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Peierls distortion as a route to high thermoelectric performance in In4Se3-δ crystals

Abstract

Thermoelectric energy harvesting—the transformation of waste heat into useful electricity—is of great interest for energy sustainability. The main obstacle is the low thermoelectric efficiency of materials for converting heat to electricity, quantified by the thermoelectric figure of merit, ZT. The best available n-type materials for use in mid-temperature (500–900 K) thermoelectric generators have a relatively low ZT of 1 or less, and so there is much interest in finding avenues for increasing this figure of merit1. Here we report a binary crystalline n-type material, In4Se3-δ, which achieves the ZT value of 1.48 at 705 K—very high for a bulk material. Using high-resolution transmission electron microscopy, electron diffraction, and first-principles calculations, we demonstrate that this material supports a charge density wave instability which is responsible for the large anisotropy observed in the electric and thermal transport. The high ZT value is the result of the high Seebeck coefficient and the low thermal conductivity in the plane of the charge density wave. Our results suggest a new direction in the search for high-performance thermoelectric materials, exploiting intrinsic nanostructural bulk properties induced by charge density waves.

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Figure 1: Crystal structure of In4Se3.
Figure 2: Anisotropic thermoelectric properties, annealing effect, and angle-averaged value of Boltzmann transport calculations for In4Se3- δ (δ = 0.65) bulk crystal.
Figure 3: High-resolution TEM images and electron diffraction patterns of In4Se3- δ (δ = 0.22).
Figure 4: Fermi surface and generalized electron susceptibility of In4Se3- δ.

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References

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

    Article  ADS  CAS  Google Scholar 

  2. 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 

  3. Snyder, G. J., Christensen, M., Nishibori, E. J., Caillat, T. & Iversen, B. B. Disordered zinc in Zn4Sb3 with phonon-glass and electron-crystal thermoelectric properties. Nature Mater. 3, 458–463 (2004)

    Article  ADS  CAS  Google Scholar 

  4. Wölfing, B., Kloc, C., Teubner, J. & Bucher, E. High performance thermoelectric Tl9BiTe6 with an extremely low thermal conductivity. Phys. Rev. Lett. 86, 4350–4353 (2001)

    Article  ADS  Google Scholar 

  5. Boukai, A. I. et al. Silicon nanowires as efficient thermoelectric materials. Nature 451, 168–171 (2007)

    Article  ADS  Google Scholar 

  6. Venkatasubramanian, R., Siivola, E., Colpitts, T. & O'Quinn, B. Thin-film thermoelectric devices with high room-temperature figures of merit. Nature 413, 597–602 (2001)

    Article  ADS  CAS  Google Scholar 

  7. Dresselhaus, M. S. et al. New directions for low-dimensional thermoelectric materials. Adv. Mater. 19, 1043–1053 (2007)

    Article  CAS  Google Scholar 

  8. Lin, Y.-M. & Dresselhaus, M. S. Thermoelectric properties of superlattice nanowires. Phys. Rev. B 68, 075304 (2003)

    Article  ADS  Google Scholar 

  9. Chiritescu, C. et al. Ultralow thermal conductivity in disordered, layered WSe2 crystals. Science 315, 351–353 (2007)

    Article  ADS  CAS  Google Scholar 

  10. Güner, G. Density Waves in Solids (Addison-Wesley, 1994)

    Google Scholar 

  11. Rhyee, J. S. et al. Thermal and electronic transport properties of CeTe2-xSnx compounds. J. Appl. Phys. 105, 053712 (2009)

    Article  ADS  Google Scholar 

  12. Losovyj, Y. B. et al. The electronic structure of surface chains in the layered semiconductor In4Se3 (100). Appl. Phys. Lett. 92, 122107 (2008)

    Article  ADS  Google Scholar 

  13. Balitskii, O. A., Savchyn, V. P., Jaeckel, B. & Jaegermann, W. Surface characterization of In4Se3 single crystals. Physica E 22, 921–923 (2004)

    Article  ADS  CAS  Google Scholar 

  14. Losovyj, Y. B. et al. The anisotropic band structure of layered In4Se3 (001). J. Appl. Phys. 104, 083713 (2008)

    Article  ADS  Google Scholar 

  15. Mahan, G., Sales, B. & Sharp, J. Thermoelectric materials: new approaches to an old problem. Phys. Today 50, 42–47 (March 1997)

    Article  CAS  Google Scholar 

  16. Madsen, G. K. H. & Singh, D. J. BoltzTraP. A code for calculating band-structure dependent quantities. Comput. Phys. Commun. 175, 67–71 (2006)

    Article  ADS  CAS  Google Scholar 

  17. Shim, J. H., Kang, J.-S. & Min, B. I. Electronic structures of RTe2 (R = La, Ce): a clue to the pressure-induced superconductivity in CeTe1. 82 . Phys. Rev. Lett. 93, 156406 (2004)

    Article  ADS  CAS  Google Scholar 

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

    Article  ADS  CAS  Google Scholar 

  19. Chen, N. et al. Macroscopic thermoelectric inhomogeneities in (AgSbTe2)x(PbTe)1-x . Appl. Phys. Lett. 87, 171903 (2005)

    Article  ADS  Google Scholar 

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Acknowledgements

We thank D. Johnson, K. Koumoto and B. I. Min for discussions. We also thank H. R. Choi for TEM measurements. J.H.S. was supported by the WCU programme (KOSEF: R32-2008-000-10180-0).

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Correspondence to Sang Mock Lee.

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Rhyee, JS., Lee, K., Lee, S. et al. Peierls distortion as a route to high thermoelectric performance in In4Se3-δ crystals. Nature 459, 965–968 (2009). https://doi.org/10.1038/nature08088

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