Lattice distortion inducing exciton splitting and coherent quantum beating in CsPbI3 perovskite quantum dots

Anisotropic exchange splitting in semiconductor quantum dots results in bright-exciton fine-structure splitting important for quantum information processing. Direct measurement of fine-structure splitting usually requires single/few quantum dots at liquid-helium temperature because of its sensitivity to quantum dot size and shape, whereas measuring and controlling fine-structure splitting at an ensemble level seem to be impossible unless all the dots are made to be nearly identical. Here we report strong bright-exciton fine-structure splitting up to 1.6 meV in solution-processed CsPbI 3 perovskite quantum dots, manifested as quantum beats in ensemble-level transient absorption at liquid-nitrogen to room temperature. The splitting is robust to quantum dot size and shape heterogeneity, and increases with decreasing temperature, pointing towards a mechanism associated with orthorhombic distortion of the perovskite lattice. Effective-mass-approximation calculations reveal an intrinsic ‘fine-structure gap’ that agrees well with the observed fine-structure splitting. This gap stems from an avoided crossing of bright excitons confined in orthorhombically distorted quantum dots that are bounded by the pseudocubic {100} family of planes. Halide perovskites feature highly dynamic lattices, but their impact on exciton fine structure remains unexplored. Here, the authors show that these lattices lead to a bright-exciton fine structure gap, enabling observation of quantum beats in a non-uniform ensemble.