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Title: Emphanitic anharmonicity in PbSe at high temperature and anomalous electronic properties in the Pb Q ( Q = S , Se , Te ) system

Abstract

Here, the temperature dependence of the local structure of PbSe has been investigated using pair distribution function (PDF) analysis of x-ray and neutron powder diffraction data and density functional theory (DFT) calculations. Observation of non-Gaussian PDF peaks at high temperature indicates the presence of significant anharmonicity, which can be modeled as Pb off-centering along [100] directions that grows on warming similar to the behavior seen in PbTe and PbS and sometimes called emphanisis. Interestingly, the emphanitic response is smaller in PbSe than in both PbS and PbTe indicating a nonmonotonic response with chalcogen atomic number in the PbQ (Q = S, Se, Te) series. The DFT calculations indicate a correlation between band gap and the amplitude of [100] dipolar distortion, suggesting that emphanisis may be behind the anomalous composition and temperature dependencies of the band gaps in this series.

Authors:
 [1];  [1];  [1];  [2];  [2];  [3];  [4];  [5]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. ETH Zurich, Zurich (Switzerland)
  3. Northwestern Univ., Evanston, IL (United States)
  4. Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
  5. Brookhaven National Lab. (BNL), Upton, NY (United States); Columbia Univ., New York, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1477960
Alternate Identifier(s):
OSTI ID: 1477553; OSTI ID: 1484730
Report Number(s):
BNL-209192-2018-JAAM
Journal ID: ISSN 2469-9950; PRBMDO
Grant/Contract Number:  
SC0012704; AC02-06CH11357
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 98; Journal Issue: 14; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Yu, Runze, Bozin, Emil S., Abeykoon, Milinda, Sangiorgio, Boris, Spaldin, Nicola A., Malliakas, Christos D., Kanatzidis, Mercouri G., and Billinge, Simon J. L. Emphanitic anharmonicity in PbSe at high temperature and anomalous electronic properties in the PbQ(Q=S,Se,Te) system. United States: N. p., 2018. Web. doi:10.1103/PhysRevB.98.144108.
Yu, Runze, Bozin, Emil S., Abeykoon, Milinda, Sangiorgio, Boris, Spaldin, Nicola A., Malliakas, Christos D., Kanatzidis, Mercouri G., & Billinge, Simon J. L. Emphanitic anharmonicity in PbSe at high temperature and anomalous electronic properties in the PbQ(Q=S,Se,Te) system. United States. doi:10.1103/PhysRevB.98.144108.
Yu, Runze, Bozin, Emil S., Abeykoon, Milinda, Sangiorgio, Boris, Spaldin, Nicola A., Malliakas, Christos D., Kanatzidis, Mercouri G., and Billinge, Simon J. L. Fri . "Emphanitic anharmonicity in PbSe at high temperature and anomalous electronic properties in the PbQ(Q=S,Se,Te) system". United States. doi:10.1103/PhysRevB.98.144108. https://www.osti.gov/servlets/purl/1477960.
@article{osti_1477960,
title = {Emphanitic anharmonicity in PbSe at high temperature and anomalous electronic properties in the PbQ(Q=S,Se,Te) system},
author = {Yu, Runze and Bozin, Emil S. and Abeykoon, Milinda and Sangiorgio, Boris and Spaldin, Nicola A. and Malliakas, Christos D. and Kanatzidis, Mercouri G. and Billinge, Simon J. L.},
abstractNote = {Here, the temperature dependence of the local structure of PbSe has been investigated using pair distribution function (PDF) analysis of x-ray and neutron powder diffraction data and density functional theory (DFT) calculations. Observation of non-Gaussian PDF peaks at high temperature indicates the presence of significant anharmonicity, which can be modeled as Pb off-centering along [100] directions that grows on warming similar to the behavior seen in PbTe and PbS and sometimes called emphanisis. Interestingly, the emphanitic response is smaller in PbSe than in both PbS and PbTe indicating a nonmonotonic response with chalcogen atomic number in the PbQ (Q = S, Se, Te) series. The DFT calculations indicate a correlation between band gap and the amplitude of [100] dipolar distortion, suggesting that emphanisis may be behind the anomalous composition and temperature dependencies of the band gaps in this series.},
doi = {10.1103/PhysRevB.98.144108},
journal = {Physical Review B},
issn = {2469-9950},
number = 14,
volume = 98,
place = {United States},
year = {2018},
month = {10}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 1 work
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Figures / Tables:

FIG. 1 FIG. 1: Temperature evolution of PbSe PDF patterns over 10 K – 450 K range in 50 K increments obtained by (a) x-ray (xPDF) and (b) neutron (nPDF) total scattering. Inset to (a) shows Fm$\bar{3}$m structure of PbSe with interatomic distances color coded. (c) Waterfall representation of x-ray $G$($r$). Datamore » are offset for clarity. Vertical solid black lines mark the PDF peak positions at base temperature. Sloping dashed red lines track the apparent PDF peak centroids with temperature.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.