Zheng Rui, Fu Zhi-Hua, Deng Wei-Hua, Wen Yingyi, Wu Ai-Qian, Ye Xiao-Liang, Xu Gang
State Key Laboratory of Structural Chemistry, Fujian Institute of, Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian, 350002, China.
University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2022 Oct 24;61(43):e202212797. doi: 10.1002/anie.202212797. Epub 2022 Sep 21.
The layer-by-layer liquid-phase epitaxy (LBL-LPE) method is widely used in preparing metal-organic framework (MOF) thin films with the merits of controlling thickness and out-of-plane orientation for superior performances in applications. The LBL-LPE growth mechanism related to the grain boundary, structure defect, and orientation is critical but very challenging to study. In this work, a novel "in-plane self-limiting and self-repairing" thin-film growth mechanism is demonstrated by the combination study of the grain boundary, structure defect, and orientation of Cu (HHTP) -xC thin film via microscopic analysis techniques and electrical measurements. This mechanism results a desired high-quality MOF thin film with preferred in-plane orientations at its bottom for the first time and is very helpful for optimizing the LBL-LPE method, understanding the growth cycle-dependent properties of MOF thin film, and inspiring the investigations of the biomimetic self-repairing materials.
逐层液相外延(LBL-LPE)方法被广泛用于制备金属有机框架(MOF)薄膜,该方法具有控制厚度和面外取向的优点,可在应用中实现卓越性能。与晶界、结构缺陷和取向相关的LBL-LPE生长机制至关重要,但研究起来极具挑战性。在这项工作中,通过对Cu(HHTP)-xC薄膜的晶界、结构缺陷和取向进行微观分析技术和电学测量的联合研究,证明了一种新颖的“面内自限和自修复”薄膜生长机制。这种机制首次产生了底部具有优选面内取向的高质量MOF薄膜,对于优化LBL-LPE方法、理解MOF薄膜的生长周期依赖性特性以及激发对仿生自修复材料的研究非常有帮助。