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The Effect of Process on Ferroelectric

and Magnetic Properties in
Bi5Fe0.5Co0.5Ti3O15 Thin Films
Hui Sun

a b

, Tingting Xu , Jie Su & Changcheng Ju

National Laboratory of Solid State Microstructures and Department

of Physics, Nanjing University, Nanjing, 210093, China
b

College of Physics Science and Technology, Yangzhou University,

Yangzhou, 225002, China
Published online: 18 Dec 2012.

To cite this article: Hui Sun , Tingting Xu , Jie Su & Changcheng Ju (2012): The Effect of Process on
Ferroelectric and Magnetic Properties in Bi5Fe0.5Co0.5Ti3O15 Thin Films, Integrated Ferroelectrics: An
International Journal, 140:1, 64-70
To link to this article: http://dx.doi.org/10.1080/10584587.2012.741449

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Integrated Ferroelectrics, 140:6470, 2012

Copyright Taylor & Francis Group, LLC
ISSN: 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584587.2012.741449

The Effect of Process on Ferroelectric and Magnetic

Properties in Bi5 Fe0.5 Co0.5 Ti3 O15 Thin Films
HUI SUN,1,2, TINGTING XU,1 JIE SU,1
AND CHANGCHENG JU1

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National Laboratory of Solid State Microstructures and Department of Physics,

Nanjing University, Nanjing 210093, China
2
College of Physics Science and Technology, Yangzhou University, Yangzhou
225002, China
The Bi5 Fe0.5 Co0.5 Ti3 O15 (BFCT) polycrystalline thin films with Aurivillius phase were
prepared by the chemical solution deposition in the conventional tube furnace. The
structure and surface topography were analyzed using X-ray diffraction and field emission scanning electron microscope (FESEM). The typical ferroelectric hysteresis loops
were observed with remnant polarization 37.7 C/cm2 (2Pr ) and coercive field (Ec )
123.4 kV/cm, respectively. The magnetic M-H curve shows a well-saturated weak
ferromagnetic behaviour at room temperature and the saturated magnetization (Ms )
was 2.3 emu/cm3. Meanwhile, we also utilized the rapid thermal annealing (RTP) to
prepare the BFCT film, and the effect of different fabrication processes on ferroelectric
and magnetic properties in the BFCT film was discussed.
Keywords Layered structure; thin films; ferroelectric properties, magnetic properties

Introduction
Multiferroic materials, which have simultaneous ferroelectricity (FE), ferromagnetism
(FM), and/or ferroelasticity, exhibit the co-existence and coupling of different ferroic orders.
The coupling between the magnetic and electric behaviours, i.e the magnetoelectric (ME)
effect, is very important in multiferroic materials. These materials can offer wide scope for
potential applications in the techniques of the sensor, the spintronics, and the multi-states
memory, etc [14]. Among the rare discovered multiferroic candidates, BiFeO3 (BFO) is
one of the most studied. Unfortunately, the BFO suffers the low resistivity at room temperature (RT) which is related to oxygen non-stoichiometry and valence fluctuation of Fe ions
[56].
Recently, Bi4 Bin-3 Ti3 Fen-3 O3n+3 with a well-known Bi-based layer Aurivillius structure has been reconsidered as the candidate in single-phase multiferroics because of their
potential ME coupling behaviours [7]. The Bi5 FeTi3 O15 (n = 4, BFTO) [4, 816] is such
one of the materials. Its structure contains four-layered perovskite unit of (Bi3 FeTi3 O13 )2
sandwiched by two (Bi2 O2 )2+ layers along the c axis. Here (Bi2 O2 )2+ layer plays a key

Received June 30, 2012; in final form October 3, 2012.

Correesponding author. E-mail: hsun@yzu.edu.cn

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role in reducing leakage further for it can be as a layer of space-charge compensation

and insulation [17]. Since BFTO can also be considered as a stacking of a ferroelectric
compound Bi4 Ti3 O12 (BTO) with three-layer perovskite unit and a well-known ferromagnetic BFO, its structure, multiferroic behavior and possible ME coupling effects have been
widely investigated [1012]. Recently, Mao et al. reported the enhanced ferroelectric and
magnetic properties of BFTO ceramics at RT by substituting half Fe3+ sites with the Co3+
ions (Bi5 Fe0.5 Co0.5 Ti3 O15 : BFCT) [18].
In this paper, the BFCT thin films were prepared by the chemical solution deposition technique. And the effect of different annealing process on their crystal structure,
ferroelectric and magnetic properties was investigated.

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1. Experimental Details
The BFCT thin films were prepared by the chemical solution technique. Bismuth nitrate,
iron acetylacetonate, cobalt acetylacetonate and titanium n-butoxide were used as the
precursors materials for Bi, Fe, Co and Ti, respectively. Details of the precursor preparation
were described elsewhere [19]. The films were spin coated at 3500 rpm for 30 s, and a
two-step baking procedure was employed at the baking temperature of 200 C and 350 C
for 2 min, respectively. Finally, we utilized two kind of annealing process. (1) The deposited
films were then annealed at 750 C for 1 hour in oxygen atmosphere in the tube furnace
(BFCT-1). (2) The deposited films were followed using the rapid thermal annealing at
750 C for 4 min in oxygen atmosphere layer by layer (BFCT-2).
To measure the electric properties, top Pt electrodes with 0.3 mm were deposited
on the surface of the film. The crystal structures of the films were analyzed by X-ray
diffraction (XRD, Bruker D8) with Cu K . The surface morphology was investigated by a
field emission scanning electron microscope (FESEM: Hitachi, S-4800). The ferroelectric
responses were carried out using the TF 2000 standard ferroelectric test unit. The magnetic
measurement was performed using a vibrating sample magnetometer (VSM ADE EV-7).

2. Results and Discussion

XRD pattern of the BFCT-1 thin films, as shown in Figure 1, indicates that the film is
single Aurivillus phase without any other impurity phase. It is seen that the four-layered
perovskite structure has come into being due to the similar ionic radius of Ti4+ (0.68 )

Figure 1. X-ray diffraction pattern of the BFCT film.

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Hui Sun et al.

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Figure 2. (a) SEM surface morphology and (b) cross-sectional image of the BFCT film.

and Fe3+ ions (0.64 ). Moreover, the result is also consistent with earlier reports [18].
And the full-width at half-maximum (FWHM) of the main diffraction peak (119) of the
present film is as narrow as 0.22 , indicating good crystallinity. While the BFCT-2 film
[20] shows relative high c-axis orientation. It seems that the rapid thermal annealing may
leads to relative high c-axis orientation.
Figure. 2(a) illustrates the FESEM surface morphology of the BFCT-1 film. A dense
and homogeneous film with the large flake grains around 400 500 nm was observed,
which is comparable to that of layered bismuth titanate SrBi4 Ti4 O15 (SBTi) films with a
similar fabrication process [2122]. While the BFCT-2 film [20] exhibits ellipsoidal grains
with smaller size of 200300 nm for its annealing with long time leads to the larger and
plate like grains. Fig. 2(b) reveals a clear and sharp boundary between the film and the
substrate, suggesting no obvious inter-diffusion across the capacitor. The thickness of the
film is estimated to be about 500 nm.
The ferroelectric hysteresis loops of the BFCT-1 film are plotted in Figs. 3(a), and
Fig. 3(b) shows the corresponding switching current. With the increasing electric filed,
the squareness of the loops is well improved and the peak of the current increases. Welldefined P-E loop and the I-E loop can be observed, implying typical ferroelectric nature. The

Figure 3. (a) Hysteresis loops of the Pt/BFCT/Pt capacitor under various applied electric field. Fig. 3
(b) Corresponding switching current of the BFCT film.

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remnant polarization 2Pr and the coercive field Ec are 37.7 C/cm2 and 123.4 kV/cm
at the maximum electric field of 240 kV/cm, respectively. Compared with the BFCT-2,
the present film shows relative larger remnant polarization, which is mainly attributed to
the different processing characteristics and nucleation process. There are different aspects
between the BFCT-1 and the rapid-thermal-annealed BFCT-2 film as follows. Firstly, the
present BFCT film shows randomly oriented, whereas the BFCT-2 film indicates relatively
high c-orientation. As reported [23], the random orientation is relative to the mechanism
of homogeneous nucleation in the film, because of the existence of porosity or residual
organics in the amorphous film, which are homogeneously distributed nucleation sites. By
means of rapid crystallization thermal treatments, the main center of nucleation is located
at the substrate-film interface, tending to form oriented films. The spontaneous polarization
in layered perovskite structure along a/b plane is much larger than that of c-orientation
[24, 25]. Secondly, the present BFCT-1 film shows larger grain size (400 500 nm) than
that of the rapid-thermal-annealed BFCT-2 film (200300 nm). The larger grain may be
helpful to the ferroelectric domain switching, leading to larger remnant polarization [26].
Figure 4 shows the characteristics of fatigue in BFCT-1 film using 182 kV/cm and
100 kHz bipolar square wave. The inset presents the P-E loop before and after fatigue test.
The normalized polarization decreases to 75.8% after 109 switching cycles, which is
almost similar with that of the Nd-doped BFTO film [16] and better than that of the BFTO
film [13]. However, it is still not as good as that of V-doped SBTi (SBTV) film [22]. It
is well known that the oxygen vacancies play a key role for the fatigue behavior in the
ferroelectrics [2728]. The A site was occupied by the stable Sr ions and a few of B-site
ions were replaced by the higher-valence V ions, which can effectively reduce the oxygen
concentration in the SBTV. And Fe2+ ions may occur in the BFCT during high temperature
process. So the concentration of oxygen vacancies in BFCT may higher than that in SBTV.
Furthermore, there are three kinds of ions (Fe, Co, and Ti ions) with difference chemical
valence, ion radius and binding energy at B site in BFCT, which should give rise to more
internal stress in BFCT than the one in SBTV. Both causes mentioned above led to the
present fatigue property in BFCT film.
The magnetic hysteresis M-H loop of BFCT-1 film was measured at RT, as shown
in Figure 5. The BFCT-1 film exhibits well-saturated weak ferromagnetic characteristics.
The saturated magnetization (M s ) is2.3 emu/cm3, which is also smaller than that of the

Figure 4. Fatigue characteristics of BFCT film as a function of switching cycles. The inset shows
hysteresis loops before and after fatigue.

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Figure 5. Magnetic M-H hysteresis loop of the BFCT film measured at RT.

rapid-thermal-annealed BFCT-2 film (M s 2.6 emu/cm3) [20], which may be related to

the different grain size also. The origin of weak ferromagnetism in BFCT film have been
discussed elsewhere [20], including F-center exchange (FCE) mechanism [29], the clusters
of Fe2+-O-Fe3+ [30, 31], and the Fe-O-Co coupling [18].

3. Conclusion
In summary, single phase Bi5 Fe0.5 Co0.5 Ti3 O15 (BFCT-1) thin films were prepared by the
chemical solution deposition route. The crystal structure, surface topography and crosssectional microstructure were investigated via XRD and FESEM. Coexistence of the ferroelectric and ferromagnetic properties at RT confirmed the multiferroic behavior of the
BFCT film. Meanwhile, the different ferroelectric and magnetic properties in BFCT films
prepared with different annealing processes were compared and discussed.

Acknowledgment
This work was supported by the National Science Foundation (Grant No. 50832002,
50972056, 51002075) and 973 Project of MOST (Grant Nos. 2009CB623303,
2009CB929501). This work was also supported by the Chinese National Natural Science
Foundation (Grant No. 51072177).

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