Stereochemically Active Lone Pairs and Nonlinear Optical Properties of Two-Dimensional Multilayered Tin and Germanium Iodide Perovskites

Abstract

Two-dimensional (2D) metal halide perovskites are promising tunable semiconductors. Previous studies have focused on Pb-based structures, whereas the multilayered Sn- and Ge-based analogues are largely unexplored, even though they potentially exhibit more diverse structural chemistry and properties associated with the more polarizable ns2 lone-pair electrons. Herein, we report the synthesis and structures of 2D tin iodide perovskites (BA)₂(A)Sn₂I₇, where BA = n-butylammonium and A = methylammonium, formamidinium, dimethylammonium, guanidinium, or acetamidinium, and those of 2D germanium iodide perovskites (BA)₂(A)Ge₂I₇, where A = methylammonium or formamidinium. By comparing these structures along with their Pb counterparts, we establish correlations between the effect of group IV-cation’s lone-pair stereochemical activity on the perovskite crystal structures and the resulting semiconducting properties such as bandgaps and carrier–phonon interactions and nonlinear optical properties. We find that the strength of carrier–phonon interaction increases with increasing lone-pair activity, leading to a more prominent photoluminescence tail on the low-energy side. Moreover, (BA)₂(A)Ge₂I₇ exhibit strong second harmonic generation with second-order nonlinear coefficients of ∼10 pm V⁻¹ that are at least 10 times those of Sn counterparts and 100 times those of Pb counterparts. We also report the third-order two-photon absorption coefficients of (BA)₂(A)Sn₂I₇ to be ∼10 cm MW⁻¹, which are one order of magnitude larger than those of the Pb counterparts and traditional inorganic semiconductors. These results not only highlight the role of lone-pair activity in linking the compositions and physical properties of 2D halide perovskites but also demonstrate 2D tin and germanium iodide perovskites as promising lead-free alternatives for nonlinear optoelectronic devices.