Photocatalytic Property and Electronic Structure of Lanthanide-based Oxysulfides

Lanthanide-based oxysulfides and sulfide, LnTaO_3.5S_0.5, Ln₁₀OS₁₄ (Ln = La, Pr, Nd, Sm) and La₄In₅S₁₃, were successively synthesized by sulfurization in a flowing H₂S. The sulfurization decreased the band-gap energies from >4 eV to <3eV, because of the formation of occupied S3p orbitals on the top of valence band. In accordance with the small band gap, the H₂ evolution from a 0.01 M Na₂S and 0.01 M Na₂SO₃ solution system was observed under irradiation of light up to >500 nm. The rate of H₂ evolution under light irradiation of >500 nm increased in the order of Ni/LaTaO_3.5S_0.5 < Ru/La₁₀OS₁₄ < Pt/La₄In₅S₁₃.     

InxGa1−xAs ohmic contacts to n-type GaAs with a tungsten nitride barrier

Significant reduction of the contact resistance of In_0.7Ga_0.3As/Ni/W contacts (which were previously developed by sputtering in our laboratory) was achieved by depositing a W₂N barrier layer between the Ni layer and W layer. The In_0.7Ga_0.3 As/Ni/W₂N/W contact prepared by the radio-frequency sputtering technique showed the lowest contact resistance of 0.2 Ωmm after annealing at 550°C for 10 s. This contact also provided a smooth surface, good reproducibility, and excellent thermal stability at 400°C. The polycrystalline W₂N layer was found to suppress the In diffusion to the contact surface, leading to improvement of the surface morphology and an increase in the total area of the In_xGa−As between metal and the GaAs substrate. These improvements are believed to reduce the contact resistance.     

A video DSP with a macroblock-level-pipeline and a SIMD typevector-pipeline architecture for MPEG2 CODEC

A video DSP with macroblock-level-pipeline and a SIMD type vector-pipeline architecture (VDSP2) has been developed, using 0.5 μm triple-layer-metal CMOS technology. This 17.00 mm×15.00 mm chip consists of 2.5 M transistors, and operates at 100 MHz. The real-time encoder and decoder specified in the MPEG2 main profile at the main level can be realized with two VDSP2's and a motion estimation (ME) unit, and one VDSP2 respectively, at an 80 MHz clock rate, with a total power dissipation of 4.2 W at 3.3 V     

NiCoFe/C cathode electrocatalysts for direct ethanol fuel cells

A direct ethanol fuel cell (DEFC), which is less prone to ethanol crossover, is reported. The cell consists of PtRu/C catalyst as the anode, Nafion^® 117 membrane, and Ni–Co–Fe (NCF) composite catalyst as the cathode. The NCF catalyst was synthesized by mixing Ni, Co, and Fe complexes into a polymer matrix (melamine-formaldehyde resins), followed by heating the mixture at 800 °C under inert atmosphere. TEM and EDX experiments suggest that the NCF catalyst has alloy structures of Ni, Co and Fe. The catalytic activity of the NCF catalyst for the oxygen reduction reaction (ORR) was compared with that of commercially available Pt/C (CAP) catalyst at different ethanol concentrations. The decrease in open circuit voltage (V_oc) of the DEFC equipped with the NCF catalysts was less than that of CAP catalyst at higher ethanol concentrations. The NCF catalyst was less prone to ethanol oxidation at cathode even when ethanol crossover occurred through the Nafion^®117 film, which prevents voltage drop at the cathode. However, the CAP catalyst did oxidize ethanol at the cathode and caused a decrease in voltage at higher ethanol concentrations.     

Fabrication of damascene Cu wirings using solid acidic catalyst

The copper damascene process is one of the most promising technologies for fabricating Cu wirings for electronic devices such as LSIs. In this research, the fabrication of damascene Cu wirings was conducted using solid acidic catalyst. When a Cu-plated wafer, whose oxide is a basic oxide is dipped into a mixture of oxidizing solution and acidic solution, surface atoms are ionized and etched off into the solution. However, because conventional nonelectrolytic etching does not have a reference surface, it is difficult to utilize for planarization. Therefore, a new nonelectrolytic machining method using a cation-exchange fabric instead of an acidic solution was developed. To be more precise, the planarization of a Cu-plated wafer was carried out by rubbing with the cation-exchange fabric in ozone water. Basically, this method exploits chemical reactions so that the physical properties of the workpiece surface are not deteriorated. Furthermore, this method uses no chemicals except for ozone water, which easily dissociates into water and oxygen molecules; thus, this method is a low-cost, environmentally friendly process. In this paper, as a preliminary experiment, the nonelectrolytic etching of a Cu sample using solutions of O₃ and CO₂ was carried out to inspect the dependence of the etching rate on [O₃] and [H⁺]. The results indicate that the etching rate increased as [O₃] and [H⁺] increased. When [H⁺] was high relative to [O₃], a smooth etch-pit-free surface was achieved. Next, nonelectrolytic etching using a cation-exchange fabric was carried out, and properties similar to those in the case of etching using solutions were obtained. Finally, damascene Cu wirings were fabricated using ozone water and a cation-exchange catalyst.     

Thermodynamic study of the phase equilibria in the Sn−Ti−Zn ternary system

The Sn−Ti−Zn ternary phase diagram has been constructed using the CALPHAD technique. The Ti−Zn binary system phase boundaries were determined using differential scanning calorimetry and the solid-liquid diffusion couples method. In addition, the formation energy of some stoichiometric compounds was obtained using first-principle band energy calculations. For the ternary system, some alloys were prepared by equilibration at 600 or 700 °C, and the compositions of the precipitates were analyzed using electron probe microanalysis. Thermodynamic assessment of the Ti−Zn and Sn−Ti−Zn systems was performed based on the experimental information and by adopting reported values of the thermodynamic properties of the Sn−Zn and Sn−Ti binary systems. Microstructural observation showed that Sn₃Ti₅Zn₁₂ exists in the ternary system. Seven types of invariant reaction on the Sn-rich liquidus surface of the ternary system are predicted by the phase diagram calculations. The ternary eutectic point falls at 0,0009 mass% Ti and 8.69 mass% Zn, at T=192.40°C, which is slightly lower than the calculated eutectic point of Sn−Zn binary alloy (T=192.41°C). Based on these results, a nonequilibrium solidification process using the Scheil model was simulated. This paper was presented at the International Symposium on User Aspects of Phase Diagrams, Materials Solutions Conference and Exposition, Columbus, Ohio, 18–20 October, 2004.     

Local disturbances preceding a running crack front in a viscoelastic solid

The local disturbances ahead of a running crack front in a viscoelastic solid were measured through noncontact electro-optical tools. It was observed that the very high local strain rate up to 200/sec exists even in the present quasistatic loading case. It may be concluded that the running crack propagation velocities, not the conventional average strain rates ranging from about 10^?4/sec to 10^?2/sec, govern the local disturbances, as the crack propagation velocities always exceed 200m/sec for both average strain rates, while the local strain rates observed do not show much differences between both average strain rate cases.     

Novel synthesis of microcrystalline titanium(IV) oxide having high thermal stability and ultra-high photocatalytic activity: thermal decomposition of titanium(IV) alkoxide in organic solvents

Thermal decomposition of titanium(IV) tetra-tert-butoxide (TTB) in inert organic solvents at 573 K yielded microcrystalline anatase (titanium(IV) oxide, TiO₂) powders with a crystallite size of ca. 9 nm and a surface area of <100 m² g^-1. Primary and secondary alkoxides of titanium(IV), however, were not decomposed under similar conditions, indicating that the thermal stability of C-O bonds in the alkoxides was a decisive factor for their decomposition. The TiO₂ prepared from TTB by this manner was thermally stable upon calcination in air and retained high surface area of ca. 100 m² g^-1 even after calcination at 823 K. The as-prepared TiO₂ powders, without calcination, exhibited much higher rate of carbon dioxide formation than any other active photocatalysts such as Degussa P-25 and Ishihara ST-01 in the photocatalytic mineralization of acetic acid in aerated aqueous solutions. The higher activity of the present TiO₂ photocatalysts is attributed to both high crystallinity and large surface of the present product. The calcination of the as-prepared TiO₂ in air reduced the photocatalytic activity, but it was still higher than the other commercially available TiO₂'s. This revised version was published online in July 2006 with corrections to the Cover Date.     

A manufacturing XML schema definition and its application to a data management system on the shop floor

Digitization for sharing knowledge on the shop floor in the machinery industry has been given much attention recently. To help engineers use digitization practically and efficiently, this paper proposes a method based on manufacturing case data that has a direct relation to manufacturing operations. The data are represented in XML schema, as it can be easily applied to Web-based systems on the shop floor. The definitions were made for eight manufacturing methods including machining and welding. The derived definitions consist of four divisions of metadata, work-piece, process and evaluation. Three divisions except for the “process” division are common to the manufacturing methods. The average number of elements for a manufacturing method is about 200. The represented schema is also used to convey knowledge such as operation standards and manufacturing troubleshooting on the shop floor. Using the definitions, a data management system is developed. It is a Web-based Q&A system, in which the engineers specify the manufacturing case data mainly by selecting from the candidates. Then, the system fills in the blank portions and/or shows messages to help complete the case data. The proposed method is evaluated through practical scenarios of arc welding and machining.     

Determination of all elastic constants of orthotropic plate specimens from group velocity data

This paper presents a novel method of nondestructively determining all nine elastic constants of fiber-reinforced orthotropic plate specimens. Group velocities of bulk quasi-longitudinal (QL), pure transverse (PT), and surface skimming pseudo-longitudinal modes are measured in glass-fiber (GF) and carbon-fiber (CF) reinforced Poly Ether Ether Ketone (PEEK) specimens by a point-source/point-receiver (PS/PR) technique. First, the pure index longitudinal moduliC ₁₁,C ₂₂, andC ₃₃, are obtained from the longitudinal (L) group velocities measured in three principal directions. Next, the pure index shear moduli,C ₄₄,C ₅₅, andC ₆₆, are determined by measuring the shear horizontally (SH) polarized PT group velocities in the symmetry planes. Finally, the mixed index elastic constantsC _ij (i j) are calculated from QL group velocities measured in the symmetry planes and using analytic formulas.