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:

Ionic high-pressure form of elemental boron

Nature volume 457, pages 863–867 (2009)Cite this article

An Addendum to this article was published on 09 July 2009

Abstract

Boron is an element of fascinating chemical complexity. Controversies have shrouded this element since its discovery was announced in 1808: the new ‘element’ turned out to be a compound containing less than 60–70% of boron, and it was not until 1909 that 99% pure boron was obtained1. And although we now know of at least 16 polymorphs2, the stable phase of boron is not yet experimentally established even at ambient conditions3. Boron’s complexities arise from frustration: situated between metals and insulators in the periodic table, boron has only three valence electrons, which would favour metallicity, but they are sufficiently localized that insulating states emerge. However, this subtle balance between metallic and insulating states is easily shifted by pressure, temperature and impurities. Here we report the results of high-pressure experiments and ab initio evolutionary crystal structure predictions4,5 that explore the structural stability of boron under pressure and, strikingly, reveal a partially ionic high-pressure boron phase. This new phase is stable between 19 and 89 GPa, can be quenched to ambient conditions, and has a hitherto unknown structure (space group Pnnm, 28 atoms in the unit cell) consisting of icosahedral B12 clusters and B2 pairs in a NaCl-type arrangement. We find that the ionicity of the phase affects its electronic bandgap, infrared adsorption and dielectric constants, and that it arises from the different electronic properties of the B2 pairs and B12 clusters and the resultant charge transfer between them.

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

Access options

Buy this article

  • Purchase on Springer Link
  • Instant access to full article PDF
Buy now

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

Figure 1: Structures of α-B12 and γ-B28.
Figure 2: Calculated and measured X-ray diffraction patterns of γ-B28.
Figure 3: Stability of boron phases.
Figure 4: Chemical bonding in γ-B28.

Similar content being viewed by others

References

  1. Petryanov-Sokolov, I. V. (ed.) Popular Library of the Elements Ch. 5 (Nauka, 1983)

    Google Scholar 

  2. Douglas, B. E. & Ho, S.-M. Structure and Chemistry of Crystalline Solids (Springer, 2006)

    Google Scholar 

  3. Chase, M. W. J. Phys. Chem. Ref. Data 9, (1998)

  4. Oganov, A. R. & Glass, C. W. Crystal structure prediction using ab initio evolutionary algorithms: Principles and applications. J. Chem. Phys. 124, 244704 (2006)

    Article  ADS  Google Scholar 

  5. Glass, C. W., Oganov, A. R. & Hansen, N. USPEX — evolutionary crystal structure prediction. Comput. Phys. Commun. 175, 713–720 (2006)

    Article  ADS  CAS  Google Scholar 

  6. Wells, A. F. Structural Inorganic Chemistry (Clarendon, 1986)

    Google Scholar 

  7. Amberger, E. & Ploog, K. Bildung der Gitter des Reinen Bors. J. Less Common Met. 23, 21–31 (1971)

    Article  CAS  Google Scholar 

  8. Vlasse, M., Naslain, R., Kasper, J. S. & Ploog, K. Crystal structure of tetragonal boron related to α-AlB12 . J. Solid State Chem. 28, 289–301 (1979)

    Article  ADS  CAS  Google Scholar 

  9. Masago, A., Shirai, K. & Katayama-Yoshida, H. Crystal stability of α- and β-boron. Phys. Rev. B 73, 104102 (2006)

    Article  ADS  Google Scholar 

  10. van Setten, M. J., Uijttewaal, M. A., de Wijs, G. A. & de Groot, R. A. Thermodynamic stability of boron: The role of defects and zero point motion. J. Am. Chem. Soc. 129, 2458–2465 (2007)

    Article  CAS  Google Scholar 

  11. Sanz, D. N., Loubeyre, P. & Mezouar, M. Equation of state and pressure induced amorphization of β-boron from X-ray measurements up to 100 GPa. Phys. Rev. Lett. 89, 245501 (2002)

    Article  ADS  Google Scholar 

  12. Häussermann, U., Simak, S. I., Ahuja, R. & Johansson, B. Metal-nonmetal transition in the boron group elements. Phys. Rev. Lett. 90, 065701 (2003)

    Article  ADS  Google Scholar 

  13. Eremets, M. I., Struzhkin, V. W., Mao, H. K. & Hemley, R. J. Superconductivity in boron. Science 293, 272–274 (2001)

    Article  ADS  CAS  Google Scholar 

  14. Ma, Y. Z., Prewitt, C. T., Zou, G. T., Mao, H. K. & Hemley, R. J. High-pressure high-temperature x-ray diffraction of β-boron to 30 GPa. Phys. Rev. B 67, 174116 (2003)

    Article  ADS  Google Scholar 

  15. McMahon, M. I. & Nelmes, R. J. High-pressure structures and phase transformations in elemental metals. Chem. Soc. Rev. 35, 943–963 (2006)

    Article  CAS  Google Scholar 

  16. Bader, R. F. W. Atoms in Molecules. A Quantum Theory (Oxford Univ. Press, 1990)

    Google Scholar 

  17. Edwards, B. & Ashcroft, N. W. Spontaneous polarization in dense hydrogen. Nature 388, 652–655 (1997)

    Article  ADS  CAS  Google Scholar 

  18. Hayami, W. Theoretical study of the stability of AB12 (A = H-Ne) icosahedral clusters. Phys. Rev. B 60, 1523–1526 (1999)

    Article  ADS  CAS  Google Scholar 

  19. Werheit, H., Luax, M. & Kuhlmann, U. Interband and gap state related transitions in β-rhombohedral boron. Phys. Status Solidi B 176, 415–432 (1993)

    Article  ADS  CAS  Google Scholar 

  20. Ma, Y. M., Tse, J. S., Klug, D. D. & Ahuja, R. Electron-phonon coupling of α-Ga boron. Phys. Rev. B 70, 214107 (2004)

    Article  ADS  Google Scholar 

  21. Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996)

    Article  ADS  CAS  Google Scholar 

  22. Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994)

    Article  ADS  Google Scholar 

  23. Kresse, G. & Furthmüller, J. Efficiency of ab initio total-energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 6, 15–50 (1996)

    Article  CAS  Google Scholar 

  24. Baroni, S., de Gironcoli, S., Dal Corso, A. & Gianozzi, P. Phonons and related crystal properties from density-functional perturbation theory. Rev. Mod. Phys. 73, 515–562 (2001)

    Article  ADS  CAS  Google Scholar 

  25. Gonze, X. et al. First-principles computation of materials properties: The ABINIT software project. Comput. Mater. Sci. 25, 478–492 (2002)

    Article  Google Scholar 

  26. Dovesi, R. et al. CRYSTAL06 User's Manual (University of Torino, 2006)

  27. Solozhenko, V. L., Le Godec, Y. & Kurakevych, O. O. Solid-state synthesis of boron subnitride, B6N: myth or reality? C.R. Chimie 9, 1472–1475 (2006)

    Article  CAS  Google Scholar 

  28. Will, G. & Kiefer, B. Electron deformation density in α-boron. Z. Anorg. Allg. Chem. 627, 2100–2104 (2001)

    Article  CAS  Google Scholar 

  29. Brazhkin, V. V., Taniguchi, T., Akaishi, M. & Popova, S. V. Fabrication of β-boron by chemical-reaction and melt-quenching methods at high pressures. J. Mater. Res. 19, 1643–1648 (2004)

    Article  ADS  CAS  Google Scholar 

Download references

Acknowledgements

A.R.O. acknowledges the Swiss National Science Foundation (grant 200021-111847/1) and the ETH Research Equipment Programme for support of this work. J.C. and T.Y. were supported by the NSF (grant EAR0711321) and the DOE (contract DE-FG02-07ER46461), Yanzhang Ma was funded by the DOE (agreement DE-FC03-03NA00144) and the NSF (grant DMR-0619215), and O.O.K. and V.L.S. were supported by the Agence Nationale de la Recherche (grant ANR-05-BLAN-0141). The use of the NSLS at Brookhaven National Laboratory was supported by the US Department of Energy under contract DE-AC02-98CH10886, and high pressure beamlines at the NSLS were supported by COMPRES under NSF cooperative agreement EAR 06-49658. Calculations were performed at CSCS (Manno), ETH Zurich, and the Joint Supercomputer Centre of the Russian Academy of Sciences.

Author Contributions A.R.O. did most of the calculations and wrote most of the paper, C.G. did most of the analysis of chemical bonding and wrote a significant part of the discussion, Yanming Ma contributed to calculations, C.W.G. wrote the first version of the USPEX code, J.C., V.L.S. and Yanzhang Ma synthesized the new phase, J.C. performed infrared absorption measurements with Z.L. and T.Y., V.L.S. did the Raman measurements and elemental analysis, V.L.S. and Yanzhang Ma did synchrotron X-ray diffraction measurements, and J.C. and O.O.K. performed the Le Bail refinement of the X-ray diffraction patterns.

Author information

Author notes

  1. Artem R. Oganov

    Present address: Present address: Department of Geosciences and New York Center for Computational Science, Stony Brook University, Stony Brook, New York 11794-2100, USA.,

Authors and Affiliations

  1. Department of Materials, Laboratory of Crystallography, ETH Zurich, Wolfgang-Pauli-Str. 10, CH-8093 Zurich, Switzerland,

    Artem R. Oganov, Yanming Ma & Colin W. Glass

  2. Geology Department, Moscow State University, 119992 Moscow, Russia

    Artem R. Oganov

  3. Center for the Study of Matter at Extreme Conditions and Department of Mechanical and Materials Engineering, Florida International University, Miami, Florida 33199, USA,

    Jiuhua Chen & Tony Yu

  4. Mineral Physics Institute and Department of Geosciences, Stony Brook University, Stony Brook, New York 11794-2100, USA,

    Jiuhua Chen

  5. CNR-ISTM Istituto di Scienze e Tecnologie Molecolari, via Golgi 19, 20133 Milano, Italy ,

    Carlo Gatti

  6. Department of Mechanical Engineering, Texas University of Technology, 7th Street & Boston Avenue, Lubbock, Texas 79409, USA,

    Yanzhang Ma

  7. National Laboratory of Superhard Materials, Jilin University, Changchun 130012, China

    Yanming Ma

  8. Geophysical Laboratory, Carnegie Institution of Washington, Washington DC 20015, USA

    Zhenxian Liu

  9. LPMTM-CNRS, Université Paris Nord, Villetaneuse, F-93430, France ,

    Oleksandr O. Kurakevych & Vladimir L. Solozhenko

Authors
  1. Artem R. Oganov
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Jiuhua Chen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Carlo Gatti
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Yanzhang Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yanming Ma
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Colin W. Glass
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Zhenxian Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Tony Yu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Oleksandr O. Kurakevych
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Vladimir L. Solozhenko
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Artem R. Oganov.

Supplementary information

Supplementary Information

This file contains Supplementary Data and Methods, Supplementary Figures S1-S5 with Legends, Supplementary Tables S1- S6 and Supplementary References (PDF 1491 kb)

PowerPoint slides

Rights and permissions

Reprints and permissions

About this article

Cite this article

Oganov, A., Chen, J., Gatti, C. et al. Ionic high-pressure form of elemental boron. Nature 457, 863–867 (2009). https://doi.org/10.1038/nature07736

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature07736

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