Achieving accurate energetics beyond (semi-)local density functional theory

Illustrated with transition metal disulfides, Cu2ZnSnS4, and Na3PS4 related semiconductors

Shunli Shang, Yi Wang, Timothy J. Anderson, Zi-kui Liu

Research output: Contribution to journalArticle

Abstract

Understanding, designing, and processing functional metal sulfides are significant challenges in part 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.

Original languageEnglish (US)
Article number015401
JournalPhysical Review Materials
Volume3
Issue number1
DOIs
StatePublished - Jan 2 2019

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disulfides
Disulfides
Transition metals
Density functional theory
Sulfides
transition metals
Semiconductor materials
density functional theory
sulfides
Metals
Enthalpy
Entropy
enthalpy
metals
entropy
thermochemical properties
Temperature
Film growth
Gibbs free energy
predictions

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Physics and Astronomy (miscellaneous)

Cite this

@article{293f317443d74d33a410090d19bb111e,
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 in part 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.",
author = "Shunli Shang and Yi Wang and Anderson, {Timothy J.} and Zi-kui Liu",
year = "2019",
month = "1",
day = "2",
doi = "10.1103/PhysRevMaterials.3.015401",
language = "English (US)",
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journal = "Physical Review Materials",
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TY - JOUR

T1 - Achieving accurate energetics beyond (semi-)local density functional theory

T2 - Illustrated with transition metal disulfides, Cu2ZnSnS4, and Na3PS4 related semiconductors

AU - Shang, Shunli

AU - Wang, Yi

AU - Anderson, Timothy J.

AU - Liu, Zi-kui

PY - 2019/1/2

Y1 - 2019/1/2

N2 - Understanding, designing, and processing functional metal sulfides are significant challenges in part 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.

AB - Understanding, designing, and processing functional metal sulfides are significant challenges in part 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.

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