Novel photoacid generators for chemically amplified resists with g-line, i-line and DUV exposure

A new class of compounds, (5-alkylsulfonyloxyimino-5H-thiophen-2-ylidene)-2-methylphenyl-acetonitriles, characterized as non-ionic and halogen-free photoacid generators (PAG's) was developed. The compounds generate various kinds of sulfonic acids, such as methane, n-propane and camphor sulfonic acid under the g-line (436nm), i-line (365 nm) and Deep UV (DUV, 248 nm or shorter) exposure and are applicable for chemically amplified (CA) photoresists. The application-relevant properties of the compounds such as solubility in propylene glycol monomethyl ether acetate (PGMEA), UV absorption, thermal stability with or without poly(4-hydroxystyrene), storage stability in a neat form, sensitivity in some model resist formulations and dissolution inhibition efficiency during development process were evaluated. The compounds exhibit enough solubility in PGMEA, red-shifted UV absorption (lambda(max): 405 nm), good thermal stability up to 140 degreesC in a phenolic matrix, effective acid generation in terms of quantum yield in an acetonitrile solution and high sensitivity in negative tone and positive tone CA resist formulations, such as tert-butyl ester type and t-BOC type formulations, with g-line, i-line and DUV exposure. The photochemical decomposition reaction of the compound was also studied. Additionally a scanning electron microscope (SEM) photography as an application example of microlithography by the CA negative tone resist with the PAG is presented.