Abstract
Lead halide perovskite nanocrystals have attracted intense interest due to their desirable optical properties, diverse structural features, and size-tunable excitonic structure. Here we show that, under ambient conditions, a non-monotonic trend in radiative lifetime emerges from the interplay of size, lattice symmetry and excitonic structure. Small nanocrystals exhibit long radiative lifetimes due to weakly emissive excitons, but the oscillator strength increases and shortens the lifetime for nanocrystals approaching intermediate confinement. For larger nanocrystals with higher exciton density of states (DOS), the radiative lifetime is lengthened due to depopulation of the bright exciton manifold into thermally accessible dim states. A size-dependent structural symmetry lowering transition from cubic to orthorhombic is observed by XRD and MD simulations, and the non-monotonic radiative lifetime trend emerges only in lower symmetry structures with an increased dim exciton DOS. These findings shed light on the impact of nanocrystal size and structure on radiative lifetime and pave the way for tailored optical materials in various optical applications.