New Metallic Ordered Phase of Perovskite CsPbI₃ under Pressure

Abstract

Pressure-induced electronic structure transition from insulating phase to metal state is a potential new paradigm for halide perovskites. The metallization based on these materials may afford a novel motif toward realizing new electronic properties even superconductivity phenomenon. Herein, how static compression modulates the crystal and electronic structure of typical perovskite semiconductors cesium lead iodine (CsPbI₃) by both experimental and theoretical studies is reported. The comprehensive studies discover the insulator-metal transition of CsPbI₃ at 39.3 GPa, and reveal the key information behind the electronic transition. The perovskite's precise structural evolution is tracked upon compression, from orthorhombic <i>Pnma</i> phase to monoclinic <i>C2/m</i> structure before the metallic transition. More interestingly, the <i>C2/m</i> phase has the most distorted octahedra and the shortest Pb-I bond length relative to the average bond length that is ever reported in a halide perovskite structure. The electronic transition stems from the structural changes accompanied by the anomalously self-distorted octahedra. These studies show that pressure can significantly alter the structural and electronic properties of these technologically important perovskites.