Dark-Bright Exciton Splitting Dominates Low-Temperature Diffusion in Halide Perovskite Nanocrystal Assemblies

Abstract: Semiconductor nanocrystals could replace conventional bulk materials completely in displays and light-emitting diodes. Exciton transport dominates over charge carrier transport for materials with high exciton binding energies and long ligands, such as halide perovskite nanocrystal films. Here, we investigate how beneficial superlattices - nearly perfect 3D nanocrystal assemblies of nanocrystals are to exciton transport. Surprisingly, the high degree of order is not as crucial as the individual nanocrystal size, which strongly influences the splitting of the excitonic manifold into bright and dark states. At very low temperatures, the energetic splitting is large for the smallest nanocrystals, and dark levels with low oscillator strength effectively trap excitons inside individual nanocrystals, suppressing diffusion. The effect is reversed at elevated temperatures, and the larger NC size becomes detrimental to exciton transport due to enhanced exciton trapping and dissociation. Our results reveal that the nanocrystal size must be strongly accounted for in design strategies of future optoelectronic applications.