Skip to main content

Thank you for visiting You are using a browser version with limited support for CSS. To obtain the best experience, we recommend you use a more up to date browser (or turn off compatibility mode in Internet Explorer). In the meantime, to ensure continued support, we are displaying the site without styles and JavaScript.

Composition and phase engineering of metal chalcogenides and phosphorous chalcogenides


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.

Your institute does not have access to this article

Access options

Buy article

Get time limited or full article access on ReadCube.


All prices are NET prices.

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.


  1. Schaibley, J. R. et al. Valleytronics in 2D materials. Nat. Rev. Mater. 1, 16055 (2016).

    CAS  Article  Google Scholar 

  2. Radisavljevic, B., Radenovic, A., Brivio, J., Giacometti, V. & Kis, A. Single-layer MoS2 transistors. Nat. Nanotechnol. 6, 147–150 (2011).

    CAS  Article  Google Scholar 

  3. Kang, K. et al. High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity. Nature 520, 656–660 (2015).

    CAS  Article  Google Scholar 

  4. Zhou, J. et al. A library of atomically thin metal chalcogenides. Nature 556, 355–359 (2018).

    CAS  Article  Google Scholar 

  5. Lee, Y. H. et al. Synthesis of large-area MoS2 atomic layers with chemical vapor deposition. Adv. Mater. 24, 2320–2325 (2012).

    CAS  Article  Google Scholar 

  6. Kang, L. et al. Phase-controllable growth of ultrathin 2D magnetic FeTe crystals. Nat. Commun. 11, 3729 (2020).

    CAS  Article  Google Scholar 

  7. Zhang, Y. et al. Ultrathin magnetic 2D single-crystal CrSe. Adv. Mater. 31, e1900056 (2019).

    Article  Google Scholar 

  8. Chu, J. et al. Sub-millimeter-scale growth of one-unit-cell-thick ferrimagnetic Cr2S3 nanosheets. Nano Lett. 19, 2154–2161 (2019).

    CAS  Article  Google Scholar 

  9. Meng, L. et al. Anomalous thickness dependence of Curie temperature in air-stable two-dimensional ferromagnetic 1T-CrTe2 grown by chemical vapor deposition. Nat. Commun. 12, 809 (2021).

    CAS  Article  Google Scholar 

  10. Ma, H. et al. Phase-tunable synthesis of ultrathin layered tetragonal CoSe and nonlayered hexagonal CoSe nanoplates. Adv. Mater. 31, e1900901 (2019).

    Article  Google Scholar 

  11. Chen, S., Liu, H., Chen, F., Zhou, K. & Xue, Y. Synthesis, transfer, and properties of layered FeTe2 nanocrystals. ACS Nano 14, 11473–11481 (2020).

    CAS  Article  Google Scholar 

  12. Shivayogimath, A. et al. A universal approach for the synthesis of two-dimensional binary compounds. Nat. Commun. 10, 2957 (2019).

    Article  Google Scholar 

  13. Zhao, B. et al. Synthetic control of two-dimensional NiTe2 single crystals with highly uniform thickness distributions. J. Am. Chem. Soc. 140, 14217–14223 (2018).

    CAS  Article  Google Scholar 

  14. Hsu, F. C. et al. Superconductivity in the PbO-type structure α-FeSe. Proc. Natl Acad. Sci. USA 105, 14262–14264 (2008).

    CAS  Article  Google Scholar 

  15. Gudelli, V. K., Kanchana, V., Vaitheeswaran, G., Valsakumar, M. C. & Mahanti, S. D. Thermoelectric properties of marcasite and pyrite FeX2 (X = Se, Te): a first principle study. RSC Adv. 4, 9424–9431 (2014).

    CAS  Article  Google Scholar 

  16. Deng, Y. et al. Gate-tunable room-temperature ferromagnetism in two-dimensional Fe3GeTe2. Nature 563, 94–99 (2018).

    CAS  Article  Google Scholar 

  17. Wang, D. et al. Evidence for Majorana bound states in an iron-based superconductor. Science 362, 333–335 (2018).

    CAS  Article  Google Scholar 

  18. Kong, L. et al. Half-integer level shift of vortex bound states in an iron-based superconductor. Nat. Phys. 15, 1181–1187 (2019).

    CAS  Article  Google Scholar 

  19. Bansal, D. et al. Magnetically driven phonon instability enables the metal–insulator transition in h-FeS. Nat. Phys. 16, 669–675 (2020).

    CAS  Article  Google Scholar 

  20. Kang, S. et al. Coherent many-body exciton in van der Waals antiferromagnet NiPS3. Nature 583, 785–789 (2020).

    CAS  Article  Google Scholar 

  21. Li, H., Li, Y., Aljarb, A., Shi, Y. & Li, L. J. Epitaxial growth of two-dimensional layered transition-metal dichalcogenides: growth mechanism, controllability, and scalability. Chem. Rev. 118, 6134–6150 (2018).

    CAS  Article  Google Scholar 

  22. Zhang, P. et al. Multiple topological states in iron-based superconductors. Nat. Phys. 15, 41–47 (2018).

    Article  Google Scholar 

  23. Wang, Z. et al. Evidence for dispersing 1D Majorana channels in an iron-based superconductor. Science 367, 104–108 (2020).

    CAS  Article  Google Scholar 

  24. Gusmao, R., Sofer, Z. & Pumera, M. Metal phosphorous trichalcogenides (MPCh3): from synthesis to contemporary energy challenges. Angew. Chem. Int. Ed. 58, 9326–9337 (2019).

    CAS  Article  Google Scholar 

  25. Cain, J. D., Shi, F., Wu, J. & Dravid, V. P. Growth mechanism of transition metal dichalcogenide monolayers: the role of self-seeding fullerene nuclei. ACS Nano 10, 5440–5445 (2016).

    CAS  Article  Google Scholar 

  26. Zhu, D. et al. Capture the growth kinetics of CVD growth of two-dimensional MoS2. npj 2D Mater. Appl. 1, 8 (2017).

    Article  Google Scholar 

  27. Li, S. et al. Vapour–liquid–solid growth of monolayer MoS2 nanoribbons. Nat. Mater. 17, 535–542 (2018).

    CAS  Article  Google Scholar 

  28. Long, G. et al. Isolation and characterization of few-layer manganese thiophosphite. ACS Nano 11, 11330–11336 (2017).

    CAS  Article  Google Scholar 

  29. Kamihara, Y., Watanabe, T., Hirano, M. & Hosono, H. Iron-based layered superconductor La[O(1–x)Fx]FeAs (x = 0.05–0.12) with Tc = 26 K. J. Am. Chem. Soc. 130, 3296–3297 (2008).

    CAS  Article  Google Scholar 

  30. Mizuguchi, Y., Tomioka, F., Tsuda, S., Yamaguchi, T. & Takano, Y. Superconductivity at 27 K in tetragonal FeSe under high pressure. Appl. Phys. Lett. 93, 152505 (2008).

    Article  Google Scholar 

  31. Si, W. et al. Superconductivity in epitaxial thin films of Fe1.08Te:Ox. Phys. Rev. B 81, 092506 (2010).

  32. Margadonna, S. et al. Crystal structure of the new FeSe(1–x) superconductor. Chem. Commun. 2008, 5607–5609 (2008).

  33. McQueen, T. M. et al. Tetragonal-to-orthorhombic structural phase transition at 90 K in the superconductor Fe1.01Se. Phys. Rev. Lett. 103, 057002 (2009).

    CAS  Article  Google Scholar 

  34. Li, S. et al. First-order magnetic and structural phase transitions inFe1+ySexTe1−x. Phys. Rev. B 79, 054503 (2009).

    Article  Google Scholar 

  35. Kuhn, S. J. et al. Structure and property correlations in FeS. Phys. C Supercond. Appl. 534, 29–36 (2017).

    CAS  Article  Google Scholar 

  36. Terashima, T. et al. Upper critical field and quantum oscillations in tetragonal superconducting FeS. Phys. Rev. B 94, 100503 (2016).

    Article  Google Scholar 

  37. Lai, X. et al. Observation of superconductivity in tetragonal FeS. J. Am. Chem. Soc. 137, 10148–10151 (2015).

    CAS  Article  Google Scholar 

  38. Puthirath, A. B. et al. Apparent ferromagnetism in exfoliated ultrathin pyrite sheets. J. Phys. Chem. C 125, 18927–18935 (2021).

    CAS  Article  Google Scholar 

Download references


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).

Author information

Authors and Affiliations



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.

Ethics declarations

Competing interests

The authors declare no competing interests.

Peer review

Peer review information

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

Additional information

Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary information

Supplementary Information

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

Rights and permissions

Reprints and Permissions

About this article

Verify currency and authenticity via CrossMark

Cite this article

Zhou, J., Zhu, C., Zhou, Y. et al. Composition and phase engineering of metal chalcogenides and phosphorous chalcogenides. Nat. Mater. (2022).

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI:

Further reading


Quick links

Nature Briefing

Sign up for the Nature Briefing newsletter — what matters in science, free to your inbox daily.

Get the most important science stories of the day, free in your inbox. Sign up for Nature Briefing