A negative tone photoresist film, consisting of a molecular glass, a photoacid generator, and an acid labile crosslinker, was prepared by physical vapor deposition, a solvent-free process. Subsequent to deposition, the coevaporated monomers were exposed using 365 nm radiation, subjected to a post exposure bake step, and developed in aqueous base to produce sub-micron patterns. Combinatorial techniques were used to aid optimization of the photoresist by systematic variations in composition and exposure dose. Development factors such as concentration and time were also optimized.