Valence Band Modification and High Thermoelectric Performance in SnTe Heavily Alloyed with MnTe

Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang; Chi, Hang; Bailey, Trevor P.; Zhao, Li-Dong; Uher, Ctirad; Wolverton, Chris; Dravid, Vinayak P.; Kanatzidis, Mercouri G.

doi:10.1021/jacs.5b07284

Valence Band Modification and High Thermoelectric Performance in SnTe Heavily Alloyed with MnTe

Journal Article · Wed Aug 26 00:00:00 EDT 2015 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.5b07284· OSTI ID:1370358

Tan, Gangjian ^[1]; Shi, Fengyuan ^[1]; Hao, Shiqiang ^[1]; Chi, Hang ^[2]; Bailey, Trevor P. ^[2]; Zhao, Li-Dong ^[3]; Uher, Ctirad ^[2]; Wolverton, Chris ^[1]; Dravid, Vinayak P. ^[1]; Kanatzidis, Mercouri G. ^[4]

Northwestern Univ., Evanston, IL (United States)
Univ. of Michigan, Ann Arbor, MI (United States)
Beihang Univ., Beijing (China)
Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Herein we demonstrate a high solubility limit of >9 mol% for MnTe alloying in SnTe. The electrical conductivity of SnTe decreases gradually while the Seebeck coefficient increases remarkably with increasing MnTe content, leading to enhanced power factors. The room-temperature Seebeck coefficients of Mn-doped SnTe are significantly higher than those predicted by theoretical Pisarenko plots for pure SnTe, indicating a modified band structure. The high-temperature Hall data of Sn_1–xMn_xTe show strong temperature dependence, suggestive of a two-valence-band conduction behavior. Moreover, the peak temperature of the Hall plot of Sn_1–xMn_xTe shifts toward lower temperature as MnTe content is increased, which is clear evidence of decreased energy separation (band convergence) between the two valence bands. The first-principles electronic structure calculations based on density functional theory also support this point. The higher doping fraction (>9%) of Mn in comparison with ~3% for Cd and Hg in SnTe gives rise to a much better valence band convergence that is responsible for the observed highest Seebeck coefficient of ~230 μV/K at 900 K. The high doping fraction of Mn in SnTe also creates stronger point defect scattering, which when combined with ubiquitous endotaxial MnTe nanostructures when the solubility of Mn is exceeded scatters a wide spectrum of phonons for a low lattice thermal conductivity of 0.9 W m^–1 K^–1 at 800 K. The synergistic role that Mn plays in regulating the electron and phonon transport of SnTe yields a high thermoelectric figure of merit of 1.3 at 900 K.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Revolutionary Materials for Solid State Energy Conversion (RMSSEC); Michigan State Univ., East Lansing, MI (United States)

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

Grant/Contract Number:: SC0001054

OSTI ID:: 1370358

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 35 Vol. 137; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Simultaneous Boost of Power Factor and Figure‐of‐Merit in In–Cu Codoped SnTe Guo, Fengkai; Cui, Bo; Geng, Huiyuan Small, Vol. 15, Issue 36 https://doi.org/10.1002/smll.201902493	journal	July 2019
SnSe + Ag2Se composite engineering with ball milling for enhanced thermoelectric performance Feng, Dan; Chen, Yue-Xing; Fu, Liang-Wei Rare Metals, Vol. 37, Issue 4 https://doi.org/10.1007/s12598-017-0994-6	journal	December 2017
Non-equilibrium processing leads to record high thermoelectric figure of merit in PbTe–SrTe Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang Nature Communications, Vol. 7, Issue 1 https://doi.org/10.1038/ncomms12167	journal	July 2016
Valleytronics in thermoelectric materials Xin, Jiazhan; Tang, Yinglu; Liu, Yintu npj Quantum Materials, Vol. 3, Issue 1 https://doi.org/10.1038/s41535-018-0083-6	journal	February 2018
Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe Wu, Haijun; Chang, Cheng; Feng, Dan Energy & Environmental Science, Vol. 8, Issue 11 https://doi.org/10.1039/c5ee02423d	journal	January 2015
Revisiting AgCrSe ₂ as a promising thermoelectric material Wu, Di; Huang, Sizhao; Feng, Dan Physical Chemistry Chemical Physics, Vol. 18, Issue 34 https://doi.org/10.1039/c6cp04791b	journal	January 2016
The origin of low thermal conductivity in Sn _1−x Sb _x Te: phonon scattering via layered intergrowth nanostructures Banik, Ananya; Vishal, Badri; Perumal, Suresh Energy & Environmental Science, Vol. 9, Issue 6 https://doi.org/10.1039/c6ee00728g	journal	January 2016
SnSe: a remarkable new thermoelectric material Zhao, Li-Dong; Chang, Cheng; Tan, Gangjian Energy & Environmental Science, Vol. 9, Issue 10 https://doi.org/10.1039/c6ee01755j	journal	January 2016
Multiple effects of Bi doping in enhancing the thermoelectric properties of SnTe Zhou, Zhiwei; Yang, Junyou; Jiang, Qinghui Journal of Materials Chemistry A, Vol. 4, Issue 34 https://doi.org/10.1039/c6ta04240f	journal	January 2016
Defect chemistry and enhancement of thermoelectric performance in Ag-doped Sn _1+δ−x Ag _x Te Lee, Min Ho; Byeon, Do-Gyun; Rhyee, Jong-Soo Journal of Materials Chemistry A, Vol. 5, Issue 5 https://doi.org/10.1039/c6ta09941f	journal	January 2017
Optimization of thermoelectric properties of n-type Ti, Pb co-doped SnSe Li, Fu; Wang, Wenting; Qiu, Xincheng Inorganic Chemistry Frontiers, Vol. 4, Issue 10 https://doi.org/10.1039/c7qi00436b	journal	January 2017
Effective dopants in p-type elementary Te thermoelectrics Qian, Xin; Xiao, Yu; Zheng, Lei RSC Advances, Vol. 7, Issue 29 https://doi.org/10.1039/c7ra01706e	journal	January 2017
Performance optimization and single parabolic band behavior of thermoelectric MnTe Xu, Yidong; Li, Wen; Wang, Chen Journal of Materials Chemistry A, Vol. 5, Issue 36 https://doi.org/10.1039/c7ta04842d	journal	January 2017
Recent progress towards high performance of tin chalcogenide thermoelectric materials Li, Shan; Li, Xiaofang; Ren, Zhifeng Journal of Materials Chemistry A, Vol. 6, Issue 6 https://doi.org/10.1039/c7ta09941j	journal	January 2018
The journey of tin chalcogenides towards high-performance thermoelectrics and topological materials Banik, Ananya; Roychowdhury, Subhajit; Biswas, Kanishka Chemical Communications, Vol. 54, Issue 50 https://doi.org/10.1039/c8cc02230e	journal	January 2018
Engineering ferroelectric instability to achieve ultralow thermal conductivity and high thermoelectric performance in Sn _1−x Ge _x Te Banik, Ananya; Ghosh, Tanmoy; Arora, Raagya Energy & Environmental Science, Vol. 12, Issue 2 https://doi.org/10.1039/c8ee03162b	journal	January 2019
High thermoelectric performance of Cu ₃ SbSe ₄ nanocrystals with Cu _2−x Se in situ inclusions synthesized by a microwave-assisted solvothermal method Xie, Dandan; Zhang, Bin; Zhang, Aijuan Nanoscale, Vol. 10, Issue 30 https://doi.org/10.1039/c8nr03550d	journal	January 2018
Effect of single metal doping on the thermoelectric properties of SnTe Aminzare, Masoud; Tseng, Yu-Chih; Ramakrishnan, Anbalagan Sustainable Energy & Fuels, Vol. 3, Issue 1 https://doi.org/10.1039/c8se00385h	journal	January 2019
Lead-free MnTe mid-temperature thermoelectric materials: facile synthesis, p-type doping and transport properties Dong, Jinfeng; Wu, Chao-Feng; Pei, Jun Journal of Materials Chemistry C, Vol. 6, Issue 15 https://doi.org/10.1039/c8tc00904j	journal	January 2018
Thermoelectric transport properties of rock-salt SnSe: first-principles investigation Wang, Dongyang; He, Wenke; Chang, Cheng Journal of Materials Chemistry C, Vol. 6, Issue 44 https://doi.org/10.1039/c8tc01314d	journal	January 2018
High thermoelectric performance of Ag doped SnTe polycrystalline bulks via the synergistic manipulation of electrical and thermal transport Zhao, Lanling; Wang, Jun; Li, Jichao Physical Chemistry Chemical Physics, Vol. 21, Issue 32 https://doi.org/10.1039/c9cp03534f	journal	January 2019
Discordant nature of Cd in PbSe: off-centering and core–shell nanoscale CdSe precipitates lead to high thermoelectric performance Cai, Songting; Hao, Shiqiang; Luo, Zhong-Zhen Energy & Environmental Science, Vol. 13, Issue 1 https://doi.org/10.1039/c9ee03087e	journal	January 2020
Seeing atomic-scale structural origins and foreseeing new pathways to improved thermoelectric materials Wu, Haijun; Zhang, Yang; Ning, Shoucong Materials Horizons, Vol. 6, Issue 8 https://doi.org/10.1039/c9mh00543a	journal	January 2019
Integration of multi-scale defects for optimizing thermoelectric properties of n-type Cu _1−x Cd _x FeS ₂ ( x = 0–0.1) Ge, Bangzhi; Hu, Jiabin; Shi, Zhongqi Nanoscale, Vol. 11, Issue 37 https://doi.org/10.1039/c9nr04693c	journal	January 2019
Transport properties of polycrystalline SnTe prepared by saturation annealing Ibrahim, Dorra; Misra, Shantanu; Migot, Sylvie RSC Advances, Vol. 10, Issue 10 https://doi.org/10.1039/c9ra10841f	journal	January 2020
Discordant nature of Cd in GeTe enhances phonon scattering and improves band convergence for high thermoelectric performance Nshimyimana, Evariste; Hao, Shiqiang; Su, Xianli Journal of Materials Chemistry A, Vol. 8, Issue 3 https://doi.org/10.1039/c9ta10436d	journal	January 2020
Eutectoid nano-precipitates inducing remarkably enhanced thermoelectric performance in (Sn _1−x Cd _x Te) _1−y (Cu ₂ Te) _y Qi, Xia; Huang, Yi; Wu, Di Journal of Materials Chemistry A, Vol. 8, Issue 5 https://doi.org/10.1039/c9ta11180h	journal	January 2020
Band structure engineering in Sn _1.03 Te through an In-induced resonant level Misra, Shantanu; Wiendlocha, Bartlomiej; Tobola, Janusz Journal of Materials Chemistry C, Vol. 8, Issue 3 https://doi.org/10.1039/c9tc04407h	journal	January 2020
Excellent thermoelectric performance achieved over broad temperature plateau in indium-doped SnTe-AgSbTe ₂ alloys He, Mingkai; Feng, Dan; Wu, Di Applied Physics Letters, Vol. 112, Issue 6 https://doi.org/10.1063/1.5018477	journal	February 2018
Promising thermoelectric properties and anisotropic electrical and thermal transport of monolayer SnTe Li, Y.; Wu, M. N.; Ding, T. Applied Physics Letters, Vol. 114, Issue 8 https://doi.org/10.1063/1.5085255	journal	February 2019
Band engineering, carrier density control, and enhanced thermoelectric performance in multi-doped SnTe Doi, A.; Shimano, S.; Inoue, D. APL Materials, Vol. 7, Issue 9 https://doi.org/10.1063/1.5116882	journal	September 2019
Advances in thermoelectrics Mao, Jun; Liu, Zihang; Zhou, Jiawei Advances in Physics, Vol. 67, Issue 2 https://doi.org/10.1080/00018732.2018.1551715	journal	April 2018
Hydrothermal synthesis of SnQ ( Q = Te, Se, S) and their thermoelectric properties Feng, Dan; Ge, Zhen-Hua; Chen, Yue-Xing Nanotechnology, Vol. 28, Issue 45 https://doi.org/10.1088/1361-6528/aa8b29	journal	October 2017
Fundamental and progress of Bi ₂ Te ₃ -based thermoelectric materials Hong, Min; Chen, Zhi-Gang; Zou, Jin Chinese Physics B, Vol. 27, Issue 4 https://doi.org/10.1088/1674-1056/27/4/048403	journal	April 2018
Effect of In and Cd co-doping on the thermoelectric properties of Sn _1−x Pb _x Te Roychowdhury, Subhajit; Biswas, Kanishka Materials Research Express, Vol. 6, Issue 10 https://doi.org/10.1088/2053-1591/ab3db8	journal	September 2019
Eco-friendly high-performance silicide thermoelectric materials Liu, Wei; Yin, Kang; Zhang, Qingjie National Science Review, Vol. 4, Issue 4 https://doi.org/10.1093/nsr/nwx011	journal	February 2017
Limit of z T enhancement in rocksalt structured chalcogenides by band convergence Hong, Min; Chen, Zhi-Gang; Pei, Yanzhong Physical Review B, Vol. 94, Issue 16 https://doi.org/10.1103/physrevb.94.161201	journal	October 2016
Comprehensive study of the low-temperature transport properties of polycrystalline S n 1 + x Te ( x = 0 and 0.03) Ibrahim, Dorra; Candolfi, Christophe; Migot, Sylvie Physical Review Materials, Vol. 3, Issue 8 https://doi.org/10.1103/physrevmaterials.3.085404	journal	August 2019
Thermoelectric performance of SnTe with ZnO carrier compensation, energy filtering, and multiscale phonon scattering Zhou, Zhiwei; Yang, Junyou; Jiang, Qinghui Journal of the American Ceramic Society, Vol. 100, Issue 12 https://doi.org/10.1111/jace.15088	journal	July 2017
High-entropy functional materials Gao, Michael C.; Miracle, Daniel B.; Maurice, David Journal of Materials Research, Vol. 33, Issue 19 https://doi.org/10.1557/jmr.2018.323	journal	September 2018