First-Principles Investigation of the Effect of M-Doped (M = Zr, Hf) TiCoSb Half-Heusler Thermoelectric Material


The M-doping (M = Zr, Hf) effects on the electronic structures and thermoelectric performance of TiCoSb were studied by first-principles calculations. The band structure analysis shows that substituting Ti with M does not change the band structures of these systems significantly. Most of the M-doped systems have a lower band gap value than that of TiCoSb; especially Ti0.5Zr0.5CoSb has the lowest energy band gap value of 0.971 eV. Besides, the amplitudes of the density of states in the region of the valence bands for M-doped systems show a similar but slightly higher value than TiCoSb. Those suggest that these compounds could have better thermoelectric performance than TiCoSb. The phonon dispersion relations show that the larger mass of Zr/Hf with respect to Ti lowers the optical modes and induces mixing with the acoustic branches. Our calculations offer a valuable insight on how to characterize complicated crystal structures of thermoelectric materials and optimize the material composition.

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Sun, G. , Li, Y. , Zhao, X. , Mi, Y. and Wang, L. (2015) First-Principles Investigation of the Effect of M-Doped (M = Zr, Hf) TiCoSb Half-Heusler Thermoelectric Material. Journal of Materials Science and Chemical Engineering, 3, 78-86. doi: 10.4236/msce.2015.312012.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Zou, D.F., Xie, S.H., Liu, Y.Y., Lin, J.G. and Li, J.Y. (2013) Electronic Structure and Thermoelectric Properties of Half-Heusler Zr0.5Hf0.5NiSn by First-Principles Calculations. Journal of Applied Physics, 113, Article ID: 193705.
[2] Ding, G.Q., Gao, G.Y. and Yao, K.L. (2014) Thermoelectric Performance of Half-Heusler Compounds MYSb (M = Ni, Pd, Pt). Journal of Physics D: Applied Physics, 47, Article ID: 385305.
[3] Geng, H.Y., Meng, X.F., Zhang, H. and Zhang, J. (2014) Lattice Thermal Conductivity of Nanograined Half-Heusler Solid Solutions. Applied Physics Letters, 104, Article ID: 202104.
[4] Culp, S.R., Poon, S.J., Hickman, N., Tritt, T.M. and Blumm, J. (2006) Effect of Substitutions on the Thermoelectric Figure of Merit of Half-Heusler Phases at 800℃. Applied Physics Letters, 88, Article ID: 042106.
[5] Bhattacharya, S., Skove, M., Russell, M., Tritt, T., Xia, Y., Ponnambalam, V., Poon, S. and Thadhani, N. (2008) Effect of Boundary Scattering on the Thermal Conductivity of TiNiSn-Based Half-Heusler Alloys. Physical Review B, 77, Article ID: 184203.
[6] Ouardi, S., Fecher, G.H., Felser, C., Blum, C.G.F., Bombor, D., Hess, C., Wurmehl, S., Büchner, B. and Ikenaga, E. (2011) Transport and Thermal Properties of Single- and Polycrystalline NiZr0.5Hf0.5Sn. Applied Physics Letters, 99, Article ID: 152112.
[7] Liu, C.R. and Li, J.B. (2011) Thermoelectric Properties of ZnO Nanowires: A First Principle Research. Physics Letters A, 375, 2878-2881.
[8] Kimura, Y., Ueno, H. and Mishima, Y. (2009) Thermoelectric Properties of Directionally Solidified Half-Heusler (M0.5a, M0.5b)NiSn (Ma, Mb = Hf, Zr, Ti) Alloys. Journal of Electronic Materials, 38, 934-939.
[9] Xie, H.H., Wang, H., Pei, Y.Z., Fu, C.G., Liu, X.H., Snyder, G.J., Zhao, X.B. and Zhou, T.J. (2013) Beneficial Contribution of Alloy Disorder to Electron and Phonon Transport in Half-Heusler Thermoelectric Materials. Advanced Functional Materials, 23, 5123-5130.
[10] Uher, C., Yang, J., Hu, S., Morelli, D.T. and Meisner, G.P. (1999) Transport Properties of Pure and Doped MNiSn (M = Zr, Hf). Physical Review B, 59, 8615.
[11] Hohl, H., Ramirez, A.P., Goldmann, C., Ernst, G., Wolfing, B. and Bucher, E. (1999) Efficient Dopants for ZrNiSn-Based Thermoelectric Materials. Journal of Physics: Condensed Matter, 11, 1697-1710.
[12] Xie, W.J., Jin, Q. and Tang, X.F. (2008) The Preparation and Thermoelectric Properties of Ti0.5Zr0.25Hf0.25Co1–xNixSb Half-Heusler Compounds. Journal of Applied Physics, 103, Article ID: 043711.
[13] Huang, X.Y., Xu, Z. and Chen, L.D. (2004) The Thermoelectric Performance of ZrNiSn/ZrO2 Composites. Solid State Communication, 130, 181-185.
[14] Sakurada, S. and Shutoh, N. (2005) Effect of Ti Substitution on the Thermoelectric Properties of (Zr,Hf)NiSn Half-Heusler Compounds. Applied Physics Letters, 86, Article ID: 082105.
[15] Lindsay, L., Broido, D.A. and Reinecke, T.L. (2013) Ab initio Thermal Transport in Compound Semiconductors. Physical Review B, 87, Article ID: 165201.
[16] Nomura, M., Nakagawa, J., Kage, Y., Maire, J., Moser, D. and Paul, O. (2015) Thermal Phonon Transport in Silicon Nanowires and Two-Dimensional Phononic Crystal Nanostructures. Applied Physics Letters, 106, Article ID: 143102.
[17] Yang, J., Meisner, G.P. and Chen, L.D. (2004) Strain Field Fluctuation Effects on Lattice Thermal Conductivity of ZrNiSn-Based Thermoelectric Compounds. Applied Physics Letters, 85, 1140.
[18] Tian, Z.T., Garg, J., Esfarjani, K., Shiga, T., Shiomi, J. and Chen, G. (2012) Phonon Conduction in PbSe, PbTe, and PbTe1–xSex from First-Principles Calculations. Physical Review B, 85, Article ID: 184303.
[19] Sekimoto, T., Kurosaki, K., Muta, H. and Yamanaka, S. (2006) Thermoelectric and Thermophysical Properties of ErPdX (X=Sb and Bi) Half-Heusler Compounds. Journal of Applied Physics, 99, Article ID: 103701.
[20] Kresse, G. and Furthmüller, J. (1996) Efficiency of Ab-Initio Total Energy Calculations for Metals and Semiconductors Using a Plane-Wave Basis Set. Computer Materials Science, 6, 15-50.
[21] Kresse, G. and Furthmüller, J. (1996) Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set. Physical Review B, 54, Article ID: 011169.
[22] Kresse, G. and Hafner, J. (1993) Ab initio Molecular Dynamics for Liquid Metals. Physical Review B, 47, 558-561.
[23] Perdew, J.P., Burke, K. and Ernzerhof, M. (1996) Generalized Gradient Approximation Made Simple. Physical Review Letter, 77, 3865-3868.
[24] Wang, L.L., Miao, L., Wang, Z.Y., Wei, W., Xiong, R., Liu, H.J., Shi, J. and Tang, X.F. (2009) Thermoelectric Performance of Half-Heusler Compounds TiNiSn and TiCoSb. Journal of Applied Physics, 105, Article ID: 013709.
[25] Sekimoto, T., Kurosaki, K., Muta, H. and Yamanaka, S. (2005) Thermoelectric Properties of (Ti,Zr,Hf)CoSb Type Half-Heusler Compounds. Materials Transactions, 46, 1481-1484.
[26] Yang, J., Li, H.M., Wu, T., Zhang, W.Q., Chen, L.D. and Yang, J.H. (2008) Evaluation of Half-Heusler Compounds as Thermoelectric Materials Based on the Calculated Electrical Transport Properties. Advanced Functional Materials, 18, 2880-2888.
[27] Khein, A., Singh, D.J. and Umrigar, C.J. (1995) All-Electron Study of Gradient Corrections to the Local-Density Functional in Metallic Systems. Physical Review B, 51, 4105-4109.
[28] Song, Y. and Guo, A.X. (2006) Electronic Structure, Stability and Bonding of the Li-N-H Hydrogen Storage System. Physical Review B, 74, Article ID: 195120.
[29] Lee, M.S., Poudeu, F.P. and Mahanti, S.D. (2011) Electronic Structure and Thermoelectric Properties of Sb-Based Semiconducting Half-Heusler Compounds. Physical Review B, 83, Article ID: 085204.
[30] Ding, G.Q., Gao, G.Y. and Yao, K.L. (2015) Examining the Thermal Conductivity of the Half-Heusler Alloy TiNiSn by First-Principles Calculations. Journal of Physics D: Applied Physics, 48, Article ID: 235302.
[31] Shiomi, J., Esfarjani, K. and Chen, G. (2011) Thermal Conductivity of Half-Heusler Compounds from First-Principles Calculations. Physical Review B, 84, Article ID: 104302.
[32] Togo, A., Oba, F. and Tanaka, I. (2008) First-Principles Calculations of the Ferroelastic Transition between Rutile-Type and CaCl2-Type SiO2 at High Pressures. Physical Review B, 78, Article ID: 134106.
[33] Xia, Y., Bhattacharya, S., Ponnambalam, V., Pope, A.L., Poon, S.J. and Tritt, T.M. (2000) Thermoelectric Properties of Semimetallic (Zr, Hf)CoSb Half-Heusler Phases. Journal of Applied Physics, 88, 1952.
[34] Qiu, P.F., Huang, X.Y., Chen, X.H. and Chen, L.D. (2009) Enhanced Thermoelectric Performance by the Combination of Alloying and Doping in TiCoSb-Based Half-Heusler Compounds. Journal of Applied Physics, 106, Article ID: 103703.

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