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Thermal Stability of the Black Perovskite Phase in Cesium Lead Iodide Nanocrystals Under Humid Conditions

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journal contribution
posted on 02.12.2019, 13:05 by Cherrelle J. Thomas, Yangning Zhang, Adrien Guillaussier, Khaled Bdeir, Omar F. Aly, Hyun Gyung Kim, Jungchul Noh, Lauren C. Reimnitz, Junjie Li, Francis Leonard Deepak, Detlef-M. Smilgies, Delia J. Milliron, Brian A. Korgel
The equilibrium phase of cesium lead iodide (CsPbI3) at room temperature is yellow and optically inactive due to its indirect band gap. The metastable black phase of CsPbI3 on the other hand exhibits optical properties that are suitable for photovoltaic and light-emitting devices. Here, we examine the stability of the black phase of ligand-stabilized CsPbI3 nanocrystals heated in humid air. Water vapor is known to catalyze the transition of CsPbI3 from the black phase to the yellow phase. Uniform nanocrystals with cube shape were synthesized with capping ligand mixtures of oleylamine and oleic acid or diisooctylphosphinic acid, assembled into superlattices with preferred crystal orientation, and studied using grazing incidence small- and wide-angle X-ray scattering with in situ heating. The black-phase nanocrystals are found to inhabit the γ-orthorhombic phase and do not revert to the equilibrium yellow δ-orthorhombic phase until reaching a relatively high temperature, between 170 and 200 °C, coinciding with superlattice degradation.