The work focuses on lithographic processes and materials for sub-50 nm lithography. Lithographic results of polymethyl methacrylates of molecular weights of 50,000, 100,000, 496,000, and 950, 000 are compared. It was found that the molecular weight and developer concentration do not affect smallest linewidth, within experimental error. However, the molecular weight does affect the line-to-line resolution in dense gratings of 40–60 nm in contrast and developer induced swelling. 40 nm period gratings are shown. The work next examines the use of chemically amplified resists for nanofabrication, with a focus on SAL-601. Sub-50 nm lines are defined with latitude of an order of magnitude in dose and a factor of two in post exposure bake time. The results are modeled with a diffusion reaction kinetic model and an approach to optimize resolution and reproducibility is presented. Challenges to attaining the ultimate resolution and line-to-line resolution in polymeric resists include contrast, mechanical stability, swelling, and adhesion. Metal binding self assembled monolayers (SAMs) are presented a class of resists, that circumvent the latter three complications. Work at the Naval Research Laboratory on SAM resists is outlined.