Photoinhibition Superresolution Lithography

While the prospect of nanoscale manufacturing has generated tremendous excitement, arbitrary patterning at nanometer length scales cannot be brought about with current photolithography -- the technology that for decades has driven electronics miniaturization and enabled mass production of digital logic, memory, MEMS and flat-panel displays. This is due to the relatively long wavelength of light and diffraction, which imposes a physical not technological limit on the resolution of a far-field optical pattern. Photoinhibited superresolution (PInSR) lithography is a new scheme designed to beat the diffraction limit through two-color confinement of photopolymerization and, via efficient single-photon absorption kinetics, also be high-throughput capable. This thesis describes development of an integrated optical and materials system for investigating spatiotemporal dynamics of photoinhibited superresolution lithography, with a demonstrated 3x superresolution beyond the diffraction limit. The two-color response, arising from orthogonal photogeneration of species that participate in competing reactions, is shown to be highly complex. This is both a direct and indirect consequence of mobility. Interesting trade-offs arise: thin-film resins (necessitated by single-photon absorption kinetics) require high viscosity for film stability, but the photoinhibition effect is suppressed in viscous resins. Despite this apparent suppression, which can be overcome with high excitation of the photoinhibition system, the low mobility afforded by viscous materials is beneficial for confinement of active species. Diffusion-induced blurring of patterned photoinhibition is problematic in a resin with viscosity η = 1,000 cP, and overcome in a resin with viscosity η = 500,000 cP. Superresolution of factor 3x beyond the diffraction limit is demonstrated at 0.2 NA, with additional results indicating superresolution ability at 1.2 NA. Investigating the effect of diminished photoinhibition efficacy with increased resin viscosity, analysis shows that it is an inevitable side-effect of reduction of the diffusion-limited termination rate constant. Further analysis confirms the experimental result that the viscosity effect may be overcome, with photogeneration of a large concentration of inhibiting radicals. Elevated radical concentration is also shown to be necessary for reducing diffusion-lengths, owing to the bimolecular nature of radical termination. The quantitative kinetics of photoinitiation, photoinhibition and chain polymerization are individually developed, validated and finally incorporated into a unified model. Finally, taking into account the complex, highly-coupled nature of PInSR requirements and operation, an alternate superresolution scheme is presented. In particular, the scheme is aimed at achieving deep-subwavelength superresolution with a single monochromatic source and multiple exposures. It utilizes a surface-tethered photochemistry that requires no films or gas-management, and essentially eliminates diffusion of active species. Preliminary, single-exposure results are shown