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Title: Correlated local dipoles in PbTe

Journal Article · · Physical Review Materials
 [1]; ORCiD logo [2];  [3];  [1];  [1];  [3];  [4];  [1];  [1]
  1. Federal Inst. of Technology, Zurich (Switzerland). Dept. of Materials
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.
  3. Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry
  4. Columbia Univ., New York, NY (United States). Dept. of Applied Physics and Applied Mathematics; Brookhaven National Lab. (BNL), Upton, NY (United States). Condensed Matter Physics and Materials Science Dept.

We present a combined single-crystal x-ray diffuse scattering and ab-initio molecular dynamics study of lead telluride, PbTe. Well-known for its thermoelectric and narrow-gap semiconducting properties, PbTe recently achieved further notoriety following the report of an unusual off-centering of the lead atoms, accompanied by a local symmetry breaking, on heating. This observation, which was named emphanisis, ignited considerable controversy regarding the details of the underlying local structure and the appropriate interpretation of the total scattering experiments. In this study, we identify an unusual correlated local dipole formation extending over several unit cells with an associated local reduction of the cubic symmetry in both our x-ray diffuse scattering measurements and our molecular dynamics simulations. Importantly, when averaged spatially or temporally, the most probable positions for the ions are at the centers of their coordination polyhedra. Our results therefore clarify the nature of the local symmetry breaking, and reveal the source of the earlier controversy regarding the existence or absence of off-centering. Finally, we provide an interpretation of the behavior in terms of coupled soft optical and acoustic modes, which is linked also to the high thermoelectric performance of PbTe.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1459170
Alternate ID(s):
OSTI ID: 1463047
Report Number(s):
BNL-206808-2018-JAAM; TRN: US1901546
Journal Information:
Physical Review Materials, Vol. 2, Issue 8; ISSN 2475-9953
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (78)

Temperature dependent band gap in PbX (X = S, Se, Te) journal December 2013
High performance bulk thermoelectrics via a panoscopic approach journal May 2013
Anomalous Lattice Dynamics near the Ferroelectric Instability in PbTe journal October 2011
Rationally Designing High-Performance Bulk Thermoelectric Materials journal August 2016
Projector augmented-wave method journal December 1994
Thermoelectric Enhancement of Different Kinds of Metal Chalcogenides journal June 2016
Outlier Treatment in Data Merging journal August 1997
Direct Observation of Lattice Polaron Formation in the Local Structure of La 1 − x Ca x MnO 3 journal July 1996
Resonant bonding leads to low lattice thermal conductivity journal April 2014
All-scale hierarchical thermoelectrics: MgTe in PbTe facilitates valence band convergence and suppresses bipolar thermal transport for high performance journal January 2013
The three-dimensional pair distribution function analysis of disordered single crystals: basic concepts journal May 2012
PDFgetX3 : a rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions journal March 2013
From ultrasoft pseudopotentials to the projector augmented-wave method journal January 1999
The self-consistent ab initio lattice dynamical method journal January 2009
Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3 journal September 2016
Fast Parallel Algorithms for Short-Range Molecular Dynamics journal March 1995
Entropically Stabilized Local Dipole Formation in Lead Chalcogenides journal December 2010
Convergence of electronic bands for high performance bulk thermoelectrics journal May 2011
Enhancement of Thermoelectric Efficiency in PbTe by Distortion of the Electronic Density of States journal July 2008
Anharmonicity and atomic distribution of SnTe and PbTe thermoelectrics journal December 2014
Band Engineering of Thermoelectric Materials journal October 2012
Yell : a computer program for diffuse scattering analysis via three-dimensional delta pair distribution function refinement journal May 2014
First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb journal March 2003
First-principles accurate total energy surfaces for polar structural distortions of BaTiO 3 , PbTiO 3 , and SrTiO 3 : Consequences for structural transition temperatures journal October 2010
Effect of thermal disorder on high figure of merit in PbTe journal July 2012
Quickstep: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach journal April 2005
Neutron scattering lengths and cross sections journal January 1992
Fermi surface evolution of Na-doped PbTe studied through density functional theory calculations and Shubnikov–de Haas measurements journal November 2016
Lattice dynamics reveals a local symmetry breaking in the emergent dipole phase of PbTe journal August 2012
Structural disorder, anisotropic micro-strain and cation vacancies in thermo-electric lead chalcogenides journal January 2016
Origin of anomalous anharmonic lattice dynamics of lead telluride journal March 2014
Paraelectric Behavior of PbTe journal July 1970
A hybrid Gaussian and plane wave density functional scheme journal October 1997
Thermoelectric enhancement in PbTe with K or Na codoping from tuning the interaction of the light- and heavy-hole valence bands journal September 2010
Structural disorder in the decagonal Al–Co–Ni. II. Modeling journal June 2005
Molecular dynamics simulations of lattice thermal conductivity and spectral phonon mean free path of PbTe: Bulk and nanostructures journal February 2012
Structural disorder in the decagonal Al – Co – Ni . I. Patterson analysis of diffuse x-ray scattering data journal June 2005
First-Principles Approach to Nonlinear Lattice Dynamics: Anomalous Spectra in PbTe journal September 2014
The panoscopic approach to high performance thermoelectrics journal January 2014
Diffuse scattering in relaxor ferroelectrics: true three-dimensional mapping, experimental artefacts and modelling journal November 2011
Phonon Self-Energy and Origin of Anomalous Neutron Scattering Spectra in SnTe and PbTe Thermoelectrics journal April 2014
New promising bulk thermoelectrics: intermetallics, pnictides and chalcogenides journal February 2014
Giant anharmonic phonon scattering in PbTe journal June 2011
Lead Is Not Off Center in PbTe: The Importance of r -Space Phase Information in Extended X-Ray Absorption Fine Structure Spectroscopy journal August 2013
Local off-centering symmetry breaking in the high-temperature regime of SnTe journal January 2014
Canonical sampling through velocity rescaling journal January 2007
Thinking Like a Chemist: Intuition in Thermoelectric Materials journal April 2016
A short history of SHELX journal December 2007
Charge density wave fluctuations, heavy electrons, and superconductivity in KNi 2 S 2 journal January 2013
First-principles theory of ferroelectric phase transitions for perovskites: The case of BaTiO 3 journal September 1995
Direct Evidence of Cation Disorder in Thermoelectric Lead Chalcogenides PbTe and PbS journal June 2013
Monoxyde quadratique PbOα(I): Description de la transition structurale ferroe´lastique journal May 1985
Molecular dynamics with coupling to an external bath journal October 1984
Materials for thermoelectric energy conversion journal April 1988
First principles phonon calculations in materials science journal November 2015
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set journal October 1996
Pseudopotentials for H to Kr optimized for gradient-corrected exchange-correlation functionals journal May 2005
Influence of the exchange-correlation functional on the quasi-harmonic lattice dynamics of II-VI semiconductors journal August 2015
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals journal July 2007
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal April 2008
Band structure engineering through orbital interaction for enhanced thermoelectric power factor journal February 2014
Non-equilibrium processing leads to record high thermoelectric figure of merit in PbTe–SrTe journal July 2016
Diffuse scattering data acquisition techniques journal October 1998
Understanding the Insulating Phase in Colossal Magnetoresistance Manganites: Shortening of the Jahn-Teller Long-Bond across the Phase Diagram of La 1 − x Ca x MnO 3 journal March 2007
Spectroscopic evidence for temperature-dependent convergence of light- and heavy-hole valence bands of PbQ (Q = Te, Se, S) journal January 2017
A high-resolution neutron powder diffraction investigation of galena (PbS) between 10 K and 350 K: no evidence for anomalies in the lattice parameters or atomic displacement parameters in galena or altaite (PbTe) at temperatures corresponding to the saturation of cation disorder journal September 2014
Stereochemistry of post-transition metal oxides: revision of the classical lone pair model journal January 2011
Phase transition in crystalline GeTe: Pitfalls of averaging effects journal October 2010
Ab initio phase diagram and nucleation of gallium journal May 2020
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets journal May 2021
Electronic structure of AlFeN films exhibiting crystallographic orientation change from c- to a-axis with Fe concentrations and annealing effect journal February 2020
The three-dimensional pair distribution function analysis of disordered single crystals: Basic concepts text January 2012
QUICKSTEP: Fast and accurate density functional calculations using a mixed Gaussian and plane waves approach text January 2005
Molecular Dynamics Simulations of Lattice Thermal Conductivity and Spectral Phonon Mean Free Path of PbTe: Bulk and Nanostructures
  • Qiu, Bo; Bao, Hua; Ruan, Xiulin
  • ASME 2012 Heat Transfer Summer Conference collocated with the ASME 2012 Fluids Engineering Division Summer Meeting and the ASME 2012 10th International Conference on Nanochannels, Microchannels, and M, Volume 1: Heat Transfer in Energy Systems; Theory and Fundamental Research; Aerospace Heat Transfer; Gas Turbine Heat Transfer; Transport Phenomena in Materials Processing and Manufacturing; Heat and https://doi.org/10.1115/ht2012-58554
conference July 2012
Thermoelectric enhancement in PbTe with K, Na co-doping from tuning the interaction of the light and heavy hole valence bands text January 2010
PDFgetX3: A rapid and highly automatable program for processing powder diffraction data into total scattering pair distribution functions text January 2012
A first-principles approach to nonlinear lattice dynamics: Anomalous spectra in PbTe text January 2013
First principles phonon calculations in materials science preprint January 2015

Cited By (2)

Anisotropy of Selected Mechanical Properties of PbTe journal February 2019
K-space algorithmic reconstruction (KAREN): a robust statistical methodology to separate Bragg and diffuse scattering journal February 2020

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