近日，北京大学刘志伟团队实现了溶剂掺入法合成零维八面体金属卤化物及其光物理性质。相关论文于2025年8月4日发表在《自然-化学》杂志上。

零维（0D）金属卤化物，其特征是分散的金属卤化物八面体点缀着大的有机铵阳离子，是卤化物钙钛矿的基石。这些材料的光学特性使它们成为发光器件的有希望的候选者。然而，开发它们的通用设计原则仍然具有挑战性。

研究组报告了一种抗溶剂掺入方法，将广泛的二维碘化锡钙钛矿转化为0D结构。这种方法适用于不同的有机阳离子和抗溶剂分子，并可扩展到锗和铅类似物。他们发现，通过有机封装来提高锡基八面体的结构刚度，可以提高辐射复合率，同时降低非辐射复合率，从而实现近单位光致发光量子产率。

基于锗和锡的结构由于局域激发态表现出大的斯托克斯位移和微秒尺度的三重态寿命，而基于铅的结构通过三重态-单线态混合表现出更快的重组，这得到了理论计算的支持。这项工作为0D金属卤化物提供了一个通用的合成平台，并加深了他们目前对卤化物钙钛矿激发态动力学的理解。

附：英文原文

Title: Synthesis of zero-dimensional octahedral metal halides through solvent incorporation and their photophysical properties

Author: Zheng, Nanlong, Cao, Songqi, Zhang, Tianhao, Huo, Peihao, Hu, Conglan, Liu, Huanyu, Guo, Ruoyao, Yan, Wenchao, Zheng, Jiayin, Jiang, Xiaofan, Zhu, Zhenyu, Sun, Junliang, Jiang, Hong, Bian, Zuqiang, Fu, Yongping, Liu, Zhiwei

Issue&Volume: 2025-08-04

Abstract: Zero-dimensional (0D) metal halides, which feature discrete metal halide octahedra interspersed with large organoammonium cations, are the building blocks of halide perovskites. The optical properties of these materials make them promising candidates in light-emitting devices. However, developing their general design principles remains challenging. Here we report an antisolvent incorporation approach that transforms a broad range of two-dimensional tin iodide perovskites into 0D structures. This approach accommodates diverse organic cations and antisolvent molecules and is extendable to germanium and lead analogues. We show that enhancing the structural rigidity in Sn-based octahedra—modulated by organic packing—increases the radiative recombination rate while decreasing the non-radiative recombination rate, achieving near-unity photoluminescence quantum yield. Ge- and Sn-based structures exhibit large Stokes shifts and microsecond-scale triplet lifetimes due to localized excited states, while their Pb-based counterpart shows faster recombination via triplet–singlet mixing, supported by theoretical calculations. This work offers a versatile synthetic platform for 0D metal halides and deepens our current understanding of excited-state dynamics in halide perovskites.

DOI: 10.1038/s41557-025-01869-x

Source: https://www.nature.com/articles/s41557-025-01869-x