Disclosed are the deactivation mechanism and
chemistry platforms that make high-
silicon hardmask films photo-imageable like positive-tone
photoresist for microphotolithography. The deactivation mechanism requires a catalyst to promote crosslinking reactions, and a
photoacid generator to deactivate the catalyst. The initial hardmask films are soluble in developers. If not radiated, films become insoluble in developers due to crosslinking reactions promoted by catalyst. If radiated, films remain soluble in developers due to deactivation of catalyst by
photoacid generator. Compositions of positive-tone photo-imageable hardmask based on the
chemistry of polysiloxane and polysilsesquioxanes are disclosed as well. Also disclosed is a method of modifying polysiloxane and polysilsesquioxane films for controlled
diffusion of catalysts,
photoacid generators, and quenchers. Further disclosed are processes of using photo-imageable hardmasks to create precursor structures on
semiconductor substrates with or without an intermediate layer.