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.     

Living cationic polymerization of vinyl monomers by organoaluminum halides

Summary Well-defined living polymers of isobutyl vinyl ether were obtained in the polymerization initiated with ethylaluminum dichloride (EtAlCl₂) in conjunction with a stoichiometric excess of dioxane (5–10 vol%) in n-hexane at 0°C. Under these conditions, the number-average molecular weight of the polymers increased in direct proportion to monomer conversion, while the molecular weight distribution stayed narrow (M_w/M_n = 1.1–1.25). In sharp contrast, the EtAlCl₂-initiated polymerization in the absence of dioxane led to non-living polymers with a broad molecular weight distribution. It was concluded that the propagating carbocation is stabilized not by the counteranion but by an externally added basic compound (dioxane) that strongly interacts with the active end.     

Buoyancy engine developed for underwater gliders

A buoyancy engine with a swashplate-type axial piston pump was developed. Its oil extrusion and drawing properties under high hydraulic pressure were evaluated. This buoyancy engine is now installed in an underwater glider that will achieve long-term monitoring of ocean environments up to 2100 m depth in a designated area with lower operational costs. This bidirectionally functioning pump can control the amount of oil in extrusion and draw operations. When drawing oil under high pressure, the hydraulic pump and the electric motor, respectively, act as a hydraulic motor and an electric generator. The generated electric power is absorbed by a damping resistor. The oil-drawing and extrusion properties were measured using a large hyperbaric chamber that is able to produce an almost identical environment to that of actual operations. Results confirmed stable oil extrusion operations up to 21 MPa. Regarding oil-drawing properties, although it was measured only up to 10 MPa in the hyperbaric chamber, it can be inferred that the system can draw the oil and can control the buoyancy precisely up to 21 MPa by replacing the two-way ball valve with an electromagnetic latching solenoid valve.     

Using selective precipitant for uranyl ions — Fundamental studies for evaluating the precipitant performance

We have developed a simple reprocessing process for spent FBR fuels using N-cyclohexyl-2-pyrrolidone (NCP) which has selective precipitation ability for UO₂²⁺ ions. It was confirmed that NCP has sufficient precipitation ability for UO₂²⁺ ions, decontamination capability (separation of UO₂²⁺ from simulated fission products), and resistance to γ-ray radiation in nitric acid solutions. These findings indicate that NCP is applicable to our reprocessing process. We have also evaluated performances of other precipitants such as N-n-propyl-2-pyrrolidone (NProP), N-n-butyl-2-pyrrolidone (NBP), and N-n-butyl-2-pyridone (NBPyr). It was found that higher decontamination factors (DFs) are obtained by using NProP and NBP. This can be interpreted that the hydrophobicity of NProP and NBP is lower than that of NCP. Furthermore, we have obtained an experimental result that the resistance of NBPyr to γ-ray radiation is superior to that of NCP.     

Calculations from texture of earing in deep drawing for FCC metal sheets

The present study aims to calculate the height at each peripheral position of a cup drawn from polycrystalline sheet using texture data. In the analytical treatment the polycrystalline sheet is simplified to an aggregation of many single crystals with various orientations, and the texture is represented by a three-dimensional crystallite orientation distribution function. The ear is calculated crystallographically using the orientation distribution function as a volume fraction of a certain oriented crystal. In the experiment aluminium, Al-Mg alloy and copper sheets which are treated under various conditions of cold rolling and heat treatment are used. The average textures over the thicknesses of the sheets are measured by the Schulz reflection method. The calculated ears based on the measured textures are compared with the experimental ears for each material. The results show that all the principal features of the ears of drawn cups are predicted satisfactorily by the calculation.     

Fabrication of optics by use of plasma chemical vaporization machining with a pipe electrode

We figure optical surfaces by plasma chemical vaporization machining (CVM) with a pipe electrode, in which an rf plasma generated at the electrode tip under approximately atmospheric pressure moves over the surfaces. We propose a shaping method in which the movement of plasma on the surfaces can be determined. Flat and aspheric surfaces are successfully figured with the desired peak-to-valley shape accuracy of 0.1 microm. The root-mean-square roughness of the resultant surfaces is at the subnanometer level. These results confirm that the plasma CVM and the shaping method have the capability to fabricate optics with high accuracy.