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Journal of Crystal Growth 291 (2006) 135139

www.elsevier.com/locate/jcrysgro

Hydrothermal synthesis of perovskite bismuth ferrite crystallites

Chao Chen, Jinrong Cheng, Shengwen Yu, Lingjuan Che, Zhongyan Meng
School of Materials Science and Engineering, Shanghai University, Shanghai 200072, PR China
Received 12 November 2005; received in revised form 25 February 2006; accepted 27 February 2006
Communicated by D.P. Norton

Abstract
A low-temperature hydrothermal synthesis route was utilized to fabricate single-phase BiFeO3 (BFO) crystallites. Effects of the initial
KOH concentration, reaction temperature and duration time on the phase evolution, the particle size and morphologies of BFO
crystallites were systematically investigated. X-ray diffraction results indicated that perovskite BFO crystallites have been synthesized at
the temperature of 200 1C using the KOH concentration of 4 M. Scanning electron microscopy observation revealed a homogeneous size
distribution of submicron BFO powders. The ferroelectric Curie temperature of our hydrothermal BFO crystallites was determined to be
825 1C by differential thermal analysis. The hydrothermal reactions to form crystalline BFO powders were discussed based on the
dissolutioncrystallization process.
r 2006 Elsevier B.V. All rights reserved.
PACS: 81.10.Dn
Keywords: A2. Hydrothermal crystal growth; B1. Bismuth ferrite crystallite; B1. Pure perovskite; B2. Multiferroics

1. Introduction
Bismuth ferrite, one of the very few multiferroics with a
simultaneous coexistence of ferroelectric and antiferromagnetic order parameters in perovskite structure, has
attracted much attention for many decades since 1960.
BiFeO3 (BFO) has a ferroelectric Curie temperature Tc of
850 1C and an antiferromagnetic Neel temperature of
370 1C [1,2]. However, potential applications of BFO in
the memory devices, sensors, satellite communications,
optical lters and smart devices were greatly limited due to
its low insulation resistance caused by the reduction of
Fe3+ species to Fe2+ and oxygen vacancies for charge
compensation [3,4]. Although great achievements have
been made for BFO thin lms prepared by the pulsed-laser
deposition (PLD) method [5,6], it was hard to avoid
generating impurity phases by the conventional solid-state
reaction in bulk materials. BFO perovskites could only
stabilize within a narrow ranged temperature. Up to date,
Corresponding author. 149 Yanchang Road, Box 32, Shanghai
200072, PR China.
E-mail address: jrcheng@staff.shu.edu.cn (J. Cheng).

0022-0248/$ - see front matter r 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2006.02.048

the synthesis of single-phase BFO crystallites or ceramics is

still a challenging issue. In the solid-state route, nitric acid
leaching was required to eliminate the impurity phases,
such as Bi2Fe4O9 and Bi25FeO40, after the calcination of
mixed bismuth and iron oxides [7], which resulted in
coarser powders and the poor reproducibility. Most
recently, Wang [3] and Pradhan et al. [8] prepared phasepure BFO ceramics by a rapid liquid-phase sintering
technique. The crystallization temperature of BFO in these
methods was required above the ferroelectric Curie
temperature Tc, which implied that the volatilization of
bismuth was hard to avoid. Moreover, Ghosh et al. [9]
made pure phase bismuth ferrite nanopowders by the
tartaric acid based solgel method coupled with the
additional calcination process. However, few works have
been done to prepare BFO crystallites by using the
hydrothermal method and the formation mechanism has
not been clearly understood yet. The advantage of soft
chemical routes was that microcrystallines could be
synthesized at a much lower temperature, and also energy
saving and cost effective.
In this paper, single-phase BFO crystallites were
prepared at around 200 1C by using the hydrothermal

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C. Chen et al. / Journal of Crystal Growth 291 (2006) 135139

method. This technique possessed the potential to produce

well-crystallized BFO powders with controlled morphology
and narrow distribution of particle size. The phase
structure evolution of BFO under different hydrothermal
conditions were investigated and discussed.

BFO was synthesized from an equimolar mixture of

Bi(NO3)3
5H2O and Fe(NO3)3
9H2O in 40 ml using KOH
as mineralizer. All source chemicals are of analytical grade.
The mixture was ultrasonically dispersed for 15 min and
then transferred into a teon-lined autoclave. The hydrothermal treatment was performed for the different reaction
temperatures, duration time and KOH concentrations.
After the hydrothermal reaction, the autoclave was cooled
naturally to room temperature. The products were ltered
and washed with 10% acetic acid and de-ionized water in
sequence to remove all soluble salts, and then dried in an
oven at 90 1C in air.
The phase structure of as-prepared BFO powders were
characterized by X-ray diffraction (XRD, Rigaku D/
MAX-3C) with graphite monochromatozed CuKa radiation (l 0:154 nm). The grain morphology and particle
size were examined with eld emission scanning electron
microscope (FESEM, JSM-6700F) operated at 10 kV.
Fourier transform infrared (FTIR) spectra of BFO
powders were taken with an AVATAR 370 infrared
spectrophotometer. Differential thermal analysis (DTA,
STD Q600) of BFO powders was carried out from room
temperature to 900 1C in nitrogen ambient at a scan rate of
10 1C/min.
3. Results and discussion
Fig. 1 shows XRD patterns of BFO powders synthesized
at 220 1C for 6 h using different initial KOH concentrations
of 4, 6 and 10 M. Diffraction peaks that come from BFO
powders synthesized with KOH concentration of 4 M can
be indexed only as BFO according to the powder data of
JCPDS card no.73-0548. This revealed that BFO crystallites had the pure perovskite structure belonging to the
polar R3m space group [10,11]. However, the presence of
impurity phases, such as Bi2Fe4O9, Bi25FeO40 was detected
in addition to the major BFO phase for specimens
synthesized with the KOH concentration of 6 and 10 M.
It concluded that appropriate amount of KOH was benet
to refraining the formation of impurity phases and therefore growing BFO powders into single-phase perovskites.
SEM images of specimens synthesized at 220 1C with initial
KOH concentrations of 4, 6 and 10 M are shown in
Fig. 2(a)(c), respectively. At the same time, Fig. 2(d) gives
the image of the specimen synthesized at 200 1C with KOH
of 4 M. According to Fig. 2(a) and (d), the grains of BFO
powders synthesized with KOH of 4 M are homogeneous
in the submicron range and which are relatively smaller
when grew at 200 1C. However, BFO powders synthesized

Bi25FeO40
(010)
(020)
Intensity (a.u.)

2. Experimental procedures

Bi2Fe4O9

(110)

(111)

4M

(121)
(120)(120)
(121)

(111)

6M

10 M

10

20

30

40

50

60

2 (deg.)
Fig. 1. XRD patterns of BFO powders synthesized at 220 1C for 6 h using
different KOH concentrations of 4, 6 and 10 M.

with the KOH concentrations of 6 and 10 M reveal a lot of

large particles with the irregular shape, as shown in
Fig. 2(b) and (c). The variation of grain morphologies
may be another evidence of the formation of impurity
phases.
The submicron and isotropy BFO crystallites obtained in
our work are quite different from the previous work, where
BFO powders agglomerated into the cubic with the side
size of 45 mm under the hydrothermal conditions [12]. The
growth of large cubic grains was usually preferred for the
hydrothermal lead zirconate titanate (PZT) particles [13].
In the hydrothermal process, the presence of alkaline
medium was found to be essential. In our cases, there
existed a critical KOH concentration above which
the formation of impurity phases was favored, and the
formation of pure BFO was tightly dependent on the KOH
concentration. The dissolution and crystallization process can be utilized to describe the hydrothermal reaction
[14]. During the hydrothermal treatment, Bi3+ and Fe3+
hydroxides underwent an attack of KOH to dissolve and
react at high temperatures and pressures, and then
precipitated as insoluble ceramic oxide particles from the
supersaturated hydrothermal uid. Crystal growth only
occurred in the region of supersaturated uid. If the
temperature and pressure conditions were carefully maintained during the duration of the experiment, neither
etching of BFO crystals nor the formation of a second
phase would be observed. Therefore, the dissolution and
crystallization process continued in supersaturated uid in
such a way that the system was self-stabilizing. We
conjectured that the dissociation of bismuth and iron
hydroxide and the formation of ionic complexes might
prevent the growth of BFO crystallites and limit the size of
BFO particles to the submicron range.
Earlier work [15] indicated that the solid-state synthesis
of BFO from Bi2O3Fe2O3 system always yielded other
compounds as impurities. Above a certain temperature,

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137

Fig. 2. SEM images of specimens synthesized with KOH concentrations of (a) 4 M, (b) 6 M, (c) 10 M at 220 1C, and (d) 4 M at 200 1C for 6 h.

Bi2Fe4O9

(110)

Bi25FeO40

(010)

Intensity (a.u.)

BFO decomposed into Bi2Fe4O9 rather than initial oxides.

In the alkaline hydrothermal conditions, the higher KOH
concentration promoted the formation of BiOBi bridges
between the non-bridging structural hydroxyl groups in the
solution [16]. The dissolved Bi3+ hydroxides formed ion
group and then Bi2O3 crystallites. At the same time, the
absorbed Fe3+ ions on Bi2O3 particles diffused into
insolvable Bi2O3 to produce precipitations of Bi2Fe4O9
and Bi25FeO40. Thus, the second phases and irregular
grains were detected in XRD patterns and SEM images
respectively for specimens synthesized with the KOH
concentration up to 6 and 10 M.
Fig. 3 represents XRD patterns of specimens synthesized
at 160, 180, 200 and 220 1C for 6 h with KOH of 4 M. It can
be seen that pure BFO crystallites were obtained with the
temperature of 4200 1C. While, for specimens prepared at
160 and 180 1C, impurity phases of Bi2Fe4O9 and
Bi25FeO40 appeared. It concluded that the formation of
second phase was favored at lower temperatures, whereas
higher reaction temperature was required to form pure
BFO crystallites. Based on the steam tables, one can
calculate the approximate pressure from the temperature
used in the system. A pressure of 4200 psi was generated
when pure water was heated to 200 1C [12]. Fig. 4 shows
XRD patterns of BFO powders synthesized for 2.5, 6 and

(121)
(120)
(120) (121)

(020)
(111)
(111)

220 oC
200 oC
180 oC
160 oC

10

20

30

40

50

60

2 (deg.)
Fig. 3. XRD patterns of BFO powders synthesized at 160, 180, 200 and
220 1C for 6 h, using the KOH concentration of 4 M.

21 h at the optimized temperature and KOH concentration

of 200 1C and 4 M respectively. No detectable impurity
phase was developed with time. It can be seen that
diffraction peaks were broadened with the relative lower
intensity for BFO synthesized within 2.5 h, which became

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C. Chen et al. / Journal of Crystal Growth 291 (2006) 135139

138

10
(110)
0
(020)
(120)

Intensity (a.u.)

(111)
21 hours

Heat Flow (mW)

(010)
(121)
(120)

(111)

(121)

-10
Endothermic
-20
-30

6 hours
-40
-50
600

2.5 hours

825.5 oC
700

800

900

Temperature (oC)
10

20

30

40

50

60

Fig. 6. DTA curves of the hydrothermal BFO powders.

2 (deg.)
Fig. 4. XRD patterns of BFO powders synthesized at 200 1C for 2.5, 6 and
21 h, using the KOH concentration of 4 M.

Transmittance (%)

21 hours

6 hours

2. 5 hours

weak after 6 h indicating the removal of water and nitrates.

Specically, the strong absorptive peaks at 400600 cm1
was attribute to the FeO stretching and bending vibration,
being characteristics of the octahedral FeO6 groups in the
perovskite compounds. The formation of perovskite
structure can be conrmed by the presence of metaloxygen band [2022]. The DTA curve shown in Fig. 6 reveals
an endothermic peak at around 825 1C, which resulted
from the ferroelectric to paraelectric phase transformation
in BFO. This is one of evidences of the ferroelectricity of
our hydrothermal BFO crystallites. The Curie temperature
of 825 1C was in agreement with references, however,
slightly dependent on the processing conditions [23,24].
The further electrical properties are under investigations
and will be reported in another paper.
4. Conclusions

4000

3500

3000

2500

2000

1500

1000

500

-1)

Wavenumber (cm

Fig. 5. Room temperature FTIR spectra of BFO powders derived from

the hydrothermal reaction for 2.5, 6 and 21 h.

sharper and stronger with extending the reaction time to 6

and 21 h. It implied that the crystallites have minor amount
of amorphous and partially crystalline structure at 2.5 h
and become fully crystalline after 6 h. The reaction further
decayed at 21 h because of the rapid consumption of
hydroxides in the supersaturated uids.
The FTIR spectra of crystalline BFO powders derived
from the hydrothermal reaction for 2.5, 6 and 21 h are
shown in Fig. 5. The broad band at 30003600 cm1 arose
from the antisymmetric and symmetric stretching of bond
H2O and OH1 groups, while a band at 1630 cm1
corresponded to the bending vibrations of H2O [17,18].
The band at around 1384 cm1 was due to the presence of
trapped nitrates [19]. The intensity of these peaks became

Single-phase BFO perovskite crystallites have been

prepared from bismuth and iron nitrates by using the
hydrothermal method. Compared with the conventional
solid-state reaction process, submicron BFO crystallites
with better homogeneity could be produced at the
temperature as low as 200 1C. The KOH concentration of
4 M was benet to refraining the formation of any impurity
phases and growing BFO crystallites into single-phase
perovskites. The hydrothermal reaction to grow BFO
crystallites was described by the dissolutioncrystallization
process.
Acknowledgments
We are pleased to acknowledge support from National
Nature Science Foundation of China under Grant nos.
50472098 and 50302006, Shanghai Rising Star Program
under Grant no. 04qmx1440, and the key subject construction project (Material Science) of Shanghai Educational
Committee.

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C. Chen et al. / Journal of Crystal Growth 291 (2006) 135139

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