Anharmonicity and Disorder in the Black Phases of Cesium Lead Iodide Used for Stable Inorganic Perovskite Solar Cells.

Hybrid organic-inorganic perovskites emerged as a new generation of absorber materials for high-efficiency low-cost solar cells in 2009. Very recently, fully inorganic perovskite quantum dots also led to promising efficiencies, making them a potentially stable and efficient alternative to their hybrid cousins. Currently, the record efficiency is obtained with CsPbI3, whose crystallographical characterization is still limited. Here, we show through high-resolution in situ synchrotron XRD measurements that CsPbI3 can be undercooled below its transition temperature and temporarily maintained in its perovskite structure down to room temperature, stabilizing a metastable perovskite polytype (black γ-phase) crucial for photovoltaic applications. Our analysis of the structural phase transitions reveals a highly anisotropic evolution of the individual lattice parameters versus temperature. Structural, vibrational, and electronic properties of all the experimentally observed black phases are further inspected based on several theoretical approaches. Whereas the black γ-phase is shown to behave harmonically around equilibrium, for the tetragonal phase, density functional theory reveals the same anharmonic behavior, with a Brillouin zone-centered double-well instability, as for the cubic phase. Using total energy and vibrational entropy calculations, we highlight the competition between all the low-temperature phases of CsPbI3 (γ, δ, ß) and show that avoiding the order-disorder entropy term arising from double-well instabilities is key to preventing the formation of the yellow perovskitoid phase. A symmetry-based tight-binding model, validated by self-consistent GW calculations including spin-orbit coupling, affords further insight into their electronic properties, with evidence of Rashba effect for both cubic and tetragonal phases when using the symmetry-breaking structures obtained through frozen phonon calculations.

Structural Instabilities Related to Highly Anharmonic Phonons in Halide Perovskites.

Hybrid perovskites have emerged over the past five years as absorber layers for novel high-efficiency low-cost solar cells combining the advantages of organic and inorganic semiconductors. Unfortunately, electrical transport in these materials is still poorly understood. Employing the linear response approach of density functional theory, we reveal strong anharmonic effects and a double-well phonon instability at the center of the Brillouin zone for both cubic and orthorhombic phases of inorganic CsPbI3. Previously reported soft phonon modes are stabilized at the actual lower-symmetry equilibrium structure, which occurs in a very flat energy landscape, highlighting the strong competition between the different phases of CsPbI3. Factoring these low-energy phonons into electron-phonon interactions and band gap calculations could help better understand the electrical transport properties in these materials. Furthermore, the perovskite oscillations through the corresponding energy barrier could explain the underlying ferroelectricity and the dynamical Rashba effect predicted in halide perovskites for photovoltaics.