美国加州大学洛杉矶分校段镶锋小组的最新研究开发出金属卤化物多孔骨架超晶格。这一研究成果发表在2025年2月5日出版的国际学术期刊《自然》上。

据介绍，化学成分空间调制的超晶格结构允许创造具有可定制的周期性电位地貌，和可调谐的电子和光学性质的人造材料。具有一维可设计电位调制的传统半导体超晶格，使高电子迁移率晶体管和量子级联激光器成为可能。

最近，通过多尺度构建单元的自组装或引导组装，已经构建了各种超晶格，包括零维纳米团簇和纳米颗粒，一维纳米棒和纳米线，二维纳米层和纳米片，以及混合二维分子组装。这些自组装的超晶格具有二维或三维的周期性结构调制，但由于组成单元之间的界面不可避免的结构无序，往往缺乏原子级别精度。

在这篇文章中，研究人员报告了由零、一维和二维建筑单元的周期性排列组成的多维单晶超晶格的一锅合成。利用锆（IV）金属有机骨架作为宿主模板，通过配位辅助组装策略实现金属卤化物亚晶格的定向成核和精确生长，研究组合成了一系列单晶多孔超晶格。

单晶X射线晶体学和高分辨率透射电子显微镜，清晰地分辨出具有确定原子坐标的高阶超晶格结构。用选定的胺分子进一步处理可产生具有高度可调光致发光，和热效应的钙钛矿样超晶格。他们的研究创造了一个高阶单晶多孔超晶格的平台，为定制传统晶体固体无法达到的电子、光学和量子特性提供了机会。

附：英文原文

Title: Metal-halide porous framework superlattices

Author: Zhang, Wenqiang, Jiang, Hong, Liu, Yikuan, Hu, Yue, Palakkal, Athulya Surendran, Zhou, Yujie, Sun, Meng, Du, Enping, Gong, Wei, Zhang, Qun, Jiang, Jianwen, Dong, Jinqiao, Liu, Yan, Li, Dehui, Zhu, Yihan, Cui, Yong, Duan, Xiangfeng

Issue&Volume: 2025-02-05

Abstract: The construction of superlattices with a spatial modulation of chemical compositions allows for the creation of artificial materials with tailorable periodic potential landscapes and tunable electronic and optical properties1,2,3,4,5. Conventional semiconductor superlattices with designable potential modulation in one dimension has enabled high-electron-mobility transistors and quantum-cascade lasers. More recently, a diverse set of superlattices has been constructed through self-assembly or guided assembly of multiscale building units, including zero-dimensional nanoclusters and nanoparticles6,7, one-dimensional nanorods and nanowires8,9, two-dimensional nanolayers and nanosheets10,11,12,13, and hybrid two-dimensional molecular assemblies14,15,16,17. These self-assembled superlattices feature periodic structural modulation in two or three dimensions, but often lack atomic precision owing to the inevitable structural disorder at the interfaces between the constituent units. Here we report a one-pot synthesis of multi-dimensional single-crystalline superlattices consisting of periodic arrangement of zero-, one- and two-dimensional building units. By exploiting zirconium (IV) metal–organic frameworks as host templates for directed nucleation and precise growth of metal-halide sublattices through a coordination-assisted assembly strategy, we synthesize a family of single-crystalline porous superlattices. Single-crystal X-ray crystallography and high-resolution transmission electron microscopy clearly resolve the high-order superlattice structure with deterministic atomic coordinates. Further treatment with selected amine molecules produces perovskite-like superlattices with highly tunable photoluminescence and chiroptical properties. Our study creates a platform of high-order single-crystalline porous superlattices, opening opportunities to tailor the electronic, optical and quantum properties beyond the reach of conventional crystalline solids.

DOI: 10.1038/s41586-024-08447-0

Source: https://www.nature.com/articles/s41586-024-08447-0