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To cite this article: MASAKI YAMAGUCHI , ASA YAMAMOTO & YOICHIRO MASUDA (2006)
THERMAL STABILITY OF PLATINUM BOTTOM ELECTRODE FOR BISMUTH TITANATE THIN FILMS,
Integrated Ferroelectrics, 79:1, 235-243, DOI: 10.1080/10584580600659894
Article views: 14
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Department of Electrical Engineering, Faculty of Engineering, Shibaura Institute
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ABSTRACT
Platinum (Pt) films were widely used as an electrode in device applications of ferro-
electric thin films. However, the surface morphology and microstructure were deformed
during ferroelectric layer preparation. In this study, consequently, thermal stability of
Pt bottom electrode for ferroelectric bismuth titanate (Bi4 Ti3 O12 ) thin film fabrication
was investigated. The deposited Pt film with thick Ti adhesion layer exhibits the differ-
ent aspect areas, which contain Ti and/or Si element diffused into Pt grain boundaries.
Therefore, the adhesion layer thickness was thinned as much as possible. Compressive
stress was relaxed by hillock formation in plastic deformation region. Therefore, It is
important to maintain the tensile stress from the substrate during the ferroelectric thin
film formation. Bi4 Ti3 O12 thin films deposited on stabilized Pt bottom electrode, exhibit
superior dielectric properties. The deposited film exhibited ferroelectric properties. The
polarization value at zero field of the strongly c-axis oriented one was 1.75 µC/cm2 . We
think that the choke of silicon and/or titanium elements, diffused into Pt electrode, were
effective against suppress hillock formation.
Keywords: Platinum bottom electrode; thermal stability; tensile stress; bismuth titanate
INTRODUCTION
[1645]/235
236/[1646] M. Yamaguchi et al.
well known has been extensively investigated, because of its excellent phys-
ical properties [2, 3]. Nevertheless, the environmentally hazardous chemistry
of PZT may ultimately prevent it from being used in many applications. As
candidate materials for lead-free ferroelectrics, bismuth titanate (Bi4 Ti3 O12 )
and related materials has been reported. These materials show lower dielectric
constant, large remanent poralization, and good fatigue characteristics. How-
ever, there have a few disadvantages, such as relatively highly crystallized
temperature [4, 5].
Platinum (Pt) films were widely used as a bottom electrode in device ap-
plications of ferroelectric thin films, because of its stability in high-temperature
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EXPERIMENTAL PROCEDURES
Table 1
Typical sputtering conditions of Pt thin films
substrates. The precursor films were dried at 150 degree Celsius in air at-
mosphere on a preheated hot plate for 5 min to remove residual solvent.
Next, the films were pre-annealed for 10 min at 550 degree Celsius in air.
Conventional furnace annealing was used to crystallize at various tempera-
tures, and the heating and cooling rates were fixed at 5 degree Celsius per
minute.
The crystal structure of the deposited films was investigated using X-ray
diffraction (XRD) pattern measurements. The thickness and surface morphol-
ogy of deposited films were observed using a scanning electron microscope
(SEM). To measure the electrical properties, Ag electrodes of 100 µm in di-
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ameter were formed on the film surface. Leakage current characteristics of the
films were measured using a pico-ampere (pA) meter/voltage source, and ferro-
electrical properties of the films were investigated using Sawyer-Tower circuit
applied sinusoidal wave at 1 kHz.
When the Pt bottom electrode fabricated directly on SiO2 layers, these films
were peeling off the substrate, because of very weak adhesion. Therefore, Ti or
TiO2 ultra-thin films were commonly used as glue layer. The surface images of
the Pt films with TiO2 adhesion layer were shown in Fig. 1. From the figures,
it is indicated that the fabricated Pt film exhibits accuracy and mirror smooth
surface. Although, when the Ti adhesion layer thickness was increases, the
different aspect areas were generated. Back-scattered electron image observed
similar tendency. Different aspect areas were composed of a light element.
Generally, the Pt films exhibits columnar structures, therefore, we think that
the Ti and Si atoms were diffused into Pt grain boundaries. Consequently, the
adhesion layer is thinned as much as possible.
Figure 2 shows the XRD patterns of Pt films fabricated at various substrate
temperatures. The deposited films were predominantly (111)-orientation, and
the diffraction angle of as-deposited films was monotonously augments by
increased with substrate temperatures. By the contrast, the diffraction angle of
annealed films was not depends on the substrate temperature.
Figure 3 shows the d-space of 111 plane calculated from X-ray diffraction
angle at various substrate temperatures without annealing treatment at 850 de-
gree Celsius in air ambient. The d-space was decreased with the increase of
the substrate temperatures, and was asymptotic in approximately 0.2258 nm.
This indicates that the as-deposited Pt film at lower substrate temperatures had
a weak compressive stress from substrates. The d-space of the films fabricated
at various crystallized temperature with annealing process were also drawn.
However, the annealed films had a weak expansion stress from substrate, and
of the d-space were not depended on substrate temperatures.
238/[1648] M. Yamaguchi et al.
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Figure 1. Surface images of Pt films with Ti adhesion layer thickness of (a) 4 nm,
(b) 8 nm, and Back scattering electron image of Pt films with 8 nm adhesion layer.
SUMMARY
Figure 2. (Continued)
Figure 5. Leakage current characteristics of Bi4 Ti3 O12 thin films deposited on thermally
stabilized and un-stabilized Pt bottom electrode.
242/[1652] M. Yamaguchi et al.
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Figure 6. Typical D-E hysteresis loops of deposited Bi4 Ti3 O12 thin films.
The d-space of 111 planes, calculated from X-ray diffraction angle, without
annealing treatment was decreased with the increase of the substrate tempera-
tures. Wherever, the annealed films had a weak expansion stress from substrate,
and of the d-space were not depended on substrate temperatures. Compressive
stress was relaxed by hillock formation in plastic deformation region. Therefore,
It is important to maintain the tensile stress from the substrate during the fer-
roelectric thin film formation.
Ferroelectric Bi4 Ti3 O12 thin films deposited on stabilized Pt bottom elec-
trode, exhibit superior dielectric properties. We think that the choke of silicon
and/or titanium elements, diffused into Pt electrode, were effective against sup-
press hillock formation.
ACKNOWLEDGMENT
This work was financially supported in part by the Foundation for Promotion
of Material Science and Technology of Japan, and Grant-in-Aid for Scientific
Research from the Ministry of Education, Culture, Sports, Science and Tech-
nology, and the Project Research of Shibaura Institute of Technology.
The authors would like to Prof. T. Shiosaki and Prof. S. Okamura for the
in-situ XRD measurement of Pt films, and Dr. T. Kijima and Mr. Y. Hamada
for measuring electrical properties of Bi4 Ti3 O12 films. The authors also thank
Mr. Y. Sato for helping with the experiment.
REFERENCES