skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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. 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 Ge 0.81 Mn 0.15 Bi 0.04 Te. Our results open the door for further studies of this exciting material for thermoelectric and othermore » applications.« less

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Univ. of Houston, 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. 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, and Ren, Zhifeng. Mon . "Phase-transition temperature suppression to achieve cubic GeTe and high thermoelectric performance by Bi and Mn codoping". United States. doi: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. 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 Ge 0.81 Mn 0.15 Bi 0.04 Te. 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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1073/pnas.1802020115

Citation Metrics:
Cited by: 13 works
Citation information provided by
Web of Science

Save / Share:

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
  • DOI: 10.1088/0022-3719/20/10/012

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

Thermoelectric properties of materials near the band crossing line in Mg2Sn–Mg2Ge–Mg2Si system
journal, January 2016


Rationally Designing High-Performance Bulk Thermoelectric Materials
journal, August 2016


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
  • DOI: 10.1557/mrs.2018.7

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
  • DOI: 10.1039/C5EE02423D

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
  • DOI: 10.1073/pnas.1711725114

Ultrahigh thermoelectric performance in Cu 2−y Se 0.5 S 0.5 liquid-like materials
journal, June 2017


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

Resonant bonding leads to low lattice thermal conductivity
journal, April 2014

  • Lee, Sangyeop; Esfarjani, Keivan; Luo, Tengfei
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4525

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


Safe radioisotope thermoelectric generators and heat sources for space applications
journal, July 2008


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

Magnetization studies of ( GeTe ) 1 x ( MnTe ) x pseudobinary alloys
journal, April 1974

  • Cochrane, R. W.; Plischke, M.; Ström-Olsen, J. O.
  • Physical Review B, Vol. 9, Issue 7
  • DOI: 10.1103/PhysRevB.9.3013

Band Engineering of Thermoelectric Materials
journal, October 2012


Semiconductor Thermoelements and Thermoelectric Cooling
journal, May 1959

  • Ioffe, A. F.; Stil'bans, L. S.; Iordanishvili, E. K.
  • Physics Today, Vol. 12, Issue 5
  • DOI: 10.1063/1.3060810

Convergence of Conduction Bands as a Means of Enhancing Thermoelectric Performance of n -Type Mg 2 Si 1 x Sn x Solid Solutions
journal, April 2012


Simultaneous Optimization of Carrier Concentration and Alloy Scattering for Ultrahigh Performance GeTe Thermoelectrics
journal, September 2017


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
  • DOI: 10.1038/am.2013.15

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

New trends, strategies and opportunities in thermoelectric materials: A perspective
journal, June 2017


Grain Boundary Engineering for Achieving High Thermoelectric Performance in n-Type Skutterudites
journal, February 2017


Thermoelectric generators: A review of applications
journal, May 2017


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
  • DOI: 10.1073/pnas.1510231112

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
  • DOI: 10.1039/C6TA06832D

The MnTeGeTe phase diagram
journal, October 1961


Oxidation states of Mn and Fe in various compound oxide systems
journal, July 2006


First-principles description of anomalously low lattice thermal conductivity in thermoelectric Cu-Sb-Se ternary semiconductors
journal, February 2012


New Insights into Intrinsic Point Defects in V 2 VI 3 Thermoelectric Materials
journal, March 2016


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 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
  • DOI: 10.1073/pnas.1615913113

The Low-Temperature Thermoelectric Power and Thermal Conductivity of GeTe and of Some GeTe-MnTe Alloys
journal, January 1968


Improved thermoelectric performance of n-type half-Heusler MCo1-xNixSb (M = Hf, Zr)
journal, June 2017


The influence of doping sites on achieving higher thermoelectric performance for nanostructured α-MgAgSb
journal, January 2017


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
  • DOI: 10.1002/aenm.201500588

Tellurium doped n-type Zintl Zr3Ni3Sb4 thermoelectric materials: Balance between carrier-scattering mechanism and bipolar effect
journal, September 2017


High Thermoelectric Performance and Enhanced Mechanical Stability of p -type Ge 1– x Sb x Te
journal, October 2015


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
  • DOI: 10.1143/JPSJ.45.1610

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
  • DOI: 10.1038/am.2016.203

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
  • DOI: 10.1103/PhysRevB.70.115334

Effect of Point Imperfections on Lattice Thermal Conductivity
journal, November 1960


Ferroelectric phase transition and the lattice thermal conductivity of Pb 1 x Ge x Te alloys
journal, April 2017


Materials for thermoelectric energy conversion
journal, April 1988


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


First principles phonon calculations in materials science
journal, November 2015


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
  • DOI: 10.1002/aenm.201200970

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
  • DOI: 10.1021/ja301245b

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
  • DOI: 10.1063/1.1555697

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
  • DOI: 10.1038/am.2017.8

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
  • DOI: 10.1039/C7EE02504A

Realizing the High Thermoelectric Performance of GeTe by Sb-Doping and Se-Alloying
journal, December 2016


On the tuning of electrical and thermal transport in thermoelectrics: an integrated theory–experiment perspective
journal, February 2016


High-Thermoelectric Performance of Nanostructured Bismuth Antimony Telluride Bulk Alloys
journal, May 2008


Ultrahigh power factor and thermoelectric performance in hole-doped single-crystal SnSe
journal, November 2015


Unfolding spinor wave functions and expectation values of general operators: Introducing the unfolding-density operator
journal, January 2015


Electronic fitness function for screening semiconductors as thermoelectric materials
journal, November 2017


    Works referencing / citing this record:

    Superior performance and high service stability for GeTe-based thermoelectric compounds
    journal, April 2019

    • Xing, Tong; Song, Qingfeng; Qiu, Pengfei
    • National Science Review, Vol. 6, Issue 5
    • DOI: 10.1093/nsr/nwz052

    Understanding the asymmetrical thermoelectric performance for discovering promising thermoelectric materials
    journal, June 2019