FeSi4P4 and CoSi3P3: Hidden Gems of Ternary Tetrel Pnictides with Outstanding Nonlinear Optical Properties

Soto, Ernesto;Lee, Shannon J.;Porter, Andrew P.;Viswanathan, Gayatri;Kovnir, Kirill;et.al.
(2024) Chemistry of Materials — Vol. 36, p. 8854 (2024)

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Authors
  • Soto, Ernestoorcid-logoDepartment of Chemistry, Iowa State University, Ames, Iowa 50011, United States
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  • Lee, Shannon J.orcid-logoDepartment of Chemistry, Iowa State University, Ames, Iowa 50011, United States
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  • Porter, Andrew P.Department of Chemistry, Iowa State University, Ames, Iowa 50011, United States
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  • Viswanathan, GayatriDepartment of Chemistry, Iowa State University, Ames, Iowa 50011, United States
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  • Trinquet, Victororcid-logoUCLouvain
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  • Brunin, GuillaumeUCLouvain
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  • Rignanese, Gian-Marcoorcid-logoUCLouvain
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  • Kovnir, Kirillorcid-logoDepartment of Chemistry, Iowa State University, Ames, Iowa 50011, United States; Ames National Laboratory, U.S. Department of Energy, Ames, Iowa 50011, United States
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Abstract
Metal silicon phosphides have shown promise as nonlinear optical materials. To be practically useful and cheap, earthabundant 3d transition metals are preferred over their scarcer and more expensive 4d and 5d counterparts. We developed a synthetic method to produce polycrystalline bulk powders and millimeter-sized single crystals of ternary compounds FeSi4P4 and CoSi3P3. Both studied compounds have noncentrosymmetric and chiral crystal structures with ordered Si/P arrangements as was confirmed by single-crystal X-ray diffraction and solid-state NMR. Despite the presence of the transition metal, FeSi4P4 and CoSi3P3 are semiconductors with direct band gaps of 1.3 and 1.6 eV, respectively, indicating low-spin d6 electronic configuration for octahedral Fe2+ and Co3+. Relative to reported sulfide materials, FeSi4P4 and CoSi3P3 small band gap semiconductors demonstrate an outstanding combination of second-harmonic generation (SHG) activity and laser damage threshold (LDT). Both studied materials are phase-matchable with a 2.09 μm laser and not only exhibit 2.5−3.0 times stronger SHG signal than that of the state-of-the-art AgGaS2 standard but also demonstrate an LDT response of 2.3−2.5 times higher than that of AgGaS2 (at 1.09 μm laser with a pulse width of 10 ns)- which is unprecedented for small band gap semiconductors.
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Soto, E., Lee, S. J., Porter, A. P., Viswanathan, G., Akopov, G., Hewage, N., Wu, K., Trinquet, V., Brunin, G., Hautier, G., Rignanese, G.-M., Rossini, A. J., & Kovnir, K. (2024). FeSi4P4 and CoSi3P3: Hidden Gems of Ternary Tetrel Pnictides with Outstanding Nonlinear Optical Properties. Chemistry of Materials, 36, 8854. https://doi.org/10.1021/acs.chemmater.4c01688 (Original work published 2024)