Rational Unraveling of Alkali Metal Concentration-Dependent Photovoltaic Performance of Halide Perovskites: Octahedron Distortion vs Surface Reconstruction.

Adding alkali metal in organic-inorganic halide perovskites effectively improves its photovoltaic performance, while excessive alkali metal incorporation would produce a detrimental effect. Through density functional theory and nonadiabatic molecular dynamics simulations, we demonstrate how and why the photogenerated carrier lifetime mutates with the increase of alkali metal concentration. A small amount of Rb doping in the lattice introduces a slight distortion of the octahedron, reducing the overlap of frontier orbitals and decreasing the nonadiabatic coupling, effectively enhancing the photogenerated carrier lifetime. In contrast, excessive Rb will introduce defect states, resulting in the low carrier lifetime by a factor of 2-3 orders of magnitude. Strikingly, the surface formamidinium (FA) cations exhibit unexpected responsibility for the carrier dynamics since its high-frequency thermal vibration strongly leads to the ultrafast hole trapping and carrier recombination. Our results provide new insight into the concentration-dependent photovoltaic performance of alkali metal cations in organic-inorganic halide perovskites.