Optical, Electronic, and Magnetic Engineering of ⟨111⟩ Layered Halide Perovskites

Antimony and bismuth ⟨111⟩ layered perovskites have recently attracted significant attention as possible, nontoxic alternatives to lead halide perovskites. Unlike lead halide perovskites, however, ⟨111⟩ halide perovskites have shown limited ability to tune their optical and electronic properties. Herein, we report on the metal alloying of manganese and copper into the family of materials with formula Cs4Mn1–xCuxSb2Cl12 (x = 0–1). By changing the concentration of manganese and copper, we show the ability to modulate the bandgap of this family of compounds over the span of 2 electron volts, from 3.0 to 1.0 eV. Furthermore, we show that in doing so, we can also adjust other relevant properties such as their magnetic behavior and their electronic structure.近年来，⟨111⟩层状锑基与铋基钙钛矿（antimony and bismuth ⟨111⟩ layered perovskites）作为卤化铅钙钛矿（lead halide perovskites）的潜在无毒替代材料，受到了学界的广泛关注。然而，与卤化铅钙钛矿不同，⟨111⟩卤化物钙钛矿在光学与电子性质的调控能力上较为有限。本文报道了将锰与铜合金化引入通式为Cs₄Mn₁₋ₓCuₓSb₂Cl₁₂（x=0~1）的材料家族的研究工作。通过调控锰与铜的掺杂浓度，我们可将该类化合物的带隙调节至2电子伏特范围内，覆盖3.0 eV至1.0 eV区间。此外，研究表明，通过该策略还可同步调控该体系的其他相关性质，例如磁学行为与电子结构。