Resist materials for 157-nm microlithography: an update

Fluorocarbon polymers and siloxane-based polymers have been identified as promising resist candidates for 157 nm material design because of their relatively high transparency at this wavelength. This paper reports our recent progress toward developing 157 nm resist materials based on the first of these two polymer systems. In addition to the 2-hydroxyhexafluoropropyl group, (alpha) -trifluoromethyl carboxylic acids have been identified as surprisingly transparent acidic functional groups. Polymers based on these groups have been prepared and preliminary imaging studies at 157 nm are described. 2-Trifluoromethyl-bicyclo[2,2,1] heptane-2-carboxylic acid methyl ester derived from methyl 2-(trifluoromethyl)acrylate was also prepared and gas-phase VUV measurements showed substantially improved transparency over norbornane. This appears to be a general characteristic of norbornane-bearing geminal electron-withdrawing substituents on the 2 carbon bridge. Unfortunately, neither the Ni<SUP>II</SUP> nor Pd<SUP>II</SUP> catalysts polymerize these transparent norbornene monomers by vinyl addition. However, several new approaches to incorporating these transparent monomers into functional polymers have been investigated. The first involved the synthesis of tricyclononene (TCN) monomers that move the bulky electron withdrawing groups further away from the site of addition. The hydrogenated geminally substituted TCN monomer still has far better transparency at 157 nm than norbornane. The second approach involved copolymerizing the norbornene monomers with carbon monoxide. The third approach involved free-radical polymerization of norbornene monomers with tetrafluoroethylene and/or other electron-deficient comonomers. All these approaches provided new materials with encouraging absorbance at 157 nm. The lithographic performance of some of these polymers is discussed.