Emphanitic anharmonicity in PbSe at high temperature and anomalous electronic properties in the system
Abstract
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 Pb Q (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:
-
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- ETH Zurich, Zurich (Switzerland)
- Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- 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)
- 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:
- 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. https://doi.org/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. https://doi.org/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 = {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 Pb Q (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},
number = 14,
volume = 98,
place = {United States},
year = {Fri Oct 12 00:00:00 EDT 2018},
month = {Fri Oct 12 00:00:00 EDT 2018}
}
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Figures / Tables:
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 »
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Works referenced in this record:
Temperature dependent band gap in PbX (X = S, Se, Te)
journal, December 2013
- Gibbs, Zachary M.; Kim, Hyoungchul; Wang, Heng
- Applied Physics Letters, Vol. 103, Issue 26
Mean Square Vibrational Amplitudes in PbTe
journal, August 1973
- Ghezzi, C.
- Physica Status Solidi (b), Vol. 58, Issue 2
Zur Theorie der spezifischen Wärmen
journal, January 1912
- Debye, P.
- Annalen der Physik, Vol. 344, Issue 14
Giant anharmonic phonon scattering in PbTe
journal, June 2011
- Delaire, O.; Ma, J.; Marty, K.
- Nature Materials, Vol. 10, Issue 8, p. 614-619
PDFgetN : a user-friendly program to extract the total scattering structure factor and the pair distribution function from neutron powder diffraction data
journal, August 2000
- Peterson, P. F.; Gutmann, M.; Proffen, Th.
- Journal of Applied Crystallography, Vol. 33, Issue 4
Beyond crystallography: the study of disorder, nanocrystallinity and crystallographically challenged materials with pair distribution functions
journal, January 2004
- Billinge, Simon J. L.; Kanatzidis, M. G.
- Chemical Communications, Issue 7
Correlated local dipoles in PbTe
journal, August 2018
- Sangiorgio, Boris; Bozin, Emil S.; Malliakas, Christos D.
- Physical Review Materials, Vol. 2, Issue 8
Anomalous Lattice Dynamics near the Ferroelectric Instability in PbTe
journal, October 2011
- Zhang, Yi; Ke, Xuezhi; Kent, Paul R. C.
- Physical Review Letters, Vol. 107, Issue 17
Lead Is Not Off Center in PbTe: The Importance of -Space Phase Information in Extended X-Ray Absorption Fine Structure Spectroscopy
journal, August 2013
- Keiber, T.; Bridges, F.; Sales, B. C.
- Physical Review Letters, Vol. 111, Issue 9
Local off-centering symmetry breaking in the high-temperature regime of SnTe
journal, January 2014
- Knox, K. R.; Bozin, E. S.; Malliakas, C. D.
- Physical Review B, Vol. 89, Issue 1
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
Energy-Gap Anomaly in the Semiconductor Sequence PbS, PbSe, and PbTe
journal, May 1971
- Dalven, Richard
- Physical Review B, Vol. 3, Issue 10
On the Temperature Dependence of the Band-Gap in Semiconductors
journal, May 1974
- Baumann, K.
- physica status solidi (b), Vol. 63, Issue 1
Lead telluride as a thermoelectric material for thermoelectric power generation
journal, September 2002
- Dughaish, Z. H.
- Physica B: Condensed Matter, Vol. 322, Issue 1-2, p. 205-223
Isotope effects on the optical spectra of semiconductors
journal, November 2005
- Cardona, Manuel; Thewalt, M. L. W.
- Reviews of Modern Physics, Vol. 77, Issue 4
Characterisation of amorphous and nanocrystalline molecular materials by total scattering
journal, January 2010
- Billinge, Simon J. L.; Dykhne, Timur; Juhás, Pavol
- CrystEngComm, Vol. 12, Issue 5
Monoxyde quadratique PbOα(I): Description de la transition structurale ferroe´lastique
journal, May 1985
- Boher, P.; Garnier, P.; Gavarri, J. R.
- Journal of Solid State Chemistry, Vol. 57, Issue 3
Temperature dependence of energy gaps in some II–VI compounds
journal, December 1973
- Tsay, Y. F.; Mitra, S. S.; Vetelino, J. F.
- Journal of Physics and Chemistry of Solids, Vol. 34, Issue 12
Measuring Correlated Atomic Motion Using X-ray Diffraction
journal, February 1999
- Jeong, Il-Kyoung; Proffen, Thomas; Mohiuddin-Jacobs, Farida
- The Journal of Physical Chemistry A, Vol. 103, Issue 7
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Dynamic Stereochemical Activity of the Sn 2+ Lone Pair in Perovskite CsSnBr 3
journal, September 2016
- Fabini, Douglas H.; Laurita, Geneva; Bechtel, Jonathon S.
- Journal of the American Chemical Society, Vol. 138, Issue 36
Nanoscale structural order from the atomic pair distribution function (PDF): There's plenty of room in the middle
journal, July 2008
- Billinge, Simon J.L.
- Journal of Solid State Chemistry, Vol. 181, Issue 7, p. 1695-1700
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
Complex modeling: a strategy and software program for combining multiple information sources to solve ill posed structure and nanostructure inverse problems
journal, September 2015
- Juhás, Pavol; Farrow, Christopher L.; Yang, Xiaohao
- Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 6, p. 562-568
Entropically Stabilized Local Dipole Formation in Lead Chalcogenides
journal, December 2010
- Bozin, E. S.; Malliakas, C. D.; Souvatzis, P.
- Science, Vol. 330, Issue 6011
PDFfit2 and PDFgui: computer programs for studying nanostructure in crystals
journal, July 2007
- Farrow, C. L.; Juhas, P.; Liu, J. W.
- Journal of Physics: Condensed Matter, Vol. 19, Issue 33
Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008
- Perdew, John P.; Ruzsinszky, Adrienn; Csonka, Gábor I.
- Physical Review Letters, Vol. 100, Issue 13
First-principles indicators of metallicity and cation off-centricity in the IV-VI rocksalt chalcogenides of divalent Ge, Sn, and Pb
journal, March 2003
- Waghmare, U. V.; Spaldin, N. A.; Kandpal, H. C.
- Physical Review B, Vol. 67, Issue 12
Origin of the temperature dependence of the band gap of PbS and PbSe quantum dots
journal, July 2013
- Dey, P.; Paul, J.; Bylsma, J.
- Solid State Communications, Vol. 165
Data Requirements for the Reliable Use of Atomic Pair Distribution Functions in Amorphous Pharmaceutical Fingerprinting
journal, January 2011
- Dykhne, Timur; Taylor, Ryan; Florence, Alastair
- Pharmaceutical Research, Vol. 28, Issue 5
Electrical and thermal transport properties of Pb-based chalcogenides: PbTe, PbSe, and PbS
journal, February 2012
- Pei, Yan-Ling; Liu, Yong
- Journal of Alloys and Compounds, Vol. 514
X-ray determination of the mean Debye-Waller factors, amplitudes of vibrations and the Debye temperatures of CdO, PbS and MnS
journal, April 1978
- Subhadra, K. G.; Sirdeshmukh, D. B.
- Pramana, Vol. 10, Issue 4
EXAFS studies of the local environment of lead and selenium atoms in PbTe1−x Sex solid solutions
journal, August 1999
- Lebedev, A. I.; Sluchinskaya, I. A.; Demin, V. N.
- Physics of the Solid State, Vol. 41, Issue 8
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
Lattice dynamics reveals a local symmetry breaking in the emergent dipole phase of PbTe
journal, August 2012
- Jensen, Kirsten M. Ø.; Božin, Emil S.; Malliakas, Christos D.
- Physical Review B, Vol. 86, Issue 8
Self-interaction correction to density-functional approximations for many-electron systems
journal, May 1981
- Perdew, J. P.; Zunger, Alex
- Physical Review B, Vol. 23, Issue 10, p. 5048-5079
The crystallography of correlated disorder
journal, May 2015
- Keen, David A.; Goodwin, Andrew L.
- Nature, Vol. 521, Issue 7552
High-temperature thermoelectric properties of -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
On the temperature dependence of the energy gap in PbSe and PbTe
journal, April 1990
- Baleva, M.; Georgiev, T.; Lashkarev, G.
- Journal of Physics: Condensed Matter, Vol. 2, Issue 13
Cubic phase of single-crystal LaAlO 3 perovskite synthesized at 4.5 GPa and 1273 K
journal, July 2005
- Nakatsuka, Akihiko; Ohtaka, Osamu; Arima, Hiroshi
- Acta Crystallographica Section E Structure Reports Online, Vol. 61, Issue 8
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
Relationship between the atomic pair distribution function and small-angle scattering: implications for modeling of nanoparticles
journal, April 2009
- Farrow, Christopher L.; Billinge, Simon J. L.
- Acta Crystallographica Section A Foundations of Crystallography, Vol. 65, Issue 3, p. 232-239
Microscopic mechanism of low thermal conductivity in lead telluride
journal, April 2012
- Shiga, Takuma; Shiomi, Junichiro; Ma, Jie
- Physical Review B, Vol. 85, Issue 15
Band gap anomaly and topological properties in lead chalcogenides
journal, March 2016
- Nie, Simin; Xu, Xiao Yan; Xu, Gang
- Chinese Physics B, Vol. 25, Issue 3
First-principles study of stability and vibrational properties of tetragonal
journal, August 1996
- García, Alberto; Vanderbilt, David
- Physical Review B, Vol. 54, Issue 6
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
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