Dissolution behavior of phenolic resins and resists as studied by quartz crystal microbalance

Hiroshi Ito; Debra Fenzel-Alexander; Gregory Breyta

doi:10.1117/12.275860

7 July 1997 Dissolution behavior of phenolic resins and resists as studied by quartz crystal microbalance

Hiroshi Ito, Debra Fenzel-Alexander, Gregory Breyta

Proceedings Volume 3049, Advances in Resist Technology and Processing XIV; (1997) https://doi.org/10.1117/12.275860
Event: Microlithography '97, 1997, Santa Clara, CA, United States

Abstract

The thin film dissolution behavior of phenolic resins such as poly(4-hydroxystyrene) and poly(4-hydroxystyrene-co-t-butyl acrylate), the dissolution inhibition effect of acid generators, and the development kinetics of the ESCAP resist are reported. All the dissolution rate measurements were carried out using a quartz crystal microbalance (QCM), which can provide valuable information on the time-dependent dissolution behavior even for an extremely fast rate of 30,000 angstroms/sec. Poly(4-hydroxystyrene)s with a wide range of molecular weights (M_n equals 2,300 - 26,000) and molecular weight distributions (1.2 - 5.5) have been found to dissolve linearly with time in a 0.21 N tetramethylammonium hydroxide (TMAH) aqueous solution. The dissolution rate of the copolymers decreases exponentially with an increase in the acrylate concentration, accompanied by an increase in an induction period. The dissolution inhibition effect of acid generators varies widely. Onium salts are excellent dissolution inhibitors, even stronger than so-called dissolution inhibitors such as t-butoxycarbonyl-protected bisphenol A. A higher loading of triphenylsulfonium triflate in the copolymer film results in a longer induction period and an exponentially slower dissolution rate. The ESCAP resist based on the copolymer begins to dissolve in a 0.26 N TMAH solution at only ca. 5% conversion of the t-butyl ester to carboxylic acid and reaches its maximum dissolution rate of 30,000 angstroms/sec at the dose to clear with ca. 60% conversion, which corresponds to the developer selectivity of greater than 15. Although the dissolution rate does not change much above the dose to clear, the induction period becomes shorter at a higher dose, which can be observed by QCM even when the full development time is less than 1 sec.

Citation Download Citation

Hiroshi Ito, Debra Fenzel-Alexander, and Gregory Breyta "Dissolution behavior of phenolic resins and resists as studied by quartz crystal microbalance", Proc. SPIE 3049, Advances in Resist Technology and Processing XIV, (7 July 1997); https://doi.org/10.1117/12.275860

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