Development of Novel Photo-Functional Materials Based on Cyclic Oligomers

Novel photo-functional materials, such as refractive-index-changing materials, argon fluoride (ArF) resist materials, and electron beam (EB) resist materials, were designed based on the structures of calixarenes, cyclodextrin, and noria. The synthesis and refractive-index properties of calixarene derivatives containing photo-reactive groups, including azobenzene, norbornadiene, anthracene, cinnamate, and chalcone, were examined, and refractive-index changes (Delta n(D)'S) of between 0.007 and 0.061. were observed. The synthesis and patterning properties of a single-layer ArF photoresist system of beta-CD derivative containing t-butyl ester and fluorine were examined, and a well-resolved 100 nm line and space pattern was obtained on a silicon wafer. A new ladder-like macrocycle, noria (water wheel in Latin), was also synthesized and its application as an EB resist material was examined. The noria derivatives noria-(COOBu)-Bu-t containing t-butyl ester groups, noria-BOC containing t-butyloxycarbonyl group, and noria-acetal containing acetal groups had good physical properties and photo-reactivity. EB-resist based on noria-(COOBu)-Bu-t and noria-BOC provided clear line and space patterns at a resolution of 70 and 50 nm, respectively.