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journal article·2022-04Open access

Heterometallic Benzenehexathiolato Coordination Nanosheets: Periodic Structure Improves Crystallinity and Electrical Conductivity

Ryojun Toyoda, Naoya Fukui, Dionisius H. L. Tjhe, Ekaterina Selezneva, Hiroaki Maeda, Cédric Bourgès, Choon Meng Tan, Kenji Takada, Yuanhui Sun, Ian Jacobs, Kazuhide Kamiya, Hiroyasu Masunaga, Takao Mori, Sono Sasaki, Henning Sirringhaus, Hiroshi Nishihara

Advanced Materials· Volume 34· Issue 13
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Abstract

Abstract Coordination nanosheets are an emerging class of 2D, bottom‐up materials having fully π‐conjugated, planar, graphite‐like structures with high electrical conductivities. Since their discovery, great effort has been devoted to expand the variety of coordination nanosheets; however, in most cases, their low crystallinity in thick films hampers practical device applications. In this study, mixtures of nickel and copper ions are employed to fabricate benzenehexathiolato (BHT)‐based coordination nanosheet films, and serendipitously, it is found that this heterometallicity preferentially forms a structural phase with improved film crystallinity. Spectroscopic and scattering measurements provide evidence for a bilayer structure with in‐plane periodic arrangement of copper and nickel ions with the NiCu2BHT formula. Compared with homometallic films, heterometallic films exhibit more crystalline microstructures with larger and more oriented grains, achieving higher electrical conductivities reaching metallic behaviors. Low dependency of Seebeck coefficient on the mixing ratio of nickel and copper ions supports that the large variation in the conductivity data is not caused by change in the intrinsic properties of the films. The findings open new pathways to improve crystallinity and to tune functional properties of 2D coordination nanosheets.
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Research context

Nanomaterials

OpenAlex topics: Metal-Organic Frameworks: Synthesis and Applications · Graphene research and applications · Organic and Molecular Conductors Research

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry, Graduate School of Science The University of Tokyo 7‐3‐1 Hongo, Bunkyo‐ku Tokyo 113‐0033 Japan

Research Center for Science and Technology Tokyo University of Science 2641 Yamazaki Noda Chiba 278‐8510 Japan

Cavendish Laboratory University of Cambridge JJ Thomson Avenue Cambridge CB3 0HE UK

WPI International Center for Materials Nanoarchitechtonics (WPI‐MANA) National Institute for Materials Science (NIMS) Namiki 1‐1 Tsukuba 305‐0044 Japan

Research Center for Solar Energy Chemistry Osaka University 1–3 Machikaneyama Toyonaka Osaka 560‐8531 Japan

Graduate School of Engineering Science Osaka University 1–3 Machikaneyama Toyonaka Osaka 560‐8531 Japan

Japan Synchrotron Radiation Research Institute (JASRI) 1‐1‐1 Kouto, Sayo‐cho Sayo‐gun Hyogo 679‐5198 Japan

Faculty of Fiber Science and Engineering Kyoto Institute of Technology 1 Matsugasaki Hashikami‐cho Sakyo‐ku Kyoto 606‐8585 Japan

RIKEN SPring‐8 Centre 1‐1‐1 Kouto, Sayo‐cho Sayo‐gun Hyogo 679‐5148 Japan

Funding

Japan Science and Technology Agency · Japan Society for the Promotion of Science · Japan Society for the Promotion of Science London · Engineering and Physical Sciences Research Council

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