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Growth of diamond in liquid metal at 1 atm pressure

Nature (2024)Cite this article

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Abstract

Natural diamonds were (and are) formed (thousands of million years ago) in the upper mantle of Earth in metallic melts at temperatures of 900–1,400 °C and at pressures of 5–6 GPa (refs. 1,2). Diamond is thermodynamically stable under high-pressure and high-temperature conditions as per the phase diagram of carbon3. Scientists at General Electric invented and used a high-pressure and high-temperature apparatus in 1955 to synthesize diamonds by using molten iron sulfide at about 7 GPa and 1,600 °C (refs. 4,5,6). There is an existing model that diamond can be grown using liquid metals only at both high pressure and high temperature7. Here we describe the growth of diamond crystals and polycrystalline diamond films with no seed particles using liquid metal but at 1 atm pressure and at 1,025 °C, breaking this pattern. Diamond grew in the subsurface of liquid metal composed of gallium, iron, nickel and silicon, by catalytic activation of methane and diffusion of carbon atoms into and within the subsurface regions. We found that the supersaturation of carbon in the liquid metal subsurface leads to the nucleation and growth of diamonds, with Si playing an important part in stabilizing tetravalently bonded carbon clusters that play a part in nucleation. Growth of (metastable) diamond in liquid metal at moderate temperature and 1 atm pressure opens many possibilities for further basic science studies and for the scaling of this type of growth.

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Fig. 1: Synthesis of diamond on a liquid metal surface that is at an interface with graphite.
Fig. 2: Characterization of 13C-labelled as-grown diamond.
Fig. 3: TEM data of cross-sectional samples prepared by SEM-FIB.

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Data availability

The published data of this study are available on the Zenodo public database at https://doi.org/10.5281/zenodo.10803625 (ref. 58). Source data are provided with this paper.

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Acknowledgements

This work was supported by the Institute for Basic Science (IBS-R019-D1). We thank S. Y. Lee for preliminary XRD measurements at the 9C beamline of Pohang Accelerator Laboratory to evaluate the crystalline property of the diamond sample, and B. Cunning for suggesting the EDM-3 Poco Graphite sheet material and for discussions. The experiments at the PLS-II 6D and 9 C beamline were supported in part by MSIT, POSTECH and UNIST Central Research Facilities. We thank K.-S. Lee of the UNIST Center Research Facilities for making the TOF-SIMS measurements. The DFT calculations were conducted on the IBS supercomputer.

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  1. Meihui Wang

    Present address: State Key Laboratory of Materials Processing and Die & Mould Technology, School of Materials Science and Engineering, Huazhong University of Science and Technology, Wuhan, China

Authors and Affiliations

  1. Center for Multidimensional Carbon Materials (CMCM), Institute for Basic Science (IBS), Ulsan, Republic of Korea

    Yan Gong, Da Luo, Myeonggi Choe, Yongchul Kim, Babu Ram, Mohammad Zafari, Won Kyung Seong, Pavel Bakharev, Meihui Wang, Zonghoon Lee & Rodney S. Ruoff

  2. Department of Chemistry, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Yan Gong, Yongchul Kim, In Kee Park, Geunsik Lee & Rodney S. Ruoff

  3. Department of Materials Science and Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Myeonggi Choe, Zonghoon Lee & Rodney S. Ruoff

  4. UNIST Central Research Facilities (UCRF), Ulsan National University of Science and Technology (UNIST), Ulsan, Republic of Korea

    Seulyi Lee

  5. Graduate School of Semiconductor Materials and Devices Engineering, Ulsan National University of Science and Technology (UNIST), Ulsan, Republic of Korea

    Tae Joo Shin

  6. School of Energy and Chemical Engineering, Ulsan National Institute of Science and Technology (UNIST), Ulsan, Republic of Korea

    Rodney S. Ruoff

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Contributions

R.S.R. supervised the project. R.S.R., D.L. and Y.G. conceived the experiments. Y.G. did the growth experiments. Y.G. and D.L. characterized the diamond samples. W.K.S. designed, assembled and built, and tested the cold-wall system and the thermocouple probe array. M.C. and Z.L. took the TEM, STEM, EELS and EDS measurements. P.B. took the XPS measurements. T.J.S. and S.L. took the XRD measurements. Y.K., B.R., M.Z., I.K.P. and G.L. performed the theoretical calculations. M.W. contributed through discussion. Y.G. wrote a draft manuscript and R.S.R., D.L. and Y.G. revised it. All co-authors commented on the manuscript before its submission.

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Correspondence to Da Luo, Won Kyung Seong or Rodney S. Ruoff.

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Competing interests

The Institute for Basic Science has filed a patent application (KR 10-2023-0052752) that lists Y.G., D.L. and R.S.R. as inventors. Other than this, the authors declare no competing interests.

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Gong, Y., Luo, D., Choe, M. et al. Growth of diamond in liquid metal at 1 atm pressure. Nature (2024). https://doi.org/10.1038/s41586-024-07339-7

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