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.

  • Article
  • Published:

Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties

Nature Materials volume 3, pages 458–463 (2004)Cite this article

Abstract

By converting waste heat into electricity, thermoelectric generators could be an important part of the solution to today's energy challenges. The compound Zn4Sb3 is one of the most efficient thermoelectric materials known. Its high efficiency results from an extraordinarily low thermal conductivity in conjunction with the electronic structure of a heavily doped semiconductor. Previous structural studies have been unable to explain this unusual combination of properties. Here, we show through a comprehensive structural analysis using single-crystal X-ray and powder-synchrotron-radiation diffraction methods, that both the electronic and thermal properties of Zn4Sb3 can be understood in terms of unique structural features that have been previously overlooked. The identification of Sb3− ions and Sb24− dimers reveals that Zn4Sb3 is a valence semiconductor with the ideal stoichiometry Zn13Sb10. In addition, the structure contains significant disorder, with zinc atoms distributed over multiple positions. The discovery of glass-like interstitial sites uncovers a highly effective mechanism for reducing thermal conductivity. Thus Zn4Sb3 is in many ways an ideal 'phonon glass, electron crystal' thermoelectric material.

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: Thermoelectric properties of Zn4Sb3 compared with other materials.
Figure 2: The crystal structure of Zn4Sb3 without Zn interstitials.
Figure 3

Similar content being viewed by others

References

  1. Caillat, T., Fleurial, J.P. & Borshchevsky, A. Preparation and thermoelectric properties of semiconducting Zn4Sb3 . J. Phys. Chem. Solids 58, 1119–1125 (1997).

    Article  CAS  Google Scholar 

  2. Skrabek, E.A. & Trimmer, D.S. in Thermoelectric Handbook (ed. Rowe, D.M.) 267–275 (CRC, Boca Raton, 1995).

    Google Scholar 

  3. Uher, C. in Recent Trends in Thermoelectric Materials Research I (ed. Tritt, T.M.) 139–253 (Academic Press, San Diego, 2001).

    Book  Google Scholar 

  4. Sales, B.C., Mandrus, D. & Williams, R.K. Filled skutterudite antimonides: A new class of thermoelectric materials. Science 272, 1325–1328 (1996).

    Article  CAS  Google Scholar 

  5. Slack, G.A. in Thermoelectric Handbook (ed. Rowe, M.) 407–440 (CRC, Boca Raton, 1995).

    Google Scholar 

  6. Sales, B.C. Electron crystals and phonon glasses: a new path to improved thermoelectric materials. Mater. Res. Soc. Bull. 23, 15–21 (1998).

    Article  CAS  Google Scholar 

  7. Mayer, H.W., Mikhail, I. & Schubert, K. Phases of ZnSbN and CdSbN mixtures. J. Less-Common Metals 59, 43–52 (1978).

    Article  CAS  Google Scholar 

  8. Caillat, T., Borshchevsky, A. & Fleurial, J.-P. in Thermoelectric Materials - New Directions and Approaches. Symposium (eds Tritt, T.M., Kanatzidis, M.G., Lyon, H.B. Jr & Mahan, G.D.) 103–108 (Materials Research Society, San Francisco, California, 1997).

    Google Scholar 

  9. Tanaka, H. et al. ENIGMA: maximum-entropy method program package for huge systems. J. Appl. Crystallogr. 35, 282–286 (2002).

    Article  CAS  Google Scholar 

  10. Bokii, G.B. & Klevzova, R.F. X-ray structure investigation of the beta-phase in the zinc-antimony system. Zh. Strukt. Khim. 6, 866 (English-translated pages 830–834) (1965).

    CAS  Google Scholar 

  11. Izard, V., Record, M.C., Tedenac, J.C. & Fries, S.G. Discussion on the stability of the antimony-zinc binary phases. CALPHAD 25, 567–581 (2001).

    Article  CAS  Google Scholar 

  12. Kim, S.G., Mazin, II & Singh, D.J. First-principles study of Zn-Sb thermoelectrics. Phys. Rev. B 57, 6199–6203 (1998).

    Article  CAS  Google Scholar 

  13. Kauzlarich, S.M. (ed.) Chemistry, Structure, and Bonding of Zintl Phases and Ions (VCH, New York, 1996).

    Google Scholar 

  14. Papoian, G.A. & Hoffmann, R. Hypervalent bonding in one, two, and three dimensions: Extending the Zintl-Klemm concept to nonclassical electron-rich networks. Angew. Chem. Intl Edn 39, 2409–2448 (2000).

    Article  CAS  Google Scholar 

  15. Rowe, D.M. (ed.) CRC Handbook of Thermoelectrics (CRC, Boca Raton, 1995).

    Book  Google Scholar 

  16. Chung, D.Y. et al. CsBi4Te6: A high-performance thermoelectric material for low-temperature applications. Science 287, 1024–1027 (2000).

    Article  CAS  Google Scholar 

  17. Miller, R.C. in Thermoelectricity: Science and Engineering (eds. Heikes, R.R. & Ure, R.W.) 405–407 (Interscience, New York, 1961).

    Google Scholar 

  18. Funke, K. in Superionic Solids and Solid Electrolytes Recent Trends (eds Laskar, A.L. & Chandra, S.) 569–629 (Academic, San Diego, 1989).

    Book  Google Scholar 

  19. Souma, T., Nakamoto, G. & Kurisu, M. Low-temperature thermoelectric properties of alpha- and beta- Zn4Sb3 bulk crystals prepared by a gradient freeze method and a spark plasma sintering method. J. Alloy. Comp. 340, 275–280 (2002).

    Article  CAS  Google Scholar 

  20. Shaver, P.J. & Blair, J. Thermal and electronic transport properties of p-Type ZnSb. Phys. Rev. 141, 649–663 (1966).

    Article  CAS  Google Scholar 

  21. Yvon, K., Baillif, R. & Flukiger, R. Positional disorder and nonstoichiometry in Cu2-XMo3S4 compounds 2: Triclinic low-temperature structure of Cu2-XMo3S4 . Acta Crystallogr. B 35, 2859–2863 (1979).

    Article  Google Scholar 

  22. Caillat, T., Fleurial, J.-P. & Snyder, G.J. Potential of Chevrel phases for thermoelectric applications. Solid State Sci. 1, 535–544 (1999).

    Article  CAS  Google Scholar 

  23. Cahill, D.G., Watson, S.K. & Pohl, R.O. Lower limit to thermal conductivity of disordered crystals. Phys. Rev. B 46, 6131–6140 (1992).

    Article  CAS  Google Scholar 

  24. Sheldrick, G.M. SHELXL-97 A Program for Crystal Structure Refinement (Univ. Göttingen, Germany, 1997).

    Google Scholar 

  25. Nishibori, E. et al. The large Debye-Scherrer camera installed at SPring-8 BL02B2 for charge density studies. Nucl. Instrum. Methods A 467, 1045–1048 (2001).

    Article  Google Scholar 

  26. Takata, M., Nishibori, E. & Sakata, M. Charge density studies utilizing powder diffraction and MEM. Exploring of high Tc superconductors, C-60 superconductors and manganites. Z. Kristall. 216, 71–86 (2001).

    CAS  Google Scholar 

Download references

Acknowledgements

We would like to thank Philippe Rabiller, Sossina Haile, Franck Gascoin and Peter Stephens for discussions and preliminary results, and Helena Kauppila for Ga-doping experiments. The Danish Research Councils are acknowledged for funding through the DANSYNC centre, and access to a 512-node PC cluster at the Danish Supercomputer Centre, Southern Denmark University. E. N. thanks M. Sakata and M. Takata for valuable discussions, and K. Kato for experimental help at SPring-8. The synchrotron radiation experiments were performed at beam line BL02B2 at SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI). We also thank the European Commission for financial support under the NANOTHERMEL contract. This work was supported in part by the National Science Foundation Center for the Science and Engineering of Materials at Caltech and the Defence Advanced Research Projects Agency at the Jet Propulsion Laboratory under contract with NASA.

Author information

Authors and Affiliations

  1. California Institute of Technology, Materials Science, 1200 East California Boulevard, Pasadena, 91125, California, USA

    G. Jeffrey Snyder

  2. Jet Propulsion Laboratory/California Institute of Technology, 4800 Oak Grove Drive, Pasadena, 91109, California, USA

    G. Jeffrey Snyder & Thierry Caillat

  3. Department of Chemistry, University of Aarhus, Aarhus, DK-8000, Denmark

    Mogens Christensen & Bo Brummerstedt Iversen

  4. Department of Applied Physics, Nagoya University, Nagoya, 464-8603, Japan

    Eiji Nishibori

Authors
  1. G. Jeffrey Snyder
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Mogens Christensen
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Eiji Nishibori
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Thierry Caillat
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Bo Brummerstedt Iversen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to G. Jeffrey Snyder.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Figures and tables

Fig. S1, Fig. S2, Table S1 and Table S2 (PDF 715 kb)

Rights and permissions

Reprints and permissions

About this article

Cite this article

Snyder, G., Christensen, M., Nishibori, E. et al. Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties. Nature Mater 3, 458–463 (2004). https://doi.org/10.1038/nmat1154

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nmat1154

This article is cited by

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