A descriptor for the structural stability of organic-inorganic hybrid perovskites based on binding mechanism in electronic structure.

The poor stability of organic-inorganic hybrid perovskites hinders its commercial application, which motivates a need for greater theoretical insight into its binding mechanism. To date, the binding mode of organic cation and anion inside organic-inorganic hybrid perovskites is still unclear and even contradictory. Therefore, in this work based on density functional theory (DFT), the binding mechanism between organic cation and anion was systematically investigated through electronic structure analysis including an examination of the electronic localization function (ELF), electron density difference (EDD), reduced density gradient (RDG), and energy decomposition analysis (EDA). The binding strength is mainly determined by Coulomb effect and orbital polarization. Based on the above analysis, a novel 2D linear regression descriptor that Eb =  - 9.75Q2/R0 + 0.00053 V∙EHL - 6.11 with coefficient of determination R2 = 0.88 was proposed to evaluate the binding strength (the units for Q, R0, V, and EHL are |e|, Å, bohr3, and eV, respectively), revealing that larger Coulomb effect (Q2/R0), smaller volume of perovskite (V), and narrower energy difference (EHL) between the lowest unoccupied molecular orbital (LUMO) of organic cation and the highest occupied molecular orbital (HOMO) of anion correspond to the stronger binding strength, which guides the design of highly stable organic-inorganic hybrid perovskites.