RESUMEN
Current syntheses of CsPbBr3 halide perovskite nanocrystals (NCs) rely on overstoichiometric amounts of Pb2+ precursors, resulting in unreacted lead ions at the end of the process. In our synthesis scheme of CsPbBr3 NCs, we replaced excess Pb2+ with different exogenous metal cations (M) and investigated their effect on the synthesis products. These cations can be divided into two groups: group 1 delivers monodisperse CsPbBr3 cubes capped with oleate species (as for the case when Pb2+ is used in excess) and with a photoluminescence quantum yield (PLQY) as high as 90% with some cations (for example with M = In3+); group 2 yields irregularly shaped CsPbBr3 NCs with broad size distributions. In both cases, the addition of a tertiary ammonium cation (didodecylmethylammonium, DDMA+) during the synthesis, after the nucleation of the NCs, reshapes the NCs to monodisperse truncated cubes. Such NCs feature a mixed oleate/DDMA+ surface termination with PLQY values of up to 97%. For group 1 cations this happens only if the ammonium cation is directly added as a salt (DDMA-Br), while for group 2 cations this happens even if the corresponding tertiary amine (DDMA) is added, instead of DDMA-Br. This is attributed to the fact that only group 2 cations can facilitate the protonation of DDMA by the excess oleic acid present in the reaction environment. In all cases studied, the incorporation of M cations is marginal, and the reshaping of the NCs is only transient: if the reactions are run for a long time, the truncated cubes evolve to cubes.
RESUMEN
Halide perovskite nanocrystals (NCs), specifically CsPbBr3, have attracted considerable interest due to their remarkable optical properties for optoelectronic devices. To achieve high-efficiency light-emitting diodes (LEDs) based on CsPbBr3 nanocrystals (NCs), it is crucial to optimize both their photoluminescence quantum yield (PLQY) and carrier transport properties when they are deposited to form films on substrates. While the exchange of native ligands with didodecyl dimethylammonium bromide (DDAB) ligand pairs has been successful in boosting their PLQY, dense DDAB coverage on the surface of NCs should impede carrier transport and limit device efficiency. Following our previous work, here, we use oleyl phosphonic acid (OLPA) as a selective stripping agent to remove a fraction of DDAB from the NC surface and demonstrate that such stripping enhances carrier transport while maintaining a high PLQY. Through systematic optimization of OLPA dosage, we significantly improve the performance of CsPbBr3 LEDs, achieving a maximum external quantum efficiency (EQE) of 15.1% at 516 nm and a maximum brightness of 5931 cd m-2. These findings underscore the potential of controlled ligand stripping to enhance the performance of CsPbBr3 NC-based optoelectronic devices.
