Hydrogen bonding and aqueous base dissolution behavior of hexafluoroisopropanol-bearing polymers

Hiroshi Ito; William D. Hinsberg; Larry F. Rhodes; Chun Chang

doi:10.1117/12.485135

12 June 2003 Hydrogen bonding and aqueous base dissolution behavior of hexafluoroisopropanol-bearing polymers

Hiroshi Ito, William D. Hinsberg, Larry F. Rhodes, Chun Chang

Proceedings Volume 5039, Advances in Resist Technology and Processing XX; (2003) https://doi.org/10.1117/12.485135
Event: Microlithography 2003, 2003, Santa Clara, California, United States

Abstract

The aqueous base dissolution behavior and hydrogen bonding interaction of polymers bearing hexafluoroisopropanol (HFA) as an acid group have been investigated. While pKa of HFA is similar to that of phenol, the dissolution rate of HFA polymers in aqueous base varies from one structure to another. Poly(norbornene hexafluoroisopropanol) (PNBHFA) dissolves in 0.26 tetramethylammonium hydroxide (TMAH) aqueous solution at a rate of 1,500-8,000 A/sec, which is not correlated to the number-average or weight-average molecular weight. Furthermore, PNGHFA exhibits a complex multi-stage dissolution kinetics in 0.21 N TMAH, depending on the molecular weight and molecular weight distribution. Hydrogen bonding of HFA polymers has been investigated using FTIR. Polynorbornene and polystyrene bearing HFA (PNBHFA and PSTHFA) are much less hydrogen-bonded than poly(4-hydroxystyrene)(PHOST). HFA-ester copolymers tend to have more free OH groups than a HOST/t-butyl acrylate copolymer. The carbonyl bond in 2-trifluoromethylacrylic units is less polarized and therefore less prone to hydrogen bonding with OH than C=O in (meth)acrylate units. The interaction of acid generators with the HFA group can be studied by ¹⁹F NMR. Both ionic iodonium and nonionic imidesulfonate acid generators interact strongly with HFA and inhibit the dissolution of HFA polymers in aqueous base while ionic acid generators are better dissolution inhibitors of phenolic resins.

Citation Download Citation

Hiroshi Ito, William D. Hinsberg, Larry F. Rhodes, and Chun Chang "Hydrogen bonding and aqueous base dissolution behavior of hexafluoroisopropanol-bearing polymers", Proc. SPIE 5039, Advances in Resist Technology and Processing XX, (12 June 2003); https://doi.org/10.1117/12.485135

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