Fluoropolymers are key materials for the single-layer resists used in 157-nm lithography. We have been studying fluoropolymers to determine their potential for use as the base resin and have developed a monocyclic fluorinated polymer with a blocking group of Cyclohexylcyclohexyloxymethyl (CCOM) that has high transmittance (an absorption coefficient of 0.64 μm-1) at a 157-nm exposure wavelength and high dry-etching resistance (a dry-etching rate of 1.75 times that of KrF resist) under organic bottom anti-reflective coating/hard mark dry-etching conditions. A resist based on our monocyclic fluoropolymer had high sensitivity. Using it, we were able to resolve a 60-nm line-and-space pattern using a 157-nm laser microstepper (numerical aperture = 0.85) with a resolution enhanced technology of an alternating phase-shifting mask. This polymer was demonstrated to simultaneously enable high transparency, high dry-etching resistance, and good imaging performance.
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.
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.