Abstract
We report a novel approach to realize the formation of well-distributed nanodispersions in n-type filled skutterudite through the manipulation of metastable void fillers by a designed sophisticated process of materials synthesis. Metastable Ga filling in CoSb3 is proved to happen at high temperature. The subsequent controlled annealing procedure drives Ga out of the crystal voids and finally leads to the homogeneous dispersion of GaSb nanodots with an average size of 11 nm in CoSb3 matrix. The grain size of nanodispersions can be manipulated by the controlled cooling procedure. The well-distributed nanodispersions are observed to enhance Seebeck coefficients and reduce lattice thermal conductivity at low temperature. Therefore, the thermoelectric performance of nanocomposite is improved in the whole temperature range. The highest figure of merit (ZT) is obtained to be 1.45 at 850 K, and an average ZT of 0.99 in 300−850 K is achieved for Yb0.26Co4Sb12/0.2GaSb nanocomposite.
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REFERENCES
H. Beyer, J. Nurnus, H. Böttner, A. Lambrecht, T. Roch, and G. Bauer: PbTe based superlattice structures with high thermoelectric efficiency. Appl. Phys. Lett. 80, 1216 (2002).
H. Böttner, G. Chen, and R. Venkatasubramanian: Aspects of thin-film superlattice thermoelectric materials, devices, and applications. MRS Bull. 31, 211 (2006).
B. Poudel, Q. Hao, Y. Ma, Y.C. Lan, A. Minnich, B. Yu, X. Yan, D.Z. Wang, A. Muto, D. Vashaee, X.Y. Chen, J.M. Liu, M.S. Dresselhaus, G. Chen, and Z. Ren: High-thermoelectric performance of nanostructured bismuth antimony telluride bulk alloys. Science 320, 634 (2008).
W. Xie, J. He, H.J. Kang, X. Tang, S. Zhu, M. Laver, S. Wang, J.R.D. Copley, C.M. Brown, Q. Zhang, and T.M. Tritt: Identifying the specific nanostructures responsible for the high thermoelectric performance of (Bi, Sb)2Te3 nanocomposites. Nano Lett. 10, 3283 (2010).
X. Ji, J. He, Z. Su, N. Gothard, and T.M. Tritt: Improved thermoelectric performance in polycrystalline p-type Bi2Te3 via an alkali metal salt hydrothermal nanocoating treatment approach. J. Appl. Phys. 104, 034907 (2008).
K.F. Hsu, S. Loo, F. Guo, W. Chen, J.S. Dyck, C. Uher, T. Hogan, E.K. Polychroniadis, and M.G. Kanatzidis: Cubic AgPbmSbTe2+m: Bulk thermoelectric materials with high figure of merit. Science 303, 818 (2004).
X. Ke, C. Chen, J. Yang, L. Wu, J. Zhou, Q. Li, Y. Zhu, and P.R.C. Kent: Microstructure and a nucleation mechanism for nanoprecipitates in PbTe-AgSbTe2. Phys. Rev. Lett. 103, 145502 (2009).
J.P. Heremans, C.M. Thrush, and D.T. Morelli: Thermopower enhancement in lead telluride nanostructures. Phys. Rev. B 70, 115334 (2004).
J. Androulakis, C.-H. Lin, H.-J. Kong, C. Uher, C.-I. Wu, T. Hogan, B.A. Cook, T. Caillat, K.M. Paraskevopoulos, and M.G. Kanatzidis: Spinodal decomposition and nucleation and growth as a means to bulk nanostructured thermoelectrics: Enhanced performance in Pb1-xSnxTe-PbS. J. Am. Chem. Soc. 129, 9780 (2007).
W. Kim, J. Zide, A. Gossard, D. Klenov, S. Stemmer, A. Shakouri, and A. Majumdar: Thermal conductivity reduction and thermoelectric figure of merit increase by embedding nanoparticles in crystalline semiconductors. Phys. Rev. Lett. 96, 045901 (2006).
T. Caillat, A. Borshchevsky, and J.P. Fleurial: Properties of single crystalline semiconducting CoSb3. J. Appl. Phys. 80, 4442 (1996).
D.T. Morelli, G.P. Meisner, B. Chen, S. Hu, and C. Uher: Cerium filling and doping of cobalt triantimonide. Phys. Rev. B 56, 7376 (1997).
B.C. Sales, D. Mandrus, and R.K. Williams: Filled skutterudite antimonides: A new class of thermoelectric materials. Science 272, 1325 (1996).
L. Xi, J. Yang, C. Lu, Z. Mei, W. Zhang, and L. Chen: Systematic study of the multiple-element filling in caged skutterudite CoSb3. Chem. Mater. 22, 2384 (2010).
X.Y. Zhao, X. Shi, L.D. Chen, W.Q. Zhang, S.Q. Bai, Y.Z. Pei, X.Y. Li, and T. Goto: Synthesis of YbyCo4Sb12/Yb2O3 composites and their thermoelectric properties. Appl. Phys. Lett. 89, 092121 (2006).
P.N. Alboni, X. Ji, J. He, N. Gothard, and M.T. Tritt: Thermoelectric properties of La0.9CoFe3Sb12-CoSb3 skutterudite nanocomposites. J. Appl. Phys. 103, 5 (2008).
Z. He, C. Stiewe, D. Platzek, G. Karpinski, E. Müller, S. Li, M. Toprak, and M. Muhammed: Nano ZrO2/CoSb3 composites with improved thermoelectric figure of merit. Nanotechnology 18, 235602 (2007).
Z. Xiong, X.H. Chen, X.Y. Zhao, S.Q. Bai, X.Y. Huang, and L.D. Chen: Effects of nano-TiO2 dispersion on the thermoelectric properties of filled-skutterudite Ba0.22Co4Sb12. Solid State Sci. 11, 1612 (2009).
H. Li, X. Tang, X. Su, and Q. Zhang: Preparation and thermoelectric properties of high-performance Sb additional Yb0.2Co4Sb12+y bulk materials with nanostructure. Appl. Phys. Lett. 92, 202114 (2008).
H. Li, X. Tang, Q. Zhang, and C. Uher: High performance InxCeyCo4Sb12 thermoelectric materials with in situ forming nanostructured InSb phase. Appl. Phys. Lett. 94, 102114 (2009).
G.S. Nolas, M. Kaeser, R.T. Littleton IV, and T.M. Tritt: High figure of merit in partially filled ytterbium skutterudite materials. Appl. Phys. Lett. 77, 1855 (2000).
L.D. Chen, T. Kawahara, X.F. Tang, T. Goto, T. Hirai, J.S. Dyck, W. Chen, and C. Uher: Anomalous barium filling fraction and n-type thermoelectric performance of BayCo4Sb12. J. Appl. Phys. 90, 1864 (2001).
X.Y. Zhao, X. Shi, L.D. Chen, W. Zhang, S.Q. Bai, Y.Z. Pei, X.Y. Li, and T. Goto: Synthesis and thermoelectric properties of Sr-filled skutterudite SryCo4Sb12. J. Appl. Phys. 99, 053711 (2006).
Y.Z. Pei, J. Yang, L.D. Chen, W. Zhang, J.R. Salvador, and J. Yang: Improving thermoelectric performance of caged compounds through light-element filling. Appl. Phys. Lett. 95, 042101 (2009).
J. Yang, Q. Hao, H. Wang, Y.C. Lan, Q.Y. He, A. Minnich, D.Z. Wang, J.A. Harriman, V.M. Varki, M.S. Dresselhaus, G. Chen, and Z.F. Ren: Solubility study of Yb in n-type skutterudites YbxCo4Sb12 and their enhanced thermoelectric properties. Phys. Rev. B 80, 115329 (2009).
G. Kresse and J. Furthmüler: Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169 (1996).
X. Shi, W. Zhang, L.D. Chen, and J. Yang: Filling fraction limit for intrinsic voids in crystals: Doping in skutterudites. Phys. Rev. Lett. 95, 185503 (2005).
J. Yang, W. Zhang, S.Q. Bai, Z. Mei, and L.D. Chen: Dual-frequency resonant phonon scattering in BaxRyCo4Sb12 (R=La, Ce, and Sr). Appl. Phys. Lett. 90, 192111 (2007).
M.W. Chase Jr., C.A. Davies, J.R. Downey Jr., D.J. Frurip, R.A. McDonald, and A.N. Syverud: JANAF thermochemical tables. Third edition. J. Phys. Chem. Ref. Data 14, 1204 (1985).
A.T. Dinsdale: SGTE Data for pure elements. Calphad 15, 317 (1991).
X.F. Sun, S. Ono, X. Zhao, Z.Q. Pang, Y. Abe, and Y. Ando: Doping dependence of phonon and quasiparticle heat transport of pure and Dy-doped Bi2Sr2CaCu2O8+δ single crystals. Phys. Rev. B 77, 094515 (2008).
G.A. Lamberton, R.H. Tedstrom, T.M. Tritt, and G.S. Nolas: Thermoelectric properties of Yb-filled Ge-compensated CoSb3 skutterudite materials. J. Appl. Phys. 97, 113715 (2005).
Z. Xiong, X. Chen, X. Huang, S.Q. Bai, and L.D. Chen: High thermoelectric performance of Yb0.26Co4Sb12/yGaSb nanocomposites originating from scattering electrons of low energy. Acta Mater. 58, 3995 (2010).
A.M. Guloy, R. Ramlau, Z. Tang, W. Schnelle, M. Baitinger, and Y. Grin: A guest-free germanium clathrate. Nature 443, 320 (2006).
E.S. Toberer, M. Christensen, B.B. Iversen, and G.J. Snyder: High temperature thermoelectric efficiency in Ba8Ga16Ge30. Phys. Rev. B 77, 075203 (2008).
ACKNOWLEDGMENTS
We thank Prof. F.F. Xu and Ms. M.L. Ruan (Shanghai Institute of Ceramics, Chinese Academy of Sciences) for their careful TEM characterization and helpful discussions and Prof. X.F. Sun (Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China) for his kind low temperature thermal conductivity measurements. This work was partially supported by the National Basic Research Program of China (2007CB607502), Natural Science Foundation of China project (No. 50821004), and Corning Inc.
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Xiong, Z., Xi, L., Ding, J. et al. Thermoelectric nanocomposite from the metastable void filling in caged skutterudite. Journal of Materials Research 26, 1848–1856 (2011). https://doi.org/10.1557/jmr.2011.90
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DOI: https://doi.org/10.1557/jmr.2011.90