Phase stability of the earth-abundant tin sulfides SnS, SnS2, and Sn2S3

L.A. Burton, A. Walsh

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Abstract

The various phases of tin sulfide have been studied as semiconductors since the 1960s and are now being investigated as potential earth-abundant photovoltaic and photocatalytic materials. Of particular note is the recent isolation of zincblende SnS in particles and thin-films. Herein, first-principles calculations are employed to better understand this novel geometry and its place within the tin sulfide multiphasic system. We report the enthalpies of formation for the known phases of SnS, SnS2, and Sn2S3, with good agreement between theory and experiment for the ground-state structures of each. While theoretical X-ray diffraction patterns do agree with the assignment of the zincblende phase demonstrated in the literature, the structure is not stable close to the lattice parameters observed experimentally, exhibiting an unfeasibly large pressure and a formation enthalpy much higher than any other phase. Ab initio molecular dynamics simulations reveal spontaneous degradation to an amorphous phase much lower in energy, as Sn(II) is inherently unstable in a regular tetrahedral environment. We conclude that the known rocksalt phase of SnS has been mis-assigned as zincblende in the recent literature.
Original languageEnglish
Pages (from-to)24262-24267
Number of pages6
JournalJournal of Physical Chemistry C
Volume116
Issue number45
DOIs
Publication statusPublished - 15 Nov 2012

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Phase stability
zincblende
Tin
sulfides
Enthalpy
tin
Earth (planet)
enthalpy
Diffraction patterns
Ground state
Lattice constants
Molecular dynamics
Semiconductor materials
X ray diffraction
Degradation
Thin films
Geometry
lattice parameters
isolation
Computer simulation

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Phase stability of the earth-abundant tin sulfides SnS, SnS2, and Sn2S3. / Burton, L.A.; Walsh, A.

In: Journal of Physical Chemistry C, Vol. 116, No. 45, 15.11.2012, p. 24262-24267.

Research output: Contribution to journalArticle

Burton, L.A. ; Walsh, A. / Phase stability of the earth-abundant tin sulfides SnS, SnS2, and Sn2S3. In: Journal of Physical Chemistry C. 2012 ; Vol. 116, No. 45. pp. 24262-24267.
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