Title

Polymorphism and second harmonic generation in a novel diamond-like semiconductor: Li2MnSnS4

Citation for published article

Devlin, K. P., Glaid, A. J., Brant, J. A., Zhang, J.-H., Srnec, M. N., Clark, D. J., Soo Kim, Y., Jang, J. I., Daley, K. R., Moreau, M. A., Madura, J. D., & Aitken, J. A. (2015). Polymorphism and second harmonic generation in a novel diamond-like semiconductor: Li2MnSnS4. Journal of Solid State Chemistry, 231, 256–266. https://doi.org/10.1016/j.jssc.2015.08.011

DOI

10.1016/j.jssc.2015.08.011

Peer Reviewed

1

Document Type

Journal Article

School

Bayer School of Natural and Environmental Sciences

Primary Author Department

Chemistry and Biochemistry

Abstract

© 2015 Elsevier Inc. All rights reserved. High-temperature, solid-state synthesis in the Li2MnSnS4 system led to the discovery of two new polymorphic compounds that were analyzed using single crystal X-ray diffraction. The α-polymorph crystallizes in Pna21 with the lithium cobalt (II) silicate, Li2CoSiO4, 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-Li2MnSnS4 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-Li2MnSnS4, as well as the hypothetical polymorph, γ-Li2MnSnS4 with the wurtz-stannite structure type, are highly similar.

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