Alternative technologies are required in order to meet a worldwide demand for clean non-polluting energy sources. Thermoelectric generators, which generate electricity from heat in a compact and reliable manner, are potential devices for waste heat recovery. However, thermoelectric performance, as encapsulated by the figure of merit ZT, has remained at around 1.0 at room temperature, which has limited practical applications. Here, we study the effects of pressure on ZT in Cr-doped PbSe, which has a maximum ZT of less than 1.0 at a temperature of about 700 K. By applying external pressure using a diamond anvil cell, we obtained a room-temperature ZT value of about 1.7. From thermoelectric, magnetoresistance and Raman measurements, as well as density functional theory calculations, a pressure-driven topological phase transition is found to enable this enhancement. Experiments also support the appearance of a topological crystalline insulator after the transition. These findings point to the possibility of using compression to increase not just ZT in existing thermoelectric materials, but also the possibility of realizing topological crystalline insulators.
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The data that support the findings of this study are available from the corresponding author upon reasonable request.
All the codes created for the analysis of the data are from the open-source software packages which are cited in the references of this paper.
Chen, G., Dresselhaus, M. S., Dresselhaus, G., Fleurial, J. P. & Cailla, T. Recent developments in thermoelectric materials. Int. Mater. Rev. 48, 45–66 (2003).
Snyder, G. J. & Toberer, E. S. Complex thermoelectric materials. Nat. Mater. 7, 105–144 (2008).
Ren, Z. F., Lan, Y. C. & Zhang, Q. Y. Advanced Thermoelectrics: Materials, Contacts, Devices, and System (CRC Press, 2017).
Poudel, B. et al. High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys. Science 320, 634–638 (2008).
Pei, Y. Z., Heinz, N. A., LaLonde, A. & Snyder, G. J. Combination of large nanostructures and complex band structure for high performance thermoelectric lead telluride. Energy Environ. Sci. 4, 3640–3645 (2011).
Biswas, K. et al. High-performance bulk thermoelectrics with all-scale hierarchical architectures. Nature 489, 414–418 (2012).
Hsu, K. F. et al. Cubic AgPbmSbTe2+m: bulk thermoelectric materials with high figure of merit. Science 303, 818–821 (2004).
Heremans, J. P. et al. Enhancement of thermoelectric efficiency in PbTe by distortion of the electronic density of states. Science 321, 554–557 (2008).
Pei, Y. Z. et al. Convergence of electronic bands for high performance bulk thermoelectrics. Nature 473, 66–69 (2011).
Liu, H. et al. Copper ion liquid-like thermoelectrics. Nat. Mater. 11, 422–425 (2012).
Zhu, T. J. et al. Hot deformation induced bulk nanostructuring of unidirectionally grown p-type (Bi,Sb)2Te3 thermoelectric materials. J. Mater. Chem. A 1, 11589–11594 (2013).
Wright, D. A. Thermoelectric properties of bismuth telluride and its alloys. Nature 181, 834–834 (1958).
Zhao, W. et al. Superparamagnetic enhancement of thermoelectric performance. Nature 549, 247–251 (2017).
Rhyee, J. S. et al. Peierls distortion as a route to high thermoelectric performance in In4Se3−δ crystals. Nature 459, 965–968 (2009).
Polvani, D. A., Meng, J. F., Chandra Shekar, N. V., Sharp, J. & Badding, J. V. Large improvement in thermoelectric properties in pressure-tuned p-type Sb1.5Bi0.5Te3. Chem. Mater. 13, 2068–2071 (2001).
Shchennikov, V. V., Ovsyannikov, S. V. & Derevskov, A. Y. Thermopower of lead chalcogenides at high pressures. Phys. Solid State 44, 1845–1849 (2002).
Yu, H. et al. Impressive enhancement of thermoelectric performance in CuInTe2 upon compression. Mater. Today Phys. 5, 1–5 (2018).
Chen, L. C. et al. Pressure-induced enhancement of thermoelectric performance in palladium sulfide. Mater. Today Phys. 5, 64–71 (2018).
Parker, D. & Singh, D. J. High-temperature thermoelectric performance of heavily doped PbSe. Phys. Rev. B 82, 035204 (2010).
Androulakis, J. et al. High-temperature thermoelectric properties of n-type PbSe doped with Ga, In, and Pb. Phys. Rev. B 83, 195209 (2011).
Lee, Y. et al. Contrasting role of antimony and bismuth dopants on the thermoelectric performance of lead selenide. Nat. Commun. 5, 3640 (2014).
Wang, H., Pei, Y. Z., LaLonde, A. D. & Snyder, G. J. Heavily doped p-type PbSe with high thermoelectric performance: an alternative for PbTe. Adv. Mater. 23, 1366–1370 (2011).
Wang, H., Gibbs, Z. M., Takagiwa, Y. & Snyder, G. J. Tuning bands of PbSe for better thermoelectric efficiency. Energy Environ. Sci. 7, 804–811 (2014).
Zhang, Q. et al. Study of the thermoelectric properties of lead selenide doped with boron, gallium, indium, or thallium. J. Am. Chem. Soc. 134, 17731–17738 (2012).
Zhang, Q. Y. et al. Enhancement of thermoelectric figure-of-merit by resonant states of aluminium doping in lead selenide. Energy Environ. Sci. 5, 5246–5251 (2012).
Zhang, Q. et al. Enhancement of thermoelectric performance of n-type PbSe by Cr doping with optimized carrier concentration. Adv. Energy Mater. 5, 1401977 (2015).
Fu, L. Topological crystalline insulators. Phys. Rev. Lett. 106, 106802 (2011).
Hsieh, T. H. et al. Topological crystalline insulators in the SnTe material class. Nat. Commun. 3, 982 (2012).
Barone, P. et al. Pressure-induced topological phase transitions in rocksalt chalcogenides. Phys. Rev. B 88, 045207 (2013).
Abrikosov, A. A. Fundamentals of the Theory of Metals (North-Holland, 1988).
Blanter, Ya. M., Kaganov, M. I., Pantsulaya, A. V. & Varlamov, A. A. The theory of electronic topological transitions. Phys. Rep. 245, 159–257 (1994).
Svane, A. et al. Quasiparticle self-consistent GW calculations for PbS, PbSe, and PbTe: band structure and pressure coefficients. Phys. Rev. B 81, 245120 (2010).
Qu, D. X., Hor, Y. S., Xiong, J., Cava, R. J. & Ong, N. P. Quantum oscillations and Hall anomaly of surface states in the topological insulator Bi2Te3. Science 329, 821–824 (2010).
Lu, H. Z. & Shen, S. Q. Weak localization of bulk channels in topological insulator thin films. Phys. Rev. B 84, 125134 (2011).
Wu, M. K. et al. Superconductivity at 93 K in a new mixed-phase Y-Ba-Cu-O compound system at ambient pressure. Phys. Rev. Lett. 58, 908–910 (1987).
Dziawa, P. et al. Topological crystalline insulator states in Pb1−xSnxSe. Nat. Mater. 11, 1023–1027 (2012).
Xu, S. Y. et al. Observation of a topological crystalline insulator phase and topological phase transition in Pb1−xSnxTe. Nat. Commun. 3, 1192 (2012).
Dimmock, J. O., Melngailis, I. & Strauss, A. J. Band structure and laser action in PbxSn1−xTe. Phys. Rev. Lett. 16, 1193–1196 (1966).
Gavriliuk, A. G., Mironovich, A. A. & Struzhkin, V. V. Miniature diamond anvil cell for broad range of high pressure measurements. Rev. Sci. Instrum. 80, 043906 (2009).
Van der Pauw, L. J. A method of measuring specific resistivity and Hall effect of discs of arbitrary shape. Philps Res. Repts. 13, 1–9 (1958).
Hammersley, A. P., Svensson, S. O., Hanfland, M., Fitch, A. N. & Hausermann, D. Two-dimensional detector software: from real detector to idealised image or two-theta scan. High. Press. Res. 14, 235–248 (1996).
Toby, B. H. E. X. P. G. U. I. a graphical user interface for GSAS. J. Appl. Cryst. 34, 210–213 (2001).
Mao, H. K., Bell, P. M., Shaner, J. W. & Stembey, D. J. Specific volume measurements of Cu, Mo, Pd, and Ag and calibration of the ruby R1 fluorescence pressure gauge from 0.06 to 1 Mbar. J. Appl. Phys. 49, 3276–3283 (1978).
Hohenberg, P. & Kohn, W. Inhomogeneous electron gas. Phys. Rev. B 136, 864–871 (1964).
Kohn, W. & Sham, L. J. Self-consistent equations including exchange and correlation effects. Phys. Rev. A 140, 1133–1138 (1965).
Hybertsen, M. S. & Louie, S. G. Electron correlation in semiconductors and insulators: band gaps and quasiparticle energies. Phys. Rev. B 34, 5390–5413 (1986).
Kresse, G. & Hafne, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558(R)–561(R) (1993).
Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251–14269 (1994).
Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).
Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996).
Mostofi, A. A. et al. An updated version of Wannier90: a tool for obtaining maximally-localised Wannier functions. Comput. Phys. Commun. 185, 2309–2310 (2014).
Souza, I., Marzari, N. & Vanderbilt, D. Maximally localized Wannier functions for entangled energy bands. Phys. Rev. B 65, 035109 (2001).
Marzari, N. & Vanderbilt, D. Maximally localized generalized Wannier functions for composite energy bands. Phys. Rev. B 56, 12847–12865 (1997).
Wu, Q. S., Zhang, S. N., Song, H. F., Troyer, M. & Soluyanov, A. A. WannierTools: an open-source software package for novel topological materials. Comput. Phys. Commun. 224, 405–416 (2018).
The work at HPSTAR was supported by the National Key R&D Programme of China (grant no. 2018YFA0305900). The work performed at the University of Houston was funded by the Department of Energy’s Basic Energy Science programme under grant no. DE-SC0010831. The work at Carnegie was funded by the US National Science Foundation under grant no. EAR-1763287. P.Q.C. acknowledges the internship programme at Carnegie Institution of Washington.
The authors declare no competing interests.
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