For 157-nm single-layer resists, dry etching resistance is an important issue because of the difficulty of striking a balance between 157-nm transparency and an acceptable level of dry etching resistance. To achieve an acceptable trade-off, the fluorine atom can be introduced into the resist polymer structure to obtain higher transparency, despite the fluorine atom’s high reactivity in the plasma etching process. We recently proposed a model for estimating dry-etching-resistance (the KI-model) and have shown that it can be effectively applied to the design of new fluoropolymer structures. Through simulation based on the KI-model, we were able to develop a new fluoropolymer with good dry etching resistance and high transparency. We found that a new protective group, 2-cyclohexylcyclohexanoxymethyl (CCOM), improved the characteristics of our novel fluoropolymer, compared with use of a MOM group, when used in the base resin of the resist. In this paper, we report on the usefulness of the KI-model for developing new fluorinated protective groups and new base polymers. Moreover, we have developed a new base fluoropolymer which has higher transparency and a similar degree of dry etching resistance as a monocyclic fluoropolymer with a CCOM protective group.
For realizing next generation 193nm immersion lithography, developing suitable high refractive index liquid is an very important issue. To overcome the trade off relationship between high refractive index (optimally more than 1.6 ) and low absorbance (similar degree with H2O 0.0036cm-1), the molecular modeling based on quantum chemical ab-initio calculation was performed. We have successfully developed the predictive method of frequency-dependent refractive index for liquid and its absorbance. Then, we tried to estimate these properties to search for optimal candidates. In this paper, we report on the estimated results of the refractive index n and the absorbance at 193nm for some candidate compounds. We believe we could demonstrate the usefulness of the predictive method by using the quantum chemical calculation for developing new liquids, even if there were some degree of errors in the absolute values. We have found the -SO2- (like sulfone, sulfonate, sulfate) containing five- and six-membered ring compounds such as sulfolane and sultone etc. would achieve both high refractive index around 1.6 and relatively low absorbance. XeF4O and Bi(CF3)3 ,unfortunately, had absorption at 193nm due to the weak binding outer valence electrons. In the case of alkyl Si and Ge, Si(CH2CH3)4 might have a good balance of refractive index 1.59 and relatively low absorbance. Si(CH3)3CH2CH2OH and Ge(CH2CH3)4 were estimated to have refractive index of over 1.6, but have been estimated these might have sightly stronger absorption.
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.