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Ferroelectric Properties of
MBi4Ti4O15 (M = Sr, Pb, Ca) Thin
Films
a

WEN XU XIANYU , TAE-YOUNG WON & WAN IN LEE

a
a

Department of Chemistry and Center for

Computational Electronics, Inha University, Incheon,
Korea, 402-751
b

Department of Electrical Engineering and Center

for Computational Electronics, Inha University,
Incheon, Korea, 402-751
Published online: 11 Aug 2010.

To cite this article: WEN XU XIANYU , TAE-YOUNG WON & WAN IN LEE (2004):
Ferroelectric Properties of MBi4Ti4O15 (M = Sr, Pb, Ca) Thin Films, Integrated
Ferroelectrics: An International Journal, 65:1, 57-67
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Integrated Ferroelectrics, 65: 5767, 2004

C Taylor & Francis Inc.
Copyright

ISSN: 1058-4587 print/ 1607-8489 online
DOI: 10.1080/10584580490892782

Ferroelectric Properties of
MBi4 Ti4 O15 (M=Sr, Pb, Ca) Thin Films
Downloaded by [Seoul National University] at 01:40 28 June 2013

WEN XU XIANYU,a, TAE-YOUNG WON,b and WAN IN LEEa,

a

Department of Chemistry and Center for Computational Electronics, Inha

University, Incheon 402-751, Korea
b
Department of Electrical Engineering and Center for Computational Electronics,
Inha University, Incheon 402-751, Korea
(Received May 1, 2004; In final form August 3, 2004)
Among the ferroelectric bismuth layered perovskites belonging to Aurivillius family, the MBi4 Ti4 O15 (MBT15, M = Sr, Ca, Pb) thin films have been fabricated by a
chemical solution deposition technique, and their structures and ferroelectric properties were investigated in this work. The SrBi4 Ti4 O15 (SBT15) film fabricated on
IrO2 presented the highest remanent polarization (Pr ) among the films in this series.
It demonstrated a saturated hysteresis loop at 5 V with Pr of 19 C/cm2 and coercive field (Ps ) of 116 kV/cm. The PbBi4 Ti4 O15 (PBT15) thin films were selectively
controlled in c-axis and off-c-axis orientation on Pt layer by adjusting the annealing condition. The off-c-axis oriented PbBi4 Ti4 O15 film demonstrated considerably
higher Pr (8.7 C/cm2 ) than that of c-axis oriented film (3.7 C/cm2 ). Regardless of
grain orientation, however, PBT15 films were not fatigued up to 1010 cycles under
9V application. The CaBi4 Ti4 O15 (CBT15) thin films were also produced on Pt and
IrO2 electrode, respectively, by controlling the annealing condition. The CBT15 film
on IrO2 presented higher Pr (10.8 C/cm2 ) than that of film (6.7 C/cm2 ) on Pt.
Keywords: Ferroelectric; layered perovskite; hysteresis loop; fatigue; thin film;
SrBi4 Ti4 O15 ; PbBi4 Ti4 O15 ; CaBi4 Ti4 O15

INTRODUCTION
Ever since the thin films of SrBi2 Ta2 O9 (SBT) has been developed by
Symetrix Corporation as a new ferroelectrics with an extended fatigue endurance, the layered perovskites belonging to Aurivillius family, denoted to
Corresponding
Present

author. E-mail: wanin@inha.ac.kr

address: Samsung Advanced Institute of Technology, P.O. Box 111, Suwon 440-

600, Korea
[393]/57

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W. X. XIANYU et al.

(Bi2 O2 )2+ (An1 Bn O3n+1 )2 where n = 2, 3, 4, 5, etc., have received great

attention [13]. These materials are constructed with stacking of n perovskite
units between Bi2 O2 2+ layers. Higher order structures may have larger remanent polarization, with the increased number of perovskite units generating
ferroelectric property. So far, high order structures, such as n = 4 or n = 5,
were often studied as bulk form, but they have scarcely been studied as thin
films [416].
In this work we focused on the ferroelectric properties of several MBT15
films belonging to n = 4 series. By varying the A-site elements to Sr, Pb
and Ca, we have produced SrBi4 Ti4 O15 (SBT15), PbBi4 Ti4 O15 (PBT15),
and CaBi4 Ti4 O15 (CBT15) films, and have tried to understand the general
trends of ferroelectric behaviors for this series. We have also provided an
optimized process for the derivation of MBT15 thin films. Their thin films
were fabricated by two different annealing processes, while Pt and IrO2 have
been utilized as substrate.

EXPERIMENTAL PROCEDURE
Preparation of SBT15, PBT15, and CBT15 Films
Acetate-based metal precursors were used in the preparation of chemical
solution for MBT15. For the preparation of sol-gel solution for SBT15,
first of all, bismuth acetate was dissolved in a mixed solution of acetic acid
and water, and the strontium acetate was then added. After the subsequent
addition of Ti(O-i-Pr)2 (AcAc)2 pre-dissolved in n-propanol to the mixture
of Bi and Sr precursor solution, the resultant solution was stirred for several
hours at room temperature. For the preparation of chemical solution for
PBT15, bismuth acetate was dissolved in a mixed solution of acetic acid
and water, and the Pb(OAc)2 3H2 O was then added. After the subsequent
addition of Ti(O-i Pr)2 (AcAc)2 stabilized in n-propanol, the resultant solution
was stirred for several hours. For the preparation of chemical solution for
PBT15, bismuth acetate was dissolved in a solution of acetic acid and water,
and calcium acetate was then added. After a subsequent addition of Ti(Oi
Pr)2 (AcAc)2 pre-dissolved in n-propanol, the resultant solution was stirred
for several hours. For all the MBT15 chemical solutions, the molar ratio of
M:Bi:Ti in the precursor solution was 1.0:4.2:4.0, respectively, and the final
concentration was adjusted to 0.40 M by adding extra n-propanol.
Two process methods were employed for the control of grain orientation
and structure in MBT15 films. First of all, the prepared solution was applied
to spin-coating at 2000 rpm, and the coated film was baked at 300 C for

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5 min. This coating and baking cycle was repeated four times, followed by a
final heat-treatment at 750 C for 30 min in an oxygen atmosphere (denoted
as Process I). Second, the films spin-coated at 2000 rpm was baked at 300 C
for 5 min, and subsequently annealed at 650 C for 5 min. After repeating this
procedure four times, the film was finally heat-treated at 750 C for 30 min in
an oxygen atmosphere (denoted as Process II). With above procedures, the
thickness of fabricated MBT15 films was controlled to 200250 nm. The
substrates used for the depositions of MBT15 films were Pt/TiO2 /SiO2 /Si
or IrO2 /TiO2 /SiO2 /Si, and the thickness of Pt or IrO2 layer was about
200 nm.

Characterization of MBT15 (M = Sr, Pb, Ca) Films

X-ray powder diffraction (XRD) patterns for the MBT15 thin films were obtained by using a Philips diffractometer (PW3020) with a monochromated
high intensity CuK radiation. The surface morphology of the MBT15 films
was observed by a field emission scanning electron microscope (FESEM, Hitachi S-4500). For the measurement of ferroelectric properties of the MBT15
films, a Pt top electrode (5 105 7 105 cm2 ) with a thickness of
100 nm was sputter deposited using a shadow mask. The hysteresis loops
and fatigue for the Pt/MBT15(200 nm)/Pt or Pt/MBT15(200 nm)/IrO2
capacitors prepared were measured using a standard precision Pro system
(Radiant Technology). Leakage currents of MBT15 capacitors were measured with a Keithley 238 high current source measure unit.

RESULTS AND DISCUSSION

Characterization of MBT15 (M = Sr, Pb, Ca) Thin Films
Two different annealing processes were applied for the formation of ferroelectric MBT15 (M = Sr, Pb, Ca) thin films, while Pt or IrO2 have been
utilized as electrode material. The XRD patterns shown in Fig. 1 indicate
that those films prepared at 750 C are basically pure layered perovskite
structures. The phase formation temperature does not seem to be greatly dependent on the A-site elements for this (Bi2 O2 )2+ (An1 Bn O3n+1 )2 (n = 4)
series. Also, their process temperature is relatively lower than that of n = 2
series, such as SrBi2 Ta2 O9 or SrBi2 Nb2 O9 , even though their structures are
much more complicated. We have also found that the orientation of grains
in the MBT15 films is greatly dependent on the annealing process and/or
electrode materials.

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FIGURE 1 XRD patterns for the MBT15 (M = Sr, Pb, Ca) thin films processed
at various conditions. (a) SBT15, (b) PBT15, and (c) CBT15 films. indicates pyrochlore phase.

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FIGURE 2 FESEM images of SBT15 thin films derived from Process I. Plan-view
image for the film deposited (a) on Pt electrode and (b) on IrO2 . Cross-sectional-view
images for the films (c) on Pt and (d) on IrO2 .

For SBT15 films, the grain structure of the film was not appreciably dependent on the annealing process, but considerably dependent on the electrode
material. That is, the SBT15 grains grown on IrO2 substrate by Process
I were relatively more randomly oriented and more crystallized, whereas
mostly c-axis oriented films were obtained on the Pt electrode, as indicated
in XRD patterns (Fig. 1(a)). FESEM image in Fig. 2(a) indicates that the
SBT15 films deposited on the Pt electrode look porous, that is, a kind of
pore structures were formed among the grains. The size of grains was about
150 nm. On the other hand, the grains of the SBT15 films grown on IrO2
looked much denser and more uniform in size, and virtually no voids were
found among the grains (Fig. 2(b)). Figure 2(c) and 2(d) show the crosssectional images of the SBT15 films deposited on Pt and IrO2 , respectively.
The SBT15 grains formed on IrO2 were grown with columnar structure and
much more crystallized.
For the PBT15 films, XRD patterns (Fig. 1(b)) are greatly dependent
on the annealing process. The grains of films prepared by Process I were
preferentially oriented to c-axis, whereas those obtained by Process II were
mainly off-c-axis oriented. In the latter films the main peaks were 119 and
200, whereas 008 and 0010 peaks, which were main peaks for the former

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W. X. XIANYU et al.

FIGURE 3 FESEM plan-view images of PBT15 thin films in (a) c-axis orientation
and (b) off-c-axis orientation.

films, were negligible. However, both films were in pure ferroelectric phase
without any impurity phases. Figure 3 shows the FESEM plan-view images
of PBT15 films obtained by two different annealing processes. For both
films the grains were highly crystallized, and no secondary phases or voids
were observed. Also the size and shape of grains were not much different.
For the c-axis oriented PBT15 film, however, most of grains stand with flat
sides turned upward, whereas the tilted grains are shown on the surface of
off-c-axis oriented film, as described in Fig. 3. It is deduced from the XRD
patterns and SEM images that the face of flat side in PBT15 grain is (00l)
plane.
CBT15 films were also prepared on Pt and IrO2 electrode by employing
two different annealing processes. For the films grown on Pt electrode, the
pyrochlore impurities were found, as shown in XRD patterns (Fig. 1(c)).
XRD data also indicate that the pyrochlore impurity was relatively reduced
by changing the annealing condition from Process I to Process II, while the
grain orientation was not appreciably changed. FESEM images in Fig. 4
indicate that the secondary phases between the ferroelectric grains were
considerably reduced by employing Process II. CBT15 films were also fabricated on the IrO2 electrode. As shown in XRD patterns in Fig. 1(c), most of
pyrochlore impurities were eliminated. Especially, the CBT15 films derived

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FIGURE 4 FESEM plan-view images of CBT15 thin films. (a) by Process I on Pt

electrode; (b) by Process II on Pt electrode; (c) by Process I on IrO2 electrode; (d)
by Process II on IrO2 electrode.

by Process II did not contain any pyrochlore phases. FESEM images shown
in Fig. 4(c) and 4(d) confirm this result obtained by XRD. The other effect of
IrO2 electrode in the formation of CBT films is to generate more off-c-axis
oriented grains. However, this effect is not so high as that of SBT15, even
though the overall trends in the formation of CBT15 and SBT15 films are
very close. We guess that the role of IrO2 layer is regarded as an excellent
diffusion barrier for Ti and Bi during the annealing at 750 C [11]. The suppression of diffusion would induce the enhancement of crystallization for
the SBT15 or CBT15 films.
Fabrication temperatures for MBT15 films are considerably lower than
that of SrBi2 Ta2 O9 (n = 2), but higher than that of Bi4 Ti3 O12 (n = 3). This
indicates that the Ti-containing layered perovskite structure can be formed at
relatively lower process temperature compared with Ta-containing structure.

Ferroelectric Properties of SBT15, PBT15 and CBT15 Films

The hysteresis behaviors and fatigue properties were analyzed for the SBT15,
PBT15, and CBT15 films derived from different annealing processes or
deposited in different bottom electrodes. Figure 5(a) shows the hysteresis
loops for the SBT15 films derived from Process I on Pt and IrO2 , respectively.

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FIGURE 5 Ferroelectric hysteresis loops for MBT15 films. (a) SBT15 films prepared by Process I on Pt or IrO2 electrodes; (b) PBT15 films prepared by Process I or
II on Pt electrode; (c) CBT15 films fabricated on Pt or IrO2 electrodes by Process II.

The SBT15 films on Pt showed relatively inferior ferroelectric properties.

The hysteresis loop was not saturated at 5 V, and the remanent polarization
(Pr ) was only 5.5 C/cm2 at this voltage application. On the other hand,
for the SBT15 film grown on IrO2 , Pr was determined to 19 C/cm2
at 5 V, and the difference between spontaneous polarization (Ps ) and Pr
was only 6 C/cm2 . However, the Ec was still very high (116 kV/cm or
2.9 V). Figure 5(b) shows the hysteresis loops for the PBT15 films deposited
on Pt layer derived from different annealing processes. As expected, the
off-c-axis oriented films obtained by Process II demonstrated considerably
higher polarizations. At 11 V application, the remanent polarization (Pr )
was 8.7 C/cm2 , whereas that of c-axis oriented film was only 3.7 C/cm2 .
However, Ec was as high as 120 kV/cm (or 3.0 V) for both films. Figure
5(c) shows the hysteresis loops for two CBT15 films, prepared by Process
II, deposited on Pt and IrO2 layer. The films grown on IrO2 layer produce
higher polarizations. At 10 V application, the remanent polarization (Pr )
of CBT15 films on IrO2 was 10.8 C/cm2 , while those on Pt were only
6.7 C/cm2 . However, Ec was as high as 120 140 kV/cm (or 3.0 3.5 V)
for both films. This high coercive voltage value is very close to that of other
materials in MBT15 series. Thus we believe that the high coercive field is

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FIGURE 6 Fatigue properties of MBT15 films. (a) SBT15 and CBT15 films on
IrO2 electrode derived from Process I and II, respectively. (b) PBT15 films in c-axis
(by Process I) and off-c-axis orientation (by Process II) deposited on Pt electrode.

an inherent property of MBT15 series. It is deduced that the change of M(II)

ions does not appreciably influence on the structural environment near the
TiO6 octahedra, considering that Ec represents the barrier energy for the
movement of Ti(IV) ion under an applied electric field.
Figure 6 indicates the fatigue endurances for the SBT15, PBT15, and
CBT15 films. That is, the remanent polarizations (Pr and - Pr ) were plotted
as a function of switching cycles. With applied 5 V step pulse in 1 MHz
frequency the remanent polarization of SBT15 film, derived from Process I,
on IrO2 layer was not appreciably changed up to 1010 switching cycles. Also
the remanent polarization of CBT15 film (by Process II) deposited on IrO2
layer showed no change at all with applied voltage of 8 V up to 1010 cycles.
For PBT15 films grown on Pt layer, no appreciable fatigue was observed
regardless of grain orientation with the switching voltage of 9 V.
The leakage current densities of Pt/SBT15/Pt and Pt/SBT15/IrO2 capacitors at 5 V were 1 107 C/cm2 and 2 105 C/cm2 , respectively. It is
believed that the higher leakage current level of SBT15 films on IrO2 layer
originates from low Schottky barrier between SBT15 and metal oxide electrode [16].
Generally, the high coercive field of MBT15 is not favorable for ordinary
ferroelectric random access memory (FRAM) applications. However, the
high Pr and large Ec might be important properties for the design of new
memory devices. For instance, it may be used as a virtual ROM (read only

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memory). That is, if both of ferroelectric SrBi2 Ta2 O9 and SBT15 capacitors
were fabricated on the same FRAM memory chip, only the SrBi2 Ta2 O9
capacitors could be switched by the application of 2 3 V. About 5 V would
be necessary to switch the SBT15 capacitors. More efforts and attentions
are required for the thin films of MBT15 series.

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CONCLUSIONS
For the SBT15 and CBT15 films, the grains were more crystallized and
rather randomly oriented on IrO2 electrode, whereas the grains were mostly
c-axis oriented on Pt electrode. Thus the SBT15 and CBT15 films grown
on IrO2 electrode show higher Pr. The grains of PBT films can selectively
be controlled to c-axis or off-c-axis orientation on Pt layer by selecting
different annealing processes. The SBT15 and CBT15 thin film capacitors
demonstrate relatively higher remanent polarization than PBT15, while the
coercive field (120 kV/cm) is not appreciably different. Relatively high Pr
and large Ec are considered to be an inherent ferroelectric property for the
layered perovskites in this series (n = 4).

ACKNOWLEDGMENT
This work has been supported by the Ministry of Information & Communication of Korea (Support Project of University ITRC Program supervised
by KIPA).

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