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Title: High Thermoelectric Performance of New Rhombohedral Phase of GeSe stabilized through Alloying with AgSbSe 2

Abstract

GeSe is a IV–VI semiconductor, like the excellent thermoelectric materials PbTe and SnSe. Orthorhombic GeSe has been predicted theoretically to have good thermoelectric performance but is difficult to dope experimentally. Like PbTe, rhombohedral GeTe has a multivalley band structure, which is ideal for thermoelectrics and also promotes the formation of Ge vacancies to provide enough carriers for electrical transport. Herein, we investigate the thermoelectric properties of GeSe alloyed with AgSbSe 2, which stabilizes a new rhombohedral structure with higher symmetry that leads to a multivalley Fermi surface and a dramatic increase in carrier concentration. The zT of GeAg 0.2Sb 0.2Se 1.4 reaches 0.86 at 710 K, which is 18 times higher than that of pristine GeSe and over four times higher than doped orthorhombic GeSe. Our results open a new avenue towards developing novel thermoelectric materials through crystal phase engineering using a strategy of entropy stabilization of high-symmetry alloys.

Authors:
 [1];  [2];  [3];  [1];  [2];  [4];  [5];  [6];  [7];  [2];  [6];  [6]
  1. Chinese Academy of Sciences (CAS), Dalian, Liaoning (China). CAS Center for Excellence in Nanoscience Inst. Dalian Inst. of Chemical Physics; Univ. of Chinese Academy of Sciences, Beijing (China)
  2. Northwestern Univ., Evanston, IL (United States). Materials Science and Engineering Dept.
  3. Chinese Academy of Sciences (CAS), Beijing (China). Beijing National Lab. for Condensed Matter Physics, Inst. of Physics
  4. Chinese Academy of Sciences (CAS), Fuzhou, Fujian (China). State Key Lab. of Structural Chemistry Fujian Inst. of Research on the Structure of Matter
  5. Beijing Inst. of Technology, Beijing (China). School of Physics
  6. Chinese Academy of Sciences (CAS), Dalian, Liaoning (China). CAS Center for Excellence in Nanoscience Inst. Dalian Inst. of Chemical Physics
  7. Chinese Academy of Sciences (CAS), Fuzhou, Fujian (China). State Key Lab. of Structural Chemistry Fujian Inst. of Research on the Structure of Matter
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Solid-State Solar-Thermal Energy Conversion Center (S3TEC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSF)
OSTI Identifier:
1470454
Grant/Contract Number:  
SC0001299; FG02-09ER46577
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie
Additional Journal Information:
Journal Volume: 129; Journal Issue: 45; Related Information: S3TEC partners with Massachusetts Institute of Technology (lead); Boston College; Oak Ridge National Laboratory; Rensselaer Polytechnic Institute; Journal ID: ISSN 0044-8249
Publisher:
German Chemical Society
Country of Publication:
United States
Language:
English
Subject:
solar (photovoltaic); solar (thermal); solid state lighting; phonons; thermal conductivity; thermoelectric; defects; mechanical behavior; charge transport; spin dynamics; materials and chemistry by design; optics; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing); Codotierung; Energieumwandlung; GeSe; Hochentropische Legierungen; Thermoelektrik; Co-doping; Energy conversion; Highly entropic alloys; thermoelectrics

Citation Formats

Huang, Zhiwei, Miller, Samuel A., Ge, Binghui, Yan, Mingtao, Anand, Shashwat, Wu, Tianmin, Nan, Pengfei, Zhu, Yuanhu, Zhuang, Wei, Snyder, G. Jeffrey, Jiang, Peng, and Bao, Xinhe. High Thermoelectric Performance of New Rhombohedral Phase of GeSe stabilized through Alloying with AgSbSe2. United States: N. p., 2017. Web. doi:10.1002/ange.201708134.
Huang, Zhiwei, Miller, Samuel A., Ge, Binghui, Yan, Mingtao, Anand, Shashwat, Wu, Tianmin, Nan, Pengfei, Zhu, Yuanhu, Zhuang, Wei, Snyder, G. Jeffrey, Jiang, Peng, & Bao, Xinhe. High Thermoelectric Performance of New Rhombohedral Phase of GeSe stabilized through Alloying with AgSbSe2. United States. doi:10.1002/ange.201708134.
Huang, Zhiwei, Miller, Samuel A., Ge, Binghui, Yan, Mingtao, Anand, Shashwat, Wu, Tianmin, Nan, Pengfei, Zhu, Yuanhu, Zhuang, Wei, Snyder, G. Jeffrey, Jiang, Peng, and Bao, Xinhe. Wed . "High Thermoelectric Performance of New Rhombohedral Phase of GeSe stabilized through Alloying with AgSbSe2". United States. doi:10.1002/ange.201708134. https://www.osti.gov/servlets/purl/1470454.
@article{osti_1470454,
title = {High Thermoelectric Performance of New Rhombohedral Phase of GeSe stabilized through Alloying with AgSbSe2},
author = {Huang, Zhiwei and Miller, Samuel A. and Ge, Binghui and Yan, Mingtao and Anand, Shashwat and Wu, Tianmin and Nan, Pengfei and Zhu, Yuanhu and Zhuang, Wei and Snyder, G. Jeffrey and Jiang, Peng and Bao, Xinhe},
abstractNote = {GeSe is a IV–VI semiconductor, like the excellent thermoelectric materials PbTe and SnSe. Orthorhombic GeSe has been predicted theoretically to have good thermoelectric performance but is difficult to dope experimentally. Like PbTe, rhombohedral GeTe has a multivalley band structure, which is ideal for thermoelectrics and also promotes the formation of Ge vacancies to provide enough carriers for electrical transport. Herein, we investigate the thermoelectric properties of GeSe alloyed with AgSbSe2, which stabilizes a new rhombohedral structure with higher symmetry that leads to a multivalley Fermi surface and a dramatic increase in carrier concentration. The zT of GeAg0.2Sb0.2Se1.4 reaches 0.86 at 710 K, which is 18 times higher than that of pristine GeSe and over four times higher than doped orthorhombic GeSe. Our results open a new avenue towards developing novel thermoelectric materials through crystal phase engineering using a strategy of entropy stabilization of high-symmetry alloys.},
doi = {10.1002/ange.201708134},
journal = {Angewandte Chemie},
issn = {0044-8249},
number = 45,
volume = 129,
place = {United States},
year = {2017},
month = {9}
}

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Works referenced in this record:

Entropy-stabilized oxides
journal, September 2015

  • Rost, Christina M.; Sachet, Edward; Borman, Trent
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9485

Thermoelectric properties of p-type polycrystalline SnSe doped with Ag
journal, January 2014

  • Chen, Cheng-Lung; Wang, Heng; Chen, Yang-Yuan
  • Journal of Materials Chemistry A, Vol. 2, Issue 29, p. 11171-11176
  • DOI: 10.1039/C4TA01643B

Colloidal Synthesis and Electrical Properties of GeSe Nanobelts
journal, September 2012

  • Vaughn, DimitriD.; Sun, Du; Levin, Scott M.
  • Chemistry of Materials, Vol. 24, Issue 18
  • DOI: 10.1021/cm3023192

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


Optimum Carrier Concentration in n-Type PbTe Thermoelectrics
journal, May 2014

  • Pei, Yanzhong; Gibbs, Zachary M.; Gloskovskii, Andrei
  • Advanced Energy Materials, Vol. 4, Issue 13
  • DOI: 10.1002/aenm.201400486

GeTe: a simple compound blessed with a plethora of properties
journal, January 2017

  • Boschker, Jos E.; Wang, Ruining; Calarco, Raffaella
  • CrystEngComm, Vol. 19, Issue 36
  • DOI: 10.1039/C7CE01040K

Assessment of the thermoelectric performance of polycrystalline p-type SnSe
journal, May 2014

  • Sassi, S.; Candolfi, C.; Vaney, J.-B.
  • Applied Physics Letters, Vol. 104, Issue 21, Article No. 212105
  • DOI: 10.1063/1.4880817

Ultrahigh Average Thermoelectric Figure of Merit, Low Lattice Thermal Conductivity and Enhanced Microhardness in Nanostructured (GeTe) x (AgSbSe 2 ) 100− x
journal, May 2017

  • Samanta, Manisha; Roychowdhury, Subhajit; Ghatak, Jay
  • Chemistry - A European Journal, Vol. 23, Issue 31
  • DOI: 10.1002/chem.201701480

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

High efficiency Bi 2 Te 3 -based materials and devices for thermoelectric power generation between 100 and 300 °C
journal, January 2016

  • Hao, Feng; Qiu, Pengfei; Tang, Yunshan
  • Energy & Environmental Science, Vol. 9, Issue 10
  • DOI: 10.1039/C6EE02017H

Ge-Te (Germanium-Tellurium)
journal, September 2000


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

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

Nature of the cubic to rhombohedral structural transformation in (AgSbTe2)15(GeTe)85 thermoelectric material
journal, March 2007

  • Cook, B. A.; Kramer, M. J.; Wei, X.
  • Journal of Applied Physics, Vol. 101, Issue 5
  • DOI: 10.1063/1.2645675

Transport properties and valence band feature of high-performance (GeTe) 85 (AgSbTe 2 ) 15 thermoelectric materials
journal, January 2014


Low Thermal Conductivity and High Thermoelectric Performance in (GeTe) 1–2 x (GeSe) x (GeS) x : Competition between Solid Solution and Phase Separation
journal, June 2017

  • Samanta, Manisha; Biswas, Kanishka
  • Journal of the American Chemical Society, Vol. 139, Issue 27
  • DOI: 10.1021/jacs.7b05143

New and Old Concepts in Thermoelectric Materials
journal, November 2009

  • Sootsman, Joseph R.; Chung, Duck Young; Kanatzidis, Mercouri G.
  • Angewandte Chemie International Edition, Vol. 48, Issue 46, p. 8616-8639
  • DOI: 10.1002/anie.200900598

Nanostructured High-Entropy Alloys with Multiple Principal Elements: Novel Alloy Design Concepts and Outcomes
journal, May 2004

  • Yeh, J.-W.; Chen, S.-K.; Lin, S.-J.
  • Advanced Engineering Materials, Vol. 6, Issue 5, p. 299-303
  • DOI: 10.1002/adem.200300567

Cooling, Heating, Generating Power, and Recovering Waste Heat with Thermoelectric Systems
journal, September 2008


The thermal expansion and high temperature transformation of GeSe
journal, January 1975

  • Wiedemeier, H.; Siemers, P. A.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 411, Issue 1
  • DOI: 10.1002/zaac.19754110110

Distinct Impact of Alkali-Ion Doping on Electrical Transport Properties of Thermoelectric p -Type Polycrystalline SnSe
journal, July 2016

  • Wei, Tian-Ran; Tan, Gangjian; Zhang, Xiaomi
  • Journal of the American Chemical Society, Vol. 138, Issue 28
  • DOI: 10.1021/jacs.6b04181

Nature of the defects in germanium telluride
journal, March 1967


Computational Prediction of High Thermoelectric Performance in Hole Doped Layered GeSe
journal, April 2016


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

Thermoelectric properties of GeSe
journal, December 2016


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

Electronic structure of intrinsic defects in crystalline germanium telluride
journal, January 2006


Phase transitions of (1− x ) PbZrO 3 + x (Na 1/2 Bi 1/2 )TiO 3 (0.01 ≤ x ≤ 0.15) solid solutions
journal, January 1999

  • Lee, Jung-Kun; Youn, Hyuk-Joon; Hong, Kug Sun
  • Journal of Materials Research, Vol. 14, Issue 1
  • DOI: 10.1557/JMR.1999.0014

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

THERMOELECTRIC MATERIALS:Holey and Unholey Semiconductors
journal, February 1999


Resonant level formed by tin in Bi 2 Te 3 and the enhancement of room-temperature thermoelectric power
journal, December 2009

  • Jaworski, Christopher M.; Kulbachinskii, Vladimir; Heremans, Joseph P.
  • Physical Review B, Vol. 80, Issue 23
  • DOI: 10.1103/PhysRevB.80.233201

High-Performance Pseudocubic Thermoelectric Materials from Non-cubic Chalcopyrite Compounds
journal, April 2014


Entropy as a Gene-Like Performance Indicator Promoting Thermoelectric Materials
journal, August 2017


Alte und neue Konzepte für thermoelektrische Materialien
journal, November 2009

  • Sootsman, Joseph R.; Chung, Duck Young; Kanatzidis, Mercouri G.
  • Angewandte Chemie, Vol. 121, Issue 46
  • DOI: 10.1002/ange.200900598

High-Temperature Crystal Structure and Chemical Bonding in Thermoelectric Germanium Selenide (GeSe)
journal, April 2017

  • Sist, Mattia; Gatti, Carlo; Nørby, Peter
  • Chemistry - A European Journal, Vol. 23, Issue 28
  • DOI: 10.1002/chem.201700536

Ternary semiconducting compounds with sodium chloride-like structure: AgSbSe 2 , AgSbTe 2 , AgBiS 2 , AgBiSe 2
journal, January 1959


Broad temperature plateau for high ZTs in heavily doped p-type SnSe single crystals
journal, January 2016

  • Peng, Kunling; Lu, Xu; Zhan, Heng
  • Energy & Environmental Science, Vol. 9, Issue 2
  • DOI: 10.1039/C5EE03366G

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

Indirect forbidden fundamental absorption edge in germanium selenide single crystals
journal, June 1986


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


Investigation of the Anisotropic Thermoelectric Properties of Oriented Polycrystalline SnSe
journal, June 2015


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


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

The germanium-selenium phase diagram
journal, April 1982

  • Ipser, Herbert; Gambino, Mich�le; Schuster, Wilfried
  • Monatshefte f�r Chemie Chemical Monthly, Vol. 113, Issue 4
  • DOI: 10.1007/BF00799914