Polymerization ofN-(tert-butyldimethylsilyloxy)maleimide and applications of the polymers as resist materials

Abstract

A new silicon-containing maleimide monomer, N-(tert-butyldimethylsilyloxy)-maleimide (SiOMI) has been synthesized. SiOMI was radically copolymerized with styrene derivatives (XSt) to obtain alternating copolymers, P(SiOMI/XSt), in high conversions. The copolymers have high glass transition temperatures above 190°C, and the tert-butyldimethylsilyloxy groups are thermally stable up to 300°C. The SiOMI units in the copolymers were converted into N-hydroxymaleimide (HOMI) units by acidolytic deprotection of the tert-butyldimethylsilyloxy protecting groups. The facile deprotection of the side-chain tert-butyldimethylsilyloxy groups from the protected copolymers provided a significant change in solubility of the polymers due to the large polarity change. Submicron positive-tone images were obtained from the copolymers containing an onium salt as a photoacid generator by irradiation with electron beam and development with alkaline solutions. The polymer films also showed very high oxygen plasma etch resistance compared with novolac resins. The silicon-containing maleimide polymers were found to have required properties, such as good alkaline solubility after deprotection, superior adhesion, low optical density, high thermal stability with high Tg, and high plasma etch resistance for applications as deep ultraviolet and electron beam resist materials. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 2507–2516, 1997