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ORIENTATION DEPENDENCE
OF FERROELECTRIC AND
DIELECTRIC PROPERTIES IN
CaBi4Ti4O15 THIN FILMS
a

D. DO , S. S. KIM , J. W. KIM , Y. I. LEE & A. S.

BHALLA

Department of Physics, Changwon National

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

Department of Chemistry, Changwon National

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

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 , S. S. KIM , J. W. KIM , Y. I. LEE & A. S. BHALLA (2009):

ORIENTATION DEPENDENCE OF FERROELECTRIC AND DIELECTRIC PROPERTIES IN
CaBi4Ti4O15 THIN FILMS, Integrated Ferroelectrics: An International Journal, 105:1,
99-106
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Integrated Ferroelectrics, 105: 99106, 2009

Copyright Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580903139883

Orientation Dependence of Ferroelectric

and Dielectric Properties in CaBi4 Ti4 O15 Thin Films
D. Do,1 S. S. Kim,1, J. W. Kim,1 Y. I. Lee,2 and A. S. Bhalla3

Downloaded by [Seoul National University] at 23:37 25 June 2013

Department of Physics, Changwon National University, Changwon, Kyungnam

641-773, Republic of Korea
2
Department of Chemistry, Changwon National University, Changwon, Kyungnam
641-773, Republic of Korea
3
Department of Electrical and Computer Engineering, The University of Texas at
San Antonio, San Antonio, Texas 78249-0669, USA

ABSTRACT
Ferroelectric CaBi4 Ti4 O15 (CBTi) thin films with random orientation and high c-axis
orientation were prepared on a Pt(111)/Ti/SiO2 /Si(100) substrate by a chemical solution
deposition method. We observed a strong dependence of ferroelectric and dielectric
properties on the film orientation. The CBTi thin film with random orientation exhibited
remnant polarization (2Pr ) of 54 C/cm2 at an applied electric field of 250 kV/cm and
dielectric constant () of 412 at a frequency of 1 kHz. The values of 2Pr and were
larger than those observed in the CBTi thin film with high c-axis orientation. In addition,
the randomly oriented thin film showed lower leakage current density than the highly
c-axis-oriented thin film.
Keywords: CaBi4 Ti4 O15 , orientation, ferroelectric property, dielectric property

Bismuth layer-structured ferroelectrics (BLSFs) have been considered of

great interest as promising materials for the application in non-volatile ferroelectric random access memory devices [1]. BLSFs belong to Aurivillius
family, denoted (Bi2 O2 )2+ (An1 Bn O3n+1 )2 , where n = 2, 3, 4, 5, etc. Ferroelectricity in BLSFs strongly depends on the crystallographic orientation of the
materials, which is the major object of continuing research [2, 3].
A typical BLSF with n = 3 is Bi4 Ti3 O12 (BIT), which has been extensively investigated because of its good ferroelectric properties such as large
Received May 1, 2009

Corresponding author: Tel.:+82-55-213-3421; fax: +82-55-267-0264. E-mail:

sskim@changwon.ac.kr
99

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D. Do et al.

spontaneous polarization and low switching field. BIT consists of triple TiO6
octahedra in the perovskite blocks, sandwiched by two neighboring (Bi2 O2 )2+
layers along the c-axis in a unit cell. The spontaneous polarization (Ps ) in a
BIT crystal was 50 C/cm2 when an electric field was applied along the aaxis while the Ps value of 4 C/cm2 was observed along the c-axis [4]. Thus,
bismuth layer-structured ferroelectric materials such as BIT have the majority
polarization vector along the a-axis in a unit cell. Curie temperature of BIT
is 675 C, which is relatively higher than those of other ferroelectric materials. Another BLSF is SrBi4 Ti4 O15 (SBTi) with n = 4, which also exhibits
anisotropic ferroelectric properties. A SBTi single crystal exhibited remnant
polarization of 29 C/cm2 along the a-axis and no remnant polarization along
the c-axis [5]. Therefore, many efforts have been concentrated on the growth
of a-axis-oriented BLSF thin films to achieve better ferroelectricity.
CaBi4 Ti4 O15 (CBTi) which has the similar structure as SBTi may exhibit
larger remnant polarization than that of BIT, because CBTi has more TiO6
octahedra in a unit cell than those in BIT. It is worth noting that TiO6 octahedra
in the perovskite structure have been known as the source of the ferroelectricity.
CBTi could be characterized by its high Curie temperature of about 790 C,
which could have special applications at relatively high temperatures. Recently,
A. Z. Simoes et al. [6] reported that CBTi thin films fabricated on a Pt/Ti/SiO2 /Si
substrate by the polymeric precursor method show Pr = 14 C/cm2 and Ec =
64 kV/cm under an applied electric field of 400 kV/cm. However, the electrical
properties of CBTi thin films have not yet been well investigated. Also, there
are almost no papers regarding orientation dependence of electrical properties
of CBTi thin films.
Here we show properties of ferroelectric CaBi4 Ti4 O15 thin films, with
particular emphasis on crystallographic orientation-dependent properties. Our
results show that the randomly oriented thin film exhibits better ferroelectric
and dielectric properties, and lower leakage current density than the highly
c-axis-oriented thin film.
Ferroelectric CaBi4 Ti4 O15 thin films were prepared on a
Pt(111)/Ti/SiO2 /Si(100) substrate by a chemical solution deposition
method. Calcium nitrate [Ca(NO3 )2 4H2 O], bismuth nitrate [Bi(NO3 )3 5H2 O],
and titanium iso-propoxide [Ti(OC3 H7 )4 ] were used as starting materials
for Ca, Bi, and Ti, respectively. Two-methoxyethanol (2-MOE) and acetic
acid were mixed at room temperature for 30 min to make a homogeneous
solution. Bismuth nitrate was completely dissolved in the above solution at
room temperature for another 30 min. Calcium nitrate was dissolved into the
Bi solution and stirred for 3 hrs. Separately, 2-MOE and acetylacetone were
mixed at room temperature in a glove box, and then the solution was stirred for
1 hr. Acetylacetone was used as a chelating agent. Titanium iso-propoxide was
dissolved in a 2-MOEacetylacetone solution, and then the solution was stirred
for additional 1.5 hrs. The titanium solution was added to the Bi-Ca solution
with continuous stirring, and the final mixture was stirred for additional 3 hrs

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Ferroelectric and Dielectric Properties in CaBi4 Ti4 O15

101

to make a homogeneous solution. The concentration of the CBTi in the final

solution was adjusted to be approximately 0.1 M.
The prepared solution was spin-coated on a Pt-coated Si substrate at a
speed of 3500 rpm for 25 s. In order to control the preferred orientation of the
thin films, two thin films were prepared with different thermal histories. The
first thin film, so-called a layer-by-layer dried thin film, was dried sequentially
at room temperature, 200 C, and 360 C for 5 min each on a hotplate. The
coating and drying procedure were repeated 15 times to achieve a thick enough
CBTi thin film. After multilayer was coated and dried, the entire thin film was
annealed at 500 C for 3 min by rapid thermal annealing (RTA) with continuous
oxygen flow. At the final stage, the thin film was annealed at 700 C for 3 min by
RTA under oxygen atmosphere. The second thin film, so-called a layer-by-layer
annealed thin film, was dried at 200 C for 5 min on a hotplate and annealed
at 650 C for 2 min by RTA with oxygen flow. After annealing the first layer,
the second layer was spin-coated, dried, and annealed. These coating, drying
and annealing procedure were repeated 15 times to obtain a thick enough CBTi
thin film. Finally, the entire thin film was annealed at 700 C for 3 min by RTA
with oxygen flow. The final heat treatment, 700 C for 3 min by RTA, was the
same for both thin films.
Structural characteristics and morphologies of both CBTi thin films prepared by different processes were analyzed using an X-ray diffractometer
equipped with Cu K radiation (Philips, APD system) and a scanning electron microscope (SEM, Hitachi, S-2400), respectively. In order to measure the
electrical properties of the thin films, gold electrodes were deposited on the top
surface of the thin films with an area of approximately 7.85 103 cm2 using a
metal shadow mask by an ion sputter. The electrical properties of the CBTi thin
film capacitors were measured using an LF impedance analyzer (HP4192A),
an electrometer (Keithley 6517A), and precision materials analyzer (Radiant
Technologies Inc., Precision LC).
The crystal structure of the samples was investigated using X-ray diffrac Figure 1 shows the XRD
tion (XRD) with Cu K radiation ( = 1.5406 A).
patterns in a 2 scan. All peaks were carefully indexed based on the powder diffraction patterns of CaBi4 Ti4 O15 (PDF # 521640). The result indicates
that two thin films show different preferred orientations in the surface normal direction. Thin films grown by layer-by-layer dried method exhibited a
polycrystalline structure with randomly oriented grains along [119], [200], and
[00l] directions while thin films grown by layer-by-layer annealed method
were mainly oriented with the c-axis. We thus expect that there are different
ferroelectric properties between two thin films.
The microstructure of CBTi thin films prepared by two different growth
methods was investigated using SEM. In bismuth layer-structured ferroelectric
thin films, there is a deep relationship between the grain orientation and the
surface morphology shape. The randomly oriented thin film showed sphericallike grains with less than 100 nm in diameter (Fig. 2(a)). The grain shape of the

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D. Do et al.

Figure 1. X-ray diffraction patterns of (a) randomly oriented and (b) highly c-axisoriented CaBi4 Ti4 O15 thin films.

highly c-axis-oriented thin film was plate-like and the average grain size was
larger than that of the randomly oriented thin film (Fig. 2(b)). A similar result
was previously reported in Bi3.15 Nd0.85 Ti3 O12 ferroelectric thin films [7]. Both
thin films were 400 nm-thick.
Ferroelectric properties of two different oriented CBTi thin films were investigated. Figure 3 shows polarization-electric field hysteresis loops measured
electrically with the randomly oriented and highly c-axis-oriented thin film capacitors. The loops were measured using 1.25 kHz triangular voltage pulses.
Both thin films exhibited a typical hysteresis loop. Comparing two loops, the
randomly oriented thin film capacitor showed better ferroelectricity than the

Figure 2. Surface morphologies of (a) randomly oriented and (b) highly c-axisoriented thin films, and cross-sectional images of (c) randomly oriented and (d) highly
c-axis-oriented thin films.

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Ferroelectric and Dielectric Properties in CaBi4 Ti4 O15

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Figure 3. Polarization-electric field hysteresis loops of randomly oriented and highly

c-axis-oriented CaBi4 Ti4 O15 thin film capacitors.

highly c-axis-oriented thin film capacitor. The values of remnant polarization

(2Pr ) and coercive field (2Ec ) of randomly oriented and highly c-axis-oriented
thin films were 54 C/cm2 and 168.5 kV/cm, and 11.7 C/cm2 and 69 kV/cm at
an applied electric field of 250 kV/cm, respectively. The observed 2Pr value of
the randomly oriented thin film is similar to that of polycrystalline CaBi4 Ti4 O15
thin films [6, 8].
Figure 4 shows the values of remnant polarization (2Pr ) and coercive field
(2Ec ) at a series of applied electric fields. The randomly oriented thin film
showed larger 2Pr than the highly c-axis-oriented thin film at the same electric
field. The 2Pr of the randomly oriented thin film increased as increasing the
electric field and was almost saturated at 250 kV/cm while the 2Pr of the
highly c-axis-oriented thin film was proportional to the electric field. A similar
tendency was observed in the 2Ec . The 2Ec of the randomly oriented thin film
was larger than the highly c-axis-oriented thin film.
Leakage current properties of two thin films were investigated at room
temperature. Under dc applied electric field, leakage current density as a function of an applied electric field was measured and plotted in Fig. 5. As shown in
Fig. 5, the randomly oriented CBTi thin film capacitor exhibited better leakage
properties than the highly a-axis-oriented thin film capacitor. The difference in
the current density was more than five orders of magnitude at an electric field
of 125 kV/cm. The leakage current can be affected by many factors such as the
effect of grain size and grain boundary [9], and the concentration of oxygen
vacancies [10]. In our case, the lower leakage current density of randomly
oriented CBTi thin film may be due to the small grain size and the high grain
density compared with those of the highly c-axis-oriented thin film (Fig. 2).

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Figure 4. (a) 2Pr and (b) 2Ec values of randomly oriented and highly c-axis-oriented
CaBi4 Ti4 O15 thin film capacitors.

The leakage current density was linearly proportional to an applied field

in the low electric field region, suggesting that the conduction mechanism was
Ohmic conduction [6,11]. The different leakage current mechanism, however,
was observed in the high electric field region. The current density increased

Figure 5. Leakage current density as a function of an applied electric field of randomly

oriented and highly c-axis-oriented CaBi4 Ti4 O15 thin film capacitors.

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Ferroelectric and Dielectric Properties in CaBi4 Ti4 O15

105

Figure 6. Frequency dependence of dielectric constant and dielectric loss of randomly

oriented and highly c-axis-oriented CaBi4 Ti4 O15 thin film capacitors.

exponentially, indicating Schottky or Poole-Frenkel emission mechanism rather

than Ohmic conduction at the high electric field region.
Figure 6 shows frequency dependence of dielectric properties measured
in ferroelectric thin film capacitors. As expected, the randomly oriented thin
film capacitor exhibited better dielectric properties. The values of dielectric constant of the randomly oriented and the highly c-axis-oriented ferroelectric thin film capacitors were 412 and 349 at a frequency of 1 kHz,
respectively. It has been reported that dielectric constant of bismuth layerstructured ferroelectrics such as Bi4 Ti3 O12 was larger along the a-axis than
along the c-axis [12]. Dielectric constant gradually decreased with increasing frequency in the measured range (100 Hz to 10 MHz). The values of
dielectric loss of the randomly oriented and the highly c-axis-oriented ferroelectric thin film capacitors were 0.03 and 0.08 at a frequency of 1 kHz,
respectively.
In summary, in order to investigate the orientation dependence of the electrical properties of CaBi4 Ti4 O15 thin films, the randomly oriented and the highly
c-axis-oriented CBTi thin films were prepared on a Pt(111)/Ti/SiO2 /Si(100)
substrate by controlling the growth process using a chemical solution deposition method. The observed values of remnant polarization and dielectric
constant of the randomly oriented CBTi thin film were larger than the highly
c-axis-oriented CBTi thin film. Also the randomly oriented CBTi thin film
showed lower leakage current density. The results clearly indicate that enhanced ferroelectric and dielectric properties can be achieved by growing CBTi
thin films with random orientation (non-a-axis) rather than the c-axis in a unit
cell.

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ACKNOWLEDGMENTS
This work was supported by the Korea Research Foundation Grant funded by
the Korean Government (MOEHRD) (KRF-2007-412-J00901).

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