Aqueous Developable and CO2‐Sourced Chemical Amplification Photoresist with High Performance

Seeking high‐performance photoresist is an important item for semiconductor industry due to the continuous miniaturization and intelligentization of integrated circuits. Polymer resin containing carbonate group has many desirable properties, such as high transmittance, acid sensitivity and chemical formulation, thus serving as potential photoresist material. In this work, a series of aqueous developable CO2‐sourced polycarbonate (CO2‐PC) were produced via alternating copolymerization of CO2 and epoxides bearing acid‐cleavable cyclic acetal groups in the presence of tetranuclear organoborane catalyst. The produced CO2‐PCs were investigated as chemical amplification resists in deep ultraviolet (DUV) lithography. Under the catalysis of photoacid, the acetal (ketal) groups in CO2‐PC were hydrolysed into two equivalents of hydroxyl groups, which changes the exposed areas from hydrophobicity to hydrophilicity, thus enabling the exposed regions to be developed in water. Through normalized remaining thickness analysis, the optimal CO2‐derived resist achieved a remarkable sensitivity of 1.9 mJ/cm2, a contrast of 7.9, a favorable resolution (750 nm, half pitch), and etching resistance (38% higher than poly(tert‐butyl acrylate)). Such performances outperforming commercial KrF and ArF chemical amplification resists (i.e., polyhydroxystyrene‐derived and polymethacrylate‐based resists), which endows broad application prospects in the field of DUV (248 nm and 193 nm) and extreme ultraviolet (EUV) lithography and nanomanufacturing.