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24 July 2002 Synthesis of novel fluoropolymers for 157-nm photoresists by cyclopolymerization
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Novel fluoropolymers having partially fluorinated monocyclic (5-membered and 6-membered ring) structure have been synthesized with radical cyclo-polymerization, which have C- F bond in the polymer main chain and also possess fluorocontaining acidic alcohol group. These polymers have excellent transparency lower than 1.0 μm-1 at 157nm wave length. The number-average molecular weight (Mn) of the polymers is 4000 to 20000, the glass transition temperature (Tg) is 130 to 155 °C and the decomposition temperature (Td) is about 400 °C. Copolymerization reaction with the other monomers (ex. fluoroolefins,(meth)acrylates and vinyl esters) were also examined. The introduction of protecting group (ex. methoxylmethly, and t-butoxycarbonyl group) to alcohol units of the polymer can be applied before or after polymerization reaction. We also evaluated fundamental resist performances. These have excellent transparency of 0.5 to 1.5 μm-1, good solubility in the standard alkaline solution (0.26N N-tetramethylammonium hydroxide aqueous solution) and relatively high sensitivities below than 10mJ/cm2. The imaging results of the above fluoropolymer based positive- working resists are presented. Under 100-nm line and space pattern are delineated in 200-nm thick film by using the phase shift mask.
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Shun-ichi Kodama, Isamu Kaneko, Yoko Takebe, Shinji Okada, Yasuhide Kawaguchi, Naomi Shida, Seiichi Ishikawa, Minoru Toriumi, and Toshiro Itani "Synthesis of novel fluoropolymers for 157-nm photoresists by cyclopolymerization", Proc. SPIE 4690, Advances in Resist Technology and Processing XIX, (24 July 2002);

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