The Orientation of Luminescent Excitons in Layered Organic Nanomaterials

A fundamental understanding of optoelectronics in organic semiconductors is complicated by the diversity of excitons which can exist within a single material system. Measurements that distinguish between different exciton types are crucial for a complete understanding of organic materials. By fitting experimental curves of angle-, polarization-, and energy-dependent PL to analytical Purcell calculations we quantify the relative dipole moments for in-plane and out-of-plane oriented excitons in organic and inorganic layered nanomaterials. In mono- and bi-layers of Molybdenum Disulfide (MoS2) and Graphene Oxide the luminescence arises only from in-plane oriented excitons. In the perylene derivative PTCDA, however, we show that PL arises from both in-plane and out-of-plane excitons. We observe a difference in emission frequency between the dipole orientations which indicates the existence of two distinct exciton species: an in-plane oriented Frenkel exciton and an out-of-plane oriented Charge Transfer exciton. Based on these results we devise and implement a method for isolating luminescence from either exciton species. We observe different temporal dynamics for the two distinct excitons, highlighting the power of this technique for fundamental studies of organic materials.