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157-nm pellicles: polymer design for transparency and lifetime

The introduction of 157 nm as the next optical lithography wavelength has created a need for new soft (polymeric) or hard (quartz) pellicle materials. Pellicles should be > 98% transparent to incident 157 nm light and, ideally, sufficiently resistant to photochemical damage to remain useful for an exposure lifetime of 7.5 kJ/cm2. The transparency specification has been met. We have developed families of experimental Teflon™AF (TAFx) polymers with > 98% transparency which can be spin coated and lifted as micron-scale, unsupported membranes. Still higher transparencies should be possible once optimization of intrinsic (composition, end groups, impurities, molecular weight) and extrinsic (oxygen, absorbed hydrocarbons, contaminants) factors are completed. The measured transparencies of actual pellicle films, however, are affected by many factors other than absorption. Film thickness must be precisely controlled so as to allow operation at the fringe maxima for the lithographic wavelength. Roughness and thickness uniformity are also critical. An important part of our program has thus been learning how to spin membranes from the solvents that dissolve our pellicle candidates. Meeting the durability specification at 157 nm remains a major concern. The 157 nm radiation durability lifetime of a polymer is determined by two fundamental properties: the fraction of 157 nm radiation absorbed and the fraction (quantum efficiency) of this absorbed radiation that results in photochemical darkening. Originally it was assumed that lifetime increases uniformly with increasing transparency. We now have cases where materials with very different absorbances (TAFx4P and 46P) have similar lifetimes and materials with similar absorptions (TAFx46P and 2P) have very different lifetimes. These findings demonstrate the importance of the relative quantum efficiencies as the 157 nm light energy distributes itself along degradative versus non-degradative pathways. In an effort to identify chemical and structural features that control lifetime, we have been studying model molecular materials, some quite similar to the monomer units used to make our pellicle candidates. Several of these models have shown transparencies much higher and lifetimes far longer than our best pellicle candidates to date.