Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping
Abstract
Germanium telluride (GeTe)-based materials, which display intriguing functionalities, have been intensively studied from both fundamental and technological perspectives. As a thermoelectric material, though, the phase transition in GeTe from a rhombohedral structure to a cubic structure at ~700 K is a major obstacle impeding applications for energy harvesting. In this work, we discovered that the phase-transition temperature can be suppressed to below 300 K by a simple Bi and Mn codoping, resulting in the high performance of cubic GeTe from 300 to 773 K. Bi doping on the Ge site was found to reduce the hole concentration and thus to enhance the thermoelectric properties. Mn alloying on the Ge site simultaneously increased the hole effective mass and the Seebeck coefficient through modification of the valence bands. Here, with the Bi and Mn codoping, the lattice thermal conductivity was also largely reduced due to the strong point-defect scattering for phonons, resulting in a peak thermoelectric figure of merit (ZT) of ~1.5 at 773 K and an average ZT of ~1.1 from 300 to 773 K in cubic Ge0.81Mn0.15Bi0.04Te. Our results open the door for further studies of this exciting material for thermoelectric and other applications.
- Authors:
-
- State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, 150001 Harbin, China,, Department of Physics, University of Houston, Houston, TX 77204-5005,, Texas Center for Superconductivity, University of Houston, Houston, TX 77204-5002,
- Department of Physics and Astronomy, University of Missouri-Columbia, Columbia, MO 65211,
- Department of Physics, University of Houston, Houston, TX 77204-5005,, Texas Center for Superconductivity, University of Houston, Houston, TX 77204-5002,
- Department of Physics, University of Houston, Houston, TX 77204-5005,, Texas Center for Superconductivity, University of Houston, Houston, TX 77204-5002,, Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, 610054 Chengdu, China
- Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, 610054 Chengdu, China
- State Key Laboratory of Advanced Welding and Joining, Harbin Institute of Technology, 150001 Harbin, China,
- Publication Date:
- Research Org.:
- Univ. of Houston, TX (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1438289
- Alternate Identifier(s):
- OSTI ID: 1540288
- Grant/Contract Number:
- SC0010831
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 115 Journal Issue: 21; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Science & Technology; Other Topics; thermoelectric; phase transition; germanium telluride; Mn alloying; band-structure engineering
Citation Formats
Liu, Zihang, Sun, Jifeng, Mao, Jun, Zhu, Hangtian, Ren, Wuyang, Zhou, Jingchao, Wang, Zhiming, Singh, David J., Sui, Jiehe, Chu, Ching-Wu, and Ren, Zhifeng. Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping. United States: N. p., 2018.
Web. doi:10.1073/pnas.1802020115.
Liu, Zihang, Sun, Jifeng, Mao, Jun, Zhu, Hangtian, Ren, Wuyang, Zhou, Jingchao, Wang, Zhiming, Singh, David J., Sui, Jiehe, Chu, Ching-Wu, & Ren, Zhifeng. Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping. United States. https://doi.org/10.1073/pnas.1802020115
Liu, Zihang, Sun, Jifeng, Mao, Jun, Zhu, Hangtian, Ren, Wuyang, Zhou, Jingchao, Wang, Zhiming, Singh, David J., Sui, Jiehe, Chu, Ching-Wu, and Ren, Zhifeng. Mon .
"Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping". United States. https://doi.org/10.1073/pnas.1802020115.
@article{osti_1438289,
title = {Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping},
author = {Liu, Zihang and Sun, Jifeng and Mao, Jun and Zhu, Hangtian and Ren, Wuyang and Zhou, Jingchao and Wang, Zhiming and Singh, David J. and Sui, Jiehe and Chu, Ching-Wu and Ren, Zhifeng},
abstractNote = {Germanium telluride (GeTe)-based materials, which display intriguing functionalities, have been intensively studied from both fundamental and technological perspectives. As a thermoelectric material, though, the phase transition in GeTe from a rhombohedral structure to a cubic structure at ~700 K is a major obstacle impeding applications for energy harvesting. In this work, we discovered that the phase-transition temperature can be suppressed to below 300 K by a simple Bi and Mn codoping, resulting in the high performance of cubic GeTe from 300 to 773 K. Bi doping on the Ge site was found to reduce the hole concentration and thus to enhance the thermoelectric properties. Mn alloying on the Ge site simultaneously increased the hole effective mass and the Seebeck coefficient through modification of the valence bands. Here, with the Bi and Mn codoping, the lattice thermal conductivity was also largely reduced due to the strong point-defect scattering for phonons, resulting in a peak thermoelectric figure of merit (ZT) of ~1.5 at 773 K and an average ZT of ~1.1 from 300 to 773 K in cubic Ge0.81Mn0.15Bi0.04Te. Our results open the door for further studies of this exciting material for thermoelectric and other applications.},
doi = {10.1073/pnas.1802020115},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 21,
volume = 115,
place = {United States},
year = {2018},
month = {5}
}
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1073/pnas.1802020115
https://doi.org/10.1073/pnas.1802020115
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 13 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Neutron diffraction study on the structural phase transition in GeTe
journal, April 1987
- Chattopadhyay, T.; Boucherle, J. X.; vonSchnering, H. G.
- Journal of Physics C: Solid State Physics, Vol. 20, Issue 10
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
Thermoelectric properties of materials near the band crossing line in Mg2Sn–Mg2Ge–Mg2Si system
journal, January 2016
- Mao, Jun; Kim, Hee Seok; Shuai, Jing
- Acta Materialia, Vol. 103
Rationally Designing High-Performance Bulk Thermoelectric Materials
journal, August 2016
- Tan, Gangjian; Zhao, Li-Dong; Kanatzidis, Mercouri G.
- Chemical Reviews, Vol. 116, Issue 19
Nano-microstructural control of phonon engineering for thermoelectric energy harvesting
journal, March 2018
- Liu, Zihang; Mao, Jun; Liu, Te-Huan
- MRS Bulletin, Vol. 43, Issue 3
Synergistically optimized electrical and thermal transport properties of SnTe via alloying high-solubility MnTe
journal, January 2015
- Wu, Haijun; Chang, Cheng; Feng, Dan
- Energy & Environmental Science, Vol. 8, Issue 11
Manipulation of ionized impurity scattering for achieving high thermoelectric performance in n-type Mg 3 Sb 2 -based materials
journal, September 2017
- Mao, Jun; Shuai, Jing; Song, Shaowei
- Proceedings of the National Academy of Sciences, Vol. 114, Issue 40
Ultrahigh thermoelectric performance in Cu 2−y Se 0.5 S 0.5 liquid-like materials
journal, June 2017
- Zhao, Kunpeng; Qiu, Pengfei; Song, Qingfeng
- Materials Today Physics, Vol. 1
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
Resonant bonding leads to low lattice thermal conductivity
journal, April 2014
- Lee, Sangyeop; Esfarjani, Keivan; Luo, Tengfei
- Nature Communications, Vol. 5, Issue 1
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Safe radioisotope thermoelectric generators and heat sources for space applications
journal, July 2008
- O’Brien, R. C.; Ambrosi, R. M.; Bannister, N. P.
- Journal of Nuclear Materials, Vol. 377, Issue 3
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
Magnetization studies of pseudobinary alloys
journal, April 1974
- Cochrane, R. W.; Plischke, M.; Ström-Olsen, J. O.
- Physical Review B, Vol. 9, Issue 7
Band Engineering of Thermoelectric Materials
journal, October 2012
- Pei, Yanzhong; Wang, Heng; Snyder, G. J.
- Advanced Materials, Vol. 24, Issue 46
Semiconductor Thermoelements and Thermoelectric Cooling
journal, May 1959
- Ioffe, A. F.; Stil'bans, L. S.; Iordanishvili, E. K.
- Physics Today, Vol. 12, Issue 5
Convergence of Conduction Bands as a Means of Enhancing Thermoelectric Performance of -Type Solid Solutions
journal, April 2012
- Liu, Wei; Tan, Xiaojian; Yin, Kang
- Physical Review Letters, Vol. 108, Issue 16
Simultaneous Optimization of Carrier Concentration and Alloy Scattering for Ultrahigh Performance GeTe Thermoelectrics
journal, September 2017
- Li, Juan; Chen, Zhiwei; Zhang, Xinyue
- Advanced Science, Vol. 4, Issue 12
High thermoelectric performance of oxyselenides: intrinsically low thermal conductivity of Ca-doped BiCuSeO
journal, May 2013
- Pei, Yan-Ling; He, Jiaqing; Li, Jing-Feng
- NPG Asia Materials, Vol. 5, Issue 5
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
New trends, strategies and opportunities in thermoelectric materials: A perspective
journal, June 2017
- Liu, Weishu; Hu, Jizhen; Zhang, Shuangmeng
- Materials Today Physics, Vol. 1
Grain Boundary Engineering for Achieving High Thermoelectric Performance in n-Type Skutterudites
journal, February 2017
- Meng, Xianfu; Liu, Zihang; Cui, Bo
- Advanced Energy Materials, Vol. 7, Issue 13
Thermoelectric generators: A review of applications
journal, May 2017
- Champier, Daniel
- Energy Conversion and Management, Vol. 140
Relationship between thermoelectric figure of merit and energy conversion efficiency
journal, June 2015
- Kim, Hee Seok; Liu, Weishu; Chen, Gang
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 27
Understanding and manipulating the intrinsic point defect in α-MgAgSb for higher thermoelectric performance
journal, January 2016
- Liu, Zihang; Geng, Huiyuan; Mao, Jun
- Journal of Materials Chemistry A, Vol. 4, Issue 43
The MnTeGeTe phase diagram
journal, October 1961
- Johnston, W. D.; Sestrich, D. E.
- Journal of Inorganic and Nuclear Chemistry, Vol. 19, Issue 3-4
Oxidation states of Mn and Fe in various compound oxide systems
journal, July 2006
- Schmid, H. K.; Mader, W.
- Micron, Vol. 37, Issue 5
First-principles description of anomalously low lattice thermal conductivity in thermoelectric Cu-Sb-Se ternary semiconductors
journal, February 2012
- Zhang, Yongsheng; Skoug, Eric; Cain, Jeffrey
- Physical Review B, Vol. 85, Issue 5
New Insights into Intrinsic Point Defects in V 2 VI 3 Thermoelectric Materials
journal, March 2016
- Zhu, Tiejun; Hu, Lipeng; Zhao, Xinbing
- Advanced Science, Vol. 3, Issue 7
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
High thermoelectricpower factor in graphene/hBN devices
journal, November 2016
- Duan, Junxi; Wang, Xiaoming; Lai, Xinyuan
- Proceedings of the National Academy of Sciences, Vol. 113, Issue 50
The Low-Temperature Thermoelectric Power and Thermal Conductivity of GeTe and of Some GeTe-MnTe Alloys
journal, January 1968
- Lewis, J. E.; Rodot, H.; Haen, P.
- Physica Status Solidi (b), Vol. 29, Issue 2
Improved thermoelectric performance of n-type half-Heusler MCo1-xNixSb (M = Hf, Zr)
journal, June 2017
- He, Ran; Zhu, Hangtian; Sun, Jingying
- Materials Today Physics, Vol. 1
The influence of doping sites on achieving higher thermoelectric performance for nanostructured α-MgAgSb
journal, January 2017
- Liu, Zihang; Wang, Yumei; Gao, Weihong
- Nano Energy, Vol. 31
High Efficiency Half-Heusler Thermoelectric Materials for Energy Harvesting
journal, July 2015
- Zhu, Tiejun; Fu, Chenguang; Xie, Hanhui
- Advanced Energy Materials, Vol. 5, Issue 19
Tellurium doped n-type Zintl Zr3Ni3Sb4 thermoelectric materials: Balance between carrier-scattering mechanism and bipolar effect
journal, September 2017
- Liu, Zihang; Mao, Jun; Peng, Shengyuan
- Materials Today Physics, Vol. 2
High Thermoelectric Performance and Enhanced Mechanical Stability of p -type Ge 1– x Sb x Te
journal, October 2015
- Perumal, Suresh; Roychowdhury, Subhajit; Negi, Devendra S.
- Chemistry of Materials, Vol. 27, Issue 20
EPR Experiments on Mn 2+ in Degenerate Semiconductor GeTe
journal, November 1978
- Inoue, Masasi; Yagi, Hisao; Tatsukawa, Toshiaki
- Journal of the Physical Society of Japan, Vol. 45, Issue 5
Perspectives on thermoelectrics: from fundamentals to device applications
journal, January 2012
- Zebarjadi, M.; Esfarjani, K.; Dresselhaus, M. S.
- Energy Environ. Sci., Vol. 5, Issue 1, p. 5147-5162
Resonant level-induced high thermoelectric response in indium-doped GeTe
journal, January 2017
- Wu, Lihua; Li, Xin; Wang, Shanyu
- NPG Asia Materials, Vol. 9, Issue 1
Thermopower enhancement in lead telluride nanostructures
journal, September 2004
- Heremans, Joseph P.; Thrush, Christopher M.; Morelli, Donald T.
- Physical Review B, Vol. 70, Issue 11
Effect of Point Imperfections on Lattice Thermal Conductivity
journal, November 1960
- Callaway, Joseph; von Baeyer, Hans C.
- Physical Review, Vol. 120, Issue 4
Ferroelectric phase transition and the lattice thermal conductivity of alloys
journal, April 2017
- Murphy, Ronan M.; Murray, Éamonn D.; Fahy, Stephen
- Physical Review B, Vol. 95, Issue 14
Materials for thermoelectric energy conversion
journal, April 1988
- Wood, C
- Reports on Progress in Physics, Vol. 51, Issue 4, p. 459-539
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
First principles phonon calculations in materials science
journal, November 2015
- Togo, Atsushi; Tanaka, Isao
- Scripta Materialia, Vol. 108
Controlling Metallurgical Phase Separation Reactions of the Ge 0.87 Pb 0.13 Te Alloy for High Thermoelectric Performance
journal, March 2013
- Gelbstein, Yaniv; Davidow, Joseph; Girard, Steven N.
- Advanced Energy Materials, Vol. 3, Issue 6
Effects of extrinsic and intrinsic perturbations on the electronic structure of graphene: Retaining an effective primitive cell band structure by band unfolding
journal, January 2014
- Medeiros, Paulo V. C.; Stafström, Sven; Björk, Jonas
- Physical Review B, Vol. 89, Issue 4
Heavy Doping and Band Engineering by Potassium to Improve the Thermoelectric Figure of Merit in p-Type PbTe, PbSe, and PbTe 1– y Se y
journal, June 2012
- Zhang, Qian; Cao, Feng; Liu, Weishu
- Journal of the American Chemical Society, Vol. 134, Issue 24
Ferromagnetic properties of IV–VI diluted magnetic semiconductor Ge1−xMnxTe films prepared by radio frequency sputtering
journal, April 2003
- Fukuma, Y.; Asada, H.; Nishimura, N.
- Journal of Applied Physics, Vol. 93, Issue 7
Electronic origin of the high thermoelectric performance of GeTe among the p-type group IV monotellurides
journal, March 2017
- Li, Juan; Chen, Zhiwei; Zhang, Xinyue
- NPG Asia Materials, Vol. 9, Issue 3
High thermoelectric performance of α-MgAgSb for power generation
journal, January 2018
- Liu, Zihang; Mao, Jun; Sui, Jiehe
- Energy & Environmental Science, Vol. 11, Issue 1
Realizing the High Thermoelectric Performance of GeTe by Sb-Doping and Se-Alloying
journal, December 2016
- Li, Juan; Zhang, Xinyue; Lin, Siqi
- Chemistry of Materials, Vol. 29, Issue 2
On the tuning of electrical and thermal transport in thermoelectrics: an integrated theory–experiment perspective
journal, February 2016
- Yang, Jiong; Xi, Lili; Qiu, Wujie
- npj Computational Materials, Vol. 2, Issue 1
High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys
journal, May 2008
- Poudel, B.; Hao, Q.; Ma, Y.
- Science, Vol. 320, Issue 5876, p. 634-638
Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe
journal, November 2015
- Zhao, L.-D.; Tan, G.; Hao, S.
- Science, Vol. 351, Issue 6269, p. 141-144
Unfolding spinor wave functions and expectation values of general operators: Introducing the unfolding-density operator
journal, January 2015
- Medeiros, Paulo V. C.; Tsirkin, Stepan S.; Stafström, Sven
- Physical Review B, Vol. 91, Issue 4
Electronic fitness function for screening semiconductors as thermoelectric materials
journal, November 2017
- Xing, Guangzong; Sun, Jifeng; Li, Yuwei
- Physical Review Materials, Vol. 1, Issue 6