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

Title: High Thermoelectric Performance and Defect Energetics of Multipocketed Full Heusler Compounds

Abstract

We report a first-principles density-functional study of electron-phonon interactions in and thermoelectric transport properties of the full Heusler compounds Sr2BiAu and Sr2SbAu. Our results show that ultrahigh intrinsic bulk thermoelectric performance across a wide range of temperatures is physically possible and point to the presence of multiply degenerate and highly dispersive carrier pockets as the key factor for achieving this. Sr2BiAu, which features ten energy-aligned low-effective-mass pockets (six along Γ-X and four at L), is predicted to deliver n-type zT=0.4-4.9 at T=100-700 K. Comparison with the previously investigated compound Ba2BiAu shows that the additional L pockets in Sr2BiAu significantly increase its low-temperature power factor to a maximum value of 12 mW m-1 K-2 near T=300 K. However, at high temperatures the power factor of Sr2BiAu drops below that of Ba2BiAu because the L states are heavier and subject to strong scattering by phonon deformation, as opposed to the lighter Γ-X states, which are limited by polar-optical scattering. Sr2SbAu is predicted to deliver a lower n-type zT=3.4 at T=750 K due to appreciable misalignment between the L and Γ-X carrier pockets, generally heavier scattering, and a slightly higher lattice thermal conductivity. Soft acoustic modes, which are responsible for the low latticemore » thermal conductivity, also increase the vibrational entropy and high-temperature stability of these Heusler compounds, suggesting that their experimental synthesis may be feasible. The dominant intrinsic defects are found to be Au vacancies, which drive the Fermi level towards the conduction band and work in favor of n-doping.« less

Authors:
ORCiD logo [1];  [2];  [1];  [1];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Northwestern Univ., Evanston, IL (United States)
  3. Yale Univ., New Haven, CT (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1783120
Grant/Contract Number:  
AC02-05CH11231; DMR-1611507; ACI-1548562
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Applied
Additional Journal Information:
Journal Volume: 14; Journal Issue: 2; Journal ID: ISSN 2331-7019
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; electron-phonon coupling; thermoelectric effects; doped semiconductors; energy materials; heusler alloy; thermoelectric systems; Boltzmann theory; Wannier function methods

Citation Formats

Park, Junsoo, Xia, Yi, Ganose, Alex M., Jain, Anubhav, and Ozoliņš, Vidvuds. High Thermoelectric Performance and Defect Energetics of Multipocketed Full Heusler Compounds. United States: N. p., 2020. Web. doi:10.1103/physrevapplied.14.024064.
Park, Junsoo, Xia, Yi, Ganose, Alex M., Jain, Anubhav, & Ozoliņš, Vidvuds. High Thermoelectric Performance and Defect Energetics of Multipocketed Full Heusler Compounds. United States. https://doi.org/10.1103/physrevapplied.14.024064
Park, Junsoo, Xia, Yi, Ganose, Alex M., Jain, Anubhav, and Ozoliņš, Vidvuds. Fri . "High Thermoelectric Performance and Defect Energetics of Multipocketed Full Heusler Compounds". United States. https://doi.org/10.1103/physrevapplied.14.024064. https://www.osti.gov/servlets/purl/1783120.
@article{osti_1783120,
title = {High Thermoelectric Performance and Defect Energetics of Multipocketed Full Heusler Compounds},
author = {Park, Junsoo and Xia, Yi and Ganose, Alex M. and Jain, Anubhav and Ozoliņš, Vidvuds},
abstractNote = {We report a first-principles density-functional study of electron-phonon interactions in and thermoelectric transport properties of the full Heusler compounds Sr2BiAu and Sr2SbAu. Our results show that ultrahigh intrinsic bulk thermoelectric performance across a wide range of temperatures is physically possible and point to the presence of multiply degenerate and highly dispersive carrier pockets as the key factor for achieving this. Sr2BiAu, which features ten energy-aligned low-effective-mass pockets (six along Γ-X and four at L), is predicted to deliver n-type zT=0.4-4.9 at T=100-700 K. Comparison with the previously investigated compound Ba2BiAu shows that the additional L pockets in Sr2BiAu significantly increase its low-temperature power factor to a maximum value of 12 mW m-1 K-2 near T=300 K. However, at high temperatures the power factor of Sr2BiAu drops below that of Ba2BiAu because the L states are heavier and subject to strong scattering by phonon deformation, as opposed to the lighter Γ-X states, which are limited by polar-optical scattering. Sr2SbAu is predicted to deliver a lower n-type zT=3.4 at T=750 K due to appreciable misalignment between the L and Γ-X carrier pockets, generally heavier scattering, and a slightly higher lattice thermal conductivity. Soft acoustic modes, which are responsible for the low lattice thermal conductivity, also increase the vibrational entropy and high-temperature stability of these Heusler compounds, suggesting that their experimental synthesis may be feasible. The dominant intrinsic defects are found to be Au vacancies, which drive the Fermi level towards the conduction band and work in favor of n-doping.},
doi = {10.1103/physrevapplied.14.024064},
journal = {Physical Review Applied},
number = 2,
volume = 14,
place = {United States},
year = {Fri Aug 21 00:00:00 EDT 2020},
month = {Fri Aug 21 00:00:00 EDT 2020}
}

Works referenced in this record:

High thermoelectric cooling performance of n-type Mg 3 Bi 2 -based materials
journal, July 2019


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

Efficient hybrid density functional calculations in solids: Assessment of the Heyd–Scuseria–Ernzerhof screened Coulomb hybrid functional
journal, July 2004

  • Heyd, Jochen; Scuseria, Gustavo E.
  • The Journal of Chemical Physics, Vol. 121, Issue 3, p. 1187-1192
  • DOI: 10.1063/1.1760074

Beware of plausible predictions of fantasy materials
journal, February 2019


Improvement of Low‐Temperature zT in a Mg 3 Sb 2 –Mg 3 Bi 2 Solid Solution via Mg‐Vapor Annealing
journal, July 2019

  • Wood, Maxwell; Kuo, Jimmy Jiahong; Imasato, Kazuki
  • Advanced Materials, Vol. 31, Issue 35
  • DOI: 10.1002/adma.201902337

Revelation of Inherently High Mobility Enables Mg 3 Sb 2 as a Sustainable Alternative to n‐Bi 2 Te 3 Thermoelectrics
journal, June 2019


Low effective mass leading to high thermoelectric performance
journal, January 2012

  • Pei, Yanzhong; LaLonde, Aaron D.; Wang, Heng
  • Energy & Environmental Science, Vol. 5, Issue 7
  • DOI: 10.1039/c2ee21536e

Projector augmented-wave method
journal, December 1994


Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

High Band Degeneracy Contributes to High Thermoelectric Performance in p-Type Half-Heusler Compounds
journal, August 2014

  • Fu, Chenguang; Zhu, Tiejun; Pei, Yanzhong
  • Advanced Energy Materials, Vol. 4, Issue 18
  • DOI: 10.1002/aenm.201400600

Electrostatic interactions between charged defects in supercells
journal, December 2010

  • Freysoldt, Christoph; Neugebauer, Jörg; Van de Walle, Chris G.
  • physica status solidi (b), Vol. 248, Issue 5
  • DOI: 10.1002/pssb.201046289

Low-Symmetry Rhombohedral GeTe Thermoelectrics
journal, May 2018


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

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

wannier90: A tool for obtaining maximally-localised Wannier functions
journal, May 2008

  • Mostofi, Arash A.; Yates, Jonathan R.; Lee, Young-Su
  • Computer Physics Communications, Vol. 178, Issue 9
  • DOI: 10.1016/j.cpc.2007.11.016

EPW: A program for calculating the electron–phonon coupling using maximally localized Wannier functions
journal, December 2010

  • Noffsinger, Jesse; Giustino, Feliciano; Malone, Brad D.
  • Computer Physics Communications, Vol. 181, Issue 12, p. 2140-2148
  • DOI: 10.1016/j.cpc.2010.08.027

Temperature dependence of the electronic structure of semiconductors and insulators
dataset, January 2021


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


Maximally localized generalized Wannier functions for composite energy bands
journal, November 1997


Periodic boundary conditions in ab initio calculations
journal, February 1995


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

Achieving high power factor and output power density in p-type half-Heuslers Nb 1-x Ti x FeSb
journal, November 2016

  • He, Ran; Kraemer, Daniel; Mao, Jun
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 48
  • DOI: 10.1073/pnas.1617663113

Thermoelectric Materials for Space and Automotive Power Generation
journal, March 2006


Band Engineering of Thermoelectric Materials
journal, October 2012


Optimized norm-conserving Vanderbilt pseudopotentials
journal, August 2013


Structural absorption by barbule microstructures of super black bird of paradise feathers
journal, January 2018


Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs
journal, December 2008


Assessing the accuracy of hybrid functionals in the determination of defect levels: Application to the As antisite in GaAs
journal, August 2011


Thermoelectric Materials, Phenomena, and Applications: A Bird's Eye View
journal, March 2006

  • Tritt, Terry M.; Subramanian, M. A.
  • MRS Bulletin, Vol. 31, Issue 3
  • DOI: 10.1557/mrs2006.44

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 developments in the Inorganic Crystal Structure Database (ICSD): accessibility in support of materials research and design
journal, May 2002

  • Belsky, Alec; Hellenbrandt, Mariette; Karen, Vicky Lynn
  • Acta Crystallographica Section B Structural Science, Vol. 58, Issue 3
  • DOI: 10.1107/S0108768102006948

Thermoelectrics
book, January 2001


Fröhlich Electron-Phonon Vertex from First Principles
journal, October 2015


Ultralow Thermal Conductivity in Full Heusler Semiconductors
journal, July 2016


BoltzTraP. A code for calculating band-structure dependent quantities
journal, July 2006


The Inorganic Crystal Structure Database (ICSD)—Present and Future
journal, January 2004


High-precision sampling for Brillouin-zone integration in metals
journal, August 1989


Accurate Band Gaps of Semiconductors and Insulators with a Semilocal Exchange-Correlation Potential
journal, June 2009


Quantum–continuum simulation of underpotential deposition at electrified metal–solution interfaces
journal, January 2017


Lattice Anharmonicity and Thermal Conductivity from Compressive Sensing of First-Principles Calculations
journal, October 2014


Dominant electron-phonon scattering mechanisms in n -type PbTe from first principles
journal, November 2018


Large Enhancements in the Thermoelectric Power Factor of Bulk PbTe at High Temperature by Synergistic Nanostructuring
journal, October 2008

  • Sootsman, Joseph R.; Kong, Huijun; Uher, Ctirad
  • Angewandte Chemie International Edition, Vol. 47, Issue 45, p. 8618-8622
  • DOI: 10.1002/anie.200803934

ShengBTE: A solver of the Boltzmann transport equation for phonons
journal, June 2014

  • Li, Wu; Carrete, Jesús; A. Katcho, Nebil
  • Computer Physics Communications, Vol. 185, Issue 6
  • DOI: 10.1016/j.cpc.2014.02.015

Advances in thermoelectrics
journal, April 2018


Compromise and Synergy in High-Efficiency Thermoelectric Materials
journal, March 2017


Thinking Like a Chemist: Intuition in Thermoelectric Materials
journal, April 2016

  • Zeier, Wolfgang G.; Zevalkink, Alex; Gibbs, Zachary M.
  • Angewandte Chemie International Edition, Vol. 55, Issue 24
  • DOI: 10.1002/anie.201508381

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Band-edge problem in the theoretical determination of defect energy levels: The O vacancy in ZnO as a benchmark case
journal, September 2011


Discovery of high-performance low-cost n-type Mg3Sb2-based thermoelectric materials with multi-valley conduction bands
journal, January 2017

  • Zhang, Jiawei; Song, Lirong; Pedersen, Steffen Hindborg
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms13901

Material descriptors for predicting thermoelectric performance
journal, January 2015

  • Yan, Jun; Gorai, Prashun; Ortiz, Brenden
  • Energy & Environmental Science, Vol. 8, Issue 3
  • DOI: 10.1039/C4EE03157A

Alignment of defect levels and band edges through hybrid functionals: Effect of screening in the exchange term
journal, May 2010


Partial indium solubility induces chemical stability and colossal thermoelectric figure of merit in Cu 2 Se
journal, January 2017

  • Olvera, A. A.; Moroz, N. A.; Sahoo, P.
  • Energy & Environmental Science, Vol. 10, Issue 7
  • DOI: 10.1039/C7EE01193H

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


Dense dislocation arrays embedded in grain boundaries for high-performance bulk thermoelectrics
journal, April 2015


Thermoelectric Properties of Bismuth‐Antimony Alloys
journal, March 1962

  • Smith, G. E.; Wolfe, R.
  • Journal of Applied Physics, Vol. 33, Issue 3
  • DOI: 10.1063/1.1777178

Temperature dependence of the electronic structure of semiconductors and insulators
journal, September 2015

  • Poncé, S.; Gillet, Y.; Laflamme Janssen, J.
  • The Journal of Chemical Physics, Vol. 143, Issue 10
  • DOI: 10.1063/1.4927081

High superionic conduction arising from aligned large lamellae and large figure of merit in bulk Cu 1.94 Al 0.02 Se
journal, September 2014

  • Zhong, Bin; Zhang, Yong; Li, Weiqian
  • Applied Physics Letters, Vol. 105, Issue 12
  • DOI: 10.1063/1.4896520

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

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


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


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


RMX compounds formed by alkaline earths, europium and ytterbium—I. Ternary phases with M ≡ Cu, Ag, Au; X ≡ Sb, Bi
journal, November 1990


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


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

  • Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
  • APL Materials, Vol. 1, Issue 1
  • DOI: 10.1063/1.4812323

High Thermoelectric Power Factor in Intermetallic Co Si Arising from Energy Filtering of Electrons by Phonon Scattering
journal, February 2019


EPW: Electron–phonon coupling, transport and superconducting properties using maximally localized Wannier functions
journal, December 2016


High Thermoelectric Figure of Merit of Full‐Heusler Ba 2 AuX (X = As, Sb, and Bi)
journal, April 2020

  • Ma, Jinlong; Nissimagoudar, Arun S.; Wang, Shudong
  • physica status solidi (RRL) – Rapid Research Letters, Vol. 14, Issue 6
  • DOI: 10.1002/pssr.202000084

Realizing zT of 2.3 in Ge 1− x y Sb x In y Te via Reducing the Phase-Transition Temperature and Introducing Resonant Energy Doping
journal, January 2018


Optimization algorithm for the generation of ONCV pseudopotentials
journal, November 2015


Implementation and Validation of Fully Relativistic GW Calculations: Spin–Orbit Coupling in Molecules, Nanocrystals, and Solids
journal, July 2016

  • Scherpelz, Peter; Govoni, Marco; Hamada, Ikutaro
  • Journal of Chemical Theory and Computation, Vol. 12, Issue 8
  • DOI: 10.1021/acs.jctc.6b00114

High Thermoelectric Power Factor and Efficiency from a Highly Dispersive Band in Ba 2 Bi Au
journal, January 2019


Ab initio study of electron mean free paths and thermoelectric properties of lead telluride
journal, September 2017


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


Advanced capabilities for materials modelling with Quantum ESPRESSO
journal, October 2017

  • Giannozzi, P.; Andreussi, O.; Brumme, T.
  • Journal of Physics: Condensed Matter, Vol. 29, Issue 46
  • DOI: 10.1088/1361-648X/aa8f79

Maximally localized Wannier functions for entangled energy bands
journal, December 2001


Large Enhancements in the Thermoelectric Power Factor of Bulk PbTe at High Temperature by Synergistic Nanostructuring
journal, October 2008

  • Sootsman, Joseph R.; Kong, Huijun; Uher, Ctirad
  • Angewandte Chemie, Vol. 120, Issue 45
  • DOI: 10.1002/ange.200803934

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


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

The Inorganic Crystal Structure Database (ICSD)—Present and Future
journal, January 2004


Advances in thermoelectric materials research: Looking back and moving forward
journal, September 2017


Defect Energy Levels in Density Functional Calculations: Alignment and Band Gap Problem
text, January 2008