Decreasing toxicity and increasing photoconversion efficiency by Sn-substitution of Pb in 5-ammonium valeric...

The toxicity of Pb in halide-based hybrid perovskite materials stands in the way of their more extensive use, despite their excellent optical properties, high stability and very good photoconversion efficiency. The presented work focuses on addressing the toxicity issues in 2D perovskites. We use 5-ammonium valeric acid (AVA) as an organic spacer and partially or completely eliminate Pb by Sn and apply first principles-based density functional theory (DFT) calculations to determine the properties of these systems. Structural insights are gained, which predict the major changes in the inorganic framework including the metal-halide bond length and the bridging angle between two octahedral configurations. The replacement of Pb by Sn leads to a drastic reduction of the electronic band gap from 1.84 to 1.04 eV. Increasing the Sn content results in Sn-I bonds being stronger than the Pb-I bonds, which entails strong s-p coupling. The calculated effective masses of excitons decrease by up to ∼23% in the case of lead-free perovskites, which can be attributed to the more dispersive band edges due to stronger s-p coupling. The reduction of the effective masses of the charge carriers and the electronic band gap results in high electrical conductivity for the AVA₂(MA)Sn₂I₇ 2D perovskite structure. The three structures compared, where AVA₂(MA)XI₇ (X = Pb₂, PbSn, Sn₂) exhibit excellent thermoelectric power factors, which suggests promising applications for heat energy conversion. Moving toward lead-free 2D perovskites, the real part of the dielectric constants enhances, which may limit the radiative recombination of charge carriers. Furthermore, reducing the bandgap values by the substitution of Sn results in a red-shift in the edge of the absorption coefficients. Using the spectroscopic limited maximum efficiency (SLME) model, the best efficiencies of 32.20 and 30.08% are achieved for the AVA₂(MA)PbSnI₇ and AVA₂(MA)Sn₂I₇ structures. The comparison of all three structures demonstrates that lead-free 2D perovskites are very good candidates for highly efficient solar energy conversion.