α-Halo Ketone for Polyhedral Perovskite Nanocrystals: Evolutions, Shape Conversions, Ligand Chemistry, and Self-Assembly

Bright lead halide perovskite nanocrystals, which have been extensively studied in the past 5 years, are mostly confined to a six faceted hexahedron (cube/platelet) shape. With variations of ligand, precursor, reaction temperature, and surface modification, their brightness has been enhanced and phase became stable, but ultimate nanocrystals still retained the hexahedron cube or platelet shape in most of the hot injection reactions. In contrast, by exploration of alpha-halo ketone in amine as a halide precursor, different shaped nanocrystals without compromising the photoluminescence quantum yield (PLQY) are reported. Confining to orthorhombic CsPbBr3, the obtained nanocrystals are stabilized by 12 facets ({200}, {020}, {112}) and led to 12 faceted rhombic dodecahedrons. These facets are absolutely different from six ({110}, {002}) equivalent facets of widely reported orthorhombic cube shaped CsPbBr3 nanocrystals. These also retained the colloidal and phase stability, as well as showed near unity PLQY. With further annealing, these are transformed to 26 faceted rhombicuboctahedrons by dissolving all their vertices. Importantly, these 12 faceted nanocrystals showed wide area self-assembly in most of the reactions. It has also been concluded that primary ammonium ions led to six faceted nanocrystals, but tertiary ammonium ions obtained in this case stabilized different group of facets. While perovskite nanocrystals were broadly confined to only nanocubes, these new nanocrystals with intense emission would certainly provide a new avenue for continuing their further research.