Combinatorial methods for the optimization of the vapor deposition of polyimide monomers and their polymerization

A combinatorial study on the synthesis and in situ orientation of thin films of aromatic polyimides on different aligning surfaces was carried out. Monomer and polyimide libraries prepared by using a combinatorial approach consisting of step gradients with different thicknesses, sectors with different compositions, and sectors with or without alignment layers were investigated. As aligning surfaces, friction deposited layers of PTFE, rubbed polyimide films, and highly oriented polyimide layers prepared by a shearing technique were used. In addition to 3,3′,4,4′-biphenyldianhydride (BPDA), only para-linked dianhydrides and diamines with different aspect ratios were utilized. Vapor deposition was performed first with individual monomers, then sequentially or by coevaporation of two or more monomers. By using this combinatorial approach, the monomer and polyimide orientation can be optimized by variation of monomer composition, film thickness, and deposition sequence. The resulting films were characterized regarding their thickness and the achieved degree of orientation by polarized FTIR and UV–vis spectroscopy. The highest degree of orientation indicated by a dichroic ratio of nine to ten was observed for 4,4″-diamino-p-terphenyl on PTFE surfaces. For other monomers, dichroic ratios of around two were determined irrespective of the aligning surface, indicating low orientation. It was found that coevaporation of both monomers yields isotropic polyimide films in good quality, whereas sequential evaporation of monomer pairs yields polyimide films with anisotropic properties.