Construction on inorganic oxide substrates of covalently self-assembled second-order nonlinear optical (NLO) materials containing a variety of acentrically organized high-beta chromophores is investigated as a function of film deposition conditions. Structurally different chromophores exhibit varying packing arrangements on the surface. Changing the medium for the chromophore deposition reaction on functionalized surfaces from a polar solvent to a nonpolar solvent and raising the temperature increases the chromophore number density on the surface and yields improved NLO response. These robust thin film materials show very high second harmonic generation (SHG) efficiencies with X(zzz)((2)) for similar to 25 Angstrom thick monolayers of up to 7 x 10(-7) esu at 1064 nm.