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

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:
Grant/Contract Number:
AC02-05CH11231
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
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1393108

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., 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. 2017. "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}
}

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