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

Title: Contrasting role of antimony and bismuth dopants on the thermoelectric performance of lead selenide

Abstract

Increasing the conversion efficiency of thermoelectric materials is a key scientific driver behind a worldwide effort to enable heat to electricity power generation at competitive cost. Here we report an increased performance for antimony-doped lead selenide with a thermoelectric figure of merit of ~1.5 at 800 K. This is in sharp contrast to bismuth doped lead selenide, which reaches a figure of merit of <1. Substituting antimony or bismuth for lead achieves maximum power factors between ~23–27μW cm–1 K–2 at temperatures above 400 K. The addition of small amounts (~0.25 mol%) of antimony generates extensive nanoscale precipitates, whereas comparable amounts of bismuth results in very few or no precipitates. The antimony-rich precipitates are endotaxial in lead selenide, and appear remarkably effective in reducing the lattice thermal conductivity. As a result, the corresponding bismuth-containing samples exhibit smaller reduction in lattice thermal conductivity.

Authors:
 [1];  [1];  [1];  [2];  [3];  [1];  [2];  [1];  [4]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of Michigan, Ann Arbor, MI (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Materials Sciences and Engineering Division; National Science Foundation (NSF); W.M. Keck Foundation; Northwestern University
OSTI Identifier:
1355912
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 5; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; thermoelectrics

Citation Formats

Lee, Yeseul, Lo, Shih -Han, Chen, Changqiang, Sun, Hui, Chung, Duck -Young, Chasapis, Thomas C., Uher, Ctirad, Dravid, Vinayak P., and Kanatzidis, Mercouri G. Contrasting role of antimony and bismuth dopants on the thermoelectric performance of lead selenide. United States: N. p., 2014. Web. doi:10.1038/ncomms4640.
Lee, Yeseul, Lo, Shih -Han, Chen, Changqiang, Sun, Hui, Chung, Duck -Young, Chasapis, Thomas C., Uher, Ctirad, Dravid, Vinayak P., & Kanatzidis, Mercouri G. Contrasting role of antimony and bismuth dopants on the thermoelectric performance of lead selenide. United States. https://doi.org/10.1038/ncomms4640
Lee, Yeseul, Lo, Shih -Han, Chen, Changqiang, Sun, Hui, Chung, Duck -Young, Chasapis, Thomas C., Uher, Ctirad, Dravid, Vinayak P., and Kanatzidis, Mercouri G. Fri . "Contrasting role of antimony and bismuth dopants on the thermoelectric performance of lead selenide". United States. https://doi.org/10.1038/ncomms4640. https://www.osti.gov/servlets/purl/1355912.
@article{osti_1355912,
title = {Contrasting role of antimony and bismuth dopants on the thermoelectric performance of lead selenide},
author = {Lee, Yeseul and Lo, Shih -Han and Chen, Changqiang and Sun, Hui and Chung, Duck -Young and Chasapis, Thomas C. and Uher, Ctirad and Dravid, Vinayak P. and Kanatzidis, Mercouri G.},
abstractNote = {Increasing the conversion efficiency of thermoelectric materials is a key scientific driver behind a worldwide effort to enable heat to electricity power generation at competitive cost. Here we report an increased performance for antimony-doped lead selenide with a thermoelectric figure of merit of ~1.5 at 800 K. This is in sharp contrast to bismuth doped lead selenide, which reaches a figure of merit of <1. Substituting antimony or bismuth for lead achieves maximum power factors between ~23–27μW cm–1 K–2 at temperatures above 400 K. The addition of small amounts (~0.25 mol%) of antimony generates extensive nanoscale precipitates, whereas comparable amounts of bismuth results in very few or no precipitates. The antimony-rich precipitates are endotaxial in lead selenide, and appear remarkably effective in reducing the lattice thermal conductivity. As a result, the corresponding bismuth-containing samples exhibit smaller reduction in lattice thermal conductivity.},
doi = {10.1038/ncomms4640},
journal = {Nature Communications},
number = ,
volume = 5,
place = {United States},
year = {Fri May 02 00:00:00 EDT 2014},
month = {Fri May 02 00:00:00 EDT 2014}
}

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

Citation Metrics:
Cited by: 91 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Raising the Thermoelectric Performance of p-Type PbS with Endotaxial Nanostructuring and Valence-Band Offset Engineering Using CdS and ZnS
journal, September 2012

  • Zhao, Li-Dong; He, Jiaqing; Hao, Shiqiang
  • Journal of the American Chemical Society, Vol. 134, Issue 39
  • DOI: 10.1021/ja306527n

Microstructure analyses and thermoelectric properties of <mml:math altimg="si0043.gif" overflow="scroll" xmlns:xocs="http://www.elsevier.com/xml/xocs/dtd" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns="http://www.elsevier.com/xml/ja/dtd" xmlns:ja="http://www.elsevier.com/xml/ja/dtd" xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:tb="http://www.elsevier.com/xml/common/table/dtd" xmlns:sb="http://www.elsevier.com/xml/common/struct-bib/dtd" xmlns:ce="http://www.elsevier.com/xml/common/dtd" xmlns:xlink="http://www.w3.org/1999/xlink" xmlns:cals="http://www.elsevier.com/xml/common/cals/dtd"><mml:msub><mml:mrow><mml:mi>Ag</mml:mi></mml:mrow><mml:mrow><mml:mn>1</mml:mn><mml:mo>−</mml:mo><mml:mi>x</mml:mi></mml:mrow></mml:msub><mml:msub><mml:mrow><mml:mi>Pb</mml:mi></mml:mrow><mml:mrow><mml:mn>18</mml:mn></mml:mrow></mml:msub><mml:msub><mml:mrow><mml:mi>Sb</mml:mi></mml:mrow><mml:mrow><mml:mn>1</mml:mn><mml:mo>+</mml:mo><mml:mi>y</mml:mi></mml:mrow></mml:msub><mml:msub><mml:mrow><mml:mi>Te</mml:mi></mml:mrow><mml:mrow><mml:mn>20</mml:mn></mml:mrow></mml:msub></mml:math>
journal, September 2012


High Thermoelectric Figure of Merit and Nanostructuring in Bulk p-type Na1−xPbmSbyTem+2
journal, June 2006

  • Poudeu, Pierre F. P.; D'Angelo, Jonathan; Downey, Adam D.
  • Angewandte Chemie International Edition, Vol. 45, Issue 23
  • DOI: 10.1002/anie.200600865

Thermodynamische Eigenschaften von IV–VI-Verbindungen: Bleichalkogenide / Thermodynamic Properties of IV–VI-Compounds: Leadchalcogenides
journal, October 1974

  • Blachnik, Roger; Igel, Rudolf
  • Zeitschrift für Naturforschung B, Vol. 29, Issue 9-10
  • DOI: 10.1515/znb-1974-9-1012

Some electrical properties of lead selenide at low temperatures (0.3°K–300°K)
journal, February 1970


Nanostructuring and High Thermoelectric Efficiency in p-Type Ag(Pb1–ySny)mSbTe2+m
journal, May 2006

  • Androulakis, J.; Hsu, K. F.; Pcionek, R.
  • Advanced Materials, Vol. 18, Issue 9, p. 1170-1173
  • DOI: 10.1002/adma.200502770

High Thermoelectric Performance via Hierarchical Compositionally Alloyed Nanostructures
journal, May 2013

  • Zhao, Li-Dong; Hao, Shiqiang; Lo, Shih-Han
  • Journal of the American Chemical Society, Vol. 135, Issue 19
  • DOI: 10.1021/ja403134b

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

Study of the Thermoelectric Properties of Lead Selenide Doped with Boron, Gallium, Indium, or Thallium
journal, October 2012

  • Zhang, Qian; Cao, Feng; Lukas, Kevin
  • Journal of the American Chemical Society, Vol. 134, Issue 42
  • DOI: 10.1021/ja307910u

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


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

Introduction
book, January 1969


Impact of energy filtering and carrier localization on the thermoelectric properties of granular semiconductors
journal, September 2012

  • Narducci, Dario; Selezneva, Ekaterina; Cerofolini, Gianfranco
  • Journal of Solid State Chemistry, Vol. 193
  • DOI: 10.1016/j.jssc.2012.03.032

Characterization and analysis of thermoelectric transport in n -type Ba 8 Ga 16 x Ge 30 + x
journal, September 2009


Graphene-Like Exfoliated Quasi-2D Thermoelectric Crystals
book, December 2017

  • Balandin, Alexander A.
  • Materials, Preparation, and Characterization in Thermoelectrics
  • DOI: 10.1201/b11891-13

Exploring the doping effects of Ag in p-type PbSe compounds with enhanced thermoelectric performance
journal, November 2011


Thermodynamic properties of PbTe, PbSe, and PbS: First-principles study
journal, July 2009


Thermoelectrics with Earth Abundant Elements: High Performance p-type PbS Nanostructured with SrS and CaS
journal, April 2012

  • Zhao, Li-Dong; He, Jiaqing; Wu, Chun-I
  • Journal of the American Chemical Society, Vol. 134, Issue 18
  • DOI: 10.1021/ja301772w

Scattering of Current Carriers and Transport Phenomena in Lead Chalcogenides II. Experiment
journal, February 1971

  • Ravich, Yu. I.; Efimova, B. A.; Tamarchenko, V. I.
  • Physica Status Solidi (b), Vol. 43, Issue 2
  • DOI: 10.1002/pssb.2220430202

Weak electron-phonon coupling contributing to high thermoelectric performance in n-type PbSe
journal, May 2012

  • Wang, H.; Pei, Y.; LaLonde, A. D.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 25
  • DOI: 10.1073/pnas.1111419109

Nanostructured Thermoelectrics: Big Efficiency Gains from Small Features
journal, July 2010

  • Vineis, Christopher J.; Shakouri, Ali; Majumdar, Arun
  • Advanced Materials, Vol. 22, Issue 36, p. 3970-3980
  • DOI: 10.1002/adma.201000839

Upper crustal abundances of trace elements: A revision and update
journal, August 2008


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

Enhancement of thermoelectric figure-of-merit by resonant states of aluminium doping in lead selenide
journal, January 2012

  • Zhang, Qinyong; Wang, Hui; Liu, Weishu
  • Energy Environ. Sci., Vol. 5, Issue 1, p. 5246-5251
  • DOI: 10.1039/C1EE02465E

Cubic AgPbmSbTe2+m: Bulk Thermoelectric Materials with High Figure of Merit
journal, February 2004


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


Strained endotaxial nanostructures with high thermoelectric figure of merit
journal, January 2011

  • Biswas, Kanishka; He, Jiaqing; Zhang, Qichun
  • Nature Chemistry, Vol. 3, Issue 2
  • DOI: 10.1038/nchem.955

Thermoelectric properties of n-type PbSe revisited
journal, June 2012

  • Parker, David; Singh, David J.; Zhang, Qinyong
  • Journal of Applied Physics, Vol. 111, Issue 12
  • DOI: 10.1063/1.4728229

Resonant States in the Electronic Structure of the High Performance Thermoelectrics A g P b m S b T e 2 + m : The Role of Ag-Sb Microstructures
journal, September 2004


The mobility of free carriers in PbSe crystals
journal, April 1973


High-temperature charge and thermal transport properties of the n -type thermoelectric material PbSe
journal, October 2011


Nanostructured Thermoelectrics: The New Paradigm?
journal, February 2010

  • Kanatzidis, Mercouri G.
  • Chemistry of Materials, Vol. 22, Issue 3
  • DOI: 10.1021/cm902195j

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

Temperature dependence of carrier mobility in Si wafers measured by infrared photocarrier radiometry
journal, June 2003

  • Batista, Jerias; Mandelis, Andreas; Shaughnessy, Derrick
  • Applied Physics Letters, Vol. 82, Issue 23
  • DOI: 10.1063/1.1582376

Thermoelectrics from Abundant Chemical Elements: High-Performance Nanostructured PbSe–PbS
journal, July 2011

  • Androulakis, John; Todorov, Iliya; He, Jiaqing
  • Journal of the American Chemical Society, Vol. 133, Issue 28
  • DOI: 10.1021/ja203022c

High-temperature thermoelectric performance of heavily doped PbSe
journal, July 2010


High-temperature thermoelectric properties of n-type PbSe doped with Ga, In, and Pb
journal, May 2011

  • Androulakis, John; Lee, Yeseul; Todorov, Iliya
  • Physical Review B, Vol. 83, Issue 19, Article No. 195209
  • DOI: 10.1103/PhysRevB.83.195209

Nanostructures Boost the Thermoelectric Performance of PbS
journal, March 2011

  • Johnsen, Simon; He, Jiaqing; Androulakis, John
  • Journal of the American Chemical Society, Vol. 133, Issue 10
  • DOI: 10.1021/ja109138p

Strong Reduction of Thermal Conductivity in Nanostructured PbTe Prepared by Matrix Encapsulation
journal, October 2006

  • Sootsman, Joseph R.; Pcionek, Robert J.; Kong, Huijun
  • Chemistry of Materials, Vol. 18, Issue 21
  • DOI: 10.1021/cm0612090

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


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

High-Performance Tellurium-Free Thermoelectrics: All-Scale Hierarchical Structuring of p-Type PbSe–MSe Systems (M = Ca, Sr, Ba)
journal, March 2013

  • Lee, Yeseul; Lo, Shih-Han; Androulakis, John
  • Journal of the American Chemical Society, Vol. 135, Issue 13
  • DOI: 10.1021/ja400069s

Near-Equilibrium Transport
book, January 2013

  • Lundstrom, Mark; Jeong, Changwook
  • Lessons from Nanoscience: A Lecture Notes Series: Volume 2
  • DOI: 10.1142/7975

High Thermoelectric Figure of Merit and Nanostructuring in Bulk p-type Na1−xPbmSbyTem+2
journal, June 2006

  • Poudeu, Pierre F. P.; D'Angelo, Jonathan; Downey, Adam D.
  • Angewandte Chemie, Vol. 118, Issue 23, p. 3919-3923
  • DOI: 10.1002/ange.200600865

Nanostructuring and High Thermoelectric Efficiency in p-Type Ag(Pb1-ySny)mSbTe2+m.
journal, July 2006

  • Androulakis, John; Hsu, Kuei Fang; Pcionek, Robert
  • ChemInform, Vol. 37, Issue 28
  • DOI: 10.1002/chin.200628009

- Graphene-Like Exfoliated Quasi-2D Thermoelectric Crystals
book, October 2018

  • Rowe, David Michael
  • Thermoelectrics and its Energy Harvesting, 2-Volume Set
  • DOI: 10.1201/b11869-16

High temperature charge and thermal transport properties of the n-type thermoelectric material PbSe
text, January 2011


Works referencing / citing this record:

High Thermoelectric Performance in Supersaturated Solid Solutions and Nanostructured n-Type PbTe-GeTe
journal, June 2018

  • Luo, Zhong-Zhen; Zhang, Xiaomi; Hua, Xia
  • Advanced Functional Materials, Vol. 28, Issue 31
  • DOI: 10.1002/adfm.201801617

Subtle Roles of Sb and S in Regulating the Thermoelectric Properties of N-Type PbTe to High Performance
journal, May 2017

  • Tan, Gangjian; Stoumpos, Constantinos C.; Wang, Si
  • Advanced Energy Materials, Vol. 7, Issue 18
  • DOI: 10.1002/aenm.201700099

High Thermoelectric Performance in PbSe–NaSbSe 2 Alloys from Valence Band Convergence and Low Thermal Conductivity
journal, July 2019

  • Slade, Tyler J.; Bailey, Trevor P.; Grovogui, Jann A.
  • Advanced Energy Materials, Vol. 9, Issue 30
  • DOI: 10.1002/aenm.201901377

Review of Thermoelectric Materials
book, January 2016


Carrier tuning and multiple phonon scattering induced high thermoelectric performance in n-type Sb-doped PbTe alloys
journal, March 2019


Enhancing Thermoelectric Performance of PbSe by Se Vacancies
journal, February 2018


Vacancy-induced dislocations within grains for high-performance PbSe thermoelectrics
journal, January 2017

  • Chen, Zhiwei; Ge, Binghui; Li, Wen
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms13828

Electrical and thermal transport properties of Pb 1−x Sn x Se solid solution thermoelectric materials
journal, January 2015

  • Wu, Chao-Feng; Wei, Tian-Ran; Li, Jing-Feng
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 19
  • DOI: 10.1039/c4cp06021k

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

High thermoelectric performance in complex phosphides enabled by stereochemically active lone pair electrons
journal, January 2018

  • Shen, Xingchen; Xia, Yi; Wang, Guiwen
  • Journal of Materials Chemistry A, Vol. 6, Issue 48
  • DOI: 10.1039/c8ta08448c

High thermoelectric performance of Ag doped SnTe polycrystalline bulks via the synergistic manipulation of electrical and thermal transport
journal, January 2019

  • Zhao, Lanling; Wang, Jun; Li, Jichao
  • Physical Chemistry Chemical Physics, Vol. 21, Issue 32
  • DOI: 10.1039/c9cp03534f

GeSe monolayer semiconductor with tunable direct band gap and small carrier effective mass
journal, September 2015

  • Hu, Yonghong; Zhang, Shengli; Sun, Shaofa
  • Applied Physics Letters, Vol. 107, Issue 12
  • DOI: 10.1063/1.4931459

Enhancing average ZT in pristine PbSe by over-stoichiometric Pb addition
journal, October 2016

  • Wu, Chao-Feng; Wei, Tian-Ran; Li, Jing-Feng
  • APL Materials, Vol. 4, Issue 10
  • DOI: 10.1063/1.4950809

Thermoelectric power generation: from new materials to devices
journal, July 2019

  • Tan, Gangjian; Ohta, Michihiro; Kanatzidis, Mercouri G.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2152
  • DOI: 10.1098/rsta.2018.0450

Review of Thermoelectric Materials
book, August 2009


Vacancy-induced dislocations within grains for high-performance PbSe thermoelectrics
journal, January 2017

  • Chen, Zhiwei; Ge, Binghui; Li, Wen
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms13828

Decreasing the Effective Thermal Conductivity in Glass Supported Thermoelectric Layers
journal, March 2016