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