Single-component chemically amplified resist materials for electron-beam and x-ray lithography

摘要

Abstract: Copolymers of 4-tert-butoxycarbonyloxystyrene (TBS) and sulfur dioxide (SO$-2$/) have been found to act as sensitive x-ray ($lambda $EQ 14 angstrom) and moderately sensitive electron-beam, single component, chemically amplified, aqueous base soluble positive acting resists. The x-ray and electron-beam response of these materials was a function of copolymer composition, where an increase in the sulfur dioxide content enhanced the resist sensitivity. Initial investigation into the radiation induced reaction mechanism provided evidence that acid formation occurs via polymer main chain scission. It is proposed that at the scission sites radical species are produced which in turn are responsible for the formation of the acidic moieties. Heat treatment of resist films after exposure converted the copolymers to poly(4- hydroxystyrene sulfone) and permitted the exposed film areas to be developed in an aqueous base solution. Preliminary lithographic evaluation has resolved 0.5 $mu@m line and space patterns in 0.65 $mu@m thick 1.75/1 TBS/SO$-2$/ resist films using an x-ray dose of 10 mJ/cm$+2$/. For a resist having a composition of 2.1/1 TBS/SO$-2$/, 0.25 $mu@m line and space features where delineated using an electron-beam dose of 90 $mu@C/cm$+2$/ at 30 KV. In addition, minimal surface residue of the exposed areas of the resist film after development was observed when the time interval between the exposure and the post-exposure baking steps was varied from 2-10 minutes.!