Kinetically Stable Single Crystals of Perovskite-Phase CsPbI3

We use a solid-state method to synthesize single crystals of perovskite-phase cesium lead iodide (γ-CsPbI3) that are kinetically stable at room temperature. Single crystal X-ray diffraction characterization shows the compound is orthorhombic with the GdFeO3 structure at room temperature. Unlike conventional semiconductors, the optical absorption and joint density-of-states of bulk γ-CsPbI3 is greatest near the band edge and decreases beyond the Eg for at least 1.9 eV. Bulk γ-CsPbI3 does not show an excitonic resonance and has an optical band gap of 1.63(3) eV, ∼90 meV smaller than has been reported in thin films; these and other differences indicate that previously measured thin film γ-CsPbI3 shows signatures of quantum confinement. By flowing gases in situ during powder X-ray diffraction measurements, we confirm that γ-CsPbI3 is stable to oxygen but rapidly and catalytically converts to non-perovskite δ-CsPbI3 in the presence of moisture. Our results provide vital parameters for theoretical and experimental investigations into perovskite-phase CsPbI3 that will the guide the design and synthesis of atmospherically stable inorganic halide perovskites.