An improved method for applying polymeric antireflective coatings to substrate surfaces and the resulting precursor structures are provided. Broadly, the methods comprise plasma enhanced chemical vapor depositing (PECVD) a polymer on the substrate surfaces. The PECVD processes comprise providing a quantity of a polymer generated by introducing monomer vapors into a plasma state followed by polymerization thereof, with assistance of plasma energy, onto the surface of a substrate. The most preferred starting monomers are phenylacetylene, 4-ethynyltoluene, and 1-ethynyl-2-fluorobenzene. The inventive methods are useful for providing highly conformal antireflective coatings on large surface substrates having super submicron (0.25 nullm or smaller) features. The process provides a much faster deposition rate than conventional chemical vapor deposition (CVD) methods, is environmentally friendly, and is economical.