DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe

Abstract

Lead chalcogenides are the most efficient thermoelectric materials. In comparison, SnTe, a lead-free analogue of PbTe, exhibits inferior thermoelectric performance due to low Seebeck coefficient and high thermal conductivity. In this report, we show that we can synergistically optimize the electrical and thermal transport properties of SnTe via alloying Mn. Further, we report that the introduction of Mn (0–50%) induces multiple effects on the band structure and microstructure of SnTe: for the former, it can tune the Fermi level and promote the convergence of the two valence bands, concurrently enhancing the Seebeck coefficient; for the latter, it can profoundly modify the microstructure into an all-scale hierarchical architecture (including nanoscale precipitates/MnTe laminates, stacking faults, layered structure, atomic-scale point defects, etc.) to scatter phonons with a broad range of mean free paths, strongly reducing the lattice thermal conductivity. Meanwhile, most significantly, the Mn alloying enlarges the energy gap of the conduction band (C band) and the light valence band (L band), thereby suppressing the bipolar thermal conductivity by increasing the band gap. The integration of these effects yields a high ZT of 1.3 at 900 K for 17% Mn alloyed SnTe.

Authors:
 [1];  [2];  [3];  [2];  [2];  [2];  [2];  [3];  [2];  [4];  [3];  [5];  [2]
  1. Beihang Univ., Beijing (China); South Univ. of Science and Technology of China, Shenzhen (China); National Univ. of Singapore (Singapore)
  2. Beihang Univ., Beijing (China)
  3. South Univ. of Science and Technology of China, Shenzhen (China)
  4. The Univ. of Hong Kong, Hong Kong SAR (China)
  5. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Revolutionary Materials for Solid State Energy Conversion (RMSSEC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Postdoctoral Science Foundation of China
OSTI Identifier:
1370346
Grant/Contract Number:  
SC0001054; 51571007; 51202008
Resource Type:
Accepted Manuscript
Journal Name:
Energy & Environmental Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 11; Related Information: RMSSEC partners with Michigan State University (lead); University of California, Los Angeles; University of Michigan; Northwestern University; Oak Ridge National Laboratory; Ohio State University; Wayne State University; Journal ID: ISSN 1754-5692
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wu, Haijun, Chang, Cheng, Feng, Dan, Xiao, Yu, Zhang, Xiao, Pei, Yanling, Zheng, Lei, Wu, Di, Gong, Shengkai, Chen, Yue, He, Jiaqing, Kanatzidis, Mercouri G., and Zhao, Li-Dong. Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe. United States: N. p., 2015. Web. doi:10.1039/c5ee02423d.
Wu, Haijun, Chang, Cheng, Feng, Dan, Xiao, Yu, Zhang, Xiao, Pei, Yanling, Zheng, Lei, Wu, Di, Gong, Shengkai, Chen, Yue, He, Jiaqing, Kanatzidis, Mercouri G., & Zhao, Li-Dong. Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe. United States. https://doi.org/10.1039/c5ee02423d
Wu, Haijun, Chang, Cheng, Feng, Dan, Xiao, Yu, Zhang, Xiao, Pei, Yanling, Zheng, Lei, Wu, Di, Gong, Shengkai, Chen, Yue, He, Jiaqing, Kanatzidis, Mercouri G., and Zhao, Li-Dong. Mon . "Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe". United States. https://doi.org/10.1039/c5ee02423d. https://www.osti.gov/servlets/purl/1370346.
@article{osti_1370346,
title = {Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe},
author = {Wu, Haijun and Chang, Cheng and Feng, Dan and Xiao, Yu and Zhang, Xiao and Pei, Yanling and Zheng, Lei and Wu, Di and Gong, Shengkai and Chen, Yue and He, Jiaqing and Kanatzidis, Mercouri G. and Zhao, Li-Dong},
abstractNote = {Lead chalcogenides are the most efficient thermoelectric materials. In comparison, SnTe, a lead-free analogue of PbTe, exhibits inferior thermoelectric performance due to low Seebeck coefficient and high thermal conductivity. In this report, we show that we can synergistically optimize the electrical and thermal transport properties of SnTe via alloying Mn. Further, we report that the introduction of Mn (0–50%) induces multiple effects on the band structure and microstructure of SnTe: for the former, it can tune the Fermi level and promote the convergence of the two valence bands, concurrently enhancing the Seebeck coefficient; for the latter, it can profoundly modify the microstructure into an all-scale hierarchical architecture (including nanoscale precipitates/MnTe laminates, stacking faults, layered structure, atomic-scale point defects, etc.) to scatter phonons with a broad range of mean free paths, strongly reducing the lattice thermal conductivity. Meanwhile, most significantly, the Mn alloying enlarges the energy gap of the conduction band (C band) and the light valence band (L band), thereby suppressing the bipolar thermal conductivity by increasing the band gap. The integration of these effects yields a high ZT of 1.3 at 900 K for 17% Mn alloyed SnTe.},
doi = {10.1039/c5ee02423d},
journal = {Energy & Environmental Science},
number = 11,
volume = 8,
place = {United States},
year = {Mon Sep 07 00:00:00 EDT 2015},
month = {Mon Sep 07 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 246 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

The crystal structure of IV-VI compounds. I. Classification and description
journal, September 1980


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Coarsening Behavior of Al<SUB>3</SUB>Sc Precipitates in an Al–Mg–Sc Alloy
journal, January 2006


Mg Alloying in SnTe Facilitates Valence Band Convergence and Optimizes Thermoelectric Properties
journal, January 2015

  • Banik, Ananya; Shenoy, U. Sandhya; Anand, Shashwat
  • Chemistry of Materials, Vol. 27, Issue 2
  • DOI: 10.1021/cm504112m

Valence Band Modification and High Thermoelectric Performance in SnTe Heavily Alloyed with MnTe
journal, August 2015

  • Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang
  • Journal of the American Chemical Society, Vol. 137, Issue 35
  • DOI: 10.1021/jacs.5b07284

The Electrical Conductivity and Thermoelectric Power of Bismuth Telluride
journal, April 1958


Microstructure-Lattice Thermal Conductivity Correlation in Nanostructured PbTe 0.7 S 0.3 Thermoelectric Materials
journal, March 2010

  • He, Jiaqing; Girard, Steven N.; Kanatzidis, Mercouri G.
  • Advanced Functional Materials, Vol. 20, Issue 5
  • DOI: 10.1002/adfm.200901905

Origin of the High Performance in GeTe-Based Thermoelectric Materials upon Bi 2 Te 3 Doping
journal, August 2014

  • Wu, Di; Zhao, Li-Dong; Hao, Shiqiang
  • Journal of the American Chemical Society, Vol. 136, Issue 32
  • DOI: 10.1021/ja504896a

Thermoelectric Property Studies on Cu-Doped n-type CuxBi2Te2.7Se0.3 Nanocomposites
journal, June 2011

  • Liu, Wei-Shu; Zhang, Qinyong; Lan, Yucheng
  • Advanced Energy Materials, Vol. 1, Issue 4, p. 577-587
  • DOI: 10.1002/aenm.201100149

Stabilizing the Optimal Carrier Concentration for High Thermoelectric Efficiency
journal, November 2011

  • Pei, Yanzhong; LaLonde, Aaron D.; Heinz, Nicholas A.
  • Advanced Materials, Vol. 23, Issue 47
  • DOI: 10.1002/adma.201103153

High thermoelectric performance of Ge1−xPbxSe0.5Te0.5 due to (Pb, Se) co-doping
journal, August 2014


Thermoelectric materials: Energy conversion between heat and electricity
journal, June 2015


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

All-scale hierarchical thermoelectrics: MgTe in PbTe facilitates valence band convergence and suppresses bipolar thermal transport for high performance
journal, January 2013

  • Zhao, L. D.; Wu, H. J.; Hao, S. Q.
  • Energy & Environmental Science, Vol. 6, Issue 11
  • DOI: 10.1039/c3ee42187b

Complex thermoelectric materials
journal, February 2008

  • Snyder, G. Jeffrey; Toberer, Eric S.
  • Nature Materials, Vol. 7, Issue 2, p. 105-114
  • DOI: 10.1038/nmat2090

Broad temperature plateau for thermoelectric figure of merit ZT>2 in phase-separated PbTe0.7S0.3
journal, July 2014

  • Wu, H. J.; Zhao, L. -D.; Zheng, F. S.
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5515

High thermoelectric performance by resonant dopant indium in nanostructured SnTe
journal, July 2013

  • Zhang, Q.; Liao, B.; Lan, Y.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 33, p. 13261-13266
  • DOI: 10.1073/pnas.1305735110

BiCuSeO oxyselenides: new promising thermoelectric materials
journal, January 2014

  • Zhao, Li-Dong; He, Jiaqing; Berardan, David
  • Energy Environ. Sci., Vol. 7, Issue 9
  • DOI: 10.1039/C4EE00997E

Codoping in SnTe: Enhancement of Thermoelectric Performance through Synergy of Resonance Levels and Band Convergence
journal, April 2015

  • Tan, Gangjian; Shi, Fengyuan; Hao, Shiqiang
  • Journal of the American Chemical Society, Vol. 137, Issue 15
  • DOI: 10.1021/jacs.5b00837

Extraordinary role of Hg in enhancing the thermoelectric performance of p-type SnTe
journal, January 2015

  • Tan, Gangjian; Shi, Fengyuan; Doak, Jeff W.
  • Energy & Environmental Science, Vol. 8, Issue 1
  • DOI: 10.1039/C4EE01463D

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


High Thermoelectric Performance Realized in a BiCuSeO System by Improving Carrier Mobility through 3D Modulation Doping
journal, September 2014

  • Pei, Yan-Ling; Wu, Haijun; Wu, Di
  • Journal of the American Chemical Society, Vol. 136, Issue 39
  • DOI: 10.1021/ja507945h

Thermoelectric study of crossroads material MnTe via sulfur doping
journal, March 2014

  • Xie, Wenjie; Populoh, Sascha; Gałązka, Krzysztof
  • Journal of Applied Physics, Vol. 115, Issue 10
  • DOI: 10.1063/1.4868584

Tuning Multiscale Microstructures to Enhance Thermoelectric Performance of n-Type Bismuth-Telluride-Based Solid Solutions
journal, June 2015


Convergence of electronic bands for high performance bulk thermoelectrics
journal, May 2011

  • Pei, Yanzhong; Shi, Xiaoya; LaLonde, Aaron
  • Nature, Vol. 473, Issue 7345, p. 66-69
  • DOI: 10.1038/nature09996

Enhancement of Thermoelectric Efficiency in PbTe by Distortion of the Electronic Density of States
journal, July 2008

  • Heremans, J. P.; Jovovic, V.; Toberer, E. S.
  • Science, Vol. 321, Issue 5888, p. 554-557
  • DOI: 10.1126/science.1159725

Transport properties of SnTe interpreted by means of a two valence band model
journal, August 1981


High Performance Thermoelectrics from Earth-Abundant Materials: Enhanced Figure of Merit in PbS by Second Phase Nanostructures
journal, December 2011

  • Zhao, Li-Dong; Lo, Shih-Han; He, Jiaqing
  • Journal of the American Chemical Society, Vol. 133, Issue 50
  • DOI: 10.1021/ja208658w

High-performance bulk thermoelectrics with all-scale hierarchical architectures
journal, September 2012

  • Biswas, Kanishka; He, Jiaqing; Blum, Ivan D.
  • Nature, Vol. 489, Issue 7416, p. 414-418
  • DOI: 10.1038/nature11439

Resonant levels in bulk thermoelectric semiconductors
journal, January 2012

  • Heremans, Joseph P.; Wiendlocha, Bartlomiej; Chamoire, Audrey M.
  • Energy Environ. Sci., Vol. 5, Issue 2
  • DOI: 10.1039/C1EE02612G

Loss in coherency and coarsening behavior of Al3Sc precipitates
journal, February 2004


High Thermoelectric Performance of p-Type SnTe via a Synergistic Band Engineering and Nanostructuring Approach
journal, May 2014

  • Tan, Gangjian; Zhao, Li-Dong; Shi, Fengyuan
  • Journal of the American Chemical Society, Vol. 136, Issue 19
  • DOI: 10.1021/ja500860m

Anomalous Thermoelectric Power as Evidence for Two-Valence Bands in SnTe
journal, July 1963


SnTe–AgBiTe 2 as an efficient thermoelectric material with low thermal conductivity
journal, January 2014

  • Tan, Gangjian; Shi, Fengyuan; Sun, Hui
  • J. Mater. Chem. A, Vol. 2, Issue 48
  • DOI: 10.1039/C4TA05530F

Bulk nanostructured thermoelectric materials: current research and future prospects
journal, January 2009

  • Minnich, A. J.; Dresselhaus, M. S.; Ren, Z. F.
  • Energy & Environmental Science, Vol. 2, Issue 5
  • DOI: 10.1039/b822664b

Ultralow thermal conductivity and high thermoelectric figure of merit in SnSe crystals
journal, April 2014

  • Zhao, Li-Dong; Lo, Shih-Han; Zhang, Yongsheng
  • Nature, Vol. 508, Issue 7496, p. 373-377
  • DOI: 10.1038/nature13184

High-performance nanostructured thermoelectric materials
journal, October 2010


Strong enhancement of phonon scattering through nanoscale grains in lead sulfide thermoelectrics
journal, June 2014

  • Wu, Haijun; Carrete, Jesús; Zhang, Zhiyun
  • NPG Asia Materials, Vol. 6, Issue 6
  • DOI: 10.1038/am.2014.39

The panoscopic approach to high performance thermoelectrics
journal, January 2014

  • Zhao, Li-Dong; Dravid, Vinayak P.; Kanatzidis, Mercouri G.
  • Energy Environ. Sci., Vol. 7, Issue 1
  • DOI: 10.1039/C3EE43099E

Heavily Doped p-Type PbSe with High Thermoelectric Performance: An Alternative for PbTe
journal, February 2011

  • Wang, Heng; Pei, Yanzhong; LaLonde, Aaron D.
  • Advanced Materials, Vol. 23, Issue 11, p. 1366-1370
  • DOI: 10.1002/adma.201004200

Point Defect Engineering of High-Performance Bismuth-Telluride-Based Thermoelectric Materials
journal, June 2014

  • Hu, Lipeng; Zhu, Tiejun; Liu, Xiaohua
  • Advanced Functional Materials, Vol. 24, Issue 33
  • DOI: 10.1002/adfm.201400474

Complex thermoelectric materials
book, October 2010


Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets
journal, May 2021


Anomalous Thermoelectric Power as Evidence for Two Valence Bands in SnTe
journal, December 1963


BiCuSeO oxyselenides: new promising thermoelectric materials [BiCuSeO оксиселенид - жаңа келешегi жоғары термоэлектрлiк материал ретiнде]
journal, January 2019


Works referencing / citing this record:

Eco-Friendly SnTe Thermoelectric Materials: Progress and Future Challenges
journal, September 2017

  • Moshwan, Raza; Yang, Lei; Zou, Jin
  • Advanced Functional Materials, Vol. 27, Issue 43
  • DOI: 10.1002/adfm.201703278

Manipulation of Band Structure and Interstitial Defects for Improving Thermoelectric SnTe
journal, June 2018


Chalcogenide Thermoelectrics Empowered by an Unconventional Bonding Mechanism
journal, August 2019

  • Yu, Yuan; Cagnoni, Matteo; Cojocaru‐Mirédin, Oana
  • Advanced Functional Materials
  • DOI: 10.1002/adfm.201904862

Promoting SnTe as an Eco-Friendly Solution for p-PbTe Thermoelectric via Band Convergence and Interstitial Defects
journal, March 2017


The Atomic Circus: Small Electron Beams Spotlight Advanced Materials Down to the Atomic Scale
journal, October 2018


Integrating Band Structure Engineering with All-Scale Hierarchical Structuring for High Thermoelectric Performance in PbTe System
journal, October 2016

  • Pei, Yanling; Tan, Gangjian; Feng, Dan
  • Advanced Energy Materials, Vol. 7, Issue 3
  • DOI: 10.1002/aenm.201601450

High Performance Thermoelectric Materials: Progress and Their Applications
journal, November 2017

  • Yang, Lei; Chen, Zhi-Gang; Dargusch, Matthew S.
  • Advanced Energy Materials, Vol. 8, Issue 6
  • DOI: 10.1002/aenm.201701797

Arrays of Planar Vacancies in Superior Thermoelectric Ge 1− x y Cd x Bi y Te with Band Convergence
journal, September 2018


Realizing High‐Ranged Out‐of‐Plane ZTs in N‐Type SnSe Crystals through Promoting Continuous Phase Transition
journal, June 2019

  • Chang, Cheng; Wang, Dongyang; He, Dongsheng
  • Advanced Energy Materials, Vol. 9, Issue 28
  • DOI: 10.1002/aenm.201901334

Simultaneous Boost of Power Factor and Figure‐of‐Merit in In–Cu Codoped SnTe
journal, July 2019


Multiscale Defects as Strong Phonon Scatters to Enhance Thermoelectric Performance in Mg 2 Sn 1– x Sb x Solid Solutions
journal, July 2019


Rapid fabrication and thermoelectric performance of SnTe via non-equilibrium laser 3D printing
journal, April 2018


Multiple effects of Bi doping in enhancing the thermoelectric properties of SnTe
journal, January 2016

  • Zhou, Zhiwei; Yang, Junyou; Jiang, Qinghui
  • Journal of Materials Chemistry A, Vol. 4, Issue 34
  • DOI: 10.1039/c6ta04240f

Enhanced thermoelectric performance of BiCuSeO by increasing Seebeck coefficient through magnetic ion incorporation
journal, January 2017

  • Wen, Qiang; Chang, Cheng; Pan, Lin
  • Journal of Materials Chemistry A, Vol. 5, Issue 26
  • DOI: 10.1039/c7ta03659k

Synergistically optimizing interdependent thermoelectric parameters of n-type PbSe through alloying CdSe
journal, January 2019

  • Qian, Xin; Wu, Haijun; Wang, Dongyang
  • Energy & Environmental Science, Vol. 12, Issue 6
  • DOI: 10.1039/c8ee03386b

Effect of Sn element on optimizing thermoelectric performance of Te nanowires
journal, January 2018

  • Sun, Pengliang; Li, Changcun; Xu, Jingkun
  • Sustainable Energy & Fuels, Vol. 2, Issue 12
  • DOI: 10.1039/c8se00297e

Effect of single metal doping on the thermoelectric properties of SnTe
journal, January 2019

  • Aminzare, Masoud; Tseng, Yu-Chih; Ramakrishnan, Anbalagan
  • Sustainable Energy & Fuels, Vol. 3, Issue 1
  • DOI: 10.1039/c8se00385h

Large enhancement of electrical transport properties of SnS in the out-of-plane direction by n-type doping: a combined ARPES and DFT study
journal, January 2018

  • Cui, Juan; Chen, Chaoyu; He, Wenke
  • Journal of Materials Chemistry A, Vol. 6, Issue 47
  • DOI: 10.1039/c8ta07090c

Seeing atomic-scale structural origins and foreseeing new pathways to improved thermoelectric materials
journal, January 2019

  • Wu, Haijun; Zhang, Yang; Ning, Shoucong
  • Materials Horizons, Vol. 6, Issue 8
  • DOI: 10.1039/c9mh00543a

Highly enhanced thermoelectric properties of nanostructured Bi 2 S 3 bulk materials via carrier modification and multi-scale phonon scattering
journal, January 2019

  • Wu, Yi; Lou, Qing; Qiu, Yang
  • Inorganic Chemistry Frontiers, Vol. 6, Issue 6
  • DOI: 10.1039/c9qi00213h

High-performance electron-doped GeMnTe 2 : hierarchical structure and low thermal conductivity
journal, January 2019

  • Dong, Jinfeng; Pei, Jun; Zhuang, Hua-Lu
  • Journal of Materials Chemistry A, Vol. 7, Issue 48
  • DOI: 10.1039/c9ta09972g

Eutectoid nano-precipitates inducing remarkably enhanced thermoelectric performance in (Sn 1−x Cd x Te) 1−y (Cu 2 Te) y
journal, January 2020

  • Qi, Xia; Huang, Yi; Wu, Di
  • Journal of Materials Chemistry A, Vol. 8, Issue 5
  • DOI: 10.1039/c9ta11180h

New insights into the role of dislocation engineering in N-type filled skutterudite CoSb 3
journal, January 2019

  • Liu, Zihang; Meng, Xianfu; Qin, Dandan
  • Journal of Materials Chemistry C, Vol. 7, Issue 43
  • DOI: 10.1039/c9tc03839f

Rare earth doping and effective band-convergence in SnTe for improved thermoelectric performance
journal, November 2018

  • Acharya, Somnath; Dey, Dibyendu; Maitra, Tulika
  • Applied Physics Letters, Vol. 113, Issue 19
  • DOI: 10.1063/1.5055250

Promising thermoelectric properties and anisotropic electrical and thermal transport of monolayer SnTe
journal, February 2019

  • Li, Y.; Wu, M. N.; Ding, T.
  • Applied Physics Letters, Vol. 114, Issue 8
  • DOI: 10.1063/1.5085255

Low lattice thermal conductivity by alloying SnTe with AgSbTe 2 and CaTe/MnTe
journal, August 2019

  • Chen, Zhiyu; Gao, Bo; Tang, Jing
  • Applied Physics Letters, Vol. 115, Issue 7
  • DOI: 10.1063/1.5109465

Band engineering, carrier density control, and enhanced thermoelectric performance in multi-doped SnTe
journal, September 2019

  • Doi, A.; Shimano, S.; Inoue, D.
  • APL Materials, Vol. 7, Issue 9
  • DOI: 10.1063/1.5116882

Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping
journal, May 2018

  • Liu, Zihang; Sun, Jifeng; Mao, Jun
  • Proceedings of the National Academy of Sciences, Vol. 115, Issue 21
  • DOI: 10.1073/pnas.1802020115

Advances in thermoelectrics
journal, April 2018


Origin of the enhancement in transport properties on polycrystalline SnSe with compositing two-dimensional material MoSe 2
journal, February 2017


Hydrothermal synthesis of SnQ ( Q = Te, Se, S) and their thermoelectric properties
journal, October 2017


3D charge and 2D phonon transports leading to high out-of-plane ZT in n-type SnSe crystals
journal, May 2018


Chalcogenide Thermoelectrics Empowered by an Unconventional Bonding Mechanism
text, January 2019


Rare Earth Doping and Effective Band-Convergence in SnTe for Improved Thermoelectric Performance
text, January 2018