Journal of Alloys and Compounds 735 (2018) 945e949

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

The structure and magnetic properties of pure single phase BiFeO3

nanoparticles by microwave-assisted sol-gel method
Shuai Zheng, Jiangying Wang*, Jingji Zhang**, Hongliang Ge***, Zhi Chen, YaFeng Gao
College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China

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

Article history: The pure single phase BiFeO3 nanoparticles have been prepared by microwave-assisted sol-gel process
Received 2 August 2017 and its structure and magnetic properties have been studied. X-ray diffractometer, infrared and trans-
Received in revised form mission electron microscope results show that the synthesized BiFeO3 nanoparticles at the calcining
27 September 2017
temperature of 450
C exhibits a rhombohedrally distorted perovskite structure without secondary phase
Accepted 17 October 2017
and the size is about 40 nm. Meanwhile, the pure single phase BiFeO3 particles exhibit typical ferro-
Available online 20 November 2017
magnetic properties at room temperature and the obvious large exchange bias phenomenon at 60 K. A
exchange bias field (HE) of 302 Oe at 60 K for pure single phase BiFeO3 nanoparticles at calcining
Keywords:
BiFeO3 nanoparticles
temperature 450
C after field cooling at 20 KOe has been observed. The MT curve at H ¼ 100 Oe shows
Sol-gel process that the FC and ZFC magnetization curves start to differ in the temperature range from 60 K to 300 K
Perovskite structure revealing spin glass behavior of BiFeO3 nanoparticles at calcining temperature 450
C, 500
C and 550
C.
Magnetic properties The ferromagnetic behavior is attributed to size of effects, which partially destroy the long-wavelength
cycloid spin structure expected in bulk BiFeO3. The exchange bias effect in single crystalline BiFeO3
nanoparticles arises from co-existence of different magnetic phases of an antiferromagnetic core and a
ferromagnetic surface. The ferromagnetic, exchange bias effect and spin glass behavior of BiFeO3
nanoparticles are assigned to the uncompensated or canted spins at the ferromagnetic surface and an
antiferromagnetic core of BiFeO3 nanoparticles.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction impurities defects or nonstoichiometry, which is mainly due to the

Magnetic nanoparticles exhibit simultaneously magnetic and
dielectric property, which have exhibited interesting physical
properties as well as possibility of practical applications for new
memory devices, microwave devices, ferrofluids, catalysis and
sensors, etc [1e5]. Bismuth ferrite (BiFeO3) with a rhombohedrally
distorted perovskite structure exhibits antiferromagnetic ordering
with high Neel temperature (~643 K) and ferroelectric behavior
with ferroelectric Curie temperature (~1103 K) [6] Due to this
magnetoelectric coupling, BiFeO3-based systems can be applied in
information storage, sensors, spintronics and microelectronic de-
vices [7e9]. However, its multiferroic properties and potential ap-
plications were great hampered by the leakage current arising from
* Corresponding author.
** Corresponding author.
*** Corresponding author.
E-mail addresses: wjyliu@163.com (J. Wang), zjjtongji@gmail.com (J. Zhang),
Hongliang_ge@cjlu.edu.cn (H. Ge).
difficulty in preparing pure BiFeO3 phase [10,11].
Wet chemical methods are a promising route to prepare fine and
homogeneous powder. The synthesis of bismuth ferrite materials
has been the subject of renewed interest, and attempts have been
made to obtain a pure phase. Various wet chemical methods such
as hydrothermal [12], co-precipitation [13], combustion synthesis
[14], molten-salt method [15], thermal decomposition [16], and sol-
gel process [17] have been developed and designed to prepare pure
BiFeO3 nanoparticles. Due to the requirement of nanosized oxides
and in order to avoid bismuth volatilization the developing of low
temperature synthesis methods is essential. A variety of methods
were also used to synthetic pure BiFeO3. The structures of pure
BiFeO3 prepared by these methods severely affect its properties and
applications. To get pure phase, many of these methods use acid-
assisted gel process. The conditions for the preparation of BiFeO3
by hydrothermal method are narrow and the particle size of the
prepared nanoparticles is usually larger than 100 nm. Comparing
with other methods, the sol-gel has overcome the disadvantages of
the volatility of Bi and get pure single phase with small particle size

https://doi.org/10.1016/j.jallcom.2017.10.133
0925-8388/© 2017 Elsevier B.V. All rights reserved.
946 S. Zheng et al. / Journal of Alloys and Compounds 735 (2018) 945e949

by solid-state methods. It is still a challenge to prepare single phase

BiFeO3 nanoparticles. Pure single phase BiFeO3 nanoparticles are
sensitive to the preparation method and its composition and
microstructure strongly affect its structure and magnetic properties
[18]. The structural, morphological, and magnetic properties of
single phase BiFeO3 nanoparticles prepared by microwave-assisted
sol-gel method are presented in this paper. In this method, the
ferromagnetic, exchange bias effect and spin glass behavior of
BiFeO3 nanoparticles simultaneously exist.

2. Experimental

Pure single phase BiFeO3 nanoparticles were prepared by

microwave-assisted sol-gel method. For sake of preparing BiFeO3
precursor solutions, stoichiometric amounts of bismuth nitrate
(Bi(NO3)3$5H2O) and ferric nitrate (Fe(NO3)3$9H2O) were dissolved
respectively in appropriate amounts of acetic acid stirred at
60e80
C until the solution became transparent. In case of Bi loss,
1% excess Bi(NO3)3$5H2O was added in acetic acid. In order to avoid Fig. 1. DSC-TG curve of BiFeO3 xerogel.

Bi hydrolysis and get clear solution acetic acid which was added
Bi(NO3)3$5H2O was heated in a microwave oven several times by
70% high fire until solution became clear. The other acetic acid
which was added Fe(NO3)3$9H2O was adopted the same method so
that solute could completely dissolved. Ethylene glycol should be
mixed respectively in these two solutions. The volume ratio of
acetic acid and ethylene glycol was 1:1. These two solutions were
mixing and stirring about 2 h at room temperature. The pH value of
the solution was adjusted to 2e3 with nitric acid. The resulting
solution was heated at 80
C by constant shirring to from trans-
parent the sol, and then was heated at 110
C to obtain the BiFeO3
xerogel. The dried gels were calcined at 400e550
C for 2 h in air to
form BiFeO3 powder.
Thermogravimetry (TG) and differential scanning calorimetry
(DSC) of product were performed in a Q600STD thermal analyzer at
a heating rate of 10
C/min in air. Crystal structure of the obtained
powders was identified with a Bruker D2 X-ray diffractometer
(XRD) using CuKa radiation and infrared (IR). The powder
morphology was observed using transmission electron microscope
Fig. 2. X-ray diffraction pattern of BiFeO3 nanoparticles calcined at 400
C, 450
C,
(TEM, JEM2010). A vibrating sample magnetometer (VSM, VERSA- 500
C, 550
C.
LAB) was used to measure the magnetic property of BiFeO3
nanoparticles.
in good agreement with the literature data (JCPDS 20-0169). The
3. Results and discussion diffraction pattern for pure BiFeO3 is consistent with a rhombo-
hedral perovskite structure with the space group R3c [19,20].
The DTA/TG curves of the BiFeO3 xerogel are given in Fig. 1. The To further investigate the structure changes with the calcining
TG curve shows two weight loss steps in the temperature ranges temperature, the IR spectra of the as-synthesized powder calcined
80e280
C and 280e500
C. The first exothermic reaction accom- at different temperature are displayed in Fig. 3. The spectra agree
panied by a large weight loss of 39% in the temperature range well with the TG-DTA curves. For the as-synthesized powder
80e280
C, is due to decomposition of organic matter and part of calcined at 400
C, the peak located at 1640 cm1 indicates the
nitrates nitrate. The second exothermic reaction with a weight loss presence of hydrates and the band in the 1300e1500 cm1 region
of 6% in the temperature range 280e500
C, may be ascribed to the can be attributed to the vibration of NO 3 [20]. The broad bands
decomposition of organic and formed of rhombohedral perovskite located at 600e400 cm1 are generated by the vibration of Fe-O
structures. No further weight loss is detected above 500
C, indi- and Bi-O in the amorphous phases. When the heat treatment
cating that the organic has been completely burned off, and the temperature increasing up to 550
C, the strong bands at ~550 and
formation of metal oxide phase of perovskite BiFeO3. And there is 444 cm1 become very strong, while other bands are very weak
almost no weight loss at the calcination temperature of 500
C, and even disappear, indicating that the powder well crystallize to
which means the bismuth evaporation is negligible. BiFeO3 perovskite phase with the R3c structure. Furthermore, the
Fig. 2 exhibits the powder XRD patterns of the BiFeO3 samples broad band that appeared at ~550 cm1 is assigned to the Fe-O
calcined at different temperature. BiFeO3 perovskite phase begins stretching vibrations of the FeO6 octahedral, and the band at
to form when calcined at 400
C, and the diffraction peaks of ~444 cm1, associated with the Fe-O bending vibrations of the FeO6
amorphous are observed in the XRD patterns. There is no obvious octahedral [21]. This is consistent with the XRD results.
amorphous peaks when calcined at 450e550
C, and diffraction The microstructures of sintered samples with different heat
peak is strong and sharp with the calcining temperature increasing, treatment temperature are shown in Fig. 4 by TEM analysis. When
indicating that BiFeO3 powder are well crystalized. It can be seen the powders were annealed at 400
C for 2 h, the grains are not
that all diffraction peaks of the samples calcined at 450e550
C are uniform and shows aggregation phenomenon between particles.
 S. Zheng et al. / Journal of Alloys and Compounds 735 (2018) 945e949
Fig. 3. The FT-IR spectra of BiFeO3 nanoparticles calcined at 400
C, 450
C, 500
C,
550
C.
Some are amorphous phases. With the increase of temperature,
particle size of nanoparticles is increasing, and the aggregation
phenomenon was weak. The nanoparticles with fairly narrow size
distribution and polyhedron morphology were observed. When the
heat treatment temperature is 450
C, 500
C, 550
C, it can be seen
from the figure that the grain size is about 40 nm, 51 nm and 60 nm
respectively. As BiFeO3 nanoparticles prepared by microwave-
assisted sol-gel method avoid bismuth nitrate hydrolysis strongly
to form insoluble bismuthyl nitrate (Bi2O3$N2O5$2H2O) and the
impurity phase such as Bi2Fe4O9 and Bi12Fe0.63O18.945 formed at
calcining temperature and get easily high quality BiFeO3 nano-
particles [19].
The magnetic hysteresis loops of BiFeO3 nanoparticles at
calcining temperature 450
C, 500
C, 550
C for 2 h, are measured
by applying a field of 20 KOe at 300 K and 60 K (Fig. 5) under the
field-cooled (FC) and zero-field-cooled (ZFC) conditions. The MeH
behavior of the BiFeO3 nanoparticles at 300 K shows a well-
saturated hysteresis loop suggesting the ferromagnetic nature,
which is quite different from the linear MeH relationship in the
Fig. 4. TEM image of BiFeO3 nanoparticles calcined at (a) 400
C (b) 450
C (c) 500
C (d) 550
C.
947
bulk [22,23]. The variation of coercivity (Hc) and saturation (Ms) as
a function of annealing temperature is shown in the inset of
Fig. 5(a). It is clear that the Ms values rises as calcining temperature
decreases, and the Hc values annealed at 500
C are found
maximum and then decrease. Under FC, the magnitude of the
magnetic field from the center line to the origin is called the ex-
change bias field HEB. Mathematically, the exchange bias field (HEB)
and the coercive force (Hc) for shifted hysteresis loop can be
expressed as HEB ¼ (HC1 þ HC2)/2 and HC ¼ (HC1  HC2)/2. HC1 and
HC2 are points where the hysteresis loop intersect magnetic field
axis. The Hc of BiFeO3 nanoparticles generated at 450
C can be
calculated to be 59 Oe in zero-field-cooling. However, In the case of
a 20 KOe field in the cooling field, the intersection of the hysteresis
loop and the magnetic field axis is significantly shifted to the left. It
is found that the HC is 93 Oe and only slightly larger than that of
zero field cooling, which is a typical characteristic of the switching
bias, the exchange bias field HE is 302 Oe. At the same time, an
upward bias of the magnetization near the zero magnetic field in
the hysteresis loop of FC conditions indicate co-existence of
different magnetic phases of core and surface spins. It is shown in
the map of Fig. 5(b) that the partial hysteresis loops of FC are higher
than that of the ZFC magnetic field in the high field region, which
indicate that the partially disordered magnetic moment in the
BiFeO3 nanoparticles under the FC conditions is oriented by the
magnetic field, resulting in the fact that the magnetic moment in-
creases in the test of ZFC conditions. In Fig. 5(c) and (d) show the
FC/ZFC hysteresis loop of BiFeO3 nanoparticles generated at 500
C
and 550
C respectively, and their HE is 270 Oe and 128 Oe.
Fig. 6 shows FC and ZFC magnetization curves of annealed
BiFeO3 nanoparticles, measured at an external field of 100 Oe in the
temperature range of 60e300 K. It can be noticed that the FC and
ZFC curves are well bifurcated with in the measured temperature
range. The divergence between FC and ZFC increases progressively
with decrease in temperature, which reveals the spin-glass-like
behavior [24,25]. The initial gradual increase in magnetization
with decreasing temperature may be attributed to the local clus-
tering of spins [26]. In the whole range of measurement, the
magnetization increases with the decrease of temperature, which
indicates exist ferromagnetic properties and a strong thermal
948 S. Zheng et al. / Journal of Alloys and Compounds 735 (2018) 945e949

Fig. 5. The hysteresis loops of BiFeO3 nanoparticles at 300 K (a) and the hysteresis loops of BiFeO3 nanoparticles calcined at (b) 450
C (c) 500
C (d) 550
C under ZFC and FC at 60 K.

Fig. 6. Temperature dependence of ZFC and FC magnetizations of BiFeO3 under the field of 100 Oe calcined at (a) 450
C (b) 500
C (c) 550
C.

irreversibility. The spin-glass state generally occurs when positions
of magnetic moments or signs of neighboring coupling appear in a
random manner. Contrasting the MT curves at generated temper-
ature at 450
C, 500
C and 550
C, respectively, With the heat
treatment temperature increases, the gap distance decreases. As
the heat treatment temperature increases, the grain size increases
and thus the magnetism decreases.
To explain the origin of the enhanced magnetization of BiFeO3
nanoparticles, the effect of antiferromagnetism, typical for bulk
BiFeO3 [27e29], should be recalled. An antiferromagnet can be
described as comprising two spin sublattices with ferromagnetic
interactions within each sublattice and antiferromagnetic intersu-
blattice interactions. Such a collinear antiparallel spin arrangement
results in zero net magnetic moment due to the complete spin
compensation between these two sublattices. However, Neel pro-
posed a model for antiferromagnetic nanoparticles based on the
presence of two sublattices: one with spins up and another with
spins down at the surface [30]. The incomplete spin compensation
is possible, and it becomes measurable in small antiferromagnetic
systems, where the long-range antiferromagnetic order is
frequently interrupted at the particle surfaces. The breaking of spin
cycloid at a size less than 62 nm (the wavelength of cycloid spin
structure in bulk BiFeO3) should produce uncompensated spins on
the surface of the BiFeO3 particles. The correlated interaction be-
tween these uncompensated spins gives rise to ferromagnetic
behavior. Hence, as the particle size reduces, the surface-to-volume
ratio increases, and the role of the surfaces in the magnetic
behavior becomes more important, and hence the magnetization is
expected to increase due to the increasing ferromagnetic compo-
nent over the decreasing bulk antiferromagnetic (AFM) component.
This trend for particle size ranging from 60 nm to 40 nm were
observed, where a steady increase in magnetization is evidenced
with decreasing particle size. The effect of canted spins in the
surface shell of BiFeO3 nanoparticles manifests itself by the un-
compensated magnetic moments of Fe3þ ions, enhancing the
tangible contribution to the particle's overall magnetization. In this
 S. Zheng et al. / Journal of Alloys and Compounds 735 (2018) 945e949
context, it is consistently explained in terms of the so-called
modified core-shell model [31], in which a competition between
the effects of spin canting and site exchange of cations in the sur-
face shell of nanoparticles plays a decisive role. Owing to the in-
crease of the stress on the surface of magnetic nanoparticles at the
nano-scale, the magnetic moment is deflected, which makes the
whole surface magnetic moment is in a state of disorder. In this
case, the antiferromagnetic moments of the surface cannot be
compensated, and it is easy to form the spin glass phase of mag-
netic moment disorder. The antiferromagnetic phase nucleus and
the surface layer of the spin glass phase are coupled to each other,
which causes the sample to produce exchange anisotropy in the
case of FC conditions, resulting in a single crystal phase of BiFeO3
nanoparticles ferromagnetic phenomenon, exchange bias effect
and spin glass behavior.
4. Conclusions
The pure-phase BiFeO3 nanoparticles with uniform size and
polyhedron morphology were synthesized by microwave-assisted
sol-gel method. XRD, IR and TEM showed that the BiFeO3 nano-
particles had a single crystalline perovskite phase. The hysteresis
loops and M-T of ZFC and FC are compared and studied. The mag-
netic measurement results show that single phase BiFeO3 nano-
particles are composed of ferromagnetic uncompensated or canted
surface spin glass phase and antiferromagnetic core. This research
is helpful to further study the novel magnetic behavior of BiFeO3
nanoparticles and to promote the application of BiFeO3 nano-
particles in spin electron devices.
Acknowledgements
The research work is supported by the National Natural Science
Foundation of China. This was financially supported by the Natural
Science Foundation of Zhejiang Province (No.Y6110475 and
LY16E020005) and the National Natural Science Foundation of
China (Grant no. 51302056).
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