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

Title: A computational assessment of the electronic, thermoelectric, and defect properties of bournonite (CuPbSbS 3) and related substitutions

Abstract

Bournonite (CuPbSbS 3) is an earth-abundant mineral with potential thermoelectric applications. This material has a complex crystal structure (space group Pmn2 1 #31) and has previously been measured to exhibit a very low thermal conductivity (κ < 1 W m -1 K -1 at T ≥ 300 K). In this study, we employ high-throughput density functional theory calculations to investigate how the properties of the bournonite crystal structure change with elemental substitutions. Specifically, we compute the stability and electronic properties of 320 structures generated via substitutions {Na-K-Cu-Ag}{Si-Ge-Sn-Pb}{N-P-As-Sb-Bi}{O-S-Se-Te} in the ABCD 3 formula. We perform two types of transport calculations: the BoltzTraP model, which has been extensively tested, and a newer AMSET model that we have developed and which incorporates scattering effects. We discuss the differences in the model results, finding qualitative agreement except in the case of degenerate bands. Based on our calculations, we identify p-type CuPbSbSe 3 , CuSnSbSe 3 and CuPbAsSe 3 as potentially promising materials for further investigation. We additionally calculate the defect properties, finding that n-type behavior in bournonite and the selected materials is highly unlikely, and p-type behavior might be enhanced by employing Sb-poor synthesis conditions to prevent the formation of Sb Pb defects. Finally,more » we discuss the origins of various trends with chemical substitution, including the possible role of stereochemically active lone pair effects in stabilizing the bournonite structure and the effect of cation and anion selection on the calculated band gap.« less

Authors:
ORCiD logo [1];  [2];  [3];  [3];  [2]; ORCiD logo [2];  [3];  [2];  [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. catholique de Louvain, Louvain-la-Neuve (Belgium)
  3. Northwestern Univ., Evanston, IL (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1393108
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 9; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Faghaninia, Alireza, Yu, Guodong, Aydemir, Umut, Wood, Max, Chen, Wei, Rignanese, Gian-Marco, Snyder, G. Jeffrey, Hautier, Geoffroy, and Jain, Anubhav. A computational assessment of the electronic, thermoelectric, and defect properties of bournonite (CuPbSbS 3) and related substitutions. United States: N. p., 2017. Web. doi:10.1039/c7cp00437k.
Faghaninia, Alireza, Yu, Guodong, Aydemir, Umut, Wood, Max, Chen, Wei, Rignanese, Gian-Marco, Snyder, G. Jeffrey, Hautier, Geoffroy, & Jain, Anubhav. A computational assessment of the electronic, thermoelectric, and defect properties of bournonite (CuPbSbS 3) and related substitutions. United States. doi:10.1039/c7cp00437k.
Faghaninia, Alireza, Yu, Guodong, Aydemir, Umut, Wood, Max, Chen, Wei, Rignanese, Gian-Marco, Snyder, G. Jeffrey, Hautier, Geoffroy, and Jain, Anubhav. Wed . "A computational assessment of the electronic, thermoelectric, and defect properties of bournonite (CuPbSbS 3) and related substitutions". United States. doi:10.1039/c7cp00437k. https://www.osti.gov/servlets/purl/1393108.
@article{osti_1393108,
title = {A computational assessment of the electronic, thermoelectric, and defect properties of bournonite (CuPbSbS 3) and related substitutions},
author = {Faghaninia, Alireza and Yu, Guodong and Aydemir, Umut and Wood, Max and Chen, Wei and Rignanese, Gian-Marco and Snyder, G. Jeffrey and Hautier, Geoffroy and Jain, Anubhav},
abstractNote = {Bournonite (CuPbSbS3) is an earth-abundant mineral with potential thermoelectric applications. This material has a complex crystal structure (space group Pmn21 #31) and has previously been measured to exhibit a very low thermal conductivity (κ < 1 W m -1 K -1 at T ≥ 300 K). In this study, we employ high-throughput density functional theory calculations to investigate how the properties of the bournonite crystal structure change with elemental substitutions. Specifically, we compute the stability and electronic properties of 320 structures generated via substitutions {Na-K-Cu-Ag}{Si-Ge-Sn-Pb}{N-P-As-Sb-Bi}{O-S-Se-Te} in the ABCD3 formula. We perform two types of transport calculations: the BoltzTraP model, which has been extensively tested, and a newer AMSET model that we have developed and which incorporates scattering effects. We discuss the differences in the model results, finding qualitative agreement except in the case of degenerate bands. Based on our calculations, we identify p-type CuPbSbSe3 , CuSnSbSe3 and CuPbAsSe3 as potentially promising materials for further investigation. We additionally calculate the defect properties, finding that n-type behavior in bournonite and the selected materials is highly unlikely, and p-type behavior might be enhanced by employing Sb-poor synthesis conditions to prevent the formation of Sb Pb defects. Finally, we discuss the origins of various trends with chemical substitution, including the possible role of stereochemically active lone pair effects in stabilizing the bournonite structure and the effect of cation and anion selection on the calculated band gap.},
doi = {10.1039/c7cp00437k},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 9,
volume = 19,
place = {United States},
year = {2017},
month = {2}
}

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

Citation Metrics:
Cited by: 9 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

Ca 3 AlSb 3 : an inexpensive, non-toxic thermoelectric material for waste heat recovery
journal, January 2011

  • Zevalkink, Alex; Toberer, Eric S.; Zeier, Wolfgang G.
  • Energy Environ. Sci., Vol. 4, Issue 2
  • DOI: 10.1039/C0EE00517G

YCuTe 2 : a member of a new class of thermoelectric materials with CuTe 4 -based layered structure
journal, January 2016

  • Aydemir, Umut; Pöhls, Jan-Hendrik; Zhu, Hong
  • Journal of Materials Chemistry A, Vol. 4, Issue 7
  • DOI: 10.1039/C5TA10330D

Projector augmented-wave method
journal, December 1994


Enhanced thermoelectric properties of the Zintl phase BaGa 2 Sb 2 via doping with Na or K
journal, January 2016

  • Aydemir, Umut; Zevalkink, Alex; Ormeci, Alim
  • Journal of Materials Chemistry A, Vol. 4, Issue 5
  • DOI: 10.1039/C5TA07612A

New opportunities for materials informatics: Resources and data mining techniques for uncovering hidden relationships
journal, April 2016

  • Jain, Anubhav; Hautier, Geoffroy; Ong, Shyue Ping
  • Journal of Materials Research, Vol. 31, Issue 8
  • DOI: 10.1557/jmr.2016.80

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

Natural mineral tetrahedrite as a direct source of thermoelectric materials
journal, January 2013

  • Lu, Xu; Morelli, Donald T.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 16
  • DOI: 10.1039/c3cp50920f

Practical doping principles
journal, July 2003


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

Multiple-Filled Skutterudites: High Thermoelectric Figure of Merit through Separately Optimizing Electrical and Thermal Transports
journal, May 2011

  • Shi, Xun; Yang, Jiong; Salvador, James R.
  • Journal of the American Chemical Society, Vol. 133, Issue 20
  • DOI: 10.1021/ja111199y

FireWorks: a dynamic workflow system designed for high-throughput applications: FireWorks: A Dynamic Workflow System Designed for High-Throughput Applications
journal, May 2015

  • Jain, Anubhav; Ong, Shyue Ping; Chen, Wei
  • Concurrency and Computation: Practice and Experience, Vol. 27, Issue 17
  • DOI: 10.1002/cpe.3505

Synthesis and Characterization of Bournonite PbCuSbS 3 Nanocrystals
journal, June 2015

  • Wei, Kaya; Martin, Joshua; Salvador, James R.
  • Crystal Growth & Design, Vol. 15, Issue 8
  • DOI: 10.1021/acs.cgd.5b00418

Bournonite PbCuSbS 3 : Stereochemically Active Lone-Pair Electrons that Induce Low Thermal Conductivity
journal, August 2015

  • Dong, Yongkwan; Khabibullin, Artem R.; Wei, Kaya
  • ChemPhysChem, Vol. 16, Issue 15
  • DOI: 10.1002/cphc.201500476

Designing high-performance layered thermoelectric materials through orbital engineering
journal, March 2016

  • Zhang, Jiawei; Song, Lirong; Madsen, Georg K. H.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms10892

First-principles search for n -type oxide, nitride, and sulfide thermoelectrics
journal, July 2016


Fully Ab Initio Finite-Size Corrections for Charged-Defect Supercell Calculations
journal, January 2009


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Automated Search for New Thermoelectric Materials: The Case of LiZnSb
journal, September 2006

  • Madsen, Georg K. H.
  • Journal of the American Chemical Society, Vol. 128, Issue 37
  • DOI: 10.1021/ja062526a

High thermoelectric figure of merit in the Cu 3 SbSe 4 -Cu 3 SbS 4 solid solution
journal, June 2011

  • Skoug, Eric J.; Cain, Jeffrey D.; Morelli, Donald T.
  • Applied Physics Letters, Vol. 98, Issue 26
  • DOI: 10.1063/1.3605246

Contribution to the crystal structures of tennantite and bournonite
journal, April 2010

  • Kharbish, Sherif; Giester, Gerald; Beran, Anton
  • Neues Jahrbuch für Mineralogie - Abhandlungen, Vol. 187, Issue 2
  • DOI: 10.1127/0077-7757/2010/0168

Thermoelectric Materials, Phenomena, and Applications: A Bird's Eye View
journal, March 2006

  • Tritt, Terry M.; Subramanian, M. A.
  • MRS Bulletin, Vol. 31, Issue 3
  • DOI: 10.1557/mrs2006.44

BoltzTraP. A code for calculating band-structure dependent quantities
journal, July 2006


Data mining our way to the next generation of thermoelectrics
journal, January 2016


Ab initio electronic transport model with explicit solution to the linearized Boltzmann transport equation
journal, June 2015


Density-Functional Theory of the Energy Gap
journal, November 1983


Semiconductors Used in Photovoltaic and Photocatalytic Devices: Assessing Fundamental Properties from DFT
journal, March 2014

  • Le Bahers, Tangui; Rérat, Michel; Sautet, Philippe
  • The Journal of Physical Chemistry C, Vol. 118, Issue 12
  • DOI: 10.1021/jp409724c

P-Type Transparent Cu-Alloyed ZnS Deposited at Room Temperature
journal, March 2016

  • Woods-Robinson, Rachel; Cooper, Jason K.; Xu, Xiaojie
  • Advanced Electronic Materials, Vol. 2, Issue 6
  • DOI: 10.1002/aelm.201500396

High-performance thermoelectric minerals: Colusites Cu 26 V 2 M 6 S 32 (M = Ge, Sn)
journal, September 2014

  • Suekuni, Koichiro; Kim, Fiseong S.; Nishiate, Hirotaka
  • Applied Physics Letters, Vol. 105, Issue 13
  • DOI: 10.1063/1.4896998

Sulfide bornite thermoelectric material: a natural mineral with ultralow thermal conductivity
journal, January 2014

  • Qiu, Pengfei; Zhang, Tiansong; Qiu, Yuting
  • Energy Environ. Sci., Vol. 7, Issue 12
  • DOI: 10.1039/C4EE02428A

Physical Content of the Exact Kohn-Sham Orbital Energies: Band Gaps and Derivative Discontinuities
journal, November 1983


On the Polar Vibrations of Alkali Halides
journal, April 1941


Accuracy of density functional theory in predicting formation energies of ternary oxides from binary oxides and its implication on phase stability
journal, April 2012


New promising bulk thermoelectrics: intermetallics, pnictides and chalcogenides
journal, February 2014


LDA + U and hybrid functional calculations for defects in ZnO, SnO2, and TiO2
journal, December 2010

  • Janotti, Anderson; Van de Walle, Chris G.
  • physica status solidi (b), Vol. 248, Issue 4
  • DOI: 10.1002/pssb.201046384

Electric properties of AgPbAsSe 3 at pressures up to 45 GPa
journal, May 2009


Computational Exploration of the Binary A 1 B 1 Chemical Space for Thermoelectric Performance
journal, September 2015


Thinking Like a Chemist: Intuition in Thermoelectric Materials
journal, April 2016

  • Zeier, Wolfgang G.; Zevalkink, Alex; Gibbs, Zachary M.
  • Angewandte Chemie International Edition, Vol. 55, Issue 24
  • DOI: 10.1002/anie.201508381

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


Material descriptors for predicting thermoelectric performance
journal, January 2015

  • Yan, Jun; Gorai, Prashun; Ortiz, Brenden
  • Energy & Environmental Science, Vol. 8, Issue 3
  • DOI: 10.1039/C4EE03157A

Verfeinerung der Kristallstruktur von Bournonit [(SbS 3 ) 2 |Cu 2 IV Pb VII Pb VIII ] und von Seligmannit [(AsS 3 ) 2 |Cu 2 IV Pb VII Pb VIII ]*
journal, January 1970


Thermoelectric properties of Sn-doped p-type Cu 3 SbSe 4 : a compound with large effective mass and small band gap
journal, January 2014

  • Wei, Tian-Ran; Wang, Heng; Gibbs, Zachary M.
  • J. Mater. Chem. A, Vol. 2, Issue 33
  • DOI: 10.1039/C4TA01957A

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


First principles phonon calculations in materials science
journal, November 2015


Thermoelectric Transport in Cu 7 PSe 6 with High Copper Ionic Mobility
journal, August 2014

  • Weldert, Kai S.; Zeier, Wolfgang G.; Day, Tristan W.
  • Journal of the American Chemical Society, Vol. 136, Issue 34
  • DOI: 10.1021/ja5056092

Zintl phases for thermoelectric devices
journal, January 2007

  • Kauzlarich, Susan M.; Brown, Shawna R.; Jeffrey Snyder, G.
  • Dalton Transactions, Issue 21
  • DOI: 10.1039/b702266b

Two‐band analysis of hole mobility and Hall factor for heavily carbon‐doped p ‐type GaAs
journal, February 1996

  • Kim, B. W.; Majerfeld, A.
  • Journal of Applied Physics, Vol. 79, Issue 4
  • DOI: 10.1063/1.361084

Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013

  • Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
  • APL Materials, Vol. 1, Issue 1
  • DOI: 10.1063/1.4812323

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

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
  • DOI: 10.1002/aenm.201200650

Isotropic Conduction Network and Defect Chemistry in Mg 3+ δ Sb 2 -Based Layered Zintl Compounds with High Thermoelectric Performance
journal, September 2016

  • Tamaki, Hiromasa; Sato, Hiroki K.; Kanno, Tsutomu
  • Advanced Materials, Vol. 28, Issue 46
  • DOI: 10.1002/adma.201603955

Apparent critical phenomena in the superionic phase transition of Cu 2- x Se
journal, January 2016


Thermoelectric cooling of microelectronic circuits and waste heat electrical power generation in a desktop personal computer
journal, March 2011

  • Gould, C. A.; Shammas, N. Y. A.; Grainger, S.
  • Materials Science and Engineering: B, Vol. 176, Issue 4
  • DOI: 10.1016/j.mseb.2010.09.010

Transport properties of the clathrate BaGe 5
journal, August 2011

  • Candolfi, C.; Aydemir, U.; Ormeci, A.
  • Journal of Applied Physics, Vol. 110, Issue 4
  • DOI: 10.1063/1.3625233

High thermoelectric performance of superionic argyrodite compound Ag 8 SnSe 6
journal, January 2016

  • Li, Lin; Liu, Yuan; Dai, Jiyan
  • Journal of Materials Chemistry C, Vol. 4, Issue 24
  • DOI: 10.1039/C6TC00810K

Role of Lone-Pair Electrons in Producing Minimum Thermal Conductivity in Nitrogen-Group Chalcogenide Compounds
journal, November 2011


High-Throughput Machine-Learning-Driven Synthesis of Full-Heusler Compounds
journal, October 2016


Benchmarking density functional perturbation theory to enable high-throughput screening of materials for dielectric constant and refractive index
journal, March 2016


Understanding thermoelectric properties from high-throughput calculations: trends, insights, and comparisons with experiment
journal, January 2016

  • Chen, Wei; Pöhls, Jan-Hendrik; Hautier, Geoffroy
  • Journal of Materials Chemistry C, Vol. 4, Issue 20
  • DOI: 10.1039/C5TC04339E

Electrostatics-based finite-size corrections for first-principles point defect calculations
journal, May 2014


Synthesis and properties of structural analogs of the mineral bournonite
journal, March 2011


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


A large family of filled skutterudites stabilized by electron count
journal, March 2015

  • Luo, Huixia; Krizan, Jason W.; Muechler, Lukas
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7489

Intrinsic point defects and complexes in the quaternary kesterite semiconductor Cu 2 ZnSnS 4
journal, June 2010


The thermodynamic scale of inorganic crystalline metastability
journal, November 2016

  • Sun, Wenhao; Dacek, Stephen T.; Ong, Shyue Ping
  • Science Advances, Vol. 2, Issue 11
  • DOI: 10.1126/sciadv.1600225

Stereochemistry of post-transition metal oxides: revision of the classical lone pair model
journal, January 2011

  • Walsh, Aron; Payne, David J.; Egdell, Russell G.
  • Chemical Society Reviews, Vol. 40, Issue 9
  • DOI: 10.1039/c1cs15098g

Electrical properties of solid electrolytes with the general formula ABCD 3 (A = Ag, Cu; B = Pb, Sn; C = As, Sb; and D = S, Se)
journal, January 2007


Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013


Thermoelectric transport in the coupled valence-band model
journal, February 2011

  • Ramu, Ashok T.; Cassels, Laura E.; Hackman, Nathan H.
  • Journal of Applied Physics, Vol. 109, Issue 3
  • DOI: 10.1063/1.3537826

    Works referencing / citing this record:

    ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences
    journal, January 2019

    • Abudurusuli, Ailijiang; Wu, Kui; Tudi, Abudukadi
    • Chemical Communications, Vol. 55, Issue 35
    • DOI: 10.1039/c9cc00560a

    Accelerating the discovery of materials for clean energy in the era of smart automation
    journal, April 2018

    • Tabor, Daniel P.; Roch, Loïc M.; Saikin, Semion K.
    • Nature Reviews Materials, Vol. 3, Issue 5
    • DOI: 10.1038/s41578-018-0005-z

    Enhancing the electronic dimensionality of hybrid organic–inorganic frameworks by hydrogen bonded molecular cations
    journal, January 2019

    • El-Mellouhi, Fedwa; Madjet, Mohamed E.; Berdiyorov, Golibjon R.
    • Materials Horizons, Vol. 6, Issue 6
    • DOI: 10.1039/c8mh01436a

    Accelerating the discovery of materials for clean energy in the era of smart automation
    journal, April 2018

    • Tabor, Daniel P.; Roch, Loïc M.; Saikin, Semion K.
    • Nature Reviews Materials, Vol. 3, Issue 5
    • DOI: 10.1038/s41578-018-0005-z

    Enhancing the electronic dimensionality of hybrid organic–inorganic frameworks by hydrogen bonded molecular cations
    journal, January 2019

    • El-Mellouhi, Fedwa; Madjet, Mohamed E.; Berdiyorov, Golibjon R.
    • Materials Horizons, Vol. 6, Issue 6
    • DOI: 10.1039/c8mh01436a

    ABaSbQ 3 (A = Li, Na; Q = S, Se): diverse arrangement modes of isolated SbQ 3 ligands regulating the magnitudes of birefringences
    journal, January 2019

    • Abudurusuli, Ailijiang; Wu, Kui; Tudi, Abudukadi
    • Chemical Communications, Vol. 55, Issue 35
    • DOI: 10.1039/c9cc00560a