Design, synthesis, and application of lithographic resists and nonlinear optical materials

Fluorinated norbornene monomers exhibit the requisite properties for inclusion in 157 nm photoresists, but traditional addition and radical polymerizations with these monomers have failed. Norbornanediols provide an alternate route to these materials via condensation polymerization, and methods have been developed for the efficient synthesis of the exo-2-syn-7- and endo-2-exo-3-dihydroxynorbornanes. Synthesis of the fluorinated analogues is complicated by steric and electronic effects; however, a high-yielding synthesis of endo-2-exo-3-dihydroxynorbornane bearing a 5-endo-[2,2-bis(trifluoromethyl)hydroxyethyl] substituent as well as its corresponding polymer are reported. As an alternative to 157 nm and other optical lithographies, Step and Flash Imprint Lithography, or S-FIL®, was introduced in 1999 by The University of Texas at Austin. It has proven to be a cost effective, high resolution alternative to traditional optical lithography. Often in the S-FIL process, residual resist may become imbedded within the template features resulting in device defects due to the imprint and repeat nature of S-FIL. The high silicon and cross-linking content of the resist formulations are extremely difficult, if not impossible to remove from quartz imprint mold without template degradation. Our approach to this problem was the synthesis of a family of thermally reversible, cross-linkable monomers that will facilitate resist removal while maintaining template integrity. Our monomers utilize classic Diels-Alder chemistry to provide thermal reversibility, while pendant acrylate functionalities facilitate cross-linking. Herein we report the synthesis of several Diels-Alder compounds, incorporate them into resist formulations, and test their efficacy for resist removal. In an effort to develop unique patternable materials, our laboratory is currently engaged in the design and development of photonic crystals comprised of organic elements with highly stable electro-optic activity. Fabrication of these devices requires polymers that can be patterned at high resolution, have large second order nonlinear optical (NLO) coefficients, and that are thermally stable after poling. Our route to these materials involves the synthesis of a prepolymer that can be spin coated, poled, and then fixed by a photochemical cross-linking reaction. We now describe an efficient synthetic route to a new class of biscross-linkable monomers and the characteristics of their corresponding nonlinear optical polymers.