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Highly sensitive EUV photoresists remain a critical challenge to enable high volume manufacturing with EUV lithography. Chemically amplified resists continue to provide the best sensitivity for EUV photoresists, but the high EUV transparency of most resists continues to waste a large percentage of EUV photons that pass through the resist film without photochemically generating acid. Highly fluorinated polymers have been proposed as more sensitive resist materials because fluorine increases EUV absorption of a material. Thus, methacrylate-like polymers with fluorinated backbones are an attractive possibility for new EUV resist materials. Trifluoromethacrylates are known to undergo free radical polymerization with electron rich comonomers such as vinyl ethers. The resulting polymers have backbone trifluoromethyl groups that enhance the absorption of EUV photons while retaining the potential for solubility change by acid-catalyzed tertiary ester deprotection similar to methacrylate-based chemically amplified resists. Interestingly, copolymerizations of trifluoromethacrylates and vinyl ethers are not particularly sensitive to traditional experimental parameters that influence polymer molecular weight. Instead, we have found that the structure of the vinyl ether comonomer has a profound impact on polymer molecular weight with acyclic vinyl ethers generating very high molecular weight polymers (Mw exceeding 100,000 g/mol) and cyclic vinyl ethers generating very low molecular weight polymers (Mw less than 10,000 g/mol) under similar conditions. Combination of cyclic and non-cyclic vinyl ethers in the monomer feed enables the synthesis of polymers at a desired molecular weight with a narrow polydispersity (PDI less than 2). Initial EUV contrast curves demonstrate potential for highly sensitive photoresists using these backbone-fluorinated polymers. A variety of polymers have been prepared to determine optimum compositions of leaving group, sensitizing, and etch resistant monomers. Additionally, compositions with a variety of functional groups were prepared to optimize the polymer properties to enable resists that form uniform films with low unexposed film thickness loss while maintaining high EUV sensitivity. EUV lithography of one of the resist materials demonstrates its utility as a photoresist capable of printing features to about 30 nm. Continued optimization of materials is focused on resolving features below 20 nm.
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