Dissolution behavior of tetrafluoroethylene-based fluoropolymers for 157-nm resist materials

We have synthesized various main-chain fluorinated polymers and studied base-resin properties, such as transparency at 157 nm, solubility in a standard alkaline developer, and lithographic performance. Main-chain-fluorinated polymers were synthesized by copolymerization of tetrafluoroethylene (TFE) with cyclic monomers, especially newly synthesized norbornene derivatives. We studied the correlation between pKa(OH) and the solubility of the copolymers of TFE and functional (fluoroalkyl alcohol group) norbornenes. Their solubility depends on the pKa value of the fluoroalkyl alcohol groups. died the impact of the polymerization initiators on base-resin properties. High transparency was obtained by using the fluorocarbon initiator. It was also confirmed that the monocyclic component improves dry-etch resistance and that fluorination at the terminal groups improves alkaline solubility. ition, we found that the development characteristics of TFE/norbornene copolymers were significantly improved by the stereoselective (endo versus exo) partial protection of the hydroxyl groups in the fluoroalkyl alcohol moiety attached to norbornene unit. The polymer protected only in the exo position of the norbornene unit in the copolymer had a higher Rmax and a higher contrast. Positive-working resists based on these fluoropolymers were developed and 55 nm dense lines could be delineated by exposure at 157 nm wavelength with an alternating phase shift mask on a 0.9 NA 157 nm exposure tool.