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MULTIFERROIC PROPERTIES
OF SrBi5FeTi4O18 THIN FILMS
PREPARED USING CHEMICAL
SOLUTION DEPOSITION METHOD
a

D. DO , J. W. KIM , S. S. KIM & A. S. BHALLA

Department of Physics, Changwon National

University, Changwon, Kyungnam, 641-773, Republic
of Korea
b

Department of Electrical and Computer

Engineering, The University of Texas at San Antonio,
San Antonio, Texas, 78249-0669, USA
Published online: 20 Sep 2010.

To cite this article: D. DO , J. W. KIM , S. S. KIM & A. S. BHALLA (2009):

MULTIFERROIC PROPERTIES OF SrBi5FeTi4O18 THIN FILMS PREPARED USING CHEMICAL
SOLUTION DEPOSITION METHOD, Integrated Ferroelectrics: An International Journal,
105:1, 66-74
To link to this article: http://dx.doi.org/10.1080/10584580903139792

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Integrated Ferroelectrics, 105: 6674, 2009

Copyright Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580903139792

Multiferroic Properties of SrBi5 FeTi4 O18 Thin

Films Prepared Using Chemical Solution
Deposition Method

Downloaded by [Seoul National University] at 23:38 25 June 2013

D. Do,1 J. W. Kim,1 S. S. Kim,1, and A. S. Bhalla2

1

Department of Physics, Changwon National University, Changwon, Kyungnam

641-773, Republic of Korea
2
Department of Electrical and Computer Engineering, The University of Texas at San
Antonio, San Antonio, Texas 78249-0669, USA

ABSTRACT
SrBi5 FeTi4 O18 (SBFT) thin films were prepared on a Pt(111)/Ti/SiO2 /Si(100) substrate
using a chemical solution deposition method and annealed at 650 C under oxygen atmosphere. It was found that the polycrystalline SBFT thin film exhibits good ferroelectric
properties. The values of remnant polarization (2Pr ) and coercive electric field (2Ec )
were 33 C/cm2 and 150 kV/cm at an applied electric field of 250 kV/cm, respectively.
Leakage current density of the thin film was 106 A/cm2 at 100 kV/cm. The values of
dielectric constant and dielectric loss were 470 and 0.05 at 1 kHz, respectively. No
significant polarization fatigue was observed up to 1.44 1010 switching cycles. Also
weak ferromagnetic properties were observed.
Keywords: SrBi5 FeTi4 O18 (SBFT) thin film, chemical solution deposition, multiferroic
properties

Ferroelectric oxide thin films have been widely studied for their potential
applications in non-volatile ferroelectric random access memory devices. Although Pb(Zr,Ti)O3 (PZT) is considered as the leading ferroelectric material,
PZT suffers from polarization fatigue with a metal electrode [1] and includes a
toxic element, Pb, which is not suitable for commercial applications.
Alternatively, bismuth layer-structured ferroelectric (BLSF) materials have
been considered of great interest since SrBi2 Ta2 O9 thin films showed almost

Received May 22, 2009.

Corresponding author:
sskim@changwon.ac.kr

Tel.:+82-55-213-3421;fax:+82-55-267-0264.

66

E-mail:

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Multiferroic SrBi5 FeTi4 O18

67

no fatigue phenomena with a metal electrode [2]. BLSFs have general formula
(Bi2 O2 )2+ (An1 Bn O3n+1 )2 , consisting of (An1 Bn O3n+1 )2 perovskite-like
blocks sandwiched by two neighboring (Bi2 O2 )2+ layers along the c-axis in
a unit cell [3]. Here, A represents Bi, Sr, Pb, Ba, Ca, K, Na, and rare earth
elements, B represents Ti, Ta, Nb, W, Mo, Fe, etc., and n is the number
of octahedral layers in perovskite-like blocks. One of the typical BLSFs is
Bi4 Ti3 O12 (BIT) with n = 3, which has relatively high Curie temperature,
675 C, compared with other ferroelectric materials. BIT is an attractive material
that has large spontaneous polarization (Ps ) and low switching field. The Ps
in a BIT single crystal was 50 C/cm2 when an electric field was applied
along the a-axis while the Ps value of 4 C/cm2 was observed along the caxis [4]. Another BLSF is SrBi4 Ti4 O15 (SBTi) with n = 4, which also exhibits
anisotropic ferroelectricity: remnant polarization (Pr ) of 29 C/cm2 along
the a-axis and no Pr was observed along the c-axis in a SBTi single crystal
[5]. In thin film forms, however, these materials showed weak ferroelectric
properties, such as small polarization and high leakage current. In order to
improve the properties of BLSF thin films, the growth of epitaxial films [6,7],
the substitution of a small amount of impurities [8,9], and mixture with other
ferroelectric or multiferroic materials have been applied [1012].
Recently, compounds from the BIT with BiFeO3 (BFO) have been studied
and it was found that Bi5 FeTi3 O15 (BFT) is a multiferroic material, which
exhibits simultaneously at least two of ferroelectricity, ferromagnetism, and
ferroelasticity in the same phase. BFT is one of the BLSFs with n = 4. BFT
thin films prepared by a pulsed laser deposition method exhibited remnant
polarization (2Pr ) of 32 C/cm2 at 1.12 MV/cm and remnant magnetization
(2Mr ) of 0.6 emu/cm3 [10]. Previously we also reported that polycrystalline
BFT thin films prepared on a Pt-coated Si substrate by using a chemical solution
deposition method showed 2Pr of 36 C/cm2 at 260 kV/cm and 2Mr of 0.02
emu/cm3 [11]. These values are comparable with BFO, which is one of the well
known multiferroics. SrBi5 FeTi4 O18 (SBFT) with n = 5 is one of SrBi4 Ti4 O15 BiFeO3 solid solution systems. In the SBFT ceramics, however, relatively small
remnant polarization was reported [12].
In this study, we prepared SrBi5 FeTi4 O18 (SBFT) thin films on a Pt-coated
Si substrate by means of a chemical solution deposition method. The purpose
of this study is to reveal electrical and magnetic properties of novel SBFT thin
films.
SrBi5 FeTi4 O18 thin films were prepared on a Pt(111)/Ti/SiO2 /Si(100) substrate using a chemical solution deposition method. Strontium nitrate, bismuth
nitrate, iron nitrate, and titanium iso-propoxide were used as the starting materials for Sr, Bi, Fe, and Ti, respectively. Strontium nitrate was completely
dissolved in heated 2-methoxyethanol (40 C) and acetic acid was added into
the solution for 1.5 hrs. And then bismuth nitrate (10 mol% excess) and iron
nitrate were dissolved in the above solution at room temperature for 2 hrs.
Separately, titanium iso-propoxide was dissolved in 2-methoxyethanol at room

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D. Do et al.

temperature, and then acetylacetone was added as a chelating agent in a glove

box for 1.5 hrs. The titanium solution was added to the strontium-bismuth-iron
solution and vigorously stirred for 3 hrs. The concentration of SBTF in the final
solution was adjusted to approximately 0.1 M.
The prepared precursor solution was spin-coated on a
Pt(111)/Ti/SiO2 /Si(100) substrate at a speed of 3500 rpm for 25 s. The
wet film was preheated sequentially at 200 C and 350 C for 5 min each on
a hotplate. The coating and the heating processes were repeated 15 times to
obtain the desired thin film thickness. Then, the thin film was subsequently
heated by rapid thermal annealing (RTA) process at 500 C for 2 min in an
oxygen atmosphere. Final annealing was performed at 650 C for 3 min in an
oxygen atmosphere by RTA process.
The crystal structure and the microstructure of the SBFT thin film annealed
at 650 C were investigated by using X-ray diffraction equipment (Philips,
XPert MPD 3040) and scanning electron microscope (Tescan, MIRA II LMH),
respectively. In order to measure electrical properties, gold top electrodes with
an area of 1.54 104 cm2 were deposited on the surface of the thin film. The
electrical properties of the thin film capacitor were measured using a ferroelectric tester (Radiant Technologies Inc., Precision LC), an LF impedance/phase
analyzer (HP 4192A), and an electrometer (Keithley 6517A). Magnetic properties were studied using a physical property measurement system (PPMS,
Quantum design).
The crystal structure of the SBFT thin film was investigated by X-ray
diffraction (XRD) studies. Figure 1 shows the result of a 2 scan us The XRD peaks were indexed based
ing Cu K radiation ( = 1.5406A).
b = 5.4625A,
and
on an orthorhombic Sr2 Bi4 Ti5 O18 phase (a = 5.4647A,
[12]. The thin film showed a polycrystalline structure without
c = 48.8515A)
any second phase.

Figure 1. XRD result of a 2 scan of SBFT thin film annealed at 650 C under an
oxygen atmosphere. The thin film was prepared on a Pt-coated Si substrate.

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Multiferroic SrBi5 FeTi4 O18

69

Figure 2. SEM image of surface morphology of SBFT thin film.

Figure 2 shows the image of surface morphology taken using scanning

electron microscope (SEM). The SEM image shows that small spherical grains
coexist with large irregular-shaped grains. The average grain size of the spherical grains is approximately 50 nm while it is around 300 to 400 nm for
the irregular-shaped grains. The thickness of the thin film was approximately
300 nm.
Polarization-electric field (P -E) hysteresis loops were measured under a
series of electric fields with 1.25 kHz triangular pulses and are shown in Fig.
3(a). Figure 3(b) shows the values of remnant polarization (2Pr ) and coercive
electric field (2Ec ) estimated from the hysteresis loops as a function of applied
electric fields. The P -E hysteresis loop measured at 250 kV/cm showed a
typical hysteresis loop. The 2Pr and 2Ec were 33 C/cm2 and 150 kV/cm at an
applied electric field of 250 kV/cm, respectively. The 2Pr value we observed is
larger than that measured in SBFT ceramics [12] and is comparable with those
of BFT thin films [10,11].
Leakage current properties were investigated by measuring leakage current density. The measurement was performed under dc applied electric fields
at room temperature. The leakage current density curve was almost symmetric
with respect to E = 0 as shown in inset of Fig. 4. Thus we studied leakage
current mechanisms on the positive electric field. Figure 4 shows the leakage
current density (J ) as a function of an applied electric field (E) in a logarithmic scale. It was found that four straight lines fit to the data. There are several

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D. Do et al.

Figure 3. (a) Polarization-electric field hysteresis loops measured at a series of electric

fields and (b) remnant polarization (2Pr ) and coercive field (2Ec ) as a function of electric
fields.

Figure 4. Leakage current density (J ) as a function of an applied electric field (E) in

a logarithmic scale. The inset shows the log(J )-E curve.

Multiferroic SrBi5 FeTi4 O18

71

conduction mechanisms to explain leakage current in ferroelectric oxide materials [13,14]. Among them, here we focus on the space charge limited conduction
(SCLC) for our thin films. At low electric field, the slope is close to 1, indicating
that the dominant mechanism is the Ohmic conduction. The leakage current
for the Ohmic conduction can be expressed by

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J = eNe E,

(1)

where e is the electron charge, is the free carrier mobility, Ne is the density
of the thermally stimulated electrons, and Eis the applied electric field. With
increasing applied electric field, the slope becomes to 2. The leakage mechanism
of this region follows the SCLC, which can be expressed by
J = 9r o V 2 /8d 3 ,

(2)

where r is the static dielectric constant, o is the permittivity of free space, is

the ratio of the density of free electrons to the trapped electrons,V is the applied
voltage, and d is the thickness of thin film. After SCLC region, leakage current
increases abruptly, which can be explained by the trap filled limit. Finally, the
slope becomes to 3, which could be due to the combined effects of SCLC and
other field-enhanced conduction mechanism. The leakage current density of
the SBFT thin film was 106 A/cm2 at 100 kV/cm, which is in a reasonable
range for the memory application.
Figure 5 shows dielectric properties of SBFT thin films. Dielectric constant
and dielectric loss were measured in the frequencies ranging from 100 Hz to
10 MHz at room temperature. The results showed that the dielectric constant
gradually decreased with increase in frequency. The decrease in dielectric constant is mainly due to the contribution of space charge polarization since the

Figure 5. Frequency dependence of dielectric constant and dielectric loss of SBFT

thin film.

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D. Do et al.

Figure 6. Switchable polarization as a function of switching cycles. The switchable

polarization was normalized to the initial value.

applied voltage (0.1 V) used in the measurement is too small to switch spontaneous polarization. The maximum contribution of space charge polarization
occurs in the low frequency region. In the high frequency region, however,
dipoles do not respond well to the applied electric field because dipole reversal
is significantly affected by duration of the applied voltage pulse. Thus dielectric constant decreases at high frequency. The values of dielectric constant and
dielectric loss were 436 and 0.03 at 100 kHz, respectively. As we expected,
these values were smaller than those measured at 1 kHz due to the restriction
of space charge polarization. The values of dielectric constant and dielectric
loss were 470 and 0.05 at 1 kHz, respectively
Polarization fatigue was measured at a frequency of 1 MHz and the result
is shown in Fig. 6. In the figure, the switchable polarization was normalized
to the initial polarization value. No significant suppression of the switchable
polarization was observed up to 1.44 1010 switching cycles. The switchable
polarization was approximately 85% of the initial value after 1.44 1010
cycles.
In order to confirm the multiferroic properties, magnetization-magnetic
field hysteresis loop was measured at room temperature and is shown in Fig
7. The thin film exhibited well saturated ferromagnetic hysteresis loop with
saturation magnetization (2Ms ) of 6 emu/cm3 . The values of remnant magnetization (2Mr ) and coercive field (2Hc ) were 0.02 emu/cm3 and 7 Oe at an
applied magnetic field of 10 kOe, respectively. The results indicate that SBFT
thin film exhibits good ferroelectricity as well as a weak ferromagnetic property
and can be utilized for new types of memory devices using the multiferroic
property.

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Multiferroic SrBi5 FeTi4 O18

73

Figure 7. Magnetization-magnetic field hysteresis loop measured at room temperature.

The inset shows an enlarged view.

In summary, the SrBi5 FeTi4 O18 thin films were prepared on a

Pt(111)/Ti/SiO2 /Si(100) substrate using a chemical solution deposition method
and annealed at 650 C in an oxygen atmosphere. Multiferroic properties of the
thin film were investigated. The values of remnant polarization (2Pr ) and coercive electric field (2Ec ) were 33 C/cm2 and 150 kV/cm at an applied electric
field of 250 kV/cm, respectively. The 2Pr value is compatible to other bismuth
layer-structured multiferroic thin films such as Bi5 FeTi3 O15 . Leakage current
mechanism was investigated from the J -E curve in a logarithmic scale and it
was found that the space charge limited conduction is the dominant conduction
mechanism in the thin film. No significant fatigue was observed up to 1.44
1010 switching cycles. Also weak ferromagnetic properties were observed at
room temperature. The results indicate that SBFT thin film can be utilized for
new types of memory devices.
ACKNOWLEDGMENTS
This work was supported by the Korea Research Foundation Grant funded by
the Korean Government (MOEHRD) (KRF-2007-412-J00901). AB acknowledges the support of NSF, USA under the grant metamaterial composites.
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