Novel second-order nonlinear optical polymers via chemical cross-linking-induced vitrification under electric field

We present a novel method of preparing highly efficient and stable second-order nonlinear optical (NLO) polymers via chemical cross-linking induced vitrification under electric field. In this method a soluble prepolymer is first prepared that contains cross-linking sites attached to the NLO-active groups. Upon preparing samples of desired thicknesses, the prepolymer is heated (precured) to enable some chemical cross-linking and thus to increase the glass transition temperature (Tg) to an optimum for poling. The precured polymer is then heated above its Tg and subjected to a high electric field to obtain the desired alignment of NLO moieties. Subsequent chemical cross-linking (curing) under electric field continues to advance the T g and hence leads to in situ vitrification of the polymer that stabilizes the electric-field-induced orientation of the NLO moieties. Detailed results of thermal, linear optical, poling kinetics, and NLO properties are described for the polymer system prepared from tetrafunctional 4-nitro 1,2-phenylenediamine and bifunctional Bisphenol-A diglycidylether as the starting monomers. The polymer which has been cured finally at 140 °C under a very high corona field exhibits d33≅14 and d 31≅3 pm/V, determined from the Maker-fringe experiments. Most significant, however, is the fact that this polymer shows no detectable decay in second harmonic generation for over 500 h under ambient conditions and no tendency of relaxation even at 85 °C.