Materials Letters 59 (2005) 4006 – 4009

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Sol–gel synthesis and properties of multiferroic BiFeO3

Jong Kuk Kim a, Sang Su Kim b,*, Won-Jeong Kim b
a
Institute of Basic Science, Changwon National University, Changwon, Kyungnam 641-773, South Korea
b
Department of Physics, Changwon National University, Changwon, Kyungnam 641-773, South Korea

Received 16 May 2005; accepted 20 July 2005

Available online 3 August 2005

Abstract

High purity multiferroic BiFeO3 (BFO) powders were synthesized by sol – gel process using bismuth nitrate and iron nitrate as sources.
The BFO powders annealed at 600 -C in nitrogen environment were mainly composed of a rhombohedral BiFeO3 phase (R-phase) with a
minor impurity phase of Bi2O3. A pure BFO R-phase has been obtained by leaching out the minor Bi2O3 phase using diluted nitric acid. A
reversible phase transformation of the BFO R-phase has been detected at 836 -C by a differential thermal analysis. The powders of BFO R-
phase exhibits a uniform feature with the particle size of ¨200 nm. The dielectric constant of the BFO R-phase is measured to be ¨15 in the
frequency range of 104¨106 Hz at room temperature.
D 2005 Elsevier B.V. All rights reserved.

PACS: 77.84.Lf
Keywords: A1. Crystal structure; A2. Growth from solutions; B1. Oxides; B2. Ferroelectric materials

1. Introduction defect density and poor sample quality [7 – 9]. In order to

Multiferroics have been known as materials exhibiting
ferromagnetic and ferroelectric properties at the same time,
which have exhibited interesting physical properties as
well as possibility of practical applications for new
memory devices [1 – 4]. The rhombohedrally distorted
simple perovskite structure of BiFeO3 is one of the
representative multiferroic materials and have been much
interested due to the antiferromagnetic behavior with a
relatively high Néel temperature (T N¨380 -C) and the
ferroelectric behavior with a high Curie temperature
(T C¨810 -C) [5,6].
Although rhombohedral BiFeO3 (BFO R-phase) has
been studied extensively since first discovery in 1960s,
electrical properties of the pure BFO R-phase have been
rarely reported due to its high conductivity, which may
originated from uncertain oxygen stoichiometry, high
* Corresponding author. Tel.: +82 55 279 7412; fax: +82 55 267 0264.
E-mail address: sskim@sarim.changwon.ac.kr (S.S. Kim).
0167-577X/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2005.07.050
understand the properties of multiferroic BFO, it is very
important that the fabrication procedure of pure BFO R-
phase should be established. If temperature and oxygen
partial pressure were not controlled accurately during
crystallization of the BFO R-phase, the kinetics of phase
formation always lead to other impurity phases in Bi – Fe–
O system, such as Bi2Fe4O9, Bi2O2.75, and Bi46Fe2O72
[8,10,11].
Recently, pure BFO ceramics, including ferroelectric
hysteresis loops at room temperature, have been inde-
pendently synthesized by the solid state reaction method
followed with leaching out the impurity phases using
diluted nitric acid and by a rapid liquid phase sintering
technique [11,12]. In spite of these preparation techni-
ques for pure BFO, studies on the phase evolution,
microstructure, and electrical properties of the BFO
prepared by a sol – gel method, which has great
advantages on thin film fabrications are still rare in the
literature.
In this paper, we described in detail the synthesis
procedures to obtain high purity as well as homogeneous
nanoscale BFO R-phase powders by a sol –gel method. The
 J.K. Kim et al. / Materials Letters 59 (2005) 4006 – 4009 4007

ceramic were measured using a LF impedance analyzer

B(102)
B : BiFeO3 N2 atmosphere
* : Bi36Fe24O57 (HP4192A).

B(104)
B(110)
v : Bi2Fe4O9

B(204)

B(116)
B(122)
Intensities (arb. units)

B(202)
+ : Bi2O3

+
* both powders were a rhombohedrally distorted perovskite BiFeO3
* v v vv *
v v *
10 20
Fig. 1. XRD patterns of the BFO powders annealed at 600 -C under
different atmospheres.
final BFO R-phase powders were characterized by X-ray,
thermogravimetric and dielectric measurements.
2. Experimental details
Sol – gel method was used to prepare BiFeO3 powders. A
transparent multi-component solution was prepared by
mixing bismuth nitrate pentahydrate [Bi(NO3)3 I 5H2O]
(Aldrich), and iron nitrate nonahydrate [Fe(NO 3 ) 3 I
9H2O](Aldrich). Bismuth nitrate pentahydrate (5 mol%
excess) was dissolved at room temperature in the 2-
methoxyethanol and acetic acid mixture. After the solution
was transparent, it was mixed with iron nitrate nonahydrate
by constant stirring at room temperature. The resultant
solution was transparent, blackish red, and clear. The
precursor solution was dried at 80 -C for about 12 h to
B(214)
B(108)
B(006)
3. Results and discussion
Fig. 1 shows the X-ray diffraction (XRD) patterns of the sol –
gel synthesized BFO powders crystallized at 600 -C for 1 h in air
Air atmosphere and N2 atmospheres, respectively. It was found that the majority of
* (R-phase), as shown in Fig. 1. Besides the formation of BFO R-
phase, the formation of the impurity phases, such as Bi2Fe4O9,
* * v * * Bi36Fe24O57, and Bi2O3, were confirmed from the XRD analysis.
vv *
In the case of crystallization in air, the BFO powder contained
small amount of non-perovskite phases, such as Bi2Fe4O9 and
30 40 50 60 Bi36Fe24O57. On the other hand, the BFO powder crystallized in N2
θ (deg.)
2θ atmosphere was composed of R-phase with a small amount Bi2O3
phase.
In order to eliminate the unwanted impurity phases, both
BFO powders have been leached with diluted nitric acids
(0.005 ¨ 0.1 M) for 30 min, which is known to be an effective
method to eliminate the impurity phases from BFO powders
prepared by a solid state reaction method [11]. Fig. 2 shows the
XRD patterns of BFO powders annealed in air followed by
leaching in nitric acids with different concentrations. Reflection
peaks related with Bi36Fe24O57 phase were nearly disappeared
after leaching in nitric acid solution. However, peaks related with
Bi2Fe4O9 phase were still observed in the XRD patterns. This
result suggests that the impurity phases cannot be removed
completely by leaching in nitric acid from the sol – gel derived
BFO powders annealed in air.
For the BFO powder annealed in N2 atmosphere, a pure BFO
R-phase was obtained by leaching out the minor Bi2O3 phase using
0.05 M nitric acid (Fig. 3). All of the reflection peaks shown in Fig.
3 can be indexed as BFO R-phase (a = 5.5781 Å, and c = 13.8593
Å), which agree well with those of the phase pure BiFeO3 ceramic
prepared by the solid state reaction method [11]. Furthermore,
B(102)

B(104)
B(110)

B : BiFeO3
obtain the BFO xerogel powder. Then the xerogel powder
B(116)
B(202)

* : Bi 36Fe24O57 B(214)
B(204)

B(108)
B(122)

was grinded in an agate crucible, and the powder was

B(006)

v : Bi 2Fe4O9
annealed at 600 -C for 30 min in air or N2 atmosphere in the vv v v
Intensities (arb. units)

(d) v v
furnace. During the annealing procedure, heating and
cooling rates of the furnace were maintained at a rate of 4
-C/min. In order to investigate the electrical properties of
BFO powder, gold electrodes were deposited on the 2 mm (c)
thick BFO pellets which have been prepared by pressing the
powders with 20 MPa.
Crystal structures and morphologies of BFO powders (b)
at every fabrication step were investigated by X-ray
diffractometer (Philips MPD system) and scanning elec- *
tron microscope (SEM, Hitachi S-2400). Energy disper- *
(a) v * v v vv * v * * * v v * **
sive X-ray spectrometer (EDS, Hitachi S-2400) was used
to investigate the chemical composition of the samples. A 10 20 30 40 50 60
thermogravimetic/differential thermal analysis (TG/DTA, θ (deg.)
2θ
TA Instruments, SDT 2960) has been used to understand Fig. 2. XRD patterns of the BFO powders annealed at 600 -C in the air
the thermodynamics of BFO powders. Electrical proper- (a), and followed by leaching with nitric acid of (b) 0.005, (c) 0.05 and
ties, including dielectric constant, of the pure BFO (d) 0.1 M.
4008 J.K. Kim et al. / Materials Letters 59 (2005) 4006 – 4009

BiFeO3

(104)
Observed

(110)
(102)
(after leaching)
Intensities (arb. units)

(116)
(006)

(204)

(214)
(122)
(108)
(113)
Simulated

Fig. 5. SEM microstructure of the pure BFO R-phase powder ceramics.

10 20 30
2θ (deg.)
Fig. 3. XRD patterns of the BFO powders annealed at 600 -C in N2
atmosphere and then leached out impurities with 0.05 M nitric acid
solution.
intensity profile of the reflection peaks are close to those reported
in JCPDS (# 86-1518), which suggests that the majority of the
sample is close to a pure R-phase within instrumental sensitivity.
Based on these results, the crystallization atmosphere to obtain a
pure BFO R-phase sintered by the sol – gel method is more
important than the leaching procedures.
The pure BFO R-phase has been investigated by DTA while
heating and cooling in the temperature range of 500¨900 -C with
heating/cooling rate of 10 -C/min in N2 atmosphere (Fig. 4). The
endothermic and exothermic peaks were observed at 836 -C during
heating and 821 -C during cooling, respectively. The observed
thermal properties of the pure BFO R-phase prepared by the sol –
gel method is similar to those of BFO ceramics prepared by the
solid state reaction method [11]. This result suggests that the
0.0
Temperature difference (oC/mg)
leached BFO powder is close to the pure R-phase having only one
40 50 60
reversible phase transformation.
Fig. 5 exhibits a SEM microstructural image of the pure BFO
R-phase powder ceramics, which was crystallized at 600 -C in N2
atmosphere followed by leaching in nitric acid. It is clear that the
BFO R-phase particles exhibits a uniform feature with approx-
imately 200 nm in size, which is smaller than 1¨3 Am of BiFeO3
powder prepared by the usual solid state reaction method [11]. It
demonstrates that sol – gel process is a good method for preparing
nanoscale BFO particles with uniform features. From the EDS
measurement, it is confirmed that the atomic ratio of Bi/Fe from the
BFO R-phase powder is close to 1.
In order to investigate the electrical properties of BFO powder,
gold electrodes were deposited on the 2 mm thick BFO pellet,
which has been prepared by pressing the powders with 20 MPa as
shown in Fig. 5. Fig. 6 shows frequency dependent dielectric
constant and dielectric loss of the BFO R-phase measured from the
gold-BFO pellet-gold capacitor using an impedance analyzer at
room temperature. Both dielectric constant and dielectric loss
decrease with increased frequencies. The dielectric constant of the
BFO R-phase was measured to be ¨15 in the frequency range of
104¨106 Hz at room temperature, which is smaller than those
reported for BFO ceramic prepared by the solid state reaction
method [11].
BiFeO3

-0.2 20 0.10
Dielectric constant

0.05
Dielectric loss

-0.4 15
endo
836oC
0.00
821oC
-0.6 10
-0.05
exo

-0.8 5 -0.10
500 600 700 800 900 1000 104 105 106 107
Temperature (oC) Frequency (Hz)
Fig. 4. Differential thermal analysis traces of the pure BFO R-phase powder Fig. 6. Dielectric constant and dielectric loss of the pure BFO R-phase
in N2 atmosphere followed by leaching procedure. powder ceramics as a function of frequency.
 J.K. Kim et al. / Materials Letters 59 (2005) 4006 – 4009 4009

4. Conclusions References

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