No abstract

Lead halide perovskites open great prospects for optoelectronics and a wealth of potential applications in quantum optical and spin-based technologies. Precise knowledge of the fundamental optical and spin properties of charge-carrier complexes at the origin of their luminescence is crucial in view of the development of these applications. On nearly bulk Cesium-Lead-Bromide single perovskite nanocrystals, which are the test bench materials for next-generation devices as well as theoretical modeling, we perform low temperature magneto-optical spectroscopy to reveal their entire band-edge exciton fine structure and charge-complex binding energies. We demonstrate that the ground exciton state is dark and lays several millielectronvolts below the lowest bright exciton sublevels, which settles the debate on the bright-dark exciton level ordering in these materials. More importantly, combining these results with spectroscopic measurements on various perovskite nanocrystal compounds, we show evidence for universal scaling laws relating the exciton fine structure splitting, the trion and biexciton binding energies to the band-edge exciton energy in lead-halide perovskite nanostructures, regardless of their chemical composition. These scaling laws solely based on quantum confinement effects and dimensionless energies offer a general predictive picture for the interaction energies within charge-carrier complexes photo-generated in these emerging semiconductor nanostructures.

Lead-halide perovskite nanocrystals (NCs) are attractive nano-building blocks for photovoltaics and optoelectronic devices as well as quantum light sources. Such developments require a better knowledge of the fundamental electronic and optical properties of the band-edge exciton, whose fine structure has long been debated. In this review, we give an overview of recent magneto-optical spectroscopic studies revealing the entire excitonic fine structure and relaxation mechanisms in these materials, using a single-NC approach to get rid of their inhomogeneities in morphology and crystal structure. We highlight the prominent role of the electron-hole exchange interaction in the order and splitting of the bright triplet and dark singlet exciton sublevels and discuss the effects of size, shape anisotropy and dielectric screening on the fine structure. The spectral and temporal manifestations of thermal mixing between bright and dark excitons allows extracting the specific nature and strength of the exciton–phonon coupling, which provides an explanation for their remarkably bright photoluminescence at low temperature although the ground exciton state is optically inactive. We also decipher the spectroscopic characteristics of other charge complexes whose recombination contributes to photoluminescence. With the rich knowledge gained from these experiments, we provide some perspectives on perovskite NCs as quantum light sources.