Transition from Doublet to Triplet Excitons in Single Perovskite Nanocrystals

Lead halide perovskite nanocrystals (NCs) have emerged as novel semiconductor nanostructures possessing great potential for optoelectronic, photovoltaic, and quantum information processing applications. Success in these applications requires a comprehensive understanding of the perovskite NCs' electronic structures, which mysteriously exhibit either doublet or triplet peaks of exciton luminescence at the single-particle level. Here we show that the transition from doublet- to triplet-exciton peaks can be triggered in single CsPbI₃ NCs from the same batch of samples when they are stored in the ambient environment. We propose theoretically that the doublet-exciton peaks originate from two in-plane dipole moments, while the optical transition arising from the out-of-plane dipole moment becomes prominent only after the crystal-field splitting is strongly reduced by the structural transformation in the deterioration process. Furthermore, the quantum-confinement effect is strongly reinforced in the single CsPbI₃ NCs with a triplet-exciton configuration, leading to enhanced Auger recombination and allowing us to extract the emission-energy dependence of the exciton-energy-level fine structure.