Growth mechanisms and anisotropic softness-dependent conductivity of orientation-controllable metal-organic framework nanofilms.

Yao, Ming-Shui; Otake, Ken-Ichi; Koganezawa, Tomoyuki; Ogasawara, Moe; Asakawa, Hitoshi; Tsujimoto, Masahiko; Xue, Zi-Qian; Li, Yan-Hong et al. · Proc Natl Acad Sci U S A · 2023

basic_science · Level V

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Abstract

Conductive metal-organic frameworks (<i>c</i>MOFs) manifest great potential in modern electrical devices due to their porous nature and the ability to conduct charges in a regular network. <i>c</i>MOFs applied in electrical devices normally hybridize with other materials, especially a substrate. Therefore, the precise control of the interface between <i>c</i>MOF and a substrate is particularly crucial. However, the unexplored interface chemistry of <i>c</i>MOFs makes the controlled synthesis and advanced characterization of high-quality thin films, particularly challenging. Herein, we report the development of a simplified synthesis method to grow "face-on" and "edge-on" <i>c</i>MOF nanofilms on substrates, and the establishment of operando characterization methodology using atomic force microscopy and X-ray, thereby demonstrating the relationship between the soft structure of surface-mounted oriented networks and their characteristic conductive functions. As a result, crystallinity of <i>c</i>MOF nanofilms with a thickness down to a few nanometers is obtained, the possible growth mechanisms are proposed, and the interesting anisotropic softness-dependent conducting properties (over 2 orders of magnitude change) of the <i>c</i>MOF are also illustrated.