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Acid-catalyzed degradation mechanism of poly(phthalaldehyde): Unzipping reaction of chemical amplification resist
Authors:Minoru Tsuda  Masayuki Hata  Rie Nishida  Setsuko Oikawa
Abstract:The acid-catalyzed degradation mechanism of chemical amplification resists based on end-capped poly(phthalaldehyde) has been elucidated by semi-empirical molecular orbital calculations. It is concluded that: (i) two different starting points exist in the degradation of end-capped poly(phthalaldehyde), the central part of the polymer as well as the polymer end; (ii) in both cases, after the first protonation, cationic hydroxyl compounds generated decompose to the identical cation intermediate, which can unzip itself to phthalaldehyde monomers successively (unzipping reaction); (iii) the hemiacetal type intermediates hardly degrade to the same intermediate without acid catalyst; (iv) the overall activation energy for the degradation reaction is less than 14 kcal/mol in all the cases. Thus, the poly(phthalaldehyde) resist can easily self-develop below 100°C, as reported in the literature. © 1997 John Wiley & Sons, Inc.
Keywords:poly(phthalaldehyde)  degradation mechanism  molecular orbital theory  activation energy of degradation  acid catalyzed degradation  unzipping reaction  resist  chemical amplification
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