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

Title: First-principles calculation of intrinsic defect chemistry and self-doping in PbTe

Abstract

Semiconductor dopability is inherently limited by intrinsic defect chemistry. In many thermoelectric materials, narrow band gaps due to strong spin-orbit interactions make accurate atomic level predictions of intrinsic defect chemistry and self-doping computationally challenging. For this study, we use different levels of theory to model point defects in PbTe, and compare and contrast the results against each other and a large body of experimental data. We find that to accurately reproduce the intrinsic defect chemistry and known self-doping behavior of PbTe, it is essential to (a) go beyond the semi-local GGA approximation to density functional theory, (b) include spin-orbit coupling, and (c) utilize many-body GW theory to describe the positions of individual band edges. The hybrid HSE functional with spin-orbit coupling included, in combination with the band edge shifts from G0W0 is the only approach that accurately captures both the intrinsic conductivity type of PbTe as function of synthesis conditions as well as the measured charge carrier concentrations, without the need for experimental inputs. Our results reaffirm the critical role of the position of individual band edges in defect calculations, and demonstrate that dopability can be accurately predicted in such challenging narrow band gap materials.

Authors:
 [1];  [1];  [1];  [1]
  1. Colorado School of Mines, Golden, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE); National Science Foundation (NSF)
OSTI Identifier:
1432441
Report Number(s):
NREL/JA-5K00-71271
Journal ID: ISSN 2057-3960
Grant/Contract Number:  
AC36-08GO28308; DMR-1309980; 1334713
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
npj Computational Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2057-3960
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; electronic structure; semiconductors; thermoelectrics

Citation Formats

Goyal, Anuj, Gorai, Prashun, Toberer, Eric S., and Stevanovic, Vladan. First-principles calculation of intrinsic defect chemistry and self-doping in PbTe. United States: N. p., 2017. Web. doi:10.1038/s41524-017-0047-6.
Goyal, Anuj, Gorai, Prashun, Toberer, Eric S., & Stevanovic, Vladan. First-principles calculation of intrinsic defect chemistry and self-doping in PbTe. United States. doi:10.1038/s41524-017-0047-6.
Goyal, Anuj, Gorai, Prashun, Toberer, Eric S., and Stevanovic, Vladan. Fri . "First-principles calculation of intrinsic defect chemistry and self-doping in PbTe". United States. doi:10.1038/s41524-017-0047-6. https://www.osti.gov/servlets/purl/1432441.
@article{osti_1432441,
title = {First-principles calculation of intrinsic defect chemistry and self-doping in PbTe},
author = {Goyal, Anuj and Gorai, Prashun and Toberer, Eric S. and Stevanovic, Vladan},
abstractNote = {Semiconductor dopability is inherently limited by intrinsic defect chemistry. In many thermoelectric materials, narrow band gaps due to strong spin-orbit interactions make accurate atomic level predictions of intrinsic defect chemistry and self-doping computationally challenging. For this study, we use different levels of theory to model point defects in PbTe, and compare and contrast the results against each other and a large body of experimental data. We find that to accurately reproduce the intrinsic defect chemistry and known self-doping behavior of PbTe, it is essential to (a) go beyond the semi-local GGA approximation to density functional theory, (b) include spin-orbit coupling, and (c) utilize many-body GW theory to describe the positions of individual band edges. The hybrid HSE functional with spin-orbit coupling included, in combination with the band edge shifts from G0W0 is the only approach that accurately captures both the intrinsic conductivity type of PbTe as function of synthesis conditions as well as the measured charge carrier concentrations, without the need for experimental inputs. Our results reaffirm the critical role of the position of individual band edges in defect calculations, and demonstrate that dopability can be accurately predicted in such challenging narrow band gap materials.},
doi = {10.1038/s41524-017-0047-6},
journal = {npj Computational Materials},
issn = {2057-3960},
number = 1,
volume = 3,
place = {United States},
year = {2017},
month = {11}
}

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

Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

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 Performance and Defect Chemistry in n-Type Zintl KGaSb 4
journal, May 2017


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

Theoretical calculations of heterojunction discontinuities in the Si/Ge system
journal, October 1986


Practical doping principles
journal, July 2003


First-Principles Approach to Insulators in Finite Electric Fields
journal, August 2002


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

Theoretical study of deep-defect states in bulk PbTe and in thin films
journal, September 2007


Composition Limits of Stability of PbTe
journal, June 1960

  • Brebrick, R. F.; Allgaier, R. S.
  • The Journal of Chemical Physics, Vol. 32, Issue 6
  • DOI: 10.1063/1.1731029

Unraveling the Native Conduction of Trichalcogenides and Its Ideal Band Alignment for New Photovoltaic Interfaces
journal, January 2016

  • Tumelero, Milton A.; Faccio, Ricardo; Pasa, Andre A.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 3
  • DOI: 10.1021/acs.jpcc.5b10233

Ab initio studies of the electronic structure of defects in PbTe
journal, October 2006


Accurate prediction of defect properties in density functional supercell calculations
journal, November 2009


The high-throughput highway to computational materials design
journal, February 2013

  • Curtarolo, Stefano; Hart, Gus L. W.; Nardelli, Marco Buongiorno
  • Nature Materials, Vol. 12, Issue 3
  • DOI: 10.1038/nmat3568

Hydrogen as a Cause of Doping in Zinc Oxide
journal, July 2000


Computationally guided discovery of thermoelectric materials
journal, August 2017


A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

Electronic and structural anomalies in lead chalcogenides
journal, May 1997


Nonstoichiometry and point defects in PbTe
journal, January 1988

  • Schenk, M.; Berger, H.; Klimakow, A.
  • Crystal Research and Technology, Vol. 23, Issue 1
  • DOI: 10.1002/crat.2170230111

Dopability, Intrinsic Conductivity, and Nonstoichiometry of Transparent Conducting Oxides
journal, January 2007


Correcting density functional theory for accurate predictions of compound enthalpies of formation: Fitted elemental-phase reference energies
journal, March 2012


Electrical and Optical Properties of Epitaxial Films of PbS, PbSe, PbTe, and SnTe
journal, October 1965

  • Zemel, Jay N.; Jensen, James D.; Schoolar, Richard B.
  • Physical Review, Vol. 140, Issue 1A
  • DOI: 10.1103/PhysRev.140.A330

Theoretical and experimental investigations of the thermoelectric properties of Bi 2 S 3
journal, March 2015

  • Chmielowski, Radoslaw; Péré, Daniel; Bera, Chandan
  • Journal of Applied Physics, Vol. 117, Issue 12
  • DOI: 10.1063/1.4916528

Electronic structure calculations of lead chalcogenides PbS, PbSe, PbTe
journal, May 2002

  • Lach-hab, Mohammed; Papaconstantopoulos, Dimitrios A.; Mehl, Michael J.
  • Journal of Physics and Chemistry of Solids, Vol. 63, Issue 5
  • DOI: 10.1016/S0022-3697(01)00237-2

Composition Stability Limits of PbTe. II
journal, March 1962

  • Brebrick, R. F.; Gubner, E.
  • The Journal of Chemical Physics, Vol. 36, Issue 5
  • DOI: 10.1063/1.1732728

Index matching far-infrared method for measuring the static dielectric constant of PbTe
journal, November 1976


Thermal physics of the lead chalcogenides PbS, PbSe, and PbTe from first principles
journal, May 2014


A computational framework for automation of point defect calculations
journal, April 2017


Native defects in second-generation topological insulators: Effect of spin-orbit interaction on Bi 2 Se 3
journal, September 2012


First-principles calculations for defects and impurities: Applications to III-nitrides
journal, April 2004

  • Van de Walle, Chris G.; Neugebauer, Jörg
  • Journal of Applied Physics, Vol. 95, Issue 8
  • DOI: 10.1063/1.1682673

Surface morphology and ionization potentials of polar semiconductors: The case of GaAs
journal, January 2004


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


Structural and electronic properties of lead chalcogenides from first principles
journal, May 2007


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


Annealing studies of PbTe and Pb 1− x Sn x Te
journal, March 1973

  • Hewes, C. Robert; Adler, Michael S.; Senturia, Stephen D.
  • Journal of Applied Physics, Vol. 44, Issue 3
  • DOI: 10.1063/1.1662348

Electron and chemical reservoir corrections for point-defect formation energies
journal, April 2016


Electronic structure, structural properties, and dielectric functions of IV-VI semiconductors: PbSe and PbTe
journal, June 2000


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Calculation of the Temperature Dependence of the Energy Gaps in PbTe and SnTe
journal, February 1971


Ab initio calculation of the macroscopic dielectric constant in silicon
journal, May 1986


P - T - x Phase Diagram of the Lead Telluride System
journal, February 1966

  • Fujimoto, Masatomo; Sato, Yasuo
  • Japanese Journal of Applied Physics, Vol. 5, Issue 2
  • DOI: 10.1143/JJAP.5.128

Thermal and Optical Energy Gaps in PbTe
journal, December 1966

  • Tauber, R. N.; Machonis, A. A.; Cadoff, I. B.
  • Journal of Applied Physics, Vol. 37, Issue 13
  • DOI: 10.1063/1.1708150

First-principles calculations for point defects in solids
journal, March 2014

  • Freysoldt, Christoph; Grabowski, Blazej; Hickel, Tilmann
  • Reviews of Modern Physics, Vol. 86, Issue 1
  • DOI: 10.1103/RevModPhys.86.253

Linear optical properties in the projector-augmented wave methodology
journal, January 2006


TE Design Lab: A virtual laboratory for thermoelectric material design
journal, February 2016


Assessing capability of semiconductors to split water using ionization potentials and electron affinities only
journal, January 2014

  • Stevanović, Vladan; Lany, Stephan; Ginley, David S.
  • Physical Chemistry Chemical Physics, Vol. 16, Issue 8
  • DOI: 10.1039/c3cp54589j

Photoemission Investigation of the Band Structure of PbTe
journal, July 1965


Quasiparticle self-consistent GW calculations for PbS, PbSe, and PbTe: Band structure and pressure coefficients
journal, June 2010


Universal alignment of hydrogen levels in semiconductors, insulators and solutions
journal, June 2003


Ab initio study of intrinsic point defects in PbTe: an insight into phase stability
journal, June 2015


High throughput density functional investigations of the stability, electronic structure and thermoelectric properties of binary silicides
journal, January 2012

  • Opahle, Ingo; Madsen, Georg K. H.; Drautz, Ralf
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 47
  • DOI: 10.1039/c2cp41826f