Advanced organic materials for lithographic applications
Strahan, Jeffrey Ryan
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The microelectronics industry is driven by the need to produce smaller transistors at lower costs, and this requires an ever-changing approach to the chemistry involved in their fabrication. While photolithography has been able to keep pace with Moore’s law over the past four decades, alternative patterning technologies are now receiving increased attention to keep up with market demand. The first project describes work towards increasing the sensitivity of electron-beam resists by incorporating electron-withdrawing groups into the alpha position of methacrylates. After monomer design and synthesis, several polymers were synthesized that investigated the role of fluorine in the resists performance. G-values, electron-beam contrast curves, and EUV imaging showed that these fluorinated polymethacrylates outperformed current industrial resists. The next project deals with the design, synthesis, and evaluation of a resist that seeks to decouple chemical amplification from acid diffusion. While work was shown that a system comprised of a photo-labile polyphthalaldehyde and x novolak could achieve this process, the high dose required to image was problematic. An aliphatic dialdehyde was envisioned to account for these issues, but its synthesis was never achieved. A polyethylene glycol aldehyde was synthesized and polymerized, but its material properties did not perform the intended function. Ultimately, the stability of aliphatic aldehydes proved to be too unstable for this project to continue. While the synthesis was troublesome, a fundamental study of ceiling temperatures was undertaken. Numerical and analytical solutions were developed that describe the exact nature of the equilibrium constant on a living polymer system. These results were verified by a VT-NMR experiment, which accurately predicted the ceiling temperature of polythalaldehyde with a Van’t Hoff plot. Lastly, the self-assembly of block copolymers was investigated as a means to produce high resolution, high density nano-imprint lithography templates for bit patterned media. The first set of experiments involved synthesizing polymeric cross-linked surface treatments from substituted styrenes. The aryl substituent was shown to largely effect the surface energy, and after anionically synthesizing PS-b-PMMA, these materials were shown to effect block copolymer orientation. To produce a 3-D pattern of the self-assembled features, silicon was incorporated into one block to provide adequate etch resistance. Several monomers were investigated, and two, an isoprene and methacrylate analog, were successfully incorporated into two block copolymers. The silicon containing methacrylate derivative polymer was shown to successfully self-assemble in thin films under solvent annealing conditions.