Local energy landscape drives long exciton diffusion in 2D halide perovskite semiconductors

Abstract: Halide perovskites have emerged as disruptive semiconductors for applications including photovoltaics and light emitting devices, with modular optoelectronic properties realisable through composition and dimensionality tuning. Layered Ruddlesden-Popper perovskites of the form BA2MAn-1PbnI3n+1, where n is the number of lead-halide and methylammonium (MA) sheets spaced by longer butylammonium (BA) cations, are particularly interesting due to their unique two-dimensional character and charge carrier dynamics dominated by strongly bound excitons. However, long-range energy transport through exciton diffusion in these materials is not understood or realised. Here, we employ local time-resolved luminescence mapping techniques to visualise exciton transport in high-quality exfoliated flakes of the BA2MAn-1PbnI3n+1 perovskite family. We uncover two distinct transport regimes, depending on the temperature range studied. At temperatures above 100 K, diffusion is mediated by thermally activated hopping processes between localised states. At lower temperatures, a non-uniform energetic landscape emerges in which exciton transport is dominated by energy funnelling processes to lower energy states, leading to long range transport over hundreds of nanometres even in the absence of exciton-phonon coupling and in the presence of local optoelectronic heterogeneity. Efficient, long-range and switchable excitonic funnelling offers exciting possibilities of controlled directional long-range transport in these 2D materials for new device applications.