Integrated Ferroelectrics: An
International Journal
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ORIENTATION DEPENDENCE
OF FERROELECTRIC AND
DIELECTRIC PROPERTIES IN
CaBi4Ti4O15 THIN FILMS
a
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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
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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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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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D. Do et al.
Figure 4. (a) 2Pr and (b) 2Ec values of randomly oriented and highly c-axis-oriented
CaBi4 Ti4 O15 thin film capacitors.
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D. Do et al.
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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