Reliably accessing nanocrystal luminophores with near-unity efficiencies aids in the ability to understand the upper performance limits in optoelectronic applications that require minimal nonradiative losses. Constructing structure-function relationships at the atomic level, while accounting for inevitable defects, allows for the development of robust strategies to achieve near-unity quantum yield luminophores. For CsPbBr₃ perovskite nanocrystals, bromine vacancies leave behind undercoordinated lead atoms that act as traps, limiting the achievable optical performance of the material. We show that selective etching represents a promising path for mitigating the consequences of optical defects in CsPbBr₃ nanocrystals. A mechanistic understanding of the etching reaction is essential for developing strategies to finely control the reaction. We report a study of the selective etching mechanism of CsPbBr₃ nanocrystal cubes by controlling the etchant chemical potential. We observe optical absorption and luminescence trajectories while varying the extent and rate of lead removal, removing in some cases up to 75% of the lead from the original nanocrystal ensemble. At modest etchant chemical potentials, the size and shape uniformity of the nanocrystal ensemble improves in addition to the quantum yield, proceeding through a layer-by-layer etching mechanism. Operating with excessively high etchant chemical potentials is detrimental to the overall optical performance as the etching transitions to nonselective, while too low of a chemical potential results in incomplete etching. Through this general approach, we show how to finely control selective etching to consistently access a steady state or chemical stability zone of near-unity quantum yield CsPbBr₃ nanocrystals postsynthetically, suggesting a practical framework to extend this treatment to other perovskite compositions and sizes.

We report controllable anisotropic light emission of photons originating from vertically aligned transition dipole moments in spun-cast films of CsPbBr₃ nanocubes. By depositing films of nanocrystals on precoated substrates we can control the packing density and resultant radiation pattern of the emitted photons. We develop a technical framework to calculate the average orientation of light emitters, i.e., the angle between the transition dipole moment vector (TDM) and the substrate. This model is applicable to any emissive material with a known refractive index. Theoretical modeling indicates that oriented emission originates from an anisotropic alignment of the valence band and conduction band edge states on the ionic crystal lattice and demonstrates a general path to model the experimentally less accessible internal electric field of a nanosystem from the photoluminescent anisotropy. The uniquely accessible surface of the perovskite nanoparticles allows for perturbation of the normally isotropic emissive transition. The reported sensitive and tunable TDM orientation and control of emitted light will allow for applications of perovskite nanocrystals in a wide range of photonic technologies inaccessible to traditional light emitters.