Journal of Magnetism and Magnetic Materials 451 (2018) 183–186

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Journal of Magnetism and Magnetic Materials

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

Letter to the Editor

Room-temperature ferromagnetism in Fe-based perovskite solid

solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials
Nguyen The Hung a,b, Luong Huu Bac a, Nguyen Ngoc Trung a,⇑, Nguyen The Hoang a, Pham Van Vinh c,
Dang Duc Dung a,⇑
a
School of Engineering Physics, Ha Noi University of Science and Technology, 1 Dai Co Viet road, Ha Noi, Viet Nam
b
Department of Physics, Faculty of Basic-Fundamental Sciences, Viet Nam Maritime University, 484 Lach Tray road, Ngo Quyen, Hai Phong, Viet Nam
c
Faculty of Physics, Hanoi National University of Education, 136 Xuan Thuy, Cau Giay, Ha Noi, Viet Nam

a r t i c l e i n f o a b s t r a c t

Article history: The integration of ferromagnetism in lead-free ferroelectric materials is important to fabricate smart
Received 28 September 2017 materials for electronic devices. In this work, (1 x)Bi0.5Na0.5TiO3 + xMgFeO3-d materials (x = 0–9 mol%)
Received in revised form 26 October 2017 were prepared through sol–gel method. X-ray diffraction characterization indicated that MgFeO3-d mate-
Accepted 6 November 2017
rials existed as a well solid solution in lead-free ferroelectric Bi0.5Na0.5TiO3 materials. The rhombohedral
Available online 6 November 2017
structure of Bi0.5Na0.5TiO3 materials was distorted due to the random distribution of Mg and Fe cations
into the host lattice. The reduced optical band gap and the induced room-temperature ferromagnetism
Keywords:
were due to the spin splitting of transition metal substitution at the B-site of perovskite Bi0.5Na0.5TiO3
Bi0.5Na0.5TiO3
MgFeO3-d
and the modification by A-site co-substitution. This work elucidates the role of secondary phase as solid
Lead-free ferroelectric solution in Bi0.5Na0.5TiO3 material for development of lead-free multiferroelectric materials.
Multiferroic Ó 2017 Elsevier B.V. All rights reserved.
Sol–gel

1. Introduction indirect exchange interaction through oxygen vacancies, called F

Lead-free ferroelectric materials are being rapidly developed to
replace lead-based ones because of their environment-friendliness
and safety for human health [1].
Bi-containing perovskite materials have been increasingly
investigated because Bi3+ ions possess lone pairs similar to those
of Pb2+ ions [2,3]. Lead-free ferroelectric Bi0.5Na0.5TiO3-based mate-
rials exhibit piezoelectric and ferroelectric properties that are com-
parable with those of Pb(Zr,Ti)O3-based materials [1]. Smolensky
et al. fabricated the first Bi0.5Na0.5TiO3 materials in 1960 [4]. These
materials exhibit strong ferroelectric properties, Curie temperature
of 320 °C, remanent polarization of 38 mC/cm2, and coercive field of
73 kV/cm at room temperature [4,5]. Studies also showed that
Bi0.5Na0.5TiO3 materials possess magnetoelectric properties and
are thus suitable for fabricating next-generation electronic devices.
In particular, Bi0.5Na0.5TiO3 exerted fact room-temperature ferro-
magnetism as a result of the substitution of transition metals, such
as Fe, Co, Mn, and Cr, into the octahedral Ti site [6–9]. The room-
temperature ferromagnetism in ferroelectric Bi0.5Na0.5TiO3 materi-
als doped with transition metals possibly originates from the
⇑ Corresponding author.
E-mail addresses: trung.nguyenngoc@hust.edu.vn (N.N. Trung), dung.dangduc
@hust.edu.vn (D.D. Dung).
centers [6–10]. However, the magnetization strength of the devel-
oped materials remains low (as several memu/g) at room temper-
ature; this property hinders the application of such materials for
real devices. In addition, the paramagnetism of isolated magnetic
ions and/or antiferromagnetic polaron components is strongly
affected by the total magnetic moment of the samples. Therefore,
the magnetization of Bi0.5Na0.5TiO3 materials must be enhanced
to facilitate their application to electronic devices.
The performance of Bi0.5Na0.5TiO3 materials can be improved
using a solid solution containing various specific perovskite mate-
rials. The piezoelectric properties of Bi0.5Na0.5TiO3 materials can be
enhanced by modifying their structure [1]. Guo et al. reported that
the pyroelectric properties of Bi0.5Na0.5TiO3 were strongly influ-
enced by the addition of Ba(Zr0.055Ti0.945)O3 [11]. Ullah et al.
reported that the electric field-induced strain and dynamic piezo-
electric coefficient of Bi0.5Na0.5TiO3 materials were enhanced due
to modification of BiAlO3 materials [12]. However, Kim et al.
reported that doping LiNbO3 into Bi0.5Na0.5TiO3 affected the dielec-
tric behavior and the ferroelectric properties of the latter; that is,
the reduction in the depolarization temperature corresponds to
the conversion of the ferroelectric phase into the paraelectric phase
[13].
In this work, strong room-temperature ferromagnetism in
Bi0.5Na0.5TiO3 materials was obtained by modifying MgFeO3-d as

https://doi.org/10.1016/j.jmmm.2017.11.015
0304-8853/Ó 2017 Elsevier B.V. All rights reserved.
184 N.T. Hung et al. / Journal of Magnetism and Magnetic Materials 451 (2018) 183–186
solid solution. The optical band gap of Bi0.5Na0.5TiO3 materials
decreased from 3.09 eV for pure Bi0.5Na0.5TiO3 to 2.43 eV for 9
mol% MgFeO3-d-added Bi0.5Na0.5TiO3 materials. The induced
room-temperature ferromagnetism and the reduced optical band
gap of Bi0.5Na0.5TiO3 materials were due to the random distribution
of Mg and Fe cations into the host lattice.
2. Experimental
(1-x)Bi0.5Na0.5TiO3 + xMgFeO3-d solid solution materials (range
x = 0–9 mol% (denoted as BNT-xMgFeO3-d)) were prepared through
a sol–gel technique [8,9]. The composition of the samples was
determined by electron probe microanalysis. The crystalline struc-
tures and vibration modes of the samples were determined
through X-ray diffraction (XRD) and Raman spectroscopy analyses,
respectively. Optical properties were studied by UV–Vis spec-
troscopy. Magnetic properties were characterized by a vibrating
sample magnetometer at room temperature.
3. Results and discussion
Fig. 1(a) shows the XRD pattern of undoped and MgFeO3-d-
modified Bi0.5Na0.5TiO3 materials with various MgFeO3-d concen-
trations. The peak positions and relative intensity match well with
the perovskite structure and possess the rhombohedral symmetry,
indicating that MgFeO3-d materials existed as a well solid solution
in Bi0.5Na0.5TiO3 materials. The results were validated by applying
the Hume–Rothery rules considering the radius of the cations
[14,15]. Fig. 1(b) shows that Mg and Fe cations distorted the struc-
ture of Bi0.5Na0.5TiO3 materials; in the image, the XRD patterns of
setline (0 1 2)/(1 1 0) peaks were magnified from 31° to 34°. The
peaks tended to shift to low angles, thereby expanding the lattice
parameter. Shannon reported that the radii of Mg2+ are 0.89 Å (in
Fig. 1. (a) X-ray diffraction pattern of MgFeO3-d solid solution into Bi0.5Na0.5TiO3 with various concentrations within the 2h range of 20–70°; (b) Magnified X-ray diffraction
within 2h range of 31–34° for comparing setline (0 1 2)/(1 1 0) peaks; (c) Raman scattering spectra of MgFeO3-d solid solution into Bi0.5Na0.5TiO3 with various concentrations
at 200–1000 cm 1; and (d) deconvolution Raman peaks of pure Bi0.5Na0.5TiO3, Bi0.5Na0.5TiO3-3MgFeO3-d. and Bi0.5Na0.5TiO3-5MgFeO3-d.
coordination number 8) and 0.72 Å (in coordination number 6);
moreover, of the radius of Fe2+/3+ (0.770 Å/0.645 Å in coordination
number 6) is larger than that of Bi3+ (1.17 Å in coordination num-
ber 12), Na+ (1.39 Å in coordination number 12), and Ti4+ (0.605 Å
in coordination number 6), respectively [16]. The expansion of the
lattice parameters could be due to the substitution of Mg and Fe
cations at the Ti-site rather than at the Bi/Na-site. In addition,
the impurity phase was not detected under the resolution of XRD
method. The randomly distributed Mg and Fe cations in the crystal
lattice of Bi0.5Na0.5TiO3 altered the phonon vibration (Fig. 1(c)).
The Raman scattering of undoped and MgFeO3-d-modified
Bi0.5Na0.5TiO3 materials showed a broad band, which could be sep-
arated into three region modes due to the random distribution of Bi
and Na cations to the A-site. The first bands are mainly due to the
vibration of B-site cations, i.e., Ti–O bond, and the vibration mode
is assigned to A1(TO) [17]. The secondary bands are related to the
vibration of the TiO6 octahedra and assigned to A1(LO), A1(TO), and
E(LO) modes [18,19]. The last region bands correspond to the
rhombohedral lattice containing the octahedral distorted [TiO6]
clusters [20]. The overlapping of the Raman peaks was distin-
guished using Lorentzian fitting for the undoped and Bi0.5Na0.5TiO3
materials modified with 3 and 5 mol% MgFeO3-d (Fig. 1(d)). The
eight phonon vibration modes were recorded and indexed, consis-
tent with the calculation for Raman modes of Bi0.5Na0.5TiO3 mate-
rials [17]. The modes tended to shift to low frequencies; the
differences in the mass of Mg and Fe cations from that of the host
Ti and the type of binding with oxygen both changed the frequency
modes [8,20]. These results provide a solid evidence for the
random substitution of Mg and Fe cations into the lattice of
Bi0.5Na0.5TiO3 materials. Hence, MgFeO3-d materials existed as a
well solid solution in Bi0.5Na0.5TiO3 materials.
Fig. 2(a) shows the absorbance spectra of undoped and
MgFeO3-d-added Bi0.5Na0.5TiO3 materials. MgFeO3-d-added
Bi0.5Na0.5TiO3 samples red shifted the absorption edge. The random
 N.T. Hung et al. / Journal of Magnetism and Magnetic Materials 451 (2018) 183–186
Fig. 2. (a) UV-Vis absorption spectra of MgFeO3-d-modified Bi0.5Na0.5TiO3 samples as a function of MgFeO3-d concentration; and (b) the (ahm)2 proposal with photon energy
(hm) of Bi0.5Na0.5TiO3 samples as a function of the amount of MgFeO3-d added. The inset of (b) shows the optical band gap Eg value of Bi0.5Na0.5TiO3 samples as a function of the
amount of MgFeO3-d added.
distribution of Mg and Fe cations in the crystal structure of Bi0.5-
Na0.5TiO3 led to changes in the electronic band structure. In addi-
tion, the appearance of a tail around 487 nm in the absorbance
band could be related to the local transition of Fe cations due to
spin splitting under the crystal field [21]. Optical band gap energy
(Eg) was estimated using linear fitting from photon energy (hm)
dependent (ahm)2 (Fig. 2(b)). The Eg values were plotted as a func-
tion of MgFeO3-d amount, as shown in the inset of Fig. 2(b); the val-
ues decreased from 3.09 eV for undoped to 2.43 eV for 9 mol%
MgFeO3-d-added Bi0.5Na0.5TiO3 samples. The reduction in the opti-
cal band gap in Bi0.5Na0.5TiO3 materials could be attributed to the
following: i) spin slitting of transition metals in the crystal field,
ii) oxygen vacancies due to unbalanced charge between dopants
(i.e., Fe2+/3+, Mg2+) and Ti4+, iii) changes in the bonding type
between hybridization A–O in general ABO3 perovskite, and iv) sur-
face effect on nanocrystal size [8,9,21–24]. Thus, the reduction in
the optical band gap could improve the photovoltaic and photocat-
alytic performances of ferroelectric perovskite materials.
MgFeO3-d-modified Bi0.5Na0.5TiO3 samples exhibited enhanced
ferromagnetism at room temperature. Magnetization was depen-
dent on the applied strength in the magnetic field (M-H) curves
of undoped and MgFeO3-d-added Bi0.5Na0.5TiO3 samples with vari-
ous MgFeO3-d concentrations at room temperature (Fig. 3). The
Fig. 3. M-H curves of the pure Bi0.5Na0.5TiO3 and MgFeO3-d-modified Bi0.5Na0.5TiO3
samples added with various amounts of MgFeO3-d at room temperature.
185
undoped Bi0.5Na0.5TiO3 samples possessed anti-S shape, which
could contribute to diamagnetic and weak ferromagnetic proper-
ties. Clear hysteresis loops were obtained in the undoped Bi0.5-
Na0.5TiO3 samples after subtracting the diamagnetic component
(inset of Fig. 3). The diamagnetism and weak ferromagnetism of
the undoped Bi0.5Na0.5TiO3 samples possibly originated from the
empty 3d shell of Ti4+ and Ti4+ or O vacancies [8,9,25]. The M-H
curves showed the S-shape of the material added with MgFeO3-d
and the saturation of the magnetization in the material added with
lower than 3 mol% MgFeO3-d; the material added with high con-
centrations of MgFeO3-d showed the unsaturation of magnetization
upon the application of the magnetic field because of the contribu-
tion of the paramagnetism of the isolated Fe cations and/or antifer-
romagnetism of the magnetic polaron interaction [6–10]. The non-
zero remanence and coercivity obtained in the M-H curves were
solid evidence of the ferromagnetic ordering at room temperature.
The magnetization strength in MgFeO3-d-added Bi0.5Na0.5TiO3
materials was enhanced to around 39.6 memu/g (around 18.7
memu/g after subtracting the paramagnetic-like component) at 6
kOe. This value is higher than that of Bi0.5Na0.5TiO3 materials doped
with single Mn (9 memu/g), Cr (1.5 memu/g), Fe (11 memu/
g), and Co (3 memu/g) [6–9]. Coey et al. pointed out that the
interaction of magnetic ions through oxygen vacancies was
strongly dependent on the hydrogenic orbital of the effective
radius [10,26]. Thus, we suggest that the ferromagnetic interaction
was enhanced because Mg cations controlled the distance and
interaction of magnetic ions through oxygen vacancies.
4. Conclusion
MgFeO3-d materials existed as a well solid solution in Bi0.5Na0.5-
TiO3 materials. The random distribution of Mg and Fe cations into
the lattice of Bi0.5Na0.5TiO3 reduced the optical band gap and
strongly influenced room-temperature ferromagnetism. This work
provides a basis for integrating ferromagnetism in lead-free ferro-
electric materials to fabricate green electronic devices.
Acknowledgments
This work was financially supported by The Ministry of Educa-
tion and Training, Viet Nam, under project number B2016-BKA-25.
186 N.T. Hung et al. / Journal of Magnetism and Magnetic Materials 451 (2018) 183–186

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