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Conversion of non-van der Waals solids to 2D transition-metal chalcogenides

Abstract

Although two-dimensional (2D) atomic layers, such as transition-metal chalcogenides, have been widely synthesized using techniques such as exfoliation1,2,3 and vapour-phase growth4,5, it is still challenging to obtain phase-controlled 2D structures6,7,8. Here we demonstrate an effective synthesis strategy via the progressive transformation of non-van der Waals (non-vdW) solids to 2D vdW transition-metal chalcogenide layers with identified 2H (trigonal prismatic)/1T (octahedral) phases. The transformation, achieved by exposing non-vdW solids to chalcogen vapours, can be controlled using the enthalpies and vapour pressures of the reaction products. Heteroatom-substituted (such as yttrium and phosphorus) transition-metal chalcogenides can also be synthesized in this way, thus enabling a generic synthesis approach to engineering phase-selected 2D transition-metal chalcogenide structures with good stability at high temperatures (up to 1,373 kelvin) and achieving high-throughput production of monolayers. We anticipate that these 2D transition-metal chalcogenides will have broad applications for electronics, catalysis and energy storage.

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Fig. 1: Schematic illustration of the conversion of non-vdW solids to 2D vdW transition-metal chalcogenides.
Fig. 2: Structural characterization of 2D transition-metal chalcogenides derived from MAX phases.
Fig. 3: Structural characterization of 2D heteroatom-doped transition-metal chalcogenides with 2H phase derived from quaternary MAX phases.
Fig. 4: Structural characterization and electrical properties of 2D heteroatom (Y and P) co-doped WS2 with 1T phase derived from quaternary MAX-(W2/3Y1/3)2AlC.

Data availability

The data that support the findings of this study are available from the corresponding authors on reasonable request.

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Acknowledgements

This work was financially supported by the National Natural Science Foundation of China (grant numbers 51622203 and 51572007), the Youth 1000-Talent Program of China and the 111 Project (grant number B17002). X.Z. also thanks Shenzhen Basic Research Projects (grant number JCYJ20170407155608882), the China Postdoctoral Science Foundation (grant number 2018M631458) and the Development and Reform Commission of Shenzhen Municipality for the development of the “Low-Dimensional Materials and Devices” Discipline, Guangdong Innovative and Entrepreneurial Research Team Program (grant number 2017ZT07C341). We thank the Shanghai Synchrotron Radiation Facility and Beijing Synchrotron Radiation Facility for support. We thank X. Chen, Q. Zhang, W. Zhou and M. Li for help with the TEM analysis; S. Chen and Y. Lin for help with the EXAFS analysis; and L. Ma for suggestions.

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Contributions

S.Y., S.L. and P.M.A. supervised the project. S.Y. and Z.D. designed and carried out all of the experiments. S.Z. and X.Z. carried out the density functional theory calculations. S.W. and B.L. performed the scanning electron microscope, TEM and X-ray diffraction measurements. B.L. carried out the X-ray photoelectron spectroscopy and Raman analysis. L.S. contributed to the XANES and EXAFS measurements. Z.D. performed the atomic force microscopy. Z.D. and Y.G. designed the film electrodes and carried out the electrical and electrocatalytic measurements. All authors discussed the results and assisted during manuscript preparation.

Corresponding authors

Correspondence to Shubin Yang or Pulickel M. Ajayan.

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Peer review information Nature thanks Per Eklund, Wei Sun Leong and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Information

This file contains the Supplementary Information (sections 1-6), which includes Supplementary Materials and Methods, Supplementary Figures 1-73, Supplementary Tables 1-9, Supplementary Text and Supplementary References–see contents page for details.

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Du, Z., Yang, S., Li, S. et al. Conversion of non-van der Waals solids to 2D transition-metal chalcogenides. Nature 577, 492–496 (2020). https://doi.org/10.1038/s41586-019-1904-x

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