barre
, and
N.
Viart
, “
Raman scattering of magnetoelectric gallium ferrite thin films
,”
J. Phys. Condens. Matter
25
,
0
6
(
2013
).
32.
S.
Mukherjee
,
A.
Garg
, and
R.
Gupta
, “
Probing magnetoelastic coupling and structural changes in magnetoelectric gallium ferrite
,”
J. Phys. Condens. Matter
23
,
445403
(
2011
).
33.
M. K.
Gupta
,
R.
Mittal
,
M.
Zbiri
,
R.
Singh
,
S.
Rols
,
H.
Schober
, and
S. L.
Chaplot
, “
Spin-phonon coupling, high-pressure phase transitions, and thermal expansion of multiferroic GaFeO3: A combined first principles and inelastic neutron scattering study
,”
Phys. Rev. B Condens. Matter Mater. Phys.
90
,
1
11
(
2014
).
34.
J.
Rodríguez-Carvajal
, “
Recent advances in magnetic structure determination by neutron powder diffraction
,”
Phys. B Phys. Condens. Matter
192
,
55
69
(
1993
).
35.
K.
Momma
and
F.
Izumi
, “
VESTA: A three-dimensional visualization system for electronic and structural analysis
,”
J. Appl. Crystallogr.
41
,
653
658
(
2008
).
36.
A.
Roy
,
S.
Mukherjee
,
R.
Gupta
,
S.
Auluck
,
R.
Prasad
, and
A.
Garg
, “
Electronic structure, Born effective charges and spontaneous polarization in magnetoelectric gallium ferrite
,”
J. Phys. Condens. Matter
23
,
325902
(
2011
).
37.
M. K.
Singh
,
W.
Prellier
,
M. P.
Singh
,
R. S.
Katiyar
, and
J. F.
Scott
, “
Spin-glass transition in single-crystal BiFeO3
,”
Phys. Rev. B Condens. Matter Mater. Phys.
77
,
144403
(
2008
).
38.
W. R.
Chen
,
F. C.
Zhang
,
J.
Miao
,
B.
Xu
,
X. L.
Dong
,
L. X.
Cao
,
X. G.
Qiu
,
B. R.
Zhao
, and
P.
Dai
, “
Re-entrant spin glass behavior in Mn-rich YMnO3
,”
Appl. Phys. Lett.
87
,
042508
(
2005
).
39.
J.
Dho
,
W. S.
Kim
, and
N. H.
Hur
, “
Reentrant spin glass behavior in Cr-doped perovskite manganite
,”
Phys. Rev. Lett.
89
,
027202
(
2002
).
40.
P. C.
Hohenberg
and
B. I.
Halperin
, “
Theory of dynamic critical phenomena
,”
Rev. Mod. Phys.
49
,
435
479
(
1977
).
41.
H.
Vogel
, “
The temperature dependence law of viscosity of fluids
,”
Phys. Z.
22
,
645
646
(
1921
).
42.
G. S.
Fulcher
, “
Analysis of recent measurements of the viscosity of glasses
,”
J. Am. Ceram. Soc.
75
,
1043
1055
(
1992
).
43.
S. R.
Shinde
,
S. B.
Ogale
,
J. S.
Higgins
,
H.
Zheng
,
A. J.
Millis
,
V. N.
Kulkarni
,
R.
Ramesh
,
R. L.
Greene
, and
T.
Venkatesan
, “
Co-occurrence of superparamagnetism and anomalous Hall effect in highly reduced cobalt-doped rutile TiO2-δ films
,”
Phys. Rev. Lett.
92
,
96
99
(
2004
).
44.
J. W. J. F.
Watts
,
An Introduction of Surface Analysis and XPS
(Wiley,
2003
), Vol. 27.
45.
C. D.
Wagner
,
W. M.
Riggs
,
L. E.
Davis
,
J. F.
Moulder
, and
G. E.
Muilenberg
,
Handbook of X-ray Photoelectron Spectroscopy
(
Perkin-Elmer Corp.
,
Eden Prairie
,
1979
).
46.
V.
Singh
,
A.
Daryapurkar
,
S. S.
Rajput
,
S.
Mukherjee
,
A.
Garg
, and
R.
Gupta
, “
Effect of annealing atmosphere on leakage and dielectric characteristics of multiferroic gallium ferrite
,”
J. Am. Ceram. Soc.
100
,
5226
5238
(
2017
).
47.
K. K.
Mishra
,
S.
Chandra
,
N. P.
Salke
,
S. N.
Achary
,
A. K.
Tyagi
, and
R.
Rao
, “
Soft modes and anharmonicity in H3[Co(CN)6]: Raman spectroscopy and first-principles calculations
,”
Phys. Rev. B Condens. Matter Mater. Phys.
92
,
134112
(
2015
).
48.
P.
Kumar
,
A.
Bera
,
D. V. S.
Muthu
,
S. N.
Shirodkar
,
R.
Saha
,
A.
Shireen
,
A.
Sundaresan
,
U. V.
Waghmare
,
A. K.
Sood
, and
C. N. R.
Rao
, “
Coupled phonons, magnetic excitations, and ferroelectricity in AlFeO3: Raman and first-principles studies
,”
Phys. Rev. B Condens. Matter Mater. Phys.
85
,
134449
(
2012
).
49.
N. O.
Golosova
,
D. P.
Kozlenko
,
S. E.
Kichanov
,
E. V.
Lukin
,
L. S.
Dubrovinsky
,
A. I.
Mammadov
,
R. Z.
Mehdiyeva
,
S. H.
Jabarov
,
H. P.
Liermann
,
K. V.
Glazyrin
,
T. N.
Dang
,
V. G.
Smotrakov
,
V. V.
Eremkin
, and
B. N.
Savenko
, “
Structural, magnetic and vibrational properties of multiferroic GaFeO3 at high pressure
,”
J. Alloys Compd.
684
,
352
358
(
2016
).
50.
K. K.
Mishra
,
S.
Bevara
,
T. R.
Ravindran
,
S. J.
Patwe
,
M. K.
Gupta
,
R.
Mittal
,
R. V.
Krishnan
,
S. N.
Achary
, and
A. K.
Tyagi
, “
High pressure behavior of complex phosphate K2Ce[PO4]2: Grüneisen parameter and anharmonicity properties
,”
J. Solid State Chem.
258
,
845
853
(
2018
).
51.
D. J.
Lockwood
and
M. G.
Cottam
, “
The spin-phonon interaction in FeF2 and MnF2 studied by Raman spectroscopy
,”
J. Appl. Phys.
64
,
5876
5878
(
1988
).
52.
M. K.
Singh
and
R. S.
Katiyar
, “
Phonon anomalies near the magnetic phase transitions in BiFeO3 thin films with rhombohedral R3c symmetry
,”
J. Appl. Phys.
109
,
07D916
(
2011
).

Supplementary Material

You do not currently have access to this content.