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.

Topological versus chemical ordering in network glasses at intermediate and extended length scales

Nature volume 435, pages 75–78 (2005)Cite this article

Abstract

Atomic ordering in network glasses on length scales longer than nearest-neighbour length scales has long been a source of controversy1,2,3,4,5,6. Detailed experimental information is therefore necessary to understand both the network properties and the fundamentals of glass formation. Here we address the problem by investigating topological and chemical ordering in structurally disordered AX2 systems by applying the method of isotopic substitution in neutron diffraction to glassy ZnCl2. This system may be regarded as a prototypical ionic network forming glass, provided that ion polarization effects are taken into account7, and has thus been the focus of much attention8,9,10,11,12,13,14. By experiment, we show that both the topological and chemical ordering are described by two length scales at distances greater than nearest-neighbour length scales. One of these is associated with the intermediate range, as manifested by the appearance in the measured diffraction patterns of a first sharp diffraction peak at 1.09(3) Å-1; the other is associated with an extended range, which shows ordering in the glass out to 62(4) Å. We also find that these general features are characteristic of glassy GeSe2, a prototypical covalently bonded network material15,16. The results therefore offer structural insight into those length scales that determine many important aspects of supercooled liquid and glass phenomenology11.

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

Relevant articles

Open Access articles citing this article.

Access options

Rent or buy this article

Get just this article for as long as you need it

$39.95

Learn more

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

Figure 1: An illustration of topological versus chemical ordering in disordered network systems.
Figure 2: The measured Bhatia–Thornton partial structure factors for glassy ZnCl2 and GeSe2.
Figure 3: The measured partial pair distribution functions for glassy ZnCl2 and GeSe2.
Figure 4: Extended range ordering is found for glassy ZnCl2 and GeSe2.

References

  1. Moss, S. C. & Price, D. L. in Physics of Disordered Materials (eds Adler, D., Fritzsche, H. & Ovshinsky, S. R.) 77–95 (Plenum, New York, 1985)

    Book  Google Scholar 

  2. Elliott, S. R. Medium-range structural order in covalent amorphous solids. Nature 354, 445–452 (1991)

    Article  ADS  CAS  Google Scholar 

  3. Salmon, P. S. Real space manifestation of the first sharp diffraction peak in the structure factor of liquid and glassy materials. Proc. R. Soc. Lond. A 445, 351–365 (1994)

    Article  ADS  CAS  Google Scholar 

  4. Elliott, S. R. Extended-range order, interstitial voids and the first sharp diffraction peak of network glasses. J. Non-Cryst. Solids 182, 40–48 (1995)

    Article  ADS  CAS  Google Scholar 

  5. Gaskell, P. H. & Wallis, D. J. Medium-range order in silica, the canonical network glass. Phys. Rev. Lett. 76, 66–69 (1996)

    Article  ADS  CAS  Google Scholar 

  6. Massobrio, C., Celino, M. & Pasquarello, A. Charge fluctuations and concentration fluctuations at intermediate-range distances in the disordered network-forming materials SiO2, SiSe2, and GeSe2 . Phys. Rev. B 70, 174202 (2004)

    Article  ADS  Google Scholar 

  7. Wilson, M. & Madden, P. A. Short- and intermediate-range order in MCl2 melts: the importance of anionic polarization. J. Phys. Condens. Matter 5, 6833–6844 (1993)

    Article  ADS  CAS  Google Scholar 

  8. Angell, C. A. & Wong, J. Structure and glass transition thermodynamics of liquid zinc chloride from far-infrared, Raman and probe ion electronic and vibrational spectra. J. Chem. Phys. 53, 2053–2066 (1970)

    Article  ADS  CAS  Google Scholar 

  9. Biggin, S. & Enderby, J. E. The structure of molten zinc chloride. J. Phys. C 14, 3129–3136 (1981)

    Article  ADS  CAS  Google Scholar 

  10. Desa, J. A. E., Wright, A. C., Wong, J. & Sinclair, R. N. A neutron diffraction investigation of the structure of vitreous zinc chloride. J. Non-Cryst. Solids 51, 57–86 (1982)

    Article  ADS  CAS  Google Scholar 

  11. Angell, C. A. Spectroscopy simulation and scattering, and the medium range order problem in glass. J. Non-Cryst. Solids 73, 1–17 (1985)

    Article  ADS  CAS  Google Scholar 

  12. Wilson, M. & Madden, P. A. Voids, layers and the first sharp diffraction peak in ZnCl2 . Phys. Rev. Lett. 80, 532–535 (1998)

    Article  ADS  CAS  Google Scholar 

  13. Polsky, C. H. et al. Pressure-induced crystallization of vitreous ZnCl2 . Phys. Rev. B 61, 5934–5938 (2000)

    Article  ADS  CAS  Google Scholar 

  14. Wilson, M. Nucleation and growth of polytypic-layered crystals from the network liquid zinc chloride. J. Chem. Phys. 118, 9838–9853 (2003)

    Article  ADS  CAS  Google Scholar 

  15. Petri, I., Salmon, P. S. & Fischer, H. E. Defects in a disordered world: the structure of glassy GeSe2 . Phys. Rev. Lett. 84, 2413–2416 (2000)

    Article  ADS  CAS  Google Scholar 

  16. Salmon, P. S. & Petri, I. Structure of glassy and liquid GeSe2 . J. Phys. Condens. Matter 15, S1509–S1528 (2003)

    Article  ADS  CAS  Google Scholar 

  17. Boolchand, P. (ed.) Insulating and Semiconducting Glasses (World Scientific, Singapore, 2000)

  18. Angell, C. A. Formation of glasses from liquids and biopolymers. Science 267, 1924–1935 (1995)

    Article  ADS  CAS  Google Scholar 

  19. Crichton, W. A., Mezouar, M., Grande, T., Stølen, S. & Grzechnik, A. Breakdown of intermediate-range order in liquid GeSe2 at high pressure. Nature 414, 622–625 (2001)

    Article  ADS  CAS  Google Scholar 

  20. Martin, J. D., Goettler, S. J., Fossé, N. & Iton, L. Designing intermediate-range order in amorphous materials. Nature 419, 381–384 (2002)

    Article  ADS  CAS  Google Scholar 

  21. Salmon, P. S. Order within disorder. Nature Mater. 1, 87–88 (2002)

    Article  ADS  CAS  Google Scholar 

  22. Ziman, J. M. Models of Disorder (CUP, Cambridge, 1979)

    Google Scholar 

  23. Zachariasen, W. H. The atomic arrangement in glass. J. Am. Chem. Soc. 54, 3841–3851 (1932)

    Article  CAS  Google Scholar 

  24. Wright, A. C. et al. The structure of some simple amorphous network solids revisited. J. Non-Cryst. Solids 129, 213–232 (1991)

    Article  ADS  CAS  Google Scholar 

  25. Bhatia, A. B. & Thornton, D. E. Structural aspects of the electrical resistivity of binary alloys. Phys. Rev. B 2, 3004–3012 (1970)

    Article  ADS  Google Scholar 

  26. Salmon, P. S. The structure of molten and glassy 2:1 binary systems: an approach using the Bhatia-Thornton formalism. Proc. R. Soc. Lond. A 437, 591–606 (1992)

    Article  ADS  CAS  Google Scholar 

  27. Grimley, D. I., Wright, A. C. & Sinclair, R. N. Neutron scattering from vitreous silica. J. Non-Cryst. Solids 119, 49–64 (1990)

    Article  ADS  CAS  Google Scholar 

  28. Stølen, S., Grande, T. & Johnsen, H.-B. Fragility transition in GeSe2-Se liquids. Phys. Chem. Chem. Phys. 4, 3396–3399 (2002)

    Article  Google Scholar 

  29. Ludwig, K. F. Jr, Warburton, W. K., Wilson, L. & Bienenstock, A. I. Liquid GeBr4. 1. A test of the anomalous x-ray scattering method as applied to disordered materials. J. Chem. Phys. 87, 604–612 (1987)

    Article  ADS  CAS  Google Scholar 

  30. Sears, V. F. Neutron scattering lengths and cross sections. Neutron News 3, 26–37 (1992)

    Article  Google Scholar 

Download references

Acknowledgements

We thank M. Skeffington for permission to use his photo in Fig. 1a, R. L. McGreevy for assistance with the isotopes, P. Palleau for help with the diffraction experiment, A. C. Barnes for discussions on the SVD method, A. C. Hannon for a powder diffraction pattern on the polycrystalline phase of ZnCl2, A. C. Wright for providing his data for glassy ZnCl2, P. Buchanan and A. K. Soper for help with an earlier experiment at ISIS, R. Evans, P. A. Madden, C. Massobrio and M. Wilson for discussions, and the EPSRC and Alliance Programme for financial support. P.E.M. made the samples, G.J.C. prepared the diffractometer and R.A.M. made the data analysis. P.S.S. conceived the experiment and was involved in all aspects of the work.

Author information

Author notes

  1. Philip E. Mason

    Present address: Department of Food Science, Stocking Hall, Cornell University, Ithaca, New York, 14853, USA

Authors and Affiliations

  1. Department of Physics, University of Bath, Bath, BA2 7AY, UK

    Philip S. Salmon & Richard A. Martin

  2. HH Wills Physics Laboratory, Royal Fort, University of Bristol, Bristol, BS8 1TL, UK

    Philip E. Mason

  3. Institut Laue-Langevin, BP 156, F-38042, Cédex 9, Grenoble, France

    Gabriel J. Cuello

Authors
  1. Philip S. Salmon
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Richard A. Martin
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Philip E. Mason
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Gabriel J. Cuello
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Philip S. Salmon.

Ethics declarations

Competing interests

The authors declare that they have no competing financial interests.

Supplementary information

Supplementary Figure S1

The measured total structure factors for glassy ZnCl2 at 25(1) °C. (DOC 301 kb)

Supplementary Figure S2

The measured total pair distribution functions for glassy ZnCl2. (DOC 83 kb)

Supplementary Figure S3

The measured Faber–Ziman partial structure factors for glassy ZnCl2. (DOC 112 kb)

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Salmon, P., Martin, R., Mason, P. et al. Topological versus chemical ordering in network glasses at intermediate and extended length scales. Nature 435, 75–78 (2005). https://doi.org/10.1038/nature03475

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature03475

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

Advanced 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