Epoxy‐amine polymer thin films are fabricated by chemical vapor deposition using an aliphatic amine, which is very reactive to epoxy groups and has nonlinear optical properties. A transparent thin film is obtained by controlling the temperature and surface condition of the substrate, and the epoxy‐amine ratio during deposition. The refractive index of the film is 1.648. A slab waveguide is constructed by depositing the polymer film on SiO2 which is formed by thermal oxidation of a Si wafer. End coupling of a He‐Ne laser (632.8 nm) launches a well‐propagating beam. This is the first case in which a polymer waveguide is fabricated by dry processing.

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