First-principles study of electronic transport and structural properties of in its high-temperature phase
Abstract
We present an ab initio study of the structural and electronic transport properties of tetrahedrite, Cu12Sb4S13, in its high-temperature phase. We show how this complex compound can be seen as the outcome of an ordered arrangement of S-vacancies in a semiconducting fematinite-like structure (Cu3SbS4). Our calculations confirm that the S-vacancies are the natural doping mechanism in this thermoelectric compound and reveal a similar local chemical environment around crystallographically inequivalent Cu atoms, shedding light on the debate on x-ray photoelectron spectroscopy measurements in this compound. To access the electrical transport properties as a function of temperature we use the Kubo-Greenwood formula applied to snapshots of first-principles molecular dynamics simulations. This approach is essential to effectively account for the interaction between electrons and lattice vibrations in such a complex crystal structure where a strong anharmonicity plays a key role in stabilizing the high-temperature phase. Our results show that the Seebeck coefficient is in good agreement with experiments and the phonon-limited electrical resistivity displays a temperature trend that compares well with a wide range of experimental data. The predicted lower bound for the resistivity turns out to be remarkably low for a pristine mineral in the Cu-Sb-S system but not too far frommore »
- Authors:
- Publication Date:
- Research Org.:
- King's College, London (United Kingdom)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1638120
- Alternate Identifier(s):
- OSTI ID: 1638145
- Grant/Contract Number:
- AC36-08GO28308
- Resource Type:
- Published Article
- Journal Name:
- Physical Review Research
- Additional Journal Information:
- Journal Name: Physical Review Research Journal Volume: 2 Journal Issue: 3; Journal ID: ISSN 2643-1564
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; Chemical bonding; Electrical conductivity; First-principles calculations; Thermal conductivity; Thermoelectric effects
Citation Formats
Di Paola, Cono, Macheda, Francesco, Laricchia, Savio, Weber, Cedric, and Bonini, Nicola. First-principles study of electronic transport and structural properties of Cu 12 Sb 4 S 13 in its high-temperature phase. United States: N. p., 2020.
Web. doi:10.1103/PhysRevResearch.2.033055.
Di Paola, Cono, Macheda, Francesco, Laricchia, Savio, Weber, Cedric, & Bonini, Nicola. First-principles study of electronic transport and structural properties of Cu 12 Sb 4 S 13 in its high-temperature phase. United States. https://doi.org/10.1103/PhysRevResearch.2.033055
Di Paola, Cono, Macheda, Francesco, Laricchia, Savio, Weber, Cedric, and Bonini, Nicola. Fri .
"First-principles study of electronic transport and structural properties of Cu 12 Sb 4 S 13 in its high-temperature phase". United States. https://doi.org/10.1103/PhysRevResearch.2.033055.
@article{osti_1638120,
title = {First-principles study of electronic transport and structural properties of Cu 12 Sb 4 S 13 in its high-temperature phase},
author = {Di Paola, Cono and Macheda, Francesco and Laricchia, Savio and Weber, Cedric and Bonini, Nicola},
abstractNote = {We present an ab initio study of the structural and electronic transport properties of tetrahedrite, Cu12Sb4S13, in its high-temperature phase. We show how this complex compound can be seen as the outcome of an ordered arrangement of S-vacancies in a semiconducting fematinite-like structure (Cu3SbS4). Our calculations confirm that the S-vacancies are the natural doping mechanism in this thermoelectric compound and reveal a similar local chemical environment around crystallographically inequivalent Cu atoms, shedding light on the debate on x-ray photoelectron spectroscopy measurements in this compound. To access the electrical transport properties as a function of temperature we use the Kubo-Greenwood formula applied to snapshots of first-principles molecular dynamics simulations. This approach is essential to effectively account for the interaction between electrons and lattice vibrations in such a complex crystal structure where a strong anharmonicity plays a key role in stabilizing the high-temperature phase. Our results show that the Seebeck coefficient is in good agreement with experiments and the phonon-limited electrical resistivity displays a temperature trend that compares well with a wide range of experimental data. The predicted lower bound for the resistivity turns out to be remarkably low for a pristine mineral in the Cu-Sb-S system but not too far from the lowest experimental data reported in literature. The Lorenz number turns out to be substantially lower than what is expected from the free-electron value in the Wiedemann-Franz law, thus providing an accurate way to estimate the electronic and lattice contributions to the thermal conductivity in experiments, of great significance in this very low thermal conductivity crystalline material.},
doi = {10.1103/PhysRevResearch.2.033055},
journal = {Physical Review Research},
number = 3,
volume = 2,
place = {United States},
year = {Fri Jul 10 00:00:00 EDT 2020},
month = {Fri Jul 10 00:00:00 EDT 2020}
}
https://doi.org/10.1103/PhysRevResearch.2.033055
Works referenced in this record:
Near-Infrared Absorbing Cu 12 Sb 4 S 13 and Cu 3 SbS 4 Nanocrystals: Synthesis, Characterization, and Photoelectrochemistry
journal, July 2013
- van Embden, Joel; Latham, Kay; Duffy, Noel W.
- Journal of the American Chemical Society, Vol. 135, Issue 31
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
Structural phase transition and phonon instability in
journal, February 2016
- May, A. F.; Delaire, O.; Niedziela, J. L.
- Physical Review B, Vol. 93, Issue 6
Magnetotransport phenomena in -doped diamond from first principles
journal, November 2018
- Macheda, Francesco; Bonini, Nicola
- Physical Review B, Vol. 98, Issue 20
Thermoelectric coefficients of -doped silicon from first principles via the solution of the Boltzmann transport equation
journal, August 2016
- Fiorentini, Mattia; Bonini, Nicola
- Physical Review B, Vol. 94, Issue 8
Thermoelectric properties of the tetrahedrite–tennantite solid solutions Cu 12 Sb 4−x As x S 13 and Cu 10 Co 2 Sb 4−y As y S 13 (0 ≤ x , y ≤ 4)
journal, January 2019
- Levinsky, Petr; Candolfi, Christophe; Dauscher, Anne
- Physical Chemistry Chemical Physics, Vol. 21, Issue 8
High-performance thermoelectric mineral Cu 12− x Ni x Sb 4 S 13 tetrahedrite
journal, January 2013
- Suekuni, Koichiro; Tsuruta, Kojiro; Kunii, Masaru
- Journal of Applied Physics, Vol. 113, Issue 4
Theory-Guided Synthesis of an Eco-Friendly and Low-Cost Copper Based Sulfide Thermoelectric Material
journal, November 2016
- Chen, Kan; Du, Baoli; Bonini, Nicola
- The Journal of Physical Chemistry C, Vol. 120, Issue 48
Enhanced Thermoelectric Performance of Synthetic Tetrahedrites
journal, March 2014
- Heo, Jaeseok; Laurita, Geneva; Muir, Sean
- Chemistry of Materials, Vol. 26, Issue 6
Calculations of the transport properties within the PAW formalism
journal, January 2010
- Mazevet, S.; Torrent, M.; Recoules, V.
- High Energy Density Physics, Vol. 6, Issue 1
Potential-energy surfaces for excited states in extended systems
journal, March 2004
- Hellman, A.; Razaznejad, B.; Lundqvist, B. I.
- The Journal of Chemical Physics, Vol. 120, Issue 10
Jahn–Teller Driven Electronic Instability in Thermoelectric Tetrahedrite
journal, February 2020
- Long, Sebastian O.; Powell, Anthony V.; Hull, Stephen
- Advanced Functional Materials, Vol. 30, Issue 12
A note on the bonding, optical spectrum and composition of tetrahedrite
journal, June 1984
- Jeanloz, Raymond; Johnson, Mary L.
- Physics and Chemistry of Minerals, Vol. 11, Issue 1
Electrical conductivity for warm, dense aluminum plasmas and liquids
journal, August 2002
- Desjarlais, M. P.; Kress, J. D.; Collins, L. A.
- Physical Review E, Vol. 66, Issue 2
Thermoelectric properties of Co substituted synthetic tetrahedrite
journal, November 2015
- Chetty, R.; Bali, A.; Naik, M. H.
- Acta Materialia, Vol. 100
Lattice electrical resistivity of magnetic bcc iron from first-principles calculations
journal, January 2012
- Alfè, Dario; Pozzo, Monica; Desjarlais, Michael P.
- Physical Review B, Vol. 85, Issue 2
Electronic and thermoelectric properties of Zn and Se double substituted tetrahedrite
journal, January 2018
- Tippireddy, Sahil; Chetty, Raju; Raut, Krushna Kumari
- Physical Chemistry Chemical Physics, Vol. 20, Issue 45
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
Metric-tensor flexible-cell algorithm for isothermal–isobaric molecular dynamics simulations
journal, January 2001
- Hernández, E.
- The Journal of Chemical Physics, Vol. 115, Issue 22
Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 49, Issue 20, p. 14251-14269
Kubo–Greenwood electrical conductivity formulation and implementation for projector augmented wave datasets
journal, December 2017
- Calderín, L.; Karasiev, V. V.; Trickey, S. B.
- Computer Physics Communications, Vol. 221
Metal–Semiconductor Transition Concomitant with a Structural Transformation in Tetrahedrite Cu 12 Sb 4 S 13
journal, January 2016
- Tanaka, Hiromi I.; Suekuni, Koichiro; Umeo, Kazunori
- Journal of the Physical Society of Japan, Vol. 85, Issue 1
Inhomogeneous Electron Gas
journal, November 1964
- Hohenberg, P.; Kohn, W.
- Physical Review, Vol. 136, Issue 3B, p. B864-B871
High Performance Thermoelectricity in Earth-Abundant Compounds Based on Natural Mineral Tetrahedrites
journal, October 2012
- Lu, Xu; Morelli, Donald T.; Xia, Yi
- Advanced Energy Materials, Vol. 3, Issue 3, p. 342-348
Enhanced thermoelectric performance of Sn-doped Cu 3 SbS 4
journal, January 2018
- Chen, Kan; Di Paola, Cono; Du, Baoli
- Journal of Materials Chemistry C, Vol. 6, Issue 31
The Lorenz function: Its properties at optimum thermoelectric figure-of-merit
journal, November 2011
- Flage-Larsen, E.; Prytz, Ø.
- Applied Physics Letters, Vol. 99, Issue 20
The density functional formalism, its applications and prospects
journal, July 1989
- Jones, R. O.; Gunnarsson, O.
- Reviews of Modern Physics, Vol. 61, Issue 3
Ab initiomolecular dynamics for liquid metals
journal, January 1993
- Kresse, G.; Hafner, J.
- Physical Review B, Vol. 47, Issue 1, p. 558-561
Questaal: A package of electronic structure methods based on the linear muffin-tin orbital technique
journal, April 2020
- Pashov, Dimitar; Acharya, Swagata; Lambrecht, Walter R. L.
- Computer Physics Communications, Vol. 249
Tetrahedrite (Cu 12 Sb 4 S 13 ) Ternary Inorganic Hole Conductor for Ambient Processed Stable Perovskite Solar Cells
journal, July 2018
- Tamilselvan, Muthusamy; Bhattacharyya, Aninda J.
- ACS Applied Energy Materials, Vol. 1, Issue 8
BoltzWann: A code for the evaluation of thermoelectric and electronic transport properties with a maximally-localized Wannier functions basis
journal, January 2014
- Pizzi, Giovanni; Volja, Dmitri; Kozinsky, Boris
- Computer Physics Communications, Vol. 185, Issue 1
Electronic structure and magnetic properties of random alloys: Fully relativistic spin-polarized linear muffin-tin-orbital method
journal, July 1996
- Shick, A. B.; Drchal, V.; Kudrnovský, J.
- Physical Review B, Vol. 54, Issue 3
Adequacy of approximations in theory
journal, December 2006
- van Schilfgaarde, Mark; Kotani, Takao; Faleev, Sergey V.
- Physical Review B, Vol. 74, Issue 24
Low-Temperature Structural Phase Transitions in Thermoelectric Tetrahedrite, Cu 12 Sb 4 S 13 , and Tennantite, Cu 12 As 4 S 13
journal, May 2019
- Hathwar, Venkatesha R.; Nakamura, Atsushi; Kasai, Hidetaka
- Crystal Growth & Design, Vol. 19, Issue 7
From Bonding Asymmetry to Anharmonic Rattling in Cu 12 Sb 4 S 13 Tetrahedrites: When Lone-Pair Electrons Are Not So Lonely
journal, May 2015
- Lai, Wei; Wang, Yuxing; Morelli, Donald T.
- Advanced Functional Materials, Vol. 25, Issue 24
Statistical-Mechanical Theory of Irreversible Processes. I. General Theory and Simple Applications to Magnetic and Conduction Problems
journal, June 1957
- Kubo, Ryogo
- Journal of the Physical Society of Japan, Vol. 12, Issue 6
Low-Temperature Structure and Thermoelectric Properties of Pristine Synthetic Tetrahedrite Cu 12 Sb 4 S 13
journal, September 2016
- Nasonova, Daria I.; Verchenko, Valeriy Yu.; Tsirlin, Alexander A.
- Chemistry of Materials, Vol. 28, Issue 18
Cu12Sb4S13: A Temperature-Dependent Structure Investigation
journal, June 1997
- Pfitzner, A.; Evain, M.; Petricek, V.
- Acta Crystallographica Section B Structural Science, Vol. 53, Issue 3
The Boltzmann Equation in the Theory of Electrical Conduction in Metals
journal, April 1958
- Greenwood, D. A.
- Proceedings of the Physical Society, Vol. 71, Issue 4
Preparation and enhanced thermoelectric performance of Pb-doped tetrahedrite Cu12-xPbxSb4S13
journal, November 2018
- Huang, L. L.; Wang, Y. S.; Zhu, C.
- Journal of Alloys and Compounds, Vol. 769
Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965
- Kohn, W.; Sham, L. J.
- Physical Review, Vol. 140, Issue 4A, p. A1133-A1138