Symmetry-Based Tight Binding Modeling of Halide Perovskite Semiconductors.

On the basis of a general symmetry analysis, this paper presents an empirical tight-binding (TB) model for the reference Pm-3m perovskite cubic phase of halide perovskites of general formula ABX3. The TB electronic band diagram, with and without spin orbit coupling effect of MAPbI3 has been determined based on state of the art density functional theory results including many body corrections (DFT+GW). It affords access to various properties, including distorted structures, at a significantly reduced computational cost. This is illustrated with the calculation of the band-to-band absorption spectrum, the variation of the band gap under volumetric strain, as well as the Rashba effect for a uniaxial symmetry breaking. Compared to DFT approaches, this empirical model will help to tackle larger issues, such as the electronic band structure of large nanostructures, including many-body effects, or heterostructures relevant to perovskite device modeling suited to the description of atomic-scale features.