Trojans That Flip The Black Phase: Impurity-Driven Stabilization And Spontaneous Strain Suppression In Gamma-Cspbi3 Perovskite
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY(2021)
Abstract
The technological progress and widespread adoption of all-organic CsPbI3 perovskite devices is hampered by its thermodynamic instability at room temperature. Because of its inherent tolerance toward deep trap formation, there has been no shortage to exploring which dopants can improve the phase stability. While the relative size of the dopant is important, an assessment of the literature suggests that its relative size and impact on crystal volume do not always reveal what will beneficially shift the phase transition temperature. In this perspective, we analyze the changes in crystal symmetry of CsPbI3 perovskite as it transforms from a thermodynamically stable high-temperature cubic (alpha) structure into its distorted low-temperature tetragonal (beta) and unstable orthorhombic (gamma) perovskite structures. Quantified assessment of the symmetry-adapted strains which are introduced due to changes in temperature and composition show that the stability of gamma-CsPbI3 is best rationalized from the point of view of crystal symmetry. In particular, improved thermal-phase stability is directly traced to the suppression of spontaneous strain formation and increased crystal symmetry at room temperature.
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