Surface phase diagram of CsSnI3 from first-principles calculations

Abstract

${\mathrm{CsSnI}}_3$ is widely studied as an environmentally friendly Pb-free perovskite material for optoelectronic device applications. To further improve material and device performance, it is important to understand the surface structures of ${\mathrm{CsSnI}}_3$. We generate surface structures with various stoichiometries, perform density functional theory calculations to create phase diagrams of the ${\mathrm{CsSnI}}_3$ (001), (110), and (100) surfaces, and determine the most stable surfaces under a wide range of Cs, Sn, and I chemical potentials. Under I-rich conditions, surfaces with Cs vacancies are stable, which lead to partially occupied surface states above the valence band maximum. Under I-poor conditions, we find the stoichiometric (100) surface to be stable under a wide region of the phase diagram, which does not have any surface states and can contribute to long charge-carrier lifetimes. Consequently, the I-poor (Sn-rich) conditions will be more beneficial to improve the device performance.