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Yukihisa OKADA Ichiro KOIWA Kinya ASHIKAGA Katsuaki KAIFU
We prepared alkoxide solutions to fabricate SrBi2Ta2O9 (SBT) ferroelectric capacitors with IrO2 electrodes. In this process, to minimize excess bismuth, the Sr : Bi : Ta mole ratio was kept at 0. 9 : 2. 1 : 2. 0, i. e. , nearly stoichiometric. Three types of solution - mixed-only (MIX), complexed (COMP), and hydrolyzed (HYD) - were used. The HYD capacitor had low absolute leakage current, 10-7 A/cm2 order, and good saturation properties to 6 V. When voltage was applied to each capacitor at 2 to 6 V, MIX and COMP capacitors showed only partial hysteresis loops due to a high leakage current, reflecting the I-V characteristics. These results are probably due to film density caused by metaloxane network bonding. A fatigue endurance test was conducted using cycling of polarization switching at 6 V using the HYD capacitor with IrO2 electrodes. Slight changes were, however, observed in hysteresis loop configuration, but good hysteresis properties were kept up to 1. 04 1012 cycles. We compared SBT ferroelectric thin films fabricated with Pt electrodes and with IrO2 electrodes. Scarcely any difference due to SBT in the XRD pattern was seen, depending on the substrate material. We found that the use of IrO2 electrodes had the effect of decreasing the crystallization temperature. On Pt and IrO2 electrodes, the two films have surface morphology quite different from that of the rod-like structure wellknown for SBT films prepared using a metal 2-ethylhexanate solution. Their surfaces show a similar morphology with relatively large, closely packed grains. A comparison of the I-V characteristics after reannealing showed that the capacitor with IrO2 electrodes had a higher leakage current than that with Pt electrodes. The leakage current was probably due to the density of the film and interface between the SBT film and electrodes.
Ichiro KOIWA Takao KANEHARA Juro MITA Tetsuya OSAKA Sachiko ONO Akira SAKAKIBARA Tomonori SEKI
The crystallization process of Sr0. 7Bi2. 3Ta2O9 (SBT) ferroelectric thin films with different crystal orientations formed by chemical liquid deposition using an alkoxide precursor was investigated. One film showed strong c-axis orientation (a-type film), while another shows scarcely any c-axis orientation (b-type film). We report that the crystallization process was the same even when crystal orientation differed. Thin films first change from amorphous to fluorite fine grains; the fluorite grains then change to bismuth layer-structure grains. The different orientation of the SBT films is not caused by different crystallization process. Both SBT films with different crystal orientations consist of fine fluorite grains after 650 heat-treatment. Their leakage current density characteristics differ, however. The leakage current density of the a-type film was independent of the electric field, and showed a low value of 10-8 A/cm2. The leakage current density of the b-type film, however, was dependent on the electric field, and increased continuously with the increasing electric field. After 700 heat-treatment, both films consist of large grains with bismuth layer-structure and fine fluorite grains. The matrix of both films contains large grains with bismuth layer-structure that determines the leakage current density characteristics. Since the fluorite grain size after a 700 heat-treatment is the same as that after 650 heat-treatment, nucleation is predominant at the structural phase boundary from amorphous to fluorite. The bismuth layer-structure grains are large and single-crystal grains after both a 700 and 800 heat-treatment. Increased grain size predominates at the structural phase boundary from fluorite to bismuth layer-structure grains. Clearly, ferroelectric SBT films with bismuth layer-structure are crystallized in two steps, each having a different predominant crystal growth mechanism.
Ichiro KOIWA Takao KANEHARA Juro MITA
Protective layers in AC plasma display panels (PDP) are usually formed by vacuum vapor deposition or sputtering. It is important to study the protective MgO layer by means of screen-printing for fabricating a large size PDP and reducing its cost. With the objectives of enlarging the panel size and reducing cost, we studied the fabrication of the protective MgO layer by means of screen-printing. In this study, we succeeded in lowering the drive voltage by using a MgO powder prepared by vapor phase oxidation instead of conventional decomposition of the magnesium salt. Further, by adding a MgO liquid binder, we attained a good luminous efficiency twice as high as that attained with a sputtered protective layer and lowered the drive voltage. When this protective layer was combined with He-Xe gas enclosure, the half-life of luminance was 5,000 hours. With Ne-Xe gas, the luminance deteriorated no more than 40% after 5,000 hours. A screen-printed protective MgO layer containing no MgO liquid binder showed a short half-life of 800 hours even with the use of Ne-Xe gas. In this case, the discharge voltage changed greatly and some cells did not discharge. It is concluded that the combination of an ultrafine MgO powder prepared by vapor phase oxidation and a MgO liquid binder can clear the way for making AC PDPs with a long lifetime, high efficiency, and low voltage a practical reality.
Ichiro KOIWA Takao KANEHARA Juro MITA
We studied the application of precursor solutions that can be fired into oxides to form a protective layer for AC-type Plasma Display Panel (AC-PDP). Our study of alkoxide and metallic soap as MgO precursors revealed that the crystallinity of MgO films depends on the starting substance. Since the electric discharge characteristics of a panel and the lamination effect of the protective layer depend on precursors, it was confirmed that binders having higher crystallinity provide better characteristics. Our study revealed that a compound-oxide film has high crystallinity. The application of a Ba0.6Sr0.4Gd2O4 formation solution to a binder and the application of a Sr0.6Mg0.4Gd2O4 formation solution to a protective layer both are seemed promising We also found that a double-layer film, made by forming a protective layer of fine MgO powder and a Ba0.6Sr0.4Gd2O4 binder, on top of a protective layer made of fine MgO powder and a MgO binder, provides a luminous efficiency 5.3 times higher than that of sputtered MgO film which is one of candidates for the large panel, and the conventional electron beam evaporation is not suitable for the large panel. We further found that a triple-layer protective film made by forming a thin film of Sr0.6Mg0.4Gd2O4 provides low voltages of 1 V in firing voltage (Vf) and 35 V in sustaining voltage (Vs) compared to the double-layer film and provides a luminous efficiency 5.5 times higher than that of sputtered MgO film. A life test revealed the triple-layer film in particular providing a useful life of more than 10,000 hours. From these findings, we concluded that the compound-oxides which is composed of alkaline-earth-metal and rare-earth-element could be applied effectively to a protective layer for AC-PDP.
Tetsuya OSAKA Sachiko ONO Akira SAKAKIBARA Ichiro KOIWA
Using transmission electron microscopy (TEM), we studied structural defects in a Sr0. 7Bi2. 3Ta2O9 (SBT) thin film to be used for ferroelectric memory devices. We examined the effects of the substrate, crystal continuity, and dislocations in crystals as major causes of defects. For this study, we used an SBT thin film grown from an alkoxide solution. Since crystal growth was hardly influenced by the substrate, the substrate had little influence on the occurrence of defects resulted in misfit of lattice constant. Regions of partially low crystal continuity were observed in the SBT thin film. In these regions, the orientation was still uniform, but the continuity of the crystal grain was low because of the defects. In addition, variation in contrast was observed in the crystals, however, no obvious variation in chemical composition was found in this region of varying contrast. Therefore, the contrast variation is considered to be attributed to the dislocation. Such a dislocation was found to be occurred in the direction of the (2010) plane in many instances. The defects in the SBT film were also confirmed by the TEM observation.
Ichiro KOIWA Yukihisa OKADA Juro MITA
Sr0. 7Bi2. 3Ta2O9(SBT) films are drawing attention as fatigue-free materials. We prepared an SBT film containing discontinuous crystals in the Bi-layered compound using a misted deposition method. In comparison to films prepared by the spin-on method, leakage current was low and spontaneous polarization is high but saturation performance was low. The low saturation performance seems attributable to the inclusion of discontinuous crystals in the Bi-layered compound, while the low leakage current may be explained by the films smaller, denser particles, which form a film without voids, resulting in higher uniformity. The misted deposition method has advantages of finer grain size and higher uniformity.