Synthesis of chemically amplified photoresist polymer containing four (Meth)acrylate monomers via RAFT polymerization and its application for KrF lithography

Comprehensive studies of continuous flow reversible addition–fragmentation chain transfer copolymerization and its application for photoimaging materials

“…3b and d, the ln([M] 0 /[M]) values for both copolymerization reactions linearly scale with the reaction time to yield the k app p values of 0.0047 ± 0.0002 and 0.0269 ± 0.0010 min −1 , strongly suggesting that in the continuous flow RAFT copolymerization, the concentration of the growing radical does not change in the flow; hence, the RAFT polymerization occurs in flow mode despite the reaction geometry difference. 42 Continuous flow polymerization is considerably faster than batch copolymerization. The RAFT polymerization of various methacrylates bearing adamantyl or γ-butyrolactone pendant groups in batch mode typically requires more than 10 h to reach a conversion of >0.9, and the estimated k app p is 0.0007–0.0017 min −1 , 30 which is approximately 10 times lower than the values obtained for continuous flow copolymerization.…”

“…S20†) under the optimized reaction conditions described in the Experimental section. Then, the deacetylation reaction was performed by treatment with an aqueous ammonium hydroxide solution, 42,82 and the complete reaction was confirmed by examining the signal of the acetoxy group in the 1 H NMR and FT-IR spectra, shown in Fig. S21 †…”

Exceptional Lithography Sensitivity Boosted by Hexafluoroisopropanols in Photoresists

“…The synthesis of copolymers was performed by the free radical polymerization of monomers in 1,4-dioxane as the solvent and azobisisobutyronitrile as the radical initiator at 80 °C for 6 h in a nitrogen atmosphere, followed by ammonolysis [ 42 ] of acetoxy groups to phenolic hydroxyl groups with ammonia water ( Figure S1 ). The structures of the fluoropolymers (abbreviated as HF01~03) are shown in Scheme 1 a.…”

Exceptional Lithography Sensitivity Boosted by Hexafluoroisopropanols in Photoresists

“…The synthesis of copolymers was performed by the free radical polymerization of monomers in 1,4-dioxane as the solvent and azobisisobutyronitrile as the radical initiator at 80 • C for 6 h in a nitrogen atmosphere, followed by ammonolysis [42] of acetoxy groups to phenolic hydroxyl groups with ammonia water (Figure S1). The structures of the fluoropolymers (abbreviated as HF01~03) are shown in Scheme 1a.…”