Crystalline boron monosulfide nanosheets with tunable bandgaps

Haruki Kusaka; Ryota Ishibiki; Masayuki Toyoda; Takeshi Fujita; Tomoharu Tokunaga; Akiyasu Yamamoto; Masashi Miyakawa; Kyosuke Matsushita; Keisuke Miyazaki; Linghui Li; Satish Laxman Shinde; Mariana S. L. Lima; Takeaki Sakurai; Eiji Nishibori; Takuya Masuda; Koji Horiba; Kenji Watanabe; Susumu Saito; Masahiro Miyauchi; Takashi Taniguchi; Hideo Hosono; Takahiro Kondo

doi:10.1039/D1TA03307G

Crystalline boron monosulfide nanosheets with tunable bandgaps†

Haruki Kusaka,‡^a Ryota Ishibiki,‡^a Masayuki Toyoda,

‡^b Takeshi Fujita,

^c Tomoharu Tokunaga,^d Akiyasu Yamamoto,

^ef Masashi Miyakawa,^g Kyosuke Matsushita,^h Keisuke Miyazaki,ⁱ Linghui Li,^a Satish Laxman Shinde,^j Mariana S. L. Lima,

^a Takeaki Sakurai,

^kl Eiji Nishibori,

^lm Takuya Masuda,^h Koji Horiba,ⁿ Kenji Watanabe,

^g Susumu Saito,^bfo Masahiro Miyauchi,

ⁱ Takashi Taniguchi,^p Hideo Hosono

^fp and Takahiro Kondo

*^fjl

Author affiliations

* Corresponding authors

^a Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan

^b Department of Physics, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan

^c School of Environmental Science and Engineering, Kochi University of Technology, Kochi 782-8502, Japan

^d Graduate School of Engineering Materials Design Innovation Engineering, Nagoya University, Aichi 464-8601, Japan

^e Institute of Engineering, Tokyo University of Agriculture and Technology, Tokyo 183-8538, Japan

^f Materials Research Centre for Element Strategy, Tokyo Institute of Technology, Yokohama 226-8503, Japan

^g Research Center for Functional Materials, National Institute for Materials Science, Tsukuba 305-0044, Japan

^h Center for Green Research on Energy and Environmental Materials, National Institute for Materials Science, Tsukuba 305-0044, Japan

ⁱ Department of Materials Science and Engineering, School of Materials and Chemical Technology, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8552, Japan

^j Department of Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan

^k Department of Applied Science, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan

^l Tsukuba Research Center for Energy Materials Science, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8573, Japan

^m Department of Physics, Faculty of Pure and Applied Sciences, University of Tsukuba, Tsukuba 305-8571, Japan

ⁿ Condensed Matter Research Center and Photon Factory, Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tsukuba 305-0801, Japan

^o Advanced Research Center for Quantum Physics and Nanoscience, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551, Japan

^p International Center for Materials Nanoarchitectonics, National Institute for Materials Science, Tsukuba 305-0044, Japan

Abstract

Two-dimensional (2D) boron monosulfide (BS) nanosheets are predicted to have several stable phases and unique electronic structures, endowing them with interesting attributes, including superconducting, thermoelectric, and hydrogen storage properties. In this paper, we report the experimental realization of 2D BS nanosheets by the physical exfoliation of rhombohedral boron monosulfide (r-BS). Moreover, we demonstrate the facile separation of a mixture of 2D BS nanosheets and the r-BS powder in acetonitrile; the former were selectively separated as a dispersion in the supernatant, whereas the latter remained in the precipitate. In addition, density functional theory calculations reveal a clear dependence of the bandgap energy (E_g) on the number of layers of stacked BS nanosheets, where E_g for BS nanosheets is approximately 1.0 eV higher than that for r-BS. Atomic force microscopy, cathode luminescence, ultraviolet-visible absorption spectroscopy, and excitation emission matrix experiments revealed a consistent bandgap difference of approximately 1.0 eV between the BS nanosheets and r-BS. We also demonstrate the applications based on the properties that originated from the difference in the bandgap between r-BS and BS nanosheets using photoelectrochemical current switching. These results indicate that the nanosheet bandgap can be tuned to a desired value by controlling the number of stacked 2D BS nanosheets. Therefore, BS nanosheets are promising non-metal 2D materials for applications requiring bandgap control, such as electronics and photocatalysis.

Journal of Materials Chemistry A

Crystalline boron monosulfide nanosheets with tunable bandgaps†

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