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.

High-performance bulk thermoelectrics with all-scale hierarchical architectures

A Corrigendum to this article was published on 24 October 2012

This article has been updated

Abstract

With about two-thirds of all used energy being lost as waste heat, there is a compelling need for high-performance thermoelectric materials that can directly and reversibly convert heat to electrical energy. However, the practical realization of thermoelectric materials is limited by their hitherto low figure of merit, ZT, which governs the Carnot efficiency according to the second law of thermodynamics. The recent successful strategy of nanostructuring to reduce thermal conductivity has achieved record-high ZT values in the range 1.5–1.8 at 750–900 kelvin1,2,3, but still falls short of the generally desired threshold value of 2. Nanostructures in bulk thermoelectrics allow effective phonon scattering of a significant portion of the phonon spectrum, but phonons with long mean free paths remain largely unaffected. Here we show that heat-carrying phonons with long mean free paths can be scattered by controlling and fine-tuning the mesoscale architecture of nanostructured thermoelectric materials. Thus, by considering sources of scattering on all relevant length scales in a hierarchical fashion—from atomic-scale lattice disorder and nanoscale endotaxial precipitates to mesoscale grain boundaries—we achieve the maximum reduction in lattice thermal conductivity and a large enhancement in the thermoelectric performance of PbTe. By taking such a panoscopic approach to the scattering of heat-carrying phonons across integrated length scales, we go beyond nanostructuring and demonstrate a ZT value of 2.2 at 915 kelvin in p-type PbTe endotaxially nanostructured with SrTe at a concentration of 4 mole per cent and mesostructured with powder processing and spark plasma sintering. This increase in ZT beyond the threshold of 2 highlights the role of, and need for, multiscale hierarchical architecture in controlling phonon scattering in bulk thermoelectrics, and offers a realistic prospect of the recovery of a significant portion of waste heat.

This is a preview of subscription content

Access options

Buy article

Get time limited or full article access on ReadCube.

$32.00

All prices are NET prices.

Figure 1: All-length-scale hierarchy in thermoelectric materials.
Figure 2: Thermoelectric properties of SPS and ingot samples of PbTe–SrTe doped with 2 mol% Na.
Figure 3: Micro and nanostructures in SPS PbTe–SrTe(4 mol%) doped with 2 mol% Na.
Figure 4: Compositional analysis of SPS PbTe–SrTe(4 mol%) doped with 2 mol% Na.

Change history

  • 24 October 2012

    Nature 489, 414–418 (2012); doi:10.1038/nature11439 In this Letter, the units of thermal conductivity on the y-axes of Fig. 2d and e should be W m−1 K−1 and the y-axis label of Fig. 3d should be ‘Count (%)’. Figures 2 and 3 of the original paper have been corrected online.

References

  1. Snyder, J. G. & Toberer, E. S. Complex thermoelectric materials. Nature Mater. 7, 105–114 (2008)

    CAS  Article  ADS  Google Scholar 

  2. Chen, G., Dresselhaus, M. S., Dresselhaus, G., Fleurial, J. P. & Caillat, T. Recent development in thermoelectric materials. Int. Mater. Rev. 48, 45–66 (2003)

    CAS  Article  Google Scholar 

  3. Sootsman, J., Chung, D. Y. & Kanatzidis, M. G. New and old concepts in thermoelectric materials. Angew. Chem. Int. Ed. 48, 8616–8639 (2009)

    CAS  Article  Google Scholar 

  4. Rowe, D. M. CRC Handbook of Thermoelectrics: Macro to Nano (CRC/Taylor & Francis, 2006)

    Google Scholar 

  5. Tritt, T. M. . (ed). Recent Trends in Thermoelectric Materials Research I (Semiconductors and Semimetals Vol. 69, Academic, 2000); Recent Trends in Thermoelectric Materials Research II (Semiconductors and Semimetals Vol. 70, Academic, 2000); Recent Trends in Thermoelectric Materials Research III (Semiconductors and Semimetals Vol. 71, Academic, 2001)

  6. Poudel, B. et al. High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys. Science 320, 634–638 (2008)

    CAS  Article  ADS  Google Scholar 

  7. Venkatasubramanian, R., Siivola, E., Colpitts, V. & O’Quinn, B. Thin-film thermoelectric devices with high room-temperature figures of merit. Nature 413, 597–602 (2001)

    CAS  Article  ADS  Google Scholar 

  8. Hsu, K. F. et al. Cubic AgPbmSbTe2+m: bulk thermoelectric materials with high figure of merit. Science 303, 818–821 (2004)

    CAS  Article  ADS  Google Scholar 

  9. Poudeu, P. F. P. et al. High thermoelectric figure of merit and nanostructuring in bulk p-type Na1−xPbmSbyTe2+m . Angew. Chem. Int. Ed. 45, 3835–3839 (2006)

    CAS  Article  Google Scholar 

  10. Girard, S. N. et al. High performance Na-doped PbTe-PbS thermoelectric materials: electronic density of states modification and shape-controlled nanostructures. J. Am. Chem. Soc. 133, 16588–16597 (2011)

    CAS  Article  Google Scholar 

  11. Pei, Y. et al. Convergence of electronic bands for high-performance bulk thermoelectric. Nature 473, 66–69 (2011)

    CAS  Article  ADS  Google Scholar 

  12. Heremans, J. P. et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science 321, 554–557 (2008)

    CAS  Article  ADS  Google Scholar 

  13. Shi, X. et al. Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transport. J. Am. Chem. Soc. 133, 7837–7846 (2011)

    CAS  Article  Google Scholar 

  14. Biswas, K. et al. Strained endotaxial nanostructures with high thermoelectric figure of merit. Nature Chem. 3, 160–166 (2011)

    CAS  Article  ADS  Google Scholar 

  15. Zhu, G. H. et al. Increased phonon scattering by nanograins and point defects in nanostructured silicon with a low concentration of germanium. Phys. Rev. Lett. 102, 196803 (2009)

    CAS  Article  ADS  Google Scholar 

  16. Martin, J., Wang, L., Chen, L. & Nolas, G. S. Enhanced Seebeck coefficient through energy-barrier scattering in PbTe nanocomposite. Phys. Rev. B 79, 115311 (2009)

    Article  ADS  Google Scholar 

  17. Ravich, Y. I., Efimova, B. A. & Smirnov, I. A. Semiconducting Lead Chalcogenides Vol. 5 184–192 (Plenum, 1970)

    Book  Google Scholar 

  18. Crocker, A. J. & Rogers, L. M. Valence band structure of PbTe. J. Phys. Colloq. 29 (C4). 129–132 (1968)

    CAS  Article  Google Scholar 

  19. Airapetyants, S. V. & Vinogradova, M. N. Durbrovskaya, I. N., Kolomoets, N. V. & Rudnik, I. M. Structure of the valance band of heavily doped lead telluride. Sov. Phys. Solid State 8, 1069–1072 (1966)

    Google Scholar 

  20. Johnsen, S. et al. Nanostructures boost the thermoelectric performance of PbS. J. Am. Chem. Soc. 133, 3460–3470 (2011)

    CAS  Article  Google Scholar 

  21. May, A. F., Fleurial, J.-P. & Snyder, G. J. Thermoelectric performance of lanthanum telluride produced via mechanical alloying. Phys. Rev. B 78, 125205 (2008)

    Article  ADS  Google Scholar 

  22. Goldsmid, H. J. Thermoelectric Refrigeration (Plenum, 1964)

    Book  Google Scholar 

  23. Qiu, B., Bao, H., Zhang, G., Wu, Y. & Ruan, X. Molecular dynamics simulations of lattice thermal conductivity and spectral phonon mean free path of PbTe: bulk and nanostructures. Comput. Mater. Sci. 53, 278–285 (2012)

    CAS  Article  Google Scholar 

  24. Tian, Z. et al. Phonon conduction in PbSe, PbTe and PbTe1−xSex from first-principle calculations. Phys. Rev. B 85, 184303 (2012)

    Article  ADS  Google Scholar 

  25. Esfarjani, K., Chen, G. & Stokes, H. T. Heat transport in silicon from first-principle calculations. Phys. Rev. B 84, 085204 (2011)

    Article  ADS  Google Scholar 

  26. Hÿtch, M. J., Snoeck, E. & Kilaas, R. Quantitative measurement of displacement and strain fields from HREM micrographs. Ultramicroscopy 74, 131–146 (1998)

    Article  Google Scholar 

  27. Seidman, D. N. Three-dimensional atom-probe tomography: advances and applications. Annu. Rev. Mater. Res. 37, 127–158 (2007)

    CAS  Article  ADS  Google Scholar 

  28. Crocker, A. J. & Dorning, B. F. Diffusion of sodium in lead telluride. J. Phys. Chem. Solids 29, 155–161 (1968)

    CAS  Article  ADS  Google Scholar 

  29. Blachnik, R. & Igel, R. Thermodynamic properties of IV–VI compound: lead chalcogenides. Z. Naturforsch. B 29, 625–629 (1974)

    CAS  Article  Google Scholar 

Download references

Acknowledgements

This work was supported by the Energy Frontier Research Center for Revolutionary Materials for Solid State Energy Conversion, funded by the US Department of Energy, Office of Science, Basic Energy Sciences under award number DE-SC0001054. TEM was performed in the (EPIC) (NIFTI) (Keck-II) facility of the NUANCE Center at Northwestern University. The spark plasma sintering system at Michigan State University is supported by ONR DURIP. APT was performed at NUCAPT and supported by NSF-MRI (DMR-0420532), ONR-DURIP (N00014-0400798, N00014-0610539, N00014-0910781), MRSEC (DMR-1121262) and ISEN at Northwestern University.

Author information

Authors and Affiliations

Authors

Contributions

K.B. synthesized the samples and designed and carried out thermoelectric experiments. J.H. performed the TEM experiments. I.D.B. performed the APT measurements. C.-I.W. and T.P.H. performed the spark plasma sintering. K.B., J.H., I.D.B., D.N.S., V.P.D. and M.G.K. conceived the experiments, analysed the results and wrote and edited the manuscript.

Corresponding author

Correspondence to Mercouri G. Kanatzidis.

Ethics declarations

Competing interests

The authors declare no competing financial interests.

Supplementary information

Supplementary Information

This file contains Supplementary Text and Data, Supplementary Figures 1-8, Supplementary Tables 1-3 and Supplementary References. (PDF 656 kb)

PowerPoint slides

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Biswas, K., He, J., Blum, I. et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature 489, 414–418 (2012). https://doi.org/10.1038/nature11439

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1038/nature11439

Further reading

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