Plasma enhanced polymerization is an attractive technology to fabricate an optical polymer waveguide, because it has capability to provide an uniform thickness film on a substrate with various surface geometry, and to provide change of refractive index by controlling a proportion of source monomer mixing. In the present paper we discuss optical constants and molecule structures of the films added hetero-atoms, O, N and F in the CH
x network of polymer. Refractive index of those films changes from 1.52 to 1.63 at 1.0 μm wavelength, depending on the variety of hetero-atoms. Fluorine atoms added into a film decreases refractive index of the film. Oxygen atoms added into a film, which form ester structure (- COO-), decrease refractive index of the film, and some O atoms token into a film as OH base will increase optical absorption in inferred region for optical communication. Nitrogen atoms added increase optical absorption due to forming NH
2 base. Finally, sp
3/sp
2 fraction controlling in the film will be a suitable to control refractive index of the film for an optical waveguide, for example by using mixed monomer of C
6H
6 and C
6H
10.
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