Positive/Negative Mid Uv Resists With High Thermal Stability

New mid UV resist systems based on poly(p-vinylbenzoates) sensitized with diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate are described. t-Butyl, cyclohexenyl, a-methylbenzyl, and a-methylallyl esters are converted upon postbake to poly(p-vinylbenzoic acid) through thermolysis reaction catalyzed by the photochemically generated Bronsted acid, inducing a large change in the polarity of the repeating units. Thus, development in aqueous base such as MF312/water or alcohol provides a positive tone image of the mask, while the use of a nonpolar organic developer allows a negative tone imaging. Because the glass transition temperature of poly(p-vinylbenzoic acid) is ca. 250° C, the negative image is devoid of thermal flow to this temperature even without any hardening processes. Another interesting feature of the benzoate resists is their high opacity in the deep UV region. The optical density of a 1μ thick film of poly(p-vinylbenzoic acid) is 3.5 at 254 nm and the benzoate polymers are as absorbing as the acid polymer. This high deep UV absorption of the resin necessitates the imaging above 300 nm for good light penetration (or by e-beam or X-ray) and makes the use of this resist as an imaging layer in the PCM scheme very attractive. This imaging layer is especially useful when employed in conjunction with a planarizing layer absorbing above 240 nm (for example, PMGI) as addition of a dye is not required.