New Amorphous Fluoropolymers of Tetrafluoroethylene with Fluorinated and Non-Fluorinated Tricyclononenes. Semiconductor Photoresists for Imaging at 157 and 193 nm

Twenty-two tricyclo(4.2.1.02,5)non-7-ene (TCN) or 3-oxatricyclononene monomers, having fluorinated or nonfluorinated substituents on the four-membered rings, were prepared by cycloaddition reactions of functionalized olefins with norbornadiene or quadricyclane. Radical polymerizations with tetrafluoroethylene (TFE) and/or TFE and acrylates provided amorphous polymers with high solubility in standard organic solvents. The TFE/TCN dipolymers typically have glass transition temperatures of over 200 °C, substantially higher than TFE copolymers with norbornene. Perfluoroalkyl sulfonyl fluoride groups can be incorporated in the side chains of the TCN monomers giving soluble copolymers. Polymers which also incorporated acrylate monomers were prepared using a semibatch process to control composition. Selected polymers incorporating tertiary alkyl ester groups from the TCN monomer or acrylates have shown good image formation when compounded with a photoacid generator, imaged with 157 or 193 nm light, and developed using aqueous base.