Isao Masada

Melting and crystallization behaviors of injection‐molded polypropylene

The melting and crystallization behaviors of the skin layer in an injection-molded isotactic polypropylene (PP) have been studied, mainly in comparison with those of the core layer and subsidiarily in comparison with those of a compression-molded PP and a nucleator (talc)–added PP. The skin layer contains about 5% crystals, which have a high melting point of up to 184°C. They thermally vanish by melting once. The subsequent melting history will scarcely affect the melting behaviors. On the other hand, crystallization behaviors are strongly affected by the melting history. The skin layer crystallizes in a wide temperature range at high temperature. This tendency weakens with increasing melting temperature, approaching a constant and that of the core layer above 230°C, which suggests that the memory effect of the residual structure of PP vanishes by melting above 230°C. In explaining these experimental results, it is assumed that the residual structure substance is a melt orientation of molecular chains that works as crystallization nuclei and that the vanishing of the residual structure is nothing but a relaxation of the melt orientation.

High-index fluoride materials for 193-nm immersion lithography

BaLiF3 single crystal has been studied as the lens material for the candidate of the next generation high index immersion lithography system. Although the refractive index of BaLiF3 is 1.64 at 193nm which is not sufficient for the requirement, other optical properties such as 193nm transparency and laser durability might fulfill the requirement, and intrinsic birefringence is relatively lower than other candidate materials. It is estimated that the cause of scattering in the BaLiF3 crystal is aggregation of excess LiF component. The special annealing process to eliminate excess LiF component was applied to improve the transparency. The internal transparency was improved to more than 97%/cm by optimizing growth conditions and annealing conditions.

Microporous polypropylene fibers containing fine particles of poly(styrene-co-divinylbenzene) or poly(glycidylmethacrylate-co-divinylbenzene)

Styrene-divinylbenzene or glycidylmethacrylate-divinyl-benzene were copolymerized in powdery polypropylene suspended in water and the resultant polymer composites were blended with a definite amount of polypropylene. The products consisted of polypropylene and the fine particles of the copolymer, which were uniformly dispersed in polypropylene phase. These products were melt-spun to prepare polypropylene fibers containing the fine particles and then the fibers were stretched to make the fibers microporous. Some properties were estimated: porosity, 1.6–19.7%; average pore size, 0.004–0.009 µm; and specific surface, 9–137 m2/g.

Fluoride single crystals for the next generation lithography

BaLiF3 single crystal has been studied as the candidate for the last lens material of the next generation high index immersion lithography system. Although the refractive index of BaLiF3 is 1.64 at 193nm which is not sufficient for the requirement, other optical properties such as 193nm transparency and laser durability fulfill the requirement. It is estimated that the cause of both high SBR part and inhomogeneity of refractive index of BaLiF3 seems to present along the faces of slip planes which are observed by crossed Nicol observation. As a result of comparative study of various direction perpendiculars to the growth axis, good crystallinity with less slip planes has been obtained by shifting the growth axis from <100> which is adequate for the last lens production. MgF2 single crystal studied as the polarizer material for high power ArF laser oscillator, and crystal with excellent laser durability and large diameter (>100mm) has been developed by CZ technique. In addition crystals oriented along both c-axis and a-axis were successfully grown.

Determination of low carbon concentration in Czochralski-grown Si crystals for solar cells by luminescence activation using electron irradiation

We attempted the quantification of carbon concentration in Czochralski-grown Si crystals for solar cells by luminescence activation in the concentration range lower than the detection limit of IR absorption spectroscopy. A positive correlation was found between the relative intensity of the C-line and the substitutional carbon (Cs) concentration determined by IR absorption in the low 1015 cm−3 range. The detection limit was estimated to be approximately 5 × 1012 cm−3. We measured and compared the Cs concentrations in the wafers sliced from ingots grown under different conditions. The variations in Cs concentrations in the respective ingots were consistent with the segregation effect.

Effects of thermal budget in n-type bifacial solar cell fabrication processes on effective lifetime of crystalline silicon

The effects of residual C on cell properties are investigated from the view point of thermal budget in the n-type bifacial cell processes. Implied Voc obtained from wafers with same Oi concentration depend on the thermal budgets decreases as the Cs concentration increases. The Voc values vary depending on the wafer with different growth cooling rate. To analyze the effect of thermal budget correspond to solar cell fabrication process, CZ wafers with almost the same Oi concentrations are prepared. One of the wafers with relatively high residual Cs concentration shows the longer lifetime than the initial value after the 950 oC annealing step. On the other hand, the lifetime of a wafer with relatively low Cs concentration dramatically decreased by the same process due to the O segregation. These results suggest that it is important to choose appropriate wafer specification, starting with feedstock material, for increasing the solar cell efficiency.

Development of large size MgF2 single crystal grown by the CZ method

In the semiconductor lithography technology, the polarized illumination system is applied to make the resolution more microscopic, therefore the polarizer material with excellent durability against the high power ArF laser has been required. Magnesium fluoride (MgF2) is one of a suitable material because of its laser durability and high transparency in VUV region. Previously we reported MgF2 single crystal with diameter of 100mm by using the Czochralski (CZ) method. By optimizing the crystal growth conditions, MgF2 single crystals with over 150mm in diameter have been stably grown. Also these crystals show good optical properties and crystallinity.

High index fluoride materials for 193nm immersion lithography

We tried to investigate various kinds of metal fluoride materials which have higher gravity than CaF2 and cubic crystal system, and we found out barium lithium fluoride (BaLiF3) and potassium yttrium fluoride (KY3F10) as candidates for the last lens material. We have developed unique Czochralski (CZ) machines and techniques for the growth of large calcium fluoride single crystals. And we applied these technologies to the growth of fluoride high index materials. We have succeeded to grow the large BaLiF3 single crystal with 120mm in diameter and a KY3F10 single crystal, and measured their basic properties such as refractive index, VUV transmittance, birefringence, and so on. As a result of our basic research, we found out that BaLiF3 single crystal is transparent at VUV region, and the refractive index at 193nm is 1.64, and KY3F10 single crystal has the index of 1.59 at the wavelength of 193nm which is slightly higher than fused silica. We expect that these fluoride high index materials are useful for the last lens material of the next generation immersion lithography.

Structure and optical property of large size CaF2 single crystals grown by the CZ method

CaF2 single crystals are required for the most suitable lens materials for the ArF laser lithography stepper because of its excellent transparency and laser durability in the DUV region. We have succeeded in growing the large size and high quality CaF2 single crystals with both <111> and <100> orientation, and the diameter of 300mm by means of the Czochralski (CZ) method. The refractive index homogeneity is one of the most important optical properties required for the lithography lens material. Particularly, the residual homogeneity which is a high-order refractive index distribution after subtraction of Zernike 36 coefficient is very important. The vein-like striations were observed in the residual homogeneity pattern of the CaF2 single crystals. The structure of CaF2 single crystal correlating with the residual homogeneity is characterized by using the reflection X-ray topography. It is observed that the structure of CaF2 single crystal composed with sub-grains parted by the small-angle tilt boundaries. The sub-grains are grown along the growth direction. It is understood that the large angle tilt type sub-boundaries among the domains composed of small sub-grains correspond to the vein-like striations. In the growth of CaF2 single crystal, the sub-grain structure of seed is introduced into grown crystal. While the bending of crystal lattice plane from the neck toward the shoulder lead to the large angle tilt type sub-boundaries. Use of high crystalline seed and control of crystal lattice plane in the shoulder are effective in the growth of high crystalline CaF2 single crystal getting good residual homogeneity.