Benchmark thermodynamic analysis of methylammonium lead iodide decomposition from first principles

Abstract

Abstract Hybrid organic–inorganic perovskites (HOIPs) such as methylammonium lead iodide (MAPbI3) are promising candidates for use in photovoltaic cells and other semiconductor applications, but their limited chemical stability poses obstacles to their widespread use. Ab initio modeling of finite-temperature and pressure thermodynamic equilibria of HOIPs with their decomposition products can reveal stability limits and help develop mitigation strategies. We here use a previously published experimental temperature-pressure equilibrium to benchmark and demonstrate the applicability of the harmonic and quasiharmonic approximations, combined with a simple entropy correction for the configurational freedom of methylammonium cations in solid MAPbI3 and for several density functional approximations, to the thermodynamics of MAPbI3 decomposition. We find that these approximations, together with the dispersion-corrected hybrid density functional HSE06, yield remarkably good agreement with the experimentally assessed equilibrium between T = 326 K and T = 407 K, providing a solid foundation for future broad thermodynamic assessments of HOIP stability.