Intense optical second harmonic generation from centrosymmetric nanocrystalline para-nitroaniline

We demonstrate an approach that uses normally centrosymmetric, but highly polarizable organic molecules of para-nitroaniline (p-NA) as very efficient second harmonic generator (SHG) for near infra-red light. The approach is based on an effective manipulation of the nanocrystalline size and their assembly into a highly orientated mesocrystalline structures. The resulting mesocrystalline form of p-NA consists of multiple nanocrystals with common orientation, providing a set of surfaces with highly aligned molecules forming a head-to-tail polar arrangement. The second harmonic generation efficiency from this arrangement of mesocrystalline nanostructures is comparable to that from the conventional non-centrosymmetric organic crystals. The experimental results indicate that a very strong second-order nonlinear response can be obtained from small D-π-A organic molecules with elevated molecular hyperpolarizabilities even if these molecules tend to crystallize in centrosymmetric structures.