EaStCHEM School of Chemistry, University of St. Andrews, North Haugh, St. Andrews KY16 9ST, U.K.
Organic Semiconductor Centre, School of Physics and Astronomy, SUPA, University of St. Andrews, North Haugh, St. Andrews KY16 9SS, U.K.
Inorg Chem. 2023 Feb 27;62(8):3629-3636. doi: 10.1021/acs.inorgchem.2c04433. Epub 2023 Feb 13.
Vacancy-ordered halide perovskites have received great interest in optoelectronic applications. In this work, we report the novel inorganic halide CsMnSbCl with a distinctive 10H (10-layer hexagonal) perovskite polytype structure with (hcccc) stacking. CsMnSbCl has 30% B-site vacancies ordered at both corner- and face-sharing sites, resulting in [MnSbCl] columns, i.e., a reduction of octahedral connectivity to 1D. This results in enhanced photoluminescence in comparison to the previously reported 25% vacancy-ordered 3C polytype CsMnSbCl with 2D connectivity. This demonstrates not only the existence of the 10H perovskite structure in halides but also demonstrates the degree of B-site deficiency and stacking sequence variation as a direction to tune the optical properties of perovskite polytypes via vacancy rearrangements.
空位有序卤化物钙钛矿在光电应用中受到了广泛关注。在这项工作中，我们报道了具有独特的 10H（10 层六方）钙钛矿多型结构和（hcccc）堆叠的新型无机卤化物 CsMnSbCl。CsMnSbCl 具有 30%的 B 位空位在顶角和共面位置有序排列，形成[MnSbCl] 柱，即八面体连接性降低到 1D。与之前报道的 25%空位有序 2D 连接的 3C 多型 CsMnSbCl 相比，这导致了增强的光致发光。这不仅证明了卤化物中存在 10H 钙钛矿结构，还证明了 B 位缺陷的程度和堆叠序列变化可以通过空位重排来调节钙钛矿多型的光学性质。
