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

• Published in: Angewandte Chemie International Edition 2024-08, Vol.63 (32), p.e202401850-n/a
• Main Authors: Lu, Xin‐Yu, Zhang, Rui‐Sheng, Yang, Guan‐Wen, Li, Qiang, Li, Bo, Wu, Guang‐Peng
• Format: Article
• Language: English
• Subjects: Acetal copolymers; Amplification; Carbon dioxide; Catalysis; Catalysts; chemical amplification resist; Copolymerization; Epoxides; Hydrophobicity; Hydroxyl groups; Industrial development; Integrated circuits; Lithography; organocatalysis; Photoresists; polycarbonate; Polymers; Polymethacrylates; Resists; Sensitivity analysis; water developable
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202401850

Seeking high‐performance photoresists 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 promising photoresist material. In this work, a series of aqueous developable CO2‐sourced polycarbonates (CO2‐PCs) 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 photogenerated acid, the acetal (ketal) groups in CO2‐PC were hydrolysed into two equivalents of hydroxyl groups, which change the exposed area from hydrophobicity to hydrophilicity, thus enabling the exposed area to be developed with 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 a good etch resistance (38 % higher than poly(tert‐butyl acrylate)). Such performances outperform 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 (KrF and ArF) and extreme ultraviolet (EUV) lithography for nanomanufacturing. In this work, a set of CO2‐sourced polycarbonates containing acid‐labile cyclic acetal structures were explored as chemical amplification photoresist in deep ultraviolet lithography, and these materials exhibit a superior lithography performance than commercial KrF and ArF resists, demonstrating a promising application prospect in integrated circuit manufacture.