Syntheses and crystal structures of the quaternary thiogermanates Cu4FeGe2S7and Cu4CoGe2S7

Craig, Andrew J.; Stoyko, Stanislav S.; Bonnoni, Allyson; Aitken, Jennifer A.

doi:10.1107/s2056989020007872

Cited by 3 publications

(2 citation statements)

References 46 publications

(42 reference statements)

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“…The cationsulfur bonds containing S4 are the longest in each of their respective tetrahedra. Similar subtle structural distortions have been observed in other I 4 -II-IV 2 -VI 7 compounds, for example, Cu 4 FeGe 2 S 7 , Cu 4 CoGe 2 S 7 , Li 4 CdSn 2 S 7 , Cu 4 Mn-Ge 2 S 7 , and Cu 4 ZnGe 2 Se 7 (Craig et al, 2020;Zhang, Stoyko et al, 2020;Glenn et al, 2021;Sinagra et al, 2021).…”

Section: Resultssupporting

confidence: 76%

Crystal structure, electronic structure, and optical properties of the novel Li₄CdGe₂S₇, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Craig¹,

Shin²,

Cho³

et al. 2022

Acta Crystallogr C

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The novel quaternary thiogermanate Li4CdGe2S7 (tetralithium cadmium digermanium heptasulfide) was discovered from a solid-state reaction at 750 °C. Single-crystal X-ray diffraction data were collected and used to solve and refine the structure. Li4CdGe2S7 is a member of the small, but growing, class of I4–II–IV2–VI7 diamond-like materials. The compound adopts the Cu5Si2S7 structure type, which is a derivative of lonsdaleite. Crystallizing in the polar space group Cc, Li4CdGe2S7 contains 14 crystallographically unique ions, all residing on general positions. Like all diamond-like structures, the compound is built of corner-sharing tetrahedral units that create a relatively dense three-dimensional assembly. The title compound is the major phase of the reaction product, as evidenced by powder X-ray diffraction and optical diffuse reflectance spectroscopy. While the compound exhibits a second-harmonic generation (SHG) response comparable to that of the AgGaS2 (AGS) reference material in the IR region, its laser-induced damage threshold (LIDT) is over an order of magnitude greater than AGS for λ = 1.064 µm and τ = 30 ps. Bond valence sums, global instability index, minimum bounding ellipsoid (MBE) analysis, and electronic structure calculations using density functional theory (DFT) were used to further evaluate the crystal structure and electronic structure of the compound and provide a comparison with the analogous I2–II–IV–VI4 diamond-like compound Li2CdGeS4. Li4CdGe2S7 appears to be a better IR nonlinear optical (NLO) candidate than Li2CdGeS4 and one of the most promising contenders to date. The exceptional LIDT is likely due, at least in part, to the wider optical bandgap of ∼3.6 eV.

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Section: Resultssupporting

confidence: 76%

Crystal structure, electronic structure, and optical properties of the novel Li₄CdGe₂S₇, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Craig¹,

Shin²,

Cho³

et al. 2022

Acta Crystallogr C

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“…In this work, we targeted a new compound of the less studied I 4 –II–IV 2 –VI 7 stoichiometry, ,− namely, Li 4 CdSn 2 S 7 . We chose lithium as the I element because lithium-containing DLSs have wider bandgaps than the corresponding copper and silver analogues.…”

Section: Introductionmentioning

confidence: 99%

Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li₄CdSn₂S₇

et al. 2020

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The novel diamond-like Li4CdSn2S7 possesses many outstanding attributes that enable it to be a new, well-rounded front-runner among infrared (IR) nonlinear-optical materials, especially for high-intensity laser applications. Distortions of the metal–sulfur tetrahedra in accordance with Pauling’s second rule give rise to a significant net dipole moment, resulting in a strong second-order nonlinear optical susceptibility (χ(2)) of 35.0 ± 3.5 pm/V. Li4CdSn2S7 possesses an optical bandgap of 2.59 eV and an exceptional laser-induced damage threshold of >2.5 GW/cm2, which is more than 12.5 times greater than that of AgGaSe2 measured under identical irradiation conditions. Li4CdSn2S7 possesses a melting point of ∼780 °C and phase-matchability. All data indicate that Li4CdSn2S7 will outperform AgGaS2 and AgGaSe2 in difference frequency generation schemes for the generation of mid-IR radiation. New information on the recently reported Li2CdSiS4, which Li4CdSn2S7 also outperforms, is additionally included.

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Synthesis, structure, linear and nonlinear optical properties of noncentrosymmetric quaternary diamond-like semiconductors, Cu2ZnGeSe4 (CZGSe) and the novel Cu4ZnGe2Se7

Sinagra

Saouma

Otieno

et al. 2021

Journal of Alloys and Compounds

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Syntheses and crystal structures of the quaternary thiogermanates Cu₄FeGe₂S₇and Cu₄CoGe₂S₇

Cited by 3 publications

References 46 publications

Crystal structure, electronic structure, and optical properties of the novel Li₄CdGe₂S₇, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Crystal structure, electronic structure, and optical properties of the novel Li₄CdGe₂S₇, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li₄CdSn₂S₇

Synthesis, structure, linear and nonlinear optical properties of noncentrosymmetric quaternary diamond-like semiconductors, Cu2ZnGeSe4 (CZGSe) and the novel Cu4ZnGe2Se7

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Syntheses and crystal structures of the quaternary thiogermanates Cu4FeGe2S7and Cu4CoGe2S7

Cited by 3 publications

References 46 publications

Crystal structure, electronic structure, and optical properties of the novel Li4CdGe2S7, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Crystal structure, electronic structure, and optical properties of the novel Li4CdGe2S7, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li4CdSn2S7

Synthesis, structure, linear and nonlinear optical properties of noncentrosymmetric quaternary diamond-like semiconductors, Cu2ZnGeSe4 (CZGSe) and the novel Cu4ZnGe2Se7

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Syntheses and crystal structures of the quaternary thiogermanates Cu₄FeGe₂S₇and Cu₄CoGe₂S₇

Crystal structure, electronic structure, and optical properties of the novel Li₄CdGe₂S₇, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Crystal structure, electronic structure, and optical properties of the novel Li₄CdGe₂S₇, a wide-bandgap quaternary sulfide with a polar structure derived from lonsdaleite

Phase Matching, Strong Frequency Doubling, and Outstanding Laser-Induced Damage Threshold in the Biaxial, Quaternary Diamond-like Semiconductor Li₄CdSn₂S₇