Polymorphism and second harmonic generation in a novel diamond-like semiconductor: Li{sub 2}MnSnS{sub 4}

Journal Article · Sun Nov 15 00:00:00 EST 2015 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2015.08.011· OSTI ID:22573950

Devlin, Kasey P. ^[1]; Glaid, Andrew J. ^[1]; Brant, Jacilynn A.; Zhang, Jian-Han ^[1]; Srnec, Matthew N. ^[1]; Clark, Daniel J. ^[2]; Soo Kim, Yong ^[2]; Jang, Joon I. ^[2]; Daley, Kimberly R.; Moreau, Meghann A. ^[1]; Madura, Jeffry D. ^[1]

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1. Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15282 (United States)
2. Department of Physics, Applied Physics and Astronomy, Binghamton University, Binghamton, NY 13902 (United States)

High-temperature, solid-state synthesis in the Li{sub 2}MnSnS{sub 4} system led to the discovery of two new polymorphic compounds that were analyzed using single crystal X-ray diffraction. The α-polymorph crystallizes in Pna2{sub 1} with the lithium cobalt (II) silicate, Li{sub 2}CoSiO{sub 4}, structure type, where Z=4, R1=0.0349 and wR2=0.0514 for all data. The β-polymorph possesses the wurtz-kesterite structure type, crystallizing in Pn with Z=2, R1=0.0423, and wR2=0.0901 for all data. Rietveld refinement of synchrotron X-ray powder diffraction was utilized to quantify the phase fractions of the polymorphs in the reaction products. The α/β-Li{sub 2}MnSnS{sub 4} mixture exhibits an absorption edge of ∼2.6–3.0 eV, a wide region of optical transparency in the mid- to far-IR, and moderate SHG activity over the fundamental range of 1.1–2.1 μm. Calculations using density functional theory indicate that the ground state energies and electronic structures for α- and β-Li{sub 2}MnSnS{sub 4}, as well as the hypothetical polymorph, γ-Li{sub 2}MnSnS{sub 4} with the wurtz-stannite structure type, are highly similar. - Graphical abstract: Two polymorphs, α- and β-Li{sub 2}MnSnS{sub 4}, have been discovered using single crystal X-ray diffraction. Rietveld refinement of synchrotron X-ray powder diffraction data indicates the presence of both polymorphs in the samples that were analyzed. - Highlights: • Li{sub 2}MnSnS{sub 4} exists as two polymorphs crystallizing in the Pna2{sub 1} and Pn space groups. • The α- and β-Li{sub 2}MnSnS{sub 4} mixture exhibits a moderate SHG response over a broad range. • The α- and β-Li{sub 2}MnSnS{sub 4} mixture exhibits an optical absorption edge of ∼2.6–3.0 eV. • Synchrotron powder diffraction data are necessary to distinguish α- and β-Li{sub 2}MnSnS{sub 4.} • Electronic structure calculations show similar total energies for α- and β-Li{sub 2}MnSnS{sub 4}.

• OSTI ID: 22573950
• Journal Information: Journal of Solid State Chemistry, Vol. 231; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ABSORPTION
COBALT
DENSITY
DENSITY FUNCTIONAL METHOD
ELECTRONIC STRUCTURE
GROUND STATES
HARMONIC GENERATION
LITHIUM
MIXTURES
MONOCRYSTALS
ORTHORHOMBIC LATTICES
POWDERS
SEMICONDUCTOR MATERIALS
SILICATES
SOLIDS
SPACE GROUPS
SULFIDES
SYNTHESIS
X RADIATION
X-RAY DIFFRACTION