Publication date: 21st July 2025
Recently, we developed a new chemical route for the in situ synthesis of highly luminescent lead-halide perovskite nanocrystals (NCs) within a nickel acetate thin film. Relative humidity (RH) plays a decisive role in dictating both the structural evolution and optical performance of these NCs. [1] [2] At low RH, non-emissive 0D phases such as MA₄PbBr₆ and hydroxide species (e.g., PbBrOH) are stabilized. Increasing humidity induces a structural reorganization into highly emissive 3D perovskite NCs (e.g., MAPbBr₃), accompanied by markedly enhanced photophysical properties. The acetate matrix is central to this transformation: its inherent basicity promotes the generation of OH⁻ ions that dynamically and reversibly bind to NC surfaces [3]. This hydroxide-mediated interaction efficiently passivates trap states, enabling photoluminescence quantum yields (PLQYs) up to 80%. Importantly, the process is fully reversible—luminescence is quenched upon removal of humidity and restored upon re-exposure to water vapor—highlighting the dual structural and passivation role of hydroxide ions within the acetate environment.
In the present work, we demonstrate an alternative route in which crystallization is triggered more rapidly by exposure to carboxylic acid vapors. This approach, based on surface stripping and atom recombination, proves versatile, enabling the crystallization of diverse lead-halide perovskites (Cs⁺ and MA⁺) with distinct kinetics, emission intensities, and final PLQYs. Moreover, FA⁺-based perovskites can also be crystallized under carboxylic acid vapors, achieving strong photoluminescence, excellent stability, and PLQYs exceeding 80%. However, accelerated crystallization may also result in faster degradation, depending on the concentration and chemical nature of the acid employed. These differences are attributed to the delicate interplay between the acid’s intrinsic acidity (pKa) and its structural resemblance to the acetate matrix.
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