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Integrated Ferroelectrics: An
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FABRICATION AND ORIENTATION

DEPENDENCE ON ELECTRICAL
PROPERTIES OF Na0.5Bi4.5Ti4O15
THIN FILMS
a

J. W. KIM , D. DO , S. S. KIM , Y. I. LEE , T. K.

c

SONG , B. C. CHOI & 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 Ceramic Science and Engineering,

Changwon National University, Changwon,
Kyungnam, 641-773, Republic of Korea
d

Department of Physics, Pukyong National

University, Busan, 608-737, Republic of Korea
e

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: J. W. KIM , D. DO , S. S. KIM , Y. I. LEE , T. K. SONG , B. C. CHOI

& A. S. BHALLA (2009): FABRICATION AND ORIENTATION DEPENDENCE ON ELECTRICAL
PROPERTIES OF Na0.5Bi4.5Ti4O15 THIN FILMS, Integrated Ferroelectrics: An International
Journal, 107:1, 112-120
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Integrated Ferroelectrics, 107: 112120, 2009

Copyright Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580903325011

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Fabrication and Orientation Dependence

on Electrical Properties of Na0.5 Bi4.5 Ti4 O15
Thin Films
J. W. Kim,1 D. Do,1 S. S. Kim,1, Y. I. Lee,2 T. K. Song,3 B. C. Choi,4
and A. S. Bhalla5
1

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 Ceramic Science and Engineering, Changwon National University,
Changwon, Kyungnam 641-773, Republic of Korea
4
Department of Physics, Pukyong National University, Busan 608-737, Republic of
Korea
5
Department of Electrical and Computer Engineering, The University of Texas at San
Antonio, San Antonio, Texas 78249-0669, USA
Ferroelectric Na0.5 Bi4.5 Ti4 O15 (NaBTi) thin films, selectively controlled in c-axis and
random orientation, were fabricated on a Pt(111)/Ti/SiO2 /Si(100) substrate by using
a chemical solution deposition method. The preferred orientation of the thin films
annealed at 750 C under oxygen atmosphere was confirmed by X-ray diffraction and
scanning electron microscope studies. We found that ferroelectric, dielectric, and leakage
current properties were strongly related to the crystallographic orientation of NaBTi thin
films; the randomly oriented NaBTi thin film exhibited better properties than the c-axis
oriented thin film. The values of remnant polarization (2Pr ), dielectric constant, and
leakage current density were 21 C/cm2 at 300 kV/cm, 630 at 100 kHz, and 7.4 106
A/cm2 at 100 kV/cm for the randomly oriented thin film, respectively, and 6 C/cm2,
420, and 1.1 101 A/cm2 for the c-axis oriented thin film, respectively. Also, no
polarization fatigue was observed in both NaBTi thin films up to 107 switching cycles.
Keywords:
properties

Na0.5 Bi4.5 Ti4 O15 thin film, chemical solution deposition, electrical

Ferroelectric thin films have been extensively studied due to their potential applications in nonvolatile ferroelectric random access memories [1, 2].
Among ferroelectric materials, Pb(Zrx Ti1-x )O3 (PZT) is known to be the most

Received in final form July 14, 2009.

Corresponding author. E-mail: sskim@changwon.ac.kr

112

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Electrical Properties of Na0.5 Bi4.5 Ti4 O15 Thin Films

113

important candidate for this application and has been extensively studied due to
its excellent ferroelectric properties. However, the poor fatigue endurance with
Pt electrodes and Pb toxicity of PZT may ultimately prevent it from being used
in many applications [3]. Therefore, it is very important to develop new leadfree ferroelectric materials having good ferroelectric properties comparable
with those of PZT.
Bismuth layer-structured ferroelectrics (BLSFs) have been extensively investigated because of their promising applications in lead-free nonvolatile ferroelectric random access memory devices [4, 5]. The general formula of BLSFs
is (Bi2 O2 )2+(Am-1 Bm O3m+1 )2, where A represents Bi, Ba, Pb, Sr, Ca, K, Na,
and rare earth elements, B represents Ti, Ta, Nb, W. Mo, Fe, etc., and m = 2,
3, 4,. . . refers to the number of (Am-1 Bm O3m+1 )2- perovskite layers sandwiched
between two neighboring (Bi2 O2 )2+ layers [6]. BLSFs are characterized by
a highly anisotropic crystal structure, a high Curie temperature (TC ), a large
spontaneous polarization (Ps ), and high polarization fatigue endurance against
repeated switching of their polarization states [7]. The major contribution to the
ferroelectric polarization in BLSFs is from the displacement of A-site cations
in the perovskite units along the a-axis accompanied by octahedral rotations
around c-axes [8].
Considerable efforts have been devoted to the development of ferroelectric
devices based on BLSF SrBi2 Ta2 O9 (m = 2) [4, 9] and Bi4 Ti3 O12 (m = 3)
[10, 11], and their derivatives [2, 12, 13]. However, scientific and technological
investigations of BLSF ABi4 Ti4 O15 (m = 4) seem to be less complete. The
properties of single crystals, ceramics, and thin films of SrBi4 Ti4 O15 [1416],
CaBi4 Ti4 O15 [17, 18], BaBi4 Ti4 O15 [19, 20], and PbBi4 Ti4 O15 [20, 21] have
been investigated, while there are almost no reports regarding the properties of
(M,Bi)Bi4 Ti4 O15 (M = Na, K),especially in thin films [3, 22].
In this study, Na0.5 Bi4.5 Ti4 O15 (NaBTi) thin films have been prepared by
using a chemical solution deposition method followed by two different thermal
histories to control the orientation of the thin films. One was a c-axis preferred
growth, while the other was no preferential growth direction. Details of the
structural and electrical properties of NaBTi thin films have been investigated
systematically.
Ferroelectric Na0.5 Bi4.5 Ti4 O15 thin films were deposited on a
Pt(111)/Ti/SiO2 /Si substrate by a chemical solution deposition method. Sodium
nitrate [NaNO3 ], bismuth nitrate pentahydrate [Bi(NO3 )3 5H2 O], and titanium
isopropoxide [Ti[OCH(CH3 )2 ]4 ] were used as starting materials for Na, Bi,
and Ti, respectively. 2-methoxyethanol (2-MOE) and acetic acid were used as
a solvent and a catalyst, respectively. Sodium nitrate was completely dissolved
in 2-MOE at 40 C and stirred for 30 min. Acetic acid was added to this solution and then stirred for 30 min. Bismuth nitrate pentahydrate was dissolved
into the above sodium solution and stirred for 2 h. Separately, 2-MOE and
acetylacetone were mixed at room temperature in a glove box for 30 min to
make a homogeneous solution. Acetylacetone was used as a chelating agent.

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Titanium isopropoxide was dissolved in 2-MOE-acetylacetone and then stirred

for 1.5 h. The titanium solution was added to the sodium-bismuth solution with
continuous stirring at room temperature and the final mixture was stirred for
additional 3 h. The concentration of Na0.5 Bi4.5 Ti4 O15 in the final solution was
adjusted to approximately 0.1 M.
Two different thermal histories were used to achieve randomly oriented
and c-axis-orientated thin films. The prepared solution was spin-coated on a
Pt(111)/Ti/SiO2 /Si(100) substrate at a speed of 3500 rpm for 25 s. After spin
coating, randomly oriented and c-axis-oriented thin films were prepared by
two different ways, which are layer-by-layer dried and layer-by layer annealed
processes, respectively. The 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 obtain the desired
thickness. 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. On the other hand, the thin film prepared by
the layer-by-layer annealed process 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. The procedure of coating, drying, and annealing was repeated 15 times to obtain the
desired thickness. Finally, the entire thin film was annealed at 750 C for 3 min
by RTA under oxygen atmosphere.
Crystal structure and surface morphology of the thin films were investigated using X-ray diffractometer (Philips, XPert MPD 3040) and scanning
electron microscope (Tescan, MIRA II LMH), respectively. Gold electrodes
with an area of 1.54104 cm2 were deposited on a top surface of the thin
films using a metal shadow mask to form a capacitor structure. A precision
materials analyzer (Radiant Technologies Inc., Precision LC), a LF impedance
analyzer (HP4192A), and an electrometer (Keithley 6517A) were used for
electrical measurements.
The crystallographic orientations of the thin films were determined using X-ray diffraction (XRD) studies. X-rays with Cu K radiation (1.5406 )
were used for the XRD measurements. Figure 1 shows XRD patterns of the
NaBTi thin films deposited on a Pt(111)/Ti/SiO2 /Si(100) substrate prepared
by two different processes; (a) layer-by-layer dried thin film and (b) layerby-layer annealed thin film. All the diffraction peaks were analyzed based
on a Na0.5 Bi4.5 Ti4 O15 phase with an orthorhombic symmetry. As shown in
Fig. 1(a), the layer-by-layer dried NaBTi thin film showed no preferred orientation with the strong intensity of the (119) reflection. On the other hand,
in Fig. 1(b), the strong intensities of (00l) reflections from the layer-by-layer
annealed NaBTi thin film suggest that the surface normal direction of the thin
film is close to the c-axis of the perovskite structure. This clearly demonstrates
that the predominantly c-axis-oriented NaBTi thin film can be grown by the

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Figure 1. X-ray diffraction patterns of Na0.5 Bi4.5 Ti4 O15 thin films deposited on a
Pt(111)/Ti/SiO2 /Si(100) substrate by two different processes; (a) layer-by-layer dried
and (b) layer-by-layer annealed thin films.

layer-by-layer annealing described in Section II. From now on, the layer-bylayer dried and the layer-by-layer annealed NaBTi thin films will be called by
randomly oriented NaBTi thin film and predominantly c-axis-oriented NaBTi
thin film, respectively [23].
The changes in microstructure with two different annealing processes are
shown in Fig. 2. The images of the surface morphology show that the specimen
preparation procedure leads to a crack-free and uniform microstructure. For the
randomly oriented NaBTi thin film, grains of arbitrary shape were observed. On
the other hand, it can be seen that the c-axis oriented NaBTi thin film has only
plate-like grains. From the results of the XRD and SEM investigations, the grain
orientation of the layer-by-layer annealed NaBTi thin film is perfectly c-axis
oriented. From the cross-sectional SEM images, the thickness of the thin films
was measured to be approximately 210 nm and 230 nm for the predominantly
c-axis-oriented and randomly oriented NaBTi thin films, respectively.
Ferroelectric polarization-electric field (P-E) hysteresis loops were measured at room temperature to understand ferroelectric properties of the NaBTi
thin films. Figure 3 shows the applied electric field dependence of the
polarization-electric field hysteresis loops of the randomly oriented NaBTi
thin films. The insert of Fig. 3 shows the loops measured from the predominantly c-axis-oriented NaBTi thin films. From the loops, it was found that

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Figure 2. SEM images of the surface morphologies of (a) randomly oriented and (b)
predominantly c-axis-oriented Na0.5 Bi4.5 Ti4 O15 thin films.

the randomly oriented NaBTi thin film shows better ferroelectric properties.
At an applied electric field of 300 kV/cm, the values of remnant polarization
(2Pr ) and the coercive electric field (2Ec ) of the randomly oriented and c-axis
oriented NaBTi thin films were 21 and 6 C/cm2, and 199 and 91 kV/cm,
respectively. The 2Pr of the randomly oriented NaBTi thin film is comparable
to the previously reported values of 13 C/cm2 for the SrBi4 Ti4 O15 thin film
on a Pt layer prepared by a chemical solution deposition method [24] and
28 C/cm2 for a maximum applied electric field of 400 kV/cm of the
CaBi4 Ti4 O15 thin film on a Pt/Ti/SiO2 /Si substrate grown by the polymeric
precursor method [18].

Figure 3. P-E hysteresis loops of randomly oriented Na0.5 Bi4.5 Ti4 O15 thin film. The
insert shows P-E hysteresis loops of predominantly c-axis-oriented Na0.5 Bi4.5 Ti4 O15
thin film.

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Figure 4. Dielectric constant and dielectric loss of randomly oriented and predominantly c-axis-oriented Na0.5 Bi4.5 Ti4 O15 thin films.

According to previous reports, bismuth layer-structured ferroelectrics are

strongly anisotropic in nature in terms of ferroelectric properties such as the
polarization and the coercive field [10]. For the Bi4 Ti3 O12 single crystal, a-axis
polarization (Ps = 45 50 C/cm2) is larger than c-axis polarization (Ps =
4.5 C/cm2) [10]. Irie et al. reported on ferroelectric properties of the
SrBi4 Ti4 O15 single crystals [14]. They indicated that SrBi4 Ti4 O15 single crystals in a- and b-axis orientations showed typical ferroelectric behavior with Pr
of 29 C/cm2, whereas dielectric behavior was observed for c-axis orientation.
This indicates that the remnant polarization of polycrystalline SrBi4 Ti4 O15 film
is strongly dependent on the orientation of grains.
The frequency dependences of the dielectric constant and the dielectric
loss of the NaBTi thin film capacitors measured at room temperature are shown
in Fig. 4. With increasing frequency, the dielectric constant of the thin film
decreased gradually up to 6 MHz and then decreased quickly beyond 6 MHz.
The measured values of dielectric constant for the randomly oriented and caxis-oriented NaBTi thin film capacitors were approximately 627 and 420,
respectively, at a frequency of 100 kHz, while the values of dielectric loss were
0.04 and 0.05, respectively, at the same frequency. In comparison, the dielectric
constant and the dielectric loss of the randomly oriented CaBi4 Ti4 O15 thin film
grown by using a sol-gel spin-coating method were reported to be 300 and
0.033, respectively [25].
The results of XRD, SEM, P-E hysteresis loops, and dielectric properties are in good agreements with each other. The remnant polarization and
dielectric constant of the bismuth layer-structured ferroelectric thin films remarkably depend on grain orientation due to the anisotropic nature. The

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Figure 5. Switchable polarization as a function of switching cycles of randomly oriented and predominantly c-axis-oriented Na0.5 Bi4.5 Ti4 O15 thin films.

c-axis-oriented NaBTi thin film shows a low remnant polarization and a low
dielectric constant.
In order to study polarization fatigue, the pulse polarization (P P ) of the
NaBTi thin film capacitors annealed at 750 C for 3 min under O2 atmosphere
were measured as a function of switching cycles at an applied voltage of 5 V
with a pulse duration of 500 ns (Fig. 5). P represents the switching polarization
between two pulses with opposite polarity, and P represents nonswitching
polarization between two pulses with the same polarity. The estimated pulse
polarization was normalized to the initial value. The switchable polarization of
both NaBTi thin films is almost unchanged up to 107 cycles. The reduction in
the switchable polarization after 1.4 1010 cycles was 13% and 18% for the
randomly oriented and c-axis oriented NaBTi thin films, respectively.
The plots of leakage current density versus dc electric field of the NaBTi
thin film capacitors are shown in Fig. 6. The leakage current densities of the
randomly oriented and c-axis oriented NaBTi thin films at an electric field of
100 kV/cm were 7.4 106 and 1.1 101 A/cm2, respectively. Dielectric
properties of the randomly oriented thin film are comparable with SrBi4 Ti4 O15
thin films prepared by a refined sol-gel method [16].
In summary, ferroelectric Na0.5 Bi4.5 Ti4 O15 (NaBTi) thin films were prepared on a Pt(111)/Ti/SiO2 /Si(100) substrate by using a chemical solution
deposition method. The orientation of NaBTi thin film was controlled by different coating processes; randomly oriented and c-axis-oriented thin films. The
randomly oriented NaBTi thin film exhibited better ferroelectric, dielectric,
and leakage current properties than the c-axis oriented. The result indicates
that the ferroelectric properties of NaBTi thin film are strongly related to the

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Figure 6. Leakage current density as a function of electric field of randomly oriented

and predominantly c-axis-oriented Na0.5 Bi4.5 Ti4 O15 thin films.

crystallographic orientation and the polarization direction of NaBTi thin film

is not along the c-axis.

ACKNOWLEDGMENTS
This work was supported by the Korea Research Foundation Grant funded by
the Korean Government (MOEHRD) (KRF-2007412-J00901), AB acknowledges the support of NSF-International Network, and NSF-Metamaterials programs at UTSA.

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