Out-of-equilibrium processes in crystallization of organic-inorganic perovskites during spin coating.

Complex phenomena are prevalent during the formation of materials, which affect their processing-structure-function relationships. Thin films of methylammonium lead iodide (CH3NH3PbI3, MAPI) are processed by spin coating, antisolvent drop, and annealing of colloidal precursors. The structure and properties of transient and stable phases formed during the process are reported, and the mechanistic insights of the underlying transitions are revealed by combining in situ data from grazing-incidence wide-angle X-ray scattering and photoluminescence spectroscopy. Here, we report the detailed insights on the embryonic stages of organic-inorganic perovskite formation. The physicochemical evolution during the conversion proceeds in four steps: i) An instant nucleation of polydisperse MAPI nanocrystals on antisolvent drop, ii) the instantaneous partial conversion of metastable nanocrystals into orthorhombic solvent-complex by cluster coalescence, iii) the thermal decomposition (dissolution) of the stable solvent-complex into plumboiodide fragments upon evaporation of solvent from the complex and iv) the formation (recrystallization) of cubic MAPI crystals in thin film.

Low-dimensional perovskite nanoplatelet synthesis using in situ photophysical monitoring to establish controlled growth.

Perovskite nanoparticles have attracted the attention of research groups around the world for their impressive photophysical properties, facile synthesis and versatile surface chemistry. Here, we report a synthetic route that takes advantage of a suite of soluble precursors to generate CsPbBr3 perovskite nanoplatelets with fine control over size, thickness and optical properties. We demonstrate near unit cell precision, creating well characterized materials with sharp, narrow emission lines at 430, 460 and 490 nm corresponding to nanoplatelets that are 2, 4, and 6 unit cells thick, respectively. Nanoplatelets were characterized with optical spectroscopy, atomic force microscopy, scanning electron microscopy and transmission electron microscopy to explicitly correlate growth conditions, thickness and resulting photophysical properties. Detailed in situ photoluminescence spectroscopic studies were carried out to understand and optimize particle growth by correlating light emission with nanoplatelet growth across a range of synthetic conditions. It was found that nanoplatelet thickness and emission wavelength increase as the ratio of oleic acid to oleyl amine or the reaction temperature is increased. Using this information, we control the lateral size, width and corresponding emission wavelength of the desired nanoplatelets by modulating the temperature and ratios of the ligand.