High thermoelectric performance in (Bi0.25Sb0.75)2Te3 due to band convergence and improved by carrier concentration control

Kim, Hyun-Sik; Heinz, Nicholas A.; Gibbs, Zachary M.; Tang, Yinglu; Kang, Stephen D.; Snyder, G. Jeffrey

doi:10.1016/j.mattod.2017.02.007

High thermoelectric performance in (Bi_0.25Sb_0.75)₂Te₃ due to band convergence and improved by carrier concentration control

Journal Article · Wed Jun 28 00:00:00 EDT 2017 · Materials Today

DOI:https://doi.org/10.1016/j.mattod.2017.02.007· OSTI ID:1470452

^[1]; Heinz, Nicholas A. ^[2]; Gibbs, Zachary M. ^[2]; Tang, Yinglu ^[3]; ^[3]; Snyder, G. Jeffrey ^[3]

Northwestern Univ., Evanston, IL (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States); Samsung Advanced Institute of Technology, Samsung Electronics (South Korea)
California Inst. of Technology (CalTech), Pasadena, CA (United States)
Northwestern Univ., Evanston, IL (United States); California Inst. of Technology (CalTech), Pasadena, CA (United States)

Bi₂Te₃ has been recognized as an important cooling material for thermoelectric applications. Yet its thermoelectric performance could still be improved. Here we propose a band engineering strategy by optimizing the converging valence bands of Bi₂Te₃ and Sb₂Te₃ in the (Bi_1-xSb_x)₂Te₃ system when x = 0.75. Band convergence successfully explains the sharp increase in density-of-states effective mass yet relatively constant mobility and optical band gap measurement. This band convergence picture guides the carrier concentration tuning for optimum thermoelectric performance. To synthesize homogeneous textured and optimally doped (Bi_0.25Sb_0.75)₂Te₃, excess Te was chosen as the dopant. Uniform control of the optimized thermoelectric composition was achieved by zone-melting which utilizes separate solidus and liquidus compositions to obtain zT = 1.05 (at 300 K) without nanostructuring.

View Accepted Manuscript (DOE)

Research Organization:: Massachusetts Inst. of Technology, Cambridge, MA (United States); Energy Frontier Research Centers (EFRC) (United States). Solid-State Solar-Thermal Energy Conversion Center (S3TEC)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0001299

OSTI ID:: 1470452

Journal Information:: Materials Today, Journal Name: Materials Today Journal Issue: 8 Vol. 20; ISSN 1369-7021

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (47)

Thermoelectric Power and Scattering of Carriers in Bi2?xSnxTe3 with Layered Structure Kulbachinskii, V. A.; Negishi, H.; Sasaki, M. physica status solidi (b), Vol. 199, Issue 2 https://doi.org/10.1002/1521-3951(199702)199:2<505::AID-PSSB505>3.0.CO;2-9	journal	February 1997
Influence of Sn on Galvanomagnetic Properties of Layered p-(Bi1?xSbx)2Te3 Semiconductors Kulbachinskii, V. A.; Kaminsky, A. Yu.; Kindo, K. physica status solidi (b), Vol. 229, Issue 3 https://doi.org/10.1002/1521-3951(200202)229:3<1467::AID-PSSB1467>3.0.CO;2-T	journal	February 2002
The Criteria for Beneficial Disorder in Thermoelectric Solid Solutions Wang, Heng; LaLonde, Aaron D.; Pei, Yanzhong Advanced Functional Materials, Vol. 23, Issue 12 https://doi.org/10.1002/adfm.201201576	journal	October 2012
Applying Quantitative Microstructure Control in Advanced Functional Composites Heinz, Nicholas A.; Ikeda, Teruyuki; Pei, Yanzhong Advanced Functional Materials, Vol. 24, Issue 15 https://doi.org/10.1002/adfm.201302899	journal	December 2013
Seebeck coefficient and electrical conductivity in p-(Bi1−xSbx)2 Te3 at room temperature Süssmann, H.; Heiliger, W. Physica Status Solidi (a), Vol. 80, Issue 2 https://doi.org/10.1002/pssa.2210800215	journal	December 1983
Valence-Band Properties of Bi2Te3 from Galvanomagnetic Measurements Sologub, V. V.; Goletskaya, A. D.; Lang, I. G. Physica Status Solidi (b), Vol. 58, Issue 2 https://doi.org/10.1002/pssb.2220580205	journal	August 1973
Non-Parabolicity of the Highest Valence Band of Bi2Te3 from Shubnikov-de Haas Effect Köhler, H. physica status solidi (b), Vol. 74, Issue 2 https://doi.org/10.1002/pssb.2220740218	journal	April 1976
Investigation of the highest valence band in (Bi1-xSbx)2Te3 crystals Köhler, H.; Freudenberger, A. Physica Status Solidi (b), Vol. 84, Issue 1 https://doi.org/10.1002/pssb.2220840122	journal	November 1977
Galvanomagnetic transport properties of Sb2Te3 Eichler, W.; Simon, G. Physica Status Solidi (b), Vol. 86, Issue 1 https://doi.org/10.1002/pssb.2220860170	journal	March 1978
Investigations on a two-valence band model for Sb2Te3 Simon, G.; Eichler, W. physica status solidi (b), Vol. 107, Issue 1 https://doi.org/10.1002/pssb.2221070120	journal	September 1981
Investigation of the Valence Band Structure of Thermoelectric (Bi1−xSbx)2Te3 Single Crystals Stordeur, M.; Stölzer, M.; Sobotta, H. physica status solidi (b), Vol. 150, Issue 1 https://doi.org/10.1002/pssb.2221500120	journal	November 1988
Two Valence Subbands in Single Crystals of Bismuth Telluride Doped with Lead and Its Electrical Properties Biswas, S.; Bhattacharya, R. physica status solidi (b), Vol. 151, Issue 1 https://doi.org/10.1002/pssb.2221510123	journal	January 1989
Band structure of indium antimonide Kane, Evan O. Journal of Physics and Chemistry of Solids, Vol. 1, Issue 4 https://doi.org/10.1016/0022-3697(57)90013-6	journal	January 1957
Transport properties of p-type Bi2Te3Sb2Te3 alloys in the temperature range 80–370°K Testardi, L. R.; Bierly, J. N.; Donahoe, F. J. Journal of Physics and Chemistry of Solids, Vol. 23, Issue 9 https://doi.org/10.1016/0022-3697(62)90168-3	journal	September 1962
The optical properties of p-type Bi2Te3Sb2Te3 alloys between 2–15 microns Sehr, R.; Testardi, L. R. Journal of Physics and Chemistry of Solids, Vol. 23, Issue 9 https://doi.org/10.1016/0022-3697(62)90169-5	journal	September 1962
Doping properties of Sb2Te3 indicating a two valence band model Rönnlund, B.; Beckman, O.; Levy, H. Journal of Physics and Chemistry of Solids, Vol. 26, Issue 8 https://doi.org/10.1016/0022-3697(65)90109-5	journal	August 1965
Study of the Bi-Sb-Te ternary phase diagram Caillat, T.; Carle, M.; Perrin, D. Journal of Physics and Chemistry of Solids, Vol. 53, Issue 2, p. 227-232 https://doi.org/10.1016/0022-3697(92)90049-J	journal	February 1992
Thermoelectric properties of (BixSb1−x)2Te3 single crystal solid solutions grown by the T.H.M. method Caillat, T.; Carle, M.; Pierrat, P. Journal of Physics and Chemistry of Solids, Vol. 53, Issue 8 https://doi.org/10.1016/0022-3697(92)90087-T	journal	August 1992
Transport properties analysis of single crystals (BixSb1 − x)2Te3 grown by the traveling heater method Caillat, T.; Gailliard, L.; Scherrer, H. Journal of Physics and Chemistry of Solids, Vol. 54, Issue 5 https://doi.org/10.1016/0022-3697(93)90235-J	journal	May 1993
Evidence for a second valence band in p-type Bi2Te3 from Magneto-Seebeck and Shubnikov-De Haas-data von Middendorff, A.; Landwehr, G. Solid State Communications, Vol. 11, Issue 1 https://doi.org/10.1016/0038-1098(72)99000-X	journal	July 1972
Shubnikov-de Haas effect in p-type Sb2 Te3 von Middendorff, A.; Dietrich, K.; Landwehr, G. Solid State Communications, Vol. 13, Issue 4 https://doi.org/10.1016/0038-1098(73)90472-9	journal	August 1973
Compound tellurides and their alloys for peltier cooling—A review Yim, W. M.; Rosi, F. D. Solid-State Electronics, Vol. 15, Issue 10 https://doi.org/10.1016/0038-1101(72)90172-4	journal	October 1972
Thermoelectric properties of p-type (Bi2Te3)x(Sb2Te3)1−x crystals prepared via zone melting Jiang, Jun; Chen, Lidong; Bai, Shengqiang Journal of Crystal Growth, Vol. 277, Issue 1-4 https://doi.org/10.1016/j.jcrysgro.2004.12.144	journal	April 2005
Zone Leveling Crystal Growth of Thermoelectric PbTe Alloys with Sb ₂ Te ₃ Widmanstätten Precipitates Ikeda, Teruyuki; Marolf, Nathan J.; Snyder, G. Jeffrey Crystal Growth & Design, Vol. 11, Issue 9 https://doi.org/10.1021/cg2007588	journal	September 2011
Identifying the Specific Nanostructures Responsible for the High Thermoelectric Performance of (Bi,Sb) ₂ Te ₃ Nanocomposites Xie, Wenjie; He, Jian; Kang, Hye Jung Nano Letters, Vol. 10, Issue 9 https://doi.org/10.1021/nl100804a	journal	September 2010
Convergence of electronic bands for high performance bulk thermoelectrics Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron Nature, Vol. 473, Issue 7345, p. 66-69 https://doi.org/10.1038/nature09996	journal	May 2011
Complex thermoelectric materials Snyder, G. Jeffrey; Toberer, Eric S. Nature Materials, Vol. 7, Issue 2, p. 105-114 https://doi.org/10.1038/nmat2090	journal	February 2008
A new class of doped nanobulk high-figure-of-merit thermoelectrics by scalable bottom-up assembly Mehta, Rutvik J.; Zhang, Yanliang; Karthik, Chinnathambi Nature Materials, Vol. 11, Issue 3 https://doi.org/10.1038/nmat3213	journal	January 2012
Ambipolar field effect in the ternary topological insulator (BixSb1–x)2Te3 by composition tuning Kong, Desheng; Chen, Yulin; Cha, Judy J. Nature Nanotechnology, Vol. 6, Issue 11 https://doi.org/10.1038/nnano.2011.172	journal	October 2011
Importance of non-parabolic band effects in the thermoelectric properties of semiconductors Chen, Xin; Parker, David; Singh, David J. Scientific Reports, Vol. 3, Issue 1 https://doi.org/10.1038/srep03168	journal	November 2013
Bismuth telluride compounds with high thermoelectric figures of merit Yamashita, Osamu; Tomiyoshi, Shoichi; Makita, Ken Journal of Applied Physics, Vol. 93, Issue 1 https://doi.org/10.1063/1.1525400	journal	January 2003
Recent Studies of Bismuth Telluride and Its Alloys Goldsmid, H. J. Journal of Applied Physics, Vol. 32, Issue 10 https://doi.org/10.1063/1.1777042	journal	October 1961
Figure of merit of quaternary (Sb0.75Bi0.25)2−xInxTe3 single crystals Drašar, Č.; Hovorková, A.; Lošťák, P. Journal of Applied Physics, Vol. 104, Issue 2 https://doi.org/10.1063/1.2956608	journal	July 2008
Enhanced thermoelectric performance in p-type BiSbTe bulk alloy with nanoinclusion of ZnAlO Zhang, Ting; Zhang, Qiushi; Jiang, Jun Applied Physics Letters, Vol. 98, Issue 2 https://doi.org/10.1063/1.3541654	journal	January 2011
A high temperature apparatus for measurement of the Seebeck coefficient Iwanaga, Shiho; Toberer, Eric S.; LaLonde, Aaron Review of Scientific Instruments, Vol. 82, Issue 6 https://doi.org/10.1063/1.3601358	journal	June 2011
Temperature dependent band gap in PbX (X = S, Se, Te) Gibbs, Zachary M.; Kim, Hyoungchul; Wang, Heng Applied Physics Letters, Vol. 103, Issue 26 https://doi.org/10.1063/1.4858195	journal	December 2013
Galvanomagnetic Effects in p-Type Bismuth Telluride Drabble, J. R. Proceedings of the Physical Society, Vol. 72, Issue 3 https://doi.org/10.1088/0370-1328/72/3/308	journal	September 1958
Optical band gap and the Burstein–Moss effect in iodine doped PbTe using diffuse reflectance infrared Fourier transform spectroscopy Gibbs, Zachary M.; LaLonde, Aaron; Snyder, G. Jeffrey New Journal of Physics, Vol. 15, Issue 7 https://doi.org/10.1088/1367-2630/15/7/075020	journal	July 2013
Connecting Thermoelectric Performance and Topological-Insulator Behavior: Bi 2 Te 3 and Bi 2 Te 2 Se from First Principles Shi, Hongliang; Parker, David; Du, Mao-Hua Physical Review Applied, Vol. 3, Issue 1 https://doi.org/10.1103/PhysRevApplied.3.014004	journal	January 2015
Valence-band energy spectrum of solid solutions of narrow-gap-semiconductor Bi 2 − x Sn x Te 3 single crystals Kulbachinskii, V. A.; Inoue, M.; Sasaki, M. Physical Review B, Vol. 50, Issue 23 https://doi.org/10.1103/PhysRevB.50.16921	journal	December 1994
First-principles electronic structure and its relation to thermoelectric properties of Bi 2 Te 3 Youn, S. J.; Freeman, A. J. Physical Review B, Vol. 63, Issue 8 https://doi.org/10.1103/PhysRevB.63.085112	journal	February 2001
Effect of p 1 / 2 corrections in the electronic structure of Bi 2 Te 3 compounds Larson, P. Physical Review B, Vol. 68, Issue 15 https://doi.org/10.1103/PhysRevB.68.155121	journal	October 2003
Electronic structure of the thermoelectric materials Bi 2 Te 3 and Sb 2 Te 3 from first-principles calculations Wang, Guofeng; Cagin, Tahir Physical Review B, Vol. 76, Issue 7 https://doi.org/10.1103/PhysRevB.76.075201	journal	August 2007
High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys Poudel, B.; Hao, Q.; Ma, Y. Science, Vol. 320, Issue 5876, p. 634-638 https://doi.org/10.1126/science.1156446	journal	May 2008
Preserving Montreal Protocol Climate Benefits by Limiting HFCs Velders, G. J. M.; Ravishankara, A. R.; Miller, M. K. Science, Vol. 335, Issue 6071 https://doi.org/10.1126/science.1216414	journal	February 2012
Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics Kim, Sang Il; Lee, Kyu Hyoung; Mun, Hyeon A. Science, Vol. 348, Issue 6230 https://doi.org/10.1126/science.aaa4166	journal	April 2015
Anisotropy of plasma reflection of solid solutions (Bi2 − x Sb x )Te3 (0 < x < 1) in the Temperature Range 78–293 K Stepanov, N. P.; Kalashnikov, A. A.; Gil’fanov, A. K. Optics and Spectroscopy, Vol. 111, Issue 6 https://doi.org/10.1134/S0030400X11130236	journal	December 2011

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