We report a study on the optical properties of the layered polymorph of vacancy-ordered triple perovskite CsBiBr. The electronic structure, determined from density functional theory calculations, shows the top of the valence band and bottom of the conduction band minima are, unusually, dominated by Bi s and p states, respectively. This produces a sharp exciton peak in the absorption spectra with a binding energy that was approximated to be 940 meV, which is substantially stronger than values found in other halide perovskites and, instead, more closely reflects values seen in alkali halide crystals. This large binding energy is indicative of a strongly localized character and results in a highly structured emission at room temperature as the exciton couples to vibrations in the lattice.
The effect of preparing lead-based organohalide perovskites under inert conditions has been investigated. We find that when prepared under anhydrous conditions, only poorly crystalline powders were obtained. On exposure to small amounts of moisture a rapid crystallization into the expected cubic unit cell for CH3NH3PbBr3 and tetragonal cell for CH3NH3PbI3 is observed. While the as-prepared iodide phase is non-emissive, the lifetime of the emission for the bromide is found to be much longer when prepared under atmospheric conditions.
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