Isamu Kaneko

Synthesis of novel fluoropolymers for 157-nm photoresists by cyclopolymerization

Novel fluoropolymers having partially fluorinated monocyclic (5-membered and 6-membered ring) structure have been synthesized with radical cyclo-polymerization, which have C- F bond in the polymer main chain and also possess fluorocontaining acidic alcohol group. These polymers have excellent transparency lower than 1.0 μm-1 at 157nm wave length. The number-average molecular weight (Mn) of the polymers is 4000 to 20000, the glass transition temperature (Tg) is 130 to 155 °C and the decomposition temperature (Td) is about 400 °C. Copolymerization reaction with the other monomers (ex. fluoroolefins,(meth)acrylates and vinyl esters) were also examined. The introduction of protecting group (ex. methoxylmethly, and t-butoxycarbonyl group) to alcohol units of the polymer can be applied before or after polymerization reaction. We also evaluated fundamental resist performances. These have excellent transparency of 0.5 to 1.5 μm-1, good solubility in the standard alkaline solution (0.26N N-tetramethylammonium hydroxide aqueous solution) and relatively high sensitivities below than 10mJ/cm2. The imaging results of the above fluoropolymer based positive- working resists are presented. Under 100-nm line and space pattern are delineated in 200-nm thick film by using the phase shift mask.

SYNTHESIS OF PERFLUORINATED VINYL ETHERS HAVING ESTER GROUP

Abstract A new efficient and convenient synthetic process of perfluorinated vinyl ethers containing an ester group was developed by pyrolysis in the presence of α-trifluoromethyl moiety without loss of –COF functional group followed by alcoholysis in high yield.

Dry-etching resistance of fluoropolymers for 157-nm single-layer resists

Novel fluoropolymers having partially fluorinated monocyclic (5-membered and 6-membered ring) structure have been synthesized with radical cyclo-polymerization, which have C-F bond in the polymer main chain and also possess fluorocontaining acidic alcohol group. These polymers have excellent transparency lower than 1.0 μm-1 at 157nm wavelength, a small amount of outgassing, high sensitivity and good adhesion to the wafer. However, this fluoropolymer have lower etching resistance (half of conventional KrF resists) and it must be improved for applying to the single-layer resist. In this paper, we show the new model of the estimation of the dry-etching resistance for designing polymer compositions. It is well known that the model using carbon-atom-density as a parameter is useful for estimating dry-etching resistance. However, these models did not agree with the results of our fluoropolymers. Our new model was focused on the surface area and the volume of the polymer. We succeeded to explain the relationship between the dry-etching resistance and the composition of the fluoropolymer. According to this model, the compositions of fluoropolymer such as protective groups, protective ration and co-polymer units were optimized to improve their etching resistance.