Effects of substituents in triphenylsulfonium cation on its radiation-induced decomposition and dissolution kinetics of chemically amplified resists

Yoshika Tsuda, Y. Muroya, K. Okamoto, Takahiro Kozawa, Takuya Ikeda, Yoshitaka Komuro
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Abstract

The suppression of stochastic effects is the most important issue in the development of resist materials. To suppress the stochastic effects in chemically amplified resists, a high acid generator concentration is required, which, however, likely affects the dissolution kinetics of resist films. In this study, the effects of substituents in the phenyl group of triphenylsulfonium triflate (TPS-TF) on the decomposition and dissolution kinetics of poly(4-hydroxystyrene) (PHS) films dispersed with monosubstituted TPS-TF were investigated using electron pulse radiolysis, γ-radiolysis, electron radiolysis, and quartz crystal microbalance. The phenyl group of TPS-TF was substituted with fluorine, iodine, or methyl groups at the fourth position. The electronegativity of the substituents had little effect on the reaction rate of the methanol-solvated electrons. The dipole moment of the TPS cation affected the C-S bond cleavage. The monosubstitution of the phenyl group of the TPS cation significantly affected the dissolution rate of the PHS films.
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三苯基锍阳离子中的取代基对辐射诱导的化学放大抗蚀剂分解和溶解动力学的影响
抑制随机效应是抗蚀剂材料开发中最重要的问题。为了抑制化学放大抗蚀剂中的随机效应,需要高浓度的酸发生器,但这很可能会影响抗蚀剂薄膜的溶解动力学。本研究利用电子脉冲辐射分解、γ-辐射分解、电子辐射分解和石英晶体微天平研究了三苯基锍(TPS-TF)苯基取代基对单取代 TPS-TF 分散聚(4-羟基苯乙烯)(PHS)薄膜的分解和溶解动力学的影响。TPS-TF 的苯基在第四个位置被氟、碘或甲基取代。取代基的电负性对甲醇溶解电子的反应速率影响不大。TPS 阳离子的偶极矩会影响 C-S 键的裂解。TPS 阳离子的苯基单取代基对 PHS 薄膜的溶解速率有很大影响。
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