ARTICLE IN PRESS

Journal of Crystal Growth 310 (2008) 2934–2937

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Study on the Ce substitution effects of BiFeO3 films

on ITO/glass substrates
Hongri Liua,c,, Bowu Yanb, Xiuzhang Wangc
a
Hubei Key Laboratory of Bioanalytical Technology, Hubei Normal University, Huangshi 435002, China
b
Department of Computer Science, Huangshi Institute of Technology, Huangshi 435003, China
c
Department of Physics, Hubei Normal University, Huangshi 435002, China
Received 14 December 2007; received in revised form 31 January 2008; accepted 4 February 2008
Communicated by D.P. Norton
Available online 12 February 2008

Abstract

Ce substituted Bi1xCexFeO3 (BCFO) films with x ¼ 0–0.15 were deposited on indium tin oxide (ITO)/glass substrates by sol–gel
process annealed at 500 1C. Rhombohedral phase was confirmed by XRD study and no impure phases were observed till x ¼ 0.15.
Substantially enhanced ferroelectricity was observed at room temperature due to the substitution of Ce. In the films with x ¼ 0.05 and
0.10, the double remnant polarization are 75.5 and 57.7 mC/cm2 at an applied field 860 kV/cm. Moreover, the breakdown field was
enhanced in the films with Ce substitution.
r 2008 Elsevier B.V. All rights reserved.

PACS: 77.55.+f; 77.80.e

Keywords: A1. Ce substitution; B1. BiFeO3; B2. Ferroelectricity; B2. Leakage current

Perovskite-typed multiferroic materials such as BiFeO3
(BFO), BiMnO3, and TbMnO3 that simultaneously show
electric and magnetic orderings are currently gaining more
attention due to the fact that they are promising for the
design of multifunctional devices and also because of the
interesting physics found in this class of materials [1–3]. In
the above multiferroic materials, BFO exhibits antiferro-
magnetic ordering (TN=380 1C) and ferroelectric behavior
with high ferroelectric Curie temperature (TC=830 1C) and
it has been studied extensively since 1950s [4]. In recent
years, more attentions were focused on the preparation of
BFO films since they allow direct integration of the
material into the semiconductor technology. Magnetic
controlling sputtering method was first used to prepared
BFO film [5]. Heteroepitaxially constrained BFO thin films
of large polarization have been prepared with pulsed laser
Corresponding author at: Hubei Key Laboratory of Bioanalytical
Technology, Hubei Normal University, Huangshi 435002, China.
Tel./fax: +86 0714 6571339.
E-mail address: lhr1229@126.com (H. Liu).
deposition method on RuSrO3 coated SrTiO3 substrate
recently by Wang et al. [3]. BFO films deposited on Pt or
some conductive oxide bottom electrodes by chemical
solution deposition method usually showed a low polariza-
tion with a large DC leakage current at room temperature
[6,7]. In thin films of ferroelectrics, the leakage current is
mainly dominated by electrode effects, such as Schottky
barrier formation if one uses materials with a high work
function such as Pt. While the high DC leakage current in a
BFO thin film arises due to intrinsic low resistivity of the
film, which is attributed to the presence of Fe2+ and O
vacancies [8]. Alliovalent ion substitution on the B site such
as Ti4+ and Ni2+ showed a significant change in the
leakage current on Pt/silicon substrates [9]. Work on A site
substitution with same valence ions in such as La3+ has
also been carried out. Unsaturated electric hysteresis loops
were observed in the La substituted BiFeO3 films on
Pt/TiO2/SiO2/Si substrates prepared by pulsed laser de-
position method [10]. In our previous work, we have
prepared La substituted BiFeO3 films on LaNiO3 bottom
electrodes, and observed Pr values of several mC/cm2 [11].

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doi:10.1016/j.jcrysgro.2008.02.003
 ARTICLE IN PRESS
H. Liu et al. / Journal of Crystal Growth 310 (2008) 2934–2937
As a rare earth element, Nd was also used to substitute Bi
on A site and obtained enhanced ferroelectricity in BFO
based ferroelectric films [12]. While to our best knowledge,
there is no report on A site Ce substitution in BFO film.
Moreover, indium tin oxide (ITO) is a type of excellent
conductive oxide and was extensively used in optical
devices. While there are seldom reports on the usage as
bottom electrode to prepare ferroelectric material. In our
work, nitrate salt of Bi, Fe, and Ce were adopted as
starting materials and Ce substituted BFO films were
deposited on ITO/glass substrates by sol–gel process and
structure and electric properties were studied.
The Bi1xCexFeO3 (BCFO) films were prepared on
ITO/glass substrates by sol–gel process. The BCFO
precursor solutions were prepared using bismuth nitrate
[Bi(NO3)3  5H2O] , iron nitrate [Fe(NO3)3  9H2O], and
cerium nitrate [Ce(NO3)3  6H2O] as starting materials.
First, iron nitrate and bismuth nitrate (5% mol bismuth
excess to compensate the Bi loss) were mixed and dissolved
in 2-methoxyethanol by stirring for 30 min at room
temperature. Then cerium nitrate was also dissolved in
2-methoxyethanol under constant stirring. The above two
solutions were mixed and acetic anhydride was added to
dehydrate under constant stirring. The concentrations of
the solutions were adjusted to 0.3 M by adding acetic
anhydride. The depositions were carried out by spin
coating at 4000 rpm for 15 s. The as-deposited wet films
were pre-annealed at 350 1C for 3 min and then annealed at
500 1C for 5 min in O2. The spin coating and annealing
procedures were repeated several times to obtain the
desired thickness.
The X-ray diffractometer (XRD) patterns were recorded
with XRD (FEI-Philips) with Cu Ka radiation. The
morphology of the films was observed with scanning
electron microscopy (SEM) (JEOL-Japan). For electrical
measurements, Au dots of 0.1 mm2 were deposited through
a mask on the films by evaporation. Before measurement,
the films were annealed at 300 1C for 10 min to get full
contact with the electrodes. The area of a top electrode was
confirmed with an optical microscopy by measuring the
diameter. Ferroelectric hysteresis loops and leakage cur-
rents were obtained using a Precision Work Station
(Radiant Technology) ferroelectric tester.
The Ce substitution effects on the orientation of BFO
films were identified by XRD analyses. Fig. 1 shows the
XRD patterns of BCFO films annealed at 500 1C. The
results show that all films are well crystallized since intense
peaks of BFO are identified according to the XRD
patterns. A rhombohedral perovskite structure was identi-
fied for the films with x ¼ 0 since the XRD patterns match
the standard pattern quite well. All films are randomly
oriented and the intensity variation of (1 1 0)/(1 1 0) double
peaks is obvious. According to the XRD patterns, the
(0 1 0) peaks shift towards the small angle slightly and it
means that the lattice was distorted by the substitution.
The lattice constants, identified by (0 1 0) peaks, were 3.943,
3.946, 3.948, and 3.951 Å. In the film with x ¼ 0.00 and
2935
Fig. 1. XRD patterns of BCFO films on ITO/glass substrates.
0.10, the intensity of (1 1 0)/(1 1 0) double peaks are larger
than the two films with x ¼ 0.05 and 0.20 and it is related
to the variation of lattice constant induced by the
substitution of Ce. No pyrochlore phase or other impure
phase can be identified in all films.
Fig. 2 shows the SEM photos of BCFO films with
x ¼ 0.00–0.15. All films are well grown polycrystalline
films with average grain size of several tens of nm. The film
with x ¼ 0.00 has the most smooth surface and pinholes
can be observed. The film with x ¼ 0.05 having coarser
surface and pinholes was removed by the doping of Ce. In
the films with x ¼ 0.10 and 0.15, compact surface can be
observed and the grain boundaries are blurred. Relatively
poor crystallization can be observed in the film with
x ¼ 0.15 and it accords with the XRD results.
Fig. 3 shows the electric hysteresis loops of the BCFO
films with different x measured at different applied fields at
room temperature. The film with x ¼ 0.00 shows a double
polarization (2Pr) value of 1.96 mC/cm2 at an applied field
of 390 kV/cm, while for the film with x ¼ 0.05, the 2Pr
value increases to 75.5 mC/cm2 under an applied field of
860.3 kV/cm. It also can be seen that the 2Pr values are 57.7
and 17.1 mC/cm2 for the BCFO films with x ¼ 0.10 and
0.15 under the same applied field as the film with x ¼ 0.05.
Obviously, the ferroelectricity was substantially enhanced
by the substitution. There has also been work on A site
substitution by La and Nd, through the substitution,
enhanced ferroelectric has also been observed. Das et al.
[10] reported La A site substitution effects and obtained
unsaturated hysteresis loops. While Uchida et al. [13]
prepared La and Nd substituted BFO films on Pt bottom
electrodes and obtained saturated electric hysteresis loops.
The ferroelectricity of BiFeO3 is originated from the
relative displacement of Fe3+ to the oxygen octahedron
along (1 1 1)c [3]. In our work, the enhancement of
ferroelectricity is originated from the distortion of cell
lattice induced by the substitution of Ce. In addition,
 ARTICLE IN PRESS
2936 H. Liu et al. / Journal of Crystal Growth 310 (2008) 2934–2937

Fig. 2. Surface SEM photos of Bi1-xCexFeO3 films with (a) x ¼ 0, (b) x ¼ 0.05, (c) x ¼ 0.10, and (d) x ¼ 0.15.

Fig. 4. Current density–applied electric fields characteristics of BCFO.

Fig. 3. Polarization field hysteresis loops of BCFO films.

higher applied field is another factor for the larger Pr in the
Ce doped BiFeO3 films since under higher applied field, the
films are able to get fully polarization.
Fig. 4 shows current density vs. applied electric field
(JE) characteristics of the BCFO films with x ¼ 0–0.15.
From which we find that the BFO has the least leakage
current density at the positive bias electric field below
200 kV/cm. Near 200 kV/cm, the current density of the
BFO film (x ¼ 0) increases drastically and gets breakdown.
For the film with x ¼ 0.05, the breakdown electric field is
enhanced to about 400 kV/cm. After getting breakdown,
the films with x ¼ 0 and 0.05 show large current density
under negative bias electric fields. For the films with
x ¼ 0.10 and 0.15, small leakage current densities
below 105 A/cm2 are observed under an applied field of
535 kV/cm. The results are smaller than the La substituted
BFO film [14]. In the whole applied electric field range, no
breakdown was observed. Therefore, by the Ce substitu-
tion, the breakdown electric field was enhanced rather than
the leakage current density was reduced. We suggest that
the improvement of interface between the BCFO film and
ITO bottom electrode is responsible for the higher break-
down fields, which make the BCFO films able to bear
higher applied fields and get polarization fully.
In conclusion, Ce substituted BFO films were prepared
on ITO/glass substrates by sol–gel process at an annealing
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H. Liu et al. / Journal of Crystal Growth 310 (2008) 2934–2937 2937

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