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Quantum chemical calculation is applied to investigate the reaction mechanism of sulfonyl acid generator and the transparency of the resist material. We have found that electron absorbed dimethylsulfone can be easily decomposed by relatively low energy (2.95Kcal/mol), reaching to the decomposed status of methyl radical and CH3SO2 (methyl sulfonyl anion). This was thought to bean initial step in the electron acid generation reaction of the sulfonyl compounds. The total molecular energy of dimethyl sulfone anion was found to be higher than that of the neutral dimethylsulfone. On the other hand, sulfone derivatives with electron-withdrawing groups, such as methyl sulfonyl acetonitrile, usually have higher energy (about 41kcal/mol) than those for their anion. This suggests that the electron withdrawing groups enhance the electron affinity of the sulfone compounds, which are also considered to increase the efficiency of acid generation. Additionally, another quantum chemical study was carried out in order to improve transparency of the aromatic species in resist for ArF excimer laser. Using configuration interaction (CI) methods of molecular orbital theory, the substituent effects of UV absorption in the aromatic compounds were investigated. As a result significant red sifts in λmax were observed in the conjugated romatic rings, which increases the transparency at 193nm wavelength region.

Molecular Design of Acid Generators for EB and ArF Excimer Laser Exposure Using Molecular Orbital Calculations.