Pressure-Induced Band Structure Evolution of Halide Perovskites: A First-Principles Atomic and Electronic Structure Study

Abstract

Density functional theory (DFT) based calculations have been conducted to draw a broad picture of pressure induced band structure evolution in various phases of organic and inorganic halide perovskite materials. Under a wide range of pressure applied, distinct band structure behaviors including magnitude change of band gap, direct-indirect/indirect-direct band gap transitions and CBM/VBM shifts, have been observed between organic and inorganic perovskites among different phases. Through atomic and electronic structure calculations, band gap narrowing/widening has been rationalized through crystal orbitals coupling transformations; direct-indirect mutual transitions were explained based on structural symmetry evolution; different VBM/CBM shifts behaviors between organic and inorganic perovskites were analyzed focusing on orientation and polarity of molecules/atoms outside the octahedrals. These results provide a comprehensive guidance for further experimental investigations on pressure engineering of perovskite materials.

Pressure‐Induced Structural Evolution and Bandgap Optimization of Lead‐Free Halide Double Perovskite (NH4)2SeBr6

“…As suggested, the bandgap of perovskite materials is highly variable based on the overlap of electronic wave functions between metal B and halide X ions . Figure a shows the first‐principles DFT calculated bandgap versus pressure.…”

Theoretical Progress on the Relationship between the Structures and Properties of Perovskite Solar Cells

“…Computational studies of the tunable properties such as electronic structures under external pressure for MAPbX 3 (X = I, Br, Cl) and all‐inorganic halide perovskites CsMX 3 were reported. [ 91–94 ] Using first‐principles calculations, Liu et al. [ 95 ] found that CsPbI 3 under appropriate strain engineering exhibited ferroelectric and topological orders simultaneously, namely a ferroelectric topological insulator.…”

Structural, electronic, and optical properties of cubic formamidinium lead iodide perovskite: a first-principles investigation

“…8 There have been extensive theoretical works studying the structure and electronic, optical, and defect properties of MAPbI 3 , and these have greatly deepened the understanding of MAPbI 3 and accelerated research into its application to devices. [14][15][16][17][18][19] Although there have been some of theoretical works studying FAPbI 3 , 20-24 a systematic and comprehensive study is still absent. Pan et al investigate the geometric and electronic structures of hybrid organic-inorganic perovskites FAPbX 3 (X ¼ Cl, Br, I).…”