Dissolution behavior of bis-trifluoromethyl-carbinol-substituted polynorbornenes

As features shrink below 100 nm, new exposure technologies such as 157 nm lithography are being developed. One of the critical challenges in developing these new lithographic tools and processes is the development of appropriate resist materials that can be used at these lower exposure wavelengths. Creating organic resist polymer resins for 157 nm exposure is a particularly challenging issue since many organic functional groups absorb at this wavelength. It has been previously shown that fluorinated polymers may offer the required low optical absorbance needed to serve as resist resins for 157 nm lithography. In particular, there has been interest in bis-trifluoromethyl carbinol substituted polynorbornenes (HFAPNB) and similar materials for use in photoresists. The bis-trifluoromethyl carbinol group offers a base soluble group that is sufficiently transparent to be used at 157 nm. This work has focused on the dissolution behavior and other characteristics of bis-trifluoromethyl carbinol substituted polynorbornenes. In particular, it was found that the dissolution behavior of the HFAPNB homopolymer is strongly controlled by its ability to hydrogen bond with both neighboring chains and also other small molecule additives such as dissolution inhibitors and photoacid generators. A detailed molecular level explanation for these effects is presented. The interaction of a series of commercial photoacid generators with HFAPNB polymers are presented. The use of such information for the rational design of advanced resist materials using these polymers will be discussed.