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Title: Achieving accurate energetics beyond (semi-)local density functional theory: Illustrated with transition metal disulfides, Cu2ZnSnS4, and Na3PS4 related semiconductors

Abstract

Understanding, designing, and processing functional metal sulfides are significant challenges partially because of the high temperatures and pressures and the number of secondary phases encountered in these complex systems. In particular, the underlying thermochemical properties are not well understood that would allow prediction of equilibrium conditions and driving forces. In addition, obtaining accurate values for the energetics of metal sulfide systems is far from complete, suggesting application of density functional theory (DFT) calculations. Here, the results of an examination of 69 phases by DFT using 12 exchange-correlation (X-C) functionals indicate that (i) the key source of error in predicting the Gibbs energy of a phase is the enthalpy calculated at 0 K rather than entropy at finite temperatures from phonon calculations and (ii) an improved prediction of the thermodynamic properties at 0 K relies on the selected nonlocal X-C functional such as the hybrid potential. Regarding metal sulfides, we conclude from the present DFT results that (1) the secondary phase Cu2ZnSn3S8, associated with the desired photovoltaic material Cu2ZnSnS4, is not stable at 0 K, but it becomes slightly stable with increasing temperature (i.e., >800 K), primarily due to the vibrational entropy, which makes it difficult to be detected in amore » typical thin-film growth process; (2) the hybrid X-C functional improves the predicted energetics for most of the layered transition-metal disulfides such as TiS2, MoS2, and WS2, but not for the nonlayered RuS2, OsS2 , and IrS2 as well as the layered PdS2; and (3) the formation of the solid-state electrolyte Na3PS4 is thermodynamically favored. We further conclude that accurate energetics as a function of temperature for the materials of interest is feasible to be achieved beyond the semilocal DFT calculations with the key being enthalpy predicted at 0 K.« less

Authors:
 [1];  [1];  [2];  [1]
+ Show Author Affiliations
  1. Pennsylvania State Univ., University Park, PA (United States)
  2. Univ. of Florida, Gainesville, FL (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC)
OSTI Identifier:
1544137
Alternate Identifier(s):
OSTI ID: 1489306
Grant/Contract Number:  
CHE-1230924; CHE-1230929; AC02-05CH11231; ACI-1548562
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 3; Journal Issue: 1; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Shang, Shun-Li, Wang, Yi, Anderson, Timothy J., and Liu, Zi-Kui. Achieving accurate energetics beyond (semi-)local density functional theory: Illustrated with transition metal disulfides, Cu2ZnSnS4, and Na3PS4 related semiconductors. United States: N. p., 2019. Web. doi:10.1103/physrevmaterials.3.015401.
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Shang, Shun-Li, Wang, Yi, Anderson, Timothy J., & Liu, Zi-Kui. Achieving accurate energetics beyond (semi-)local density functional theory: Illustrated with transition metal disulfides, Cu2ZnSnS4, and Na3PS4 related semiconductors. United States. https://doi.org/10.1103/physrevmaterials.3.015401
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Shang, Shun-Li, Wang, Yi, Anderson, Timothy J., and Liu, Zi-Kui. Wed . "Achieving accurate energetics beyond (semi-)local density functional theory: Illustrated with transition metal disulfides, Cu2ZnSnS4, and Na3PS4 related semiconductors". United States. https://doi.org/10.1103/physrevmaterials.3.015401. https://www.osti.gov/servlets/purl/1544137.
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@article{osti_1544137,
title = {Achieving accurate energetics beyond (semi-)local density functional theory: Illustrated with transition metal disulfides, Cu2ZnSnS4, and Na3PS4 related semiconductors},
author = {Shang, Shun-Li and Wang, Yi and Anderson, Timothy J. and Liu, Zi-Kui},
abstractNote = {Understanding, designing, and processing functional metal sulfides are significant challenges partially because of the high temperatures and pressures and the number of secondary phases encountered in these complex systems. In particular, the underlying thermochemical properties are not well understood that would allow prediction of equilibrium conditions and driving forces. In addition, obtaining accurate values for the energetics of metal sulfide systems is far from complete, suggesting application of density functional theory (DFT) calculations. Here, the results of an examination of 69 phases by DFT using 12 exchange-correlation (X-C) functionals indicate that (i) the key source of error in predicting the Gibbs energy of a phase is the enthalpy calculated at 0 K rather than entropy at finite temperatures from phonon calculations and (ii) an improved prediction of the thermodynamic properties at 0 K relies on the selected nonlocal X-C functional such as the hybrid potential. Regarding metal sulfides, we conclude from the present DFT results that (1) the secondary phase Cu2ZnSn3S8, associated with the desired photovoltaic material Cu2ZnSnS4, is not stable at 0 K, but it becomes slightly stable with increasing temperature (i.e., >800 K), primarily due to the vibrational entropy, which makes it difficult to be detected in a typical thin-film growth process; (2) the hybrid X-C functional improves the predicted energetics for most of the layered transition-metal disulfides such as TiS2, MoS2, and WS2, but not for the nonlayered RuS2, OsS2 , and IrS2 as well as the layered PdS2; and (3) the formation of the solid-state electrolyte Na3PS4 is thermodynamically favored. We further conclude that accurate energetics as a function of temperature for the materials of interest is feasible to be achieved beyond the semilocal DFT calculations with the key being enthalpy predicted at 0 K.},
doi = {10.1103/physrevmaterials.3.015401},
journal = {Physical Review Materials},
number = 1,
volume = 3,
place = {United States},
year = {Wed Jan 02 00:00:00 EST 2019},
month = {Wed Jan 02 00:00:00 EST 2019}
}
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