Skip to main content

Thank you for visiting nature.com. 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.

  • Letter
  • Published:

Vitrification of a monatomic metallic liquid

Abstract

Although the majority of glasses in use in technology are complex mixtures of oxides or chalcogenides, there are numerous examples of pure substances—‘glassformers’—that also fail to crystallize during cooling. Most glassformers are organic molecular systems, but there are important inorganic examples too1,2, such as silicon dioxide and elemental selenium (the latter being polymeric). Bulk metallic glasses can now be made3; but, with the exception of Zr50Cu50 (ref. 4), they require multiple components to avoid crystallization during normal liquid cooling. Two-component ‘metglasses’ can often be achieved by hyperquenching, but this has not hitherto been achieved with a single-component system. Glasses form when crystal nucleation rates are slow, although the factors that create the slow nucleation conditions are not well understood. Here we apply the insights gained in a recent molecular dynamics simulation study5 to create conditions for successful vitrification of metallic liquid germanium. Our results also provide micrographic evidence for a rare polyamorphic transition preceding crystallization of the diamond cubic phase.

This is a preview of subscription content, access via your institution

Access options

Buy this article

Prices may be subject to local taxes which are calculated during checkout

Figure 1: Optical and electron micrographs of vitrified Ge.
Figure 2: Comparisons of structure factors for vitreous and liquid states of Ge from laboratory and molecular dynamics simulation studies.
Figure 3: Relation of temperature–pressure phase diagram for Ge to the temperature– λ potential diagram for Stillinger–Weber systems.

Similar content being viewed by others

References

  1. Privalko, Y. Excess entropies and related quantities in glass-forming liquids. J. Phys. Chem. 84, 3307–3312 (1980)

    Article  CAS  Google Scholar 

  2. Martinez, L. M. & Angell, C. A. A thermodynamic connection to the fragility of glass-forming liquids. Nature 410, 663–667 (2001)

    Article  ADS  CAS  Google Scholar 

  3. Johnson, W. L. Bulk glass-forming metallic alloys: science and technology. Mater. Res. Soc. Bull. 24, 42–50 (1999)

    Article  CAS  Google Scholar 

  4. Wang, W. H., Lewandowski, J. J. & Greer, A. L. Understanding the glass-forming ability of Cu50Zr50 alloys in terms of a metastable eutectic. J. Mater. Res. 20, 2307–2313 (2005)

    Article  ADS  CAS  Google Scholar 

  5. Molinero, V., Sastry, S. & Angell, C. A. Tuning of tetrahedrality in a silicon potential yields a series of monatomic (metal-like) glasse formers of very high fragility. Phys. Rev. Lett. 97, 075701 (2006)

    Article  ADS  Google Scholar 

  6. Cohen, M. H. & Turnbull, D. Composition requirements for glass formation in metallic and ionic systems. Nature 189, 131–132 (1961)

    Article  ADS  CAS  Google Scholar 

  7. van Ketel, W., Das, C. & Frenkel, D. Structural arrest in an ideal gas. Phys. Rev. Lett. 94, 135703 (2005)

    Article  ADS  Google Scholar 

  8. Hilsch, R. in Non-Crystalline Solids (ed. Frechette, V. D.) 348 (J. Wiley and Sons, New York, 1960)

    Google Scholar 

  9. Chathoth, S. M., Meyer, A., Koza, M. M. & Juranyi, F. Atomic diffusion in liquid Ni, NiP, PdNiP, and PdNiCuP alloys. Appl. Phys. Lett. 85, 4881–4883 (2004)

    Article  ADS  CAS  Google Scholar 

  10. Wachtel, E. et al. Magnetic-susceptibility and DSC study of the crystallization of melt-quenched Ni-P amorphous-alloys. Mater. Sci. Eng. A 133, 196–199 (1991)

    Article  Google Scholar 

  11. Stillinger, F. H. & Weber, T. A. Computer-simulation of local order in condensed phases of silicon. Phys. Rev. B 31, 5262–5271 (1985)

    Article  ADS  CAS  Google Scholar 

  12. Angell, C. A., Borick, S. & Grabow, M. Glass transitions and first order liquid-metal-to-semiconductor transitions in 4–5–6 covalent systems. J. Non-Cryst. Solids 207, 463–471 (1996)

    Article  ADS  Google Scholar 

  13. Brazhkin, V. V., Larchev, V. I., Popova, S. V. & Skrotskaya, G. G. The influence of high pressure on the disordering of the crystal structure of solids rapidly quenched from the melt. Phys. Scr. 39, 338–340 (1989)

    Article  ADS  CAS  Google Scholar 

  14. Tanaka, H. Simple view of waterlike anomalies of atomic liquids with directional bonding. Phys. Rev. B 66, 064202 (2002)

    Article  ADS  Google Scholar 

  15. Koga, J., Nishio, K., Yamaguchi, T. & Yonezawa, F. Tight-binding molecular dynamics study on the structural change of amorphous germanium with the increase of density. J. Phys. Soc. Jpn 73, 388–396 (2004)

    Article  ADS  CAS  Google Scholar 

  16. Schnydersy, H. S. & Van Zytveldz, J. B. Electrical resistivity and thermopower of liquid Ge and Si. J. Phys. Condens. Matter 8, 10875–10883 (1996)

    Article  ADS  Google Scholar 

  17. Zhang, F. X. & Wang, W. K. Microstructure of germanium quenched from the undercooled melt at high-pressures. Appl. Phys. Lett. 67, 617–619 (1995)

    Article  ADS  CAS  Google Scholar 

  18. Brazhkin, V. V., Lyapin, A. G., Popova, S. V. & Voloshin, R. N. Non-equilibrium phase transitions and amorphization in Si, Si/GaAs, Ge, and Ge/GaSb at the decompression of high-pressure phases. Phys. Rev. B 51, 7549–7554 (1995)

    Article  ADS  CAS  Google Scholar 

  19. Salmon, P. S. A. Neutron-diffraction study on the structure of liquid germanium. J. Phys. F 18, 2345–2352 (1988)

    Article  ADS  CAS  Google Scholar 

  20. Ankele, J., Mayer, J., Lamparter, P. & Steeb, S. Structure factor of amorphous-germanium by quantitative electron-diffraction. J. Non-Cryst. Solids 193, 679–682 (1995)

    Article  ADS  Google Scholar 

  21. Etherington, G. et al. A neutron-diffraction study of the structure of evaporated amorphous-germanium. J. Non-Cryst. Solids 48, 265–289 (1982)

    Article  ADS  CAS  Google Scholar 

  22. Benmore, C. J. et al. Intermediate range chemical ordering in amorphous and liquid water, Si, and Ge. Phys. Rev. B 72, 132201(4) (2005)

    Article  ADS  Google Scholar 

  23. Aptekar, L. I. Phase transitions in non-crystalline germanium and silicon. Sov. Phys. Dokl. 24, 993–995 (1979)

    ADS  Google Scholar 

  24. Voronin, G. A. et al. In situ X-ray diffraction study of germanium at pressures up to 11 GPa and temperatures up to 950 K. J. Phys. Chem. Solids 64, 2113–2119 (2003)

    Article  ADS  CAS  Google Scholar 

  25. Li, D. & Herbach, D. M. Containerless solidification of germanium by electromagnetic levitiatioins and in a drop-tube. J. Mater. Sci. 32, 1437–1442 (1997)

    Article  ADS  CAS  Google Scholar 

  26. Sastry, S. & Angell, C. A. Liquid–liquid phase transition in supercooled liquid silicon. Nature Mater. 2, 739–743 (2003)

    Article  ADS  CAS  Google Scholar 

  27. Ponyatovsky, G. G. A thermodynamic approach to T-P phase diagrams of substances in liquid and amorphous states. J. Phys. Condens. Matter 15, 6123–6141 (2003)

    Article  ADS  CAS  Google Scholar 

  28. Mishima, O. Reversible transition between two H2O amorphs at 0.2 GPa and 135 K. J. Chem. Phys. 100, 5910–5919 (1991)

    Article  ADS  Google Scholar 

  29. Aasland, S. & McMillan, P. F. Density-driven liquid–liquid phase-separation in the system Al2O3–Y2O3 . Nature 369, 633–636 (1994)

    Article  ADS  CAS  Google Scholar 

  30. Kurita, R. & Tanaka, H. Critical-like phenomena associated with liquid-liquid transition in a molecular liquid. Science 306, 845–848 (2004)

    Article  ADS  CAS  Google Scholar 

  31. Spaepen, F. & Turnbull, D. in Laser-Solid Interactions and Laser Processing 1978 (eds Ferris, S. D., Leamy, H. J. & Poate, J.). AIP Conf. Proc. 50, 73–83 (1979)

    Google Scholar 

  32. Stanley, H. E. et al. The puzzling behavior of water at very low temperature. Phys. Chem. Chem. Phys. 2, 1551–1558 (2000)

    Article  CAS  Google Scholar 

  33. Rez, D., Rez, P. & Grant, I. Dirac-Fock calculations of X-ray scattering factors and contributions to the mean inner potential for electron scattering. Acta Crystallogr. A 50, 481–497 (1994)

    Article  Google Scholar 

  34. Plimpton, S. Fast parallel algorithms for short-range molecular-dynamics. J. Comput. Phys. 117, 1–19 (1995)

    Article  ADS  CAS  Google Scholar 

  35. Grabow, M. H. & Gilmer, G. H. Thin-film growth modes, wetting and cluster nucleation. Surf. Sci. 194, 333–346 (1988)

    Article  ADS  CAS  Google Scholar 

  36. Yu, W. B. & Stroud, D. Molecular-dynamics study of surface segregation in liquid semiconductor alloys. Phys. Rev. B 56, 12243–12249 (1997)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

We thank C. Benmore and Q. Mei for the attempted in situ studies of melt-quenched samples at the Argonne APS. We acknowledge the allocation of computer time at the Center for High Performance Computing at the University of Utah, where the simulations on Ge were carried out. The cooperation of D. Matyushov and his group (whose Arizona State University computing facilities were used for the Si simulations) is also appreciated. We also thank our NSF-CRC colleagues P. Debenedetti, G. Stanley and P. Rossky for discussions. This work was supported by NSF grants from the Chemistry CRC (to C.A.A.), the DMR Solid State Chemistry (to C.A.A.), the NSF Chemistry (to J.L.Y.), the Carnegie/DOE Alliance Center (DOE-NNSA CDAC) (to J.L.Y.) and the Swarnajayanti Fellowship, DST, India (to S.S.). The TEM studies depended on the John M. Cowley Center for High Resolution Electron Microscopy.

Author Contributions C.A.A., V.M. and S.S. conceived the project as part of previous work5. J.L.Y. recommended and directed the DAC investigation, M.H.B. and E.S. executed the sample mounting, laser pulse melting, and Raman characterization experiments, V.C.S. and M.H.B. performed the TEM studies, V.M. carried out both preliminary Si and later Ge molecular dynamics simulations, and wrote the results analysis given in the Supplementary Information, and C.A.A. wrote the paper (with advice and criticism from all co-authors).

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to C. A. Angell.

Ethics declarations

Competing interests

Reprints and permissions information is available at www.nature.com/reprints. The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Notes illustrated with Supplementary Figures and additional refrences. (PDF 795 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Bhat, M., Molinero, V., Soignard, E. et al. Vitrification of a monatomic metallic liquid. Nature 448, 787–790 (2007). https://doi.org/10.1038/nature06044

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature06044

This article is cited by

Comments

By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.

Search

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