Sub-wavelength modulation of χ(2) optical nonlinearity in organic thin films

Modulating the second-order nonlinear optical susceptibility (χ(2)) of materials at the nanoscale represents an ongoing technological challenge for a variety of integrated frequency conversion and nonlinear nanophotonic applications. Here we exploit the large hyperpolarizability of intermolecular charge transfer states, naturally aligned at an organic semiconductor donor-acceptor (DA) interface, as a means to control the magnitude and sign of χ(2) at the nanoscale. Focusing initially on a single pentacene-C60 DA interface, we confirm that the charge transfer transition is strongly aligned orthogonal to the heterojunction and find that it is responsible for a large interfacial nonlinearity probed via second harmonic generation that is sufficient to achieve d33>10 pm V-1, when incorporated in a non-centrosymmetric DA multilayer stack. Using grating-shadowed oblique-angle deposition to laterally structure the DA interface distribution in such multilayers subsequently enables the demonstration of a χ(2) grating with 280 nm periodicity, which is the shortest reported to date.