Chemical and Lattice Stability of the Tin Sulfides

Jonathan M. Skelton; Lee A. Burton; Fumiyasu Oba; Aron Walsh

doi:10.1021/acs.jpcc.6b12581

Chemical and Lattice Stability of the Tin Sulfides

Jonathan M. Skelton, Lee A. Burton, Fumiyasu Oba, Aron Walsh

Department of Physics

Research output: Contribution to journal › Article › peer-review

68 Scopus citations

Abstract

The tin sulfides represent a materials platform for earth-abundant semiconductor technologies. We present a first-principles study of the five known and proposed phases of SnS together with SnS₂ and Sn₂S₃. Lattice-dynamics techniques are used to evaluate the dynamical stability and temperature-dependent thermodynamic free energy, and we also consider the effect of dispersion forces on the energetics. The recently identified π-cubic phase of SnS is found to be metastable with respect to the well-known orthorhombic Pnma/Cmcm equilibrium. The Cmcm phase is a low-lying saddle point between Pnma local minima on the potential-energy surface and is observed as an average structure at high temperatures. Bulk rocksalt and zincblende phases are found to be dynamically unstable, and we show that whereas rocksalt SnS can potentially be stabilized under a reduction of the lattice constant the hypothetical zincblende phase proposed in several previous studies is extremely unlikely to form. We also investigate the stability of Sn₂S₃ with respect to SnS and SnS₂ and find that both dispersion forces and vibrational contributions to the free energy are required to explain its experimentally observed resistance to decomposition.

Original language	English
Pages (from-to)	6446-6454
Number of pages	9
Journal	Journal of Physical Chemistry C
Volume	121
Issue number	12
DOIs	https://doi.org/10.1021/acs.jpcc.6b12581
State	Published - 30 Mar 2017

Bibliographical note

Funding Information:
J.M.S. acknowledges support from an EPSRC Programme Grant (grant no. EP/K004956/1). L.A.B. is an International Research Fellow of the Japan Society of Promotion of Science (JSPS; grant no. 26.04792). A.W. acknowledges support from the Royal Society and the ERC (grant no. 277757). Calculations were carried out using the SiSu supercomputer at the IT Center for Science (CSC), Finland, via the Partnership for Advanced Computing in Europe (PRACE) project no. 13DECI0317/IsoSwitch, and on the Balena HPC cluster at the University of Bath, which is maintained by Bath University Computing Services. Some of the calculations were also carried out on the U.K. national Archer HPC facility, accessed through membership of the U.K. Materials Chemistry Consortium, which is funded by EPSRC grant no. EP/ L000202.

Publisher Copyright:
© 2017 American Chemical Society.

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10.1021/acs.jpcc.6b12581

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title = "Chemical and Lattice Stability of the Tin Sulfides",

abstract = "The tin sulfides represent a materials platform for earth-abundant semiconductor technologies. We present a first-principles study of the five known and proposed phases of SnS together with SnS2 and Sn2S3. Lattice-dynamics techniques are used to evaluate the dynamical stability and temperature-dependent thermodynamic free energy, and we also consider the effect of dispersion forces on the energetics. The recently identified π-cubic phase of SnS is found to be metastable with respect to the well-known orthorhombic Pnma/Cmcm equilibrium. The Cmcm phase is a low-lying saddle point between Pnma local minima on the potential-energy surface and is observed as an average structure at high temperatures. Bulk rocksalt and zincblende phases are found to be dynamically unstable, and we show that whereas rocksalt SnS can potentially be stabilized under a reduction of the lattice constant the hypothetical zincblende phase proposed in several previous studies is extremely unlikely to form. We also investigate the stability of Sn2S3 with respect to SnS and SnS2 and find that both dispersion forces and vibrational contributions to the free energy are required to explain its experimentally observed resistance to decomposition.",

author = "Skelton, {Jonathan M.} and Burton, {Lee A.} and Fumiyasu Oba and Aron Walsh",

note = "Funding Information: J.M.S. acknowledges support from an EPSRC Programme Grant (grant no. EP/K004956/1). L.A.B. is an International Research Fellow of the Japan Society of Promotion of Science (JSPS; grant no. 26.04792). A.W. acknowledges support from the Royal Society and the ERC (grant no. 277757). Calculations were carried out using the SiSu supercomputer at the IT Center for Science (CSC), Finland, via the Partnership for Advanced Computing in Europe (PRACE) project no. 13DECI0317/IsoSwitch, and on the Balena HPC cluster at the University of Bath, which is maintained by Bath University Computing Services. Some of the calculations were also carried out on the U.K. national Archer HPC facility, accessed through membership of the U.K. Materials Chemistry Consortium, which is funded by EPSRC grant no. EP/ L000202. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

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N2 - The tin sulfides represent a materials platform for earth-abundant semiconductor technologies. We present a first-principles study of the five known and proposed phases of SnS together with SnS2 and Sn2S3. Lattice-dynamics techniques are used to evaluate the dynamical stability and temperature-dependent thermodynamic free energy, and we also consider the effect of dispersion forces on the energetics. The recently identified π-cubic phase of SnS is found to be metastable with respect to the well-known orthorhombic Pnma/Cmcm equilibrium. The Cmcm phase is a low-lying saddle point between Pnma local minima on the potential-energy surface and is observed as an average structure at high temperatures. Bulk rocksalt and zincblende phases are found to be dynamically unstable, and we show that whereas rocksalt SnS can potentially be stabilized under a reduction of the lattice constant the hypothetical zincblende phase proposed in several previous studies is extremely unlikely to form. We also investigate the stability of Sn2S3 with respect to SnS and SnS2 and find that both dispersion forces and vibrational contributions to the free energy are required to explain its experimentally observed resistance to decomposition.

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ER -

Chemical and Lattice Stability of the Tin Sulfides

Abstract

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