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Composition and phase engineering of metal chalcogenides and phosphorous chalcogenides

Abstract

Two-dimensional (2D) materials with multiphase, multielement crystals such as transition metal chalcogenides (TMCs) (based on V, Cr, Mn, Fe, Cd, Pt and Pd) and transition metal phosphorous chalcogenides (TMPCs) offer a unique platform to explore novel physical phenomena. However, the synthesis of a single-phase/single-composition crystal of these 2D materials via chemical vapour deposition is still challenging. Here we unravel a competitive-chemical-reaction-based growth mechanism to manipulate the nucleation and growth rate. Based on the growth mechanism, 67 types of TMCs and TMPCs with a defined phase, controllable structure and tunable component can be realized. The ferromagnetism and superconductivity in FeXy can be tuned by the y value, such as superconductivity observed in FeX and ferromagnetism in FeS2 monolayers, demonstrating the high quality of as-grown 2D materials. This work paves the way for the multidisciplinary exploration of 2D TMPCs and TMCs with unique properties.

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Fig. 1: Kinetic growth mode for the controllable synthesis of MaXb and MmPnXz with different phases and compositions.
Fig. 2: Optical images of as-synthesized TMCs and TMPCs.
Fig. 3: Growth mechanism of 3d-metal-based 2D materials.
Fig. 4: STEM characterizations of the as-synthesized 2D materials.
Fig. 5: Physical properties of selected Fe-based TMCs by tuning the compositions.

Data availability

The main data supporting the findings of this study are available within the article and Supplementary Information. Additional data are available from the corresponding authors upon reasonable request.

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Acknowledgements

This work was supported by the National Key R&D Program of China (grant no. 2020YFA0308800) and the NSF of China (grant nos. 62174013, 11504046 12061131002 and 11734003). This work was also supported by the National Research Foundation—Competitive Research Program (NRF-CRP22-2019-0007, NRF-CRP21-2018-0007 and NRF2020-NRF-ISF004-3520). This work was also supported by the Singapore Ministry of Education Tier 3 Programme ‘Geometrical Quantum Materials’ (MOE2018-T3-1-002), AcRF Tier 2 (MOE2019-T2-2-105) and AcRF Tier 1 RG161/19 and RG7/21. W.B.G. acknowledges the support of NRF CRP by NRF-CRP22-2019-0004. G.L. and L. Lu acknowledge fundings from the National Natural Science Foundation of China under grant numbers 92065203 and 11874406, and the Strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDB33010300). Y.Y. was supported by the National Key R&D Program of China (grant no. 2016YFA0300600). C.Z. acknowledges the Fundamental Research Funds for the central Universities. F.D. and J.D. acknowledge funding from the Institute for Basic Science, Republic of Korea (IBS‐R019‐D1) and the use of the IBS‐CMCM high‐performance computing system Cimulator. This work was also supported by the Innovation Program of Shanghai Municipal Education Commission (no. 2019-01-07-00-09-E00020) and Shanghai Municipal Science and Technology Commission (18JC1412800). Y.-C.L. and K.S. acknowledge JSPS-KAKENHI (JP16H06333 and 18K14119), JSPS A3 Foresight Program and Kazato Research Encouragement Prize. H. Yang acknowledges funding from the Chinese Academy of Sciences (grant nos. XDB33030100). Y.Y. acknowledges the Strategic Priority Research Program of the Chinese Academy of Sciences (grant no. XDB30000000).

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Authors

Contributions

J.Z. and Y. Zhou observed the growth mechanism and grew all the materials. J.Z. carried out the Raman and AFM characterizations. C.Z. performed the STEM characterizations and data analysis of the Fe-based samples other than Fe3GeTe2. Y.-C.L. and K.S. analysed Fe3GeTe2 and all the metal phosphorous chalcogenides. J.Z., Y. Zhou, C. Z. and Z.L. analysed the growth mechanism. Y. Zhou, J.Z. and B.T. performed the X-ray photoelectron spectroscopy test. Y. Zhou, H. Yu and Y.G. performed the TGA-DSC measurements. G.L., R.Z. and Y.Y. performed the electronic structure calculations. J.D. and F.D. performed the DFT calculations on the formation mechanism of FeSx with different compositions and phases. P.L. and G.L. measured the superconductivity in FeX and ferromagnetism in FeS2. J.S. measured the SHG properties in MPX3. Z.W. and W.H. used the infrared photodetector for FeTe2. J.Z., Y. Zhou, C.Z., G.-B.L., Y.Y. and Z.L. wrote the paper. All the authors discussed and commented on the manuscript.

Corresponding authors

Correspondence to Jiadong Zhou, Yeliang Wang, Yugui Yao or Zheng Liu.

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Nature Materials thanks Sufei Shi and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Supplementary Figs. 1–84, Tables 1–6 and Sections 1–5.

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Zhou, J., Zhu, C., Zhou, Y. et al. Composition and phase engineering of metal chalcogenides and phosphorous chalcogenides. Nat. Mater. (2022). https://doi.org/10.1038/s41563-022-01291-5

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