We report an epitaxial method for orienting thin films of polydiacetylenes on ordinary alignment polymers that have been stretched by rubbing. By selectively removing the alignment polymer using standard photolithographic techniques, we show that it is possible to obtain well‐oriented polydiacetylene films in desired regions. Typical values for the birefringence are 0.14±0.01 for epitaxially grown films, enough to allow the formation of gratings and channel waveguides on patterned surfaces.
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