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Integrated Ferroelectrics: An International Journal
Integrated Ferroelectrics: An International Journal
Integrated Ferroelectrics: An International Journal
Integrated Ferroelectrics: An
International Journal
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Ferroelectric Properties of
MBi4Ti4O15 (M = Sr, Pb, Ca) Thin
Films
a
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
To link to this article: http://dx.doi.org/10.1080/10584580490892782
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Ferroelectric Properties of
MBi4 Ti4 O15 (M=Sr, Pb, Ca) Thin Films
Downloaded by [Seoul National University] at 01:40 28 June 2013
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
600, Korea
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W. X. XIANYU et al.
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.
W. X. XIANYU et al.
60/[396]
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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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.
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W. X. XIANYU et al.
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.
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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.
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W. X. XIANYU et al.
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.
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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