First-principles study on the optoelectronic and mechanical properties of all-inorganic lead-free fluoride perovskites ABF3 (A = Na, K and B = Si, Ge)

Abstract

In spite of extensive studies on halide perovskites for advanced photovoltaic applications, little attention has been paid to fluoride perovskites so far. Here, we present a systematic investigation of not only the electronic and optical properties but also the mechanical and chemical stabilities of all-inorganic lead-free fluoride perovskites ABF₃ (A = Na, K and B = Si, Ge) in the cubic phase using first-principles calculations. We provide a reliable prediction of their lattice constants, band gaps, effective masses and exciton binding energies, revealing variation tendencies according to the selection of A- and B-site cations. Between the two different B-site fluoride perovskites, the silicon-based compounds ASiF₃ (A = Na, K) are highlighted as being more suitable for a light absorber of perovskite solar cells, due to their appropriate band gaps, remarkably low exciton binding energies, and ultrahigh spectroscopic limited maximum efficiency reaching ∼34% with a layer thickness over 1 μm. Through the calculations of elastic constants, phase decomposition energies and phonon dispersion curves, we further find that the all-inorganic lead-free fluoride perovskites ABF₃ are mechanically stable but only KGeF₃ is chemically stable against phase decomposition into its chemical reactants and is also thermodynamically stable. This work highlights that all-inorganic lead-free fluoride perovskites have high potentiality to be used as a promising light absorber in less toxic and high-performance perovskite solar cells.