We have successfully synthesized polystyrene(PS)-b-polymethylmethacrylate (PMMA) block copolymer that is precious with controlled molecular weight, PDI and composition ratio by living anionic polymerization method using large-scale apparatus. In addition, the influence of PDI, composition ratio and composition distribution for micro phase separation about PS-b-PMMA block copolymer is investigated. The results show that PDI is the major factor for defect, while composition ratio and composition distribution has influence for morphology. As PDI increase 1.06 to 1.13, also defects are increased a lot. As composition ratio of PS increase 51% to 60%, micro phase separation structure was changed from lamella to gyroid. Moreover, we surmised that these properties have a boundary of influence towards micro phase separation. Therefore, is necessary to control these properties by living anionic polymerization in order to use DSA materials in semiconductor process.
We have successfully synthesized various and over wide range molecular weight block copolymers (BCPs): these are polystyrene(PS)-polymethylmethacrylate(PMMA) as general components and poly(4-trimethylsilylstyrene)(PTMSS)- poly(4-hydroxystyrene)(PHS) system as very strong segregated components (high chi) and multiblock type of those copolymers which form the microphase-separated structure pattern using living anionic polymerizing method by which the size of polymer can be precisely controlled. In addition, we were able to observe alternating lamellar and cylinder structures which were formed by our various BCPs using small angle X-ray scattering (SAXS). Moreover, we have successfully developed new apparatus for high volume manufacturing including our original technologies such as purification of monomer, improvement of wetted surface, and mechanical technology for high vacuum. And we have successfully synthesized all the BCPs with narrow molecular weight distribution (PDI <1.1) with large-scale apparatus.
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