Evaluation of outgassing from a fluorinated resist for 157-nm lithography

Abstract

We have evaluated the outgassing products and the in-situ transmittance of a contaminated CaF₂ substrate for monocyclic fluoropolymers with four protecting groups: methoxymethyl (MOM), tert-butoxycarbonyl (t-BOC), menthoxymethyl (MM), and 2-cyclohexylcyclohexyloxymethyl (CCOM). We have also evaluated the same type of fluoropolymer with seven kinds of photo-acid generators (PAGs) added to a base fluoropolymer solution. We found little correlation between the total amount of outgassing from the polymer and the decreasing rate of the CaF₂ substrate transmittance caused by outgassing adhesion. Although the MOM protecting group generated the largest amount of outgassing products, the most substantial decrease in the transmittance was observed for the t-BOC protecting group. Also, the outgassing products due to use of a PAG did not greatly reduce the absorption coefficient of a CaF₂ substrate regardless of the kind of PAG. Therefore, the absorption coefficient of the outgassing-contaminated CaF₂ substrate appears to be more sensitive to the type of protecting group, especially the t-BOC protecting group including a t-butyl unit, rather than the type of fluoropolymer or PAG. We analyzed the substrate surface contaminant due to the t-butyl unit by x-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and time-of-flight secondary ion mass spectrometry (TOF-SIMS), and found that increasing amounts of organic compounds, containing mainly C- and H-atoms, were adhered to and deposited on the substrate surface with an increasing irradiation dose. We speculate that the contaminants on a CaF₂ surface with or without an anti-reflective coating were formed not only through mere physical adsorption, but also through certain chemical combinations. We conclude that in terms of material design of the fluoropolymer resist for 157-nm lithography, we need to pay attention to the protecting group of polymers, especially the t-BOC or t-butyl protecting group, which generates isobutene product during 157-nm irradiation.