Crystal structure and twinning of KCd4Ga5S12 and some isotypic AB4C5X12 compounds

Schwer, H.; Keller, Egbert; Krämer, V.

doi:10.1524/zkri.1993.204.12.203

Cited by 11 publications

(23 citation statements)

References 18 publications

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“…KHg 4 Ga 5 Se 12 belongs to an enormous compounds family in trigonal space group R 3 with an overall formula AM 4 M′ 5 Q 12 , − where A, M, M′, and Q represent an alkali metal cation with relatively large radius, a bivalent transition cation, a trivalent main group cation, and chalcogens, respectively. The most notable structural feature of the above family is a quasi-cubic closest packing of the chalcogen atoms with the tetrahedral interspaces occupied by M and M′ cations.…”

Section: Resultsmentioning

confidence: 99%

Hg-Based Infrared Nonlinear Optical Material KHg₄Ga₅Se₁₂ Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

et al. 2017

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High-performance infrared (IR) nonlinear optical (NLO) materials with large NLO response and suitable birefringence are urgently needed for various applications. A Hg-based IR NLO material KHg4Ga5Se12 with such desirable properties has been newly discovered. In the structure, obviously distorted HgSe4 and GaSe4 tetrahedra are connected to each other by vertex-sharing to form a three-dimensional framework with the counterion K+ residing in the cavities. Remarkably, all the NLO-active building units in the title compound are arranged in a completely parallel manner. Such a topological structure and the large susceptibility of the Hg–Se bonds enable the material to achieve good phase-matchability with a tremendous powder second harmonic generation (SHG) response at 2.09 μm that is about 20-times that of the benchmark material AgGaS2 (one of the largest responses among all the phase-matchable IR NLO chalcogenides reported to date). The optical band gap of KHg4Ga5Se12 was determined as 1.61 eV. Moreover, on the basis of the electronic band structure, the real-space atom-cutting analysis, the SHG-weighted electronic densities, and the local dipole moments calculations, the origin of the superior linear and nonlinear optical properties of the title compound is ascribed to the (Hg/Ga)Se4 group. The calculated values for the maximum coefficient d 33 and birefringence (Δn) at 2.09 μm are −65.257 pm/V and 0.072, respectively. Such values agree well with experimental observations. Our study demonstrates that Hg-based metal chalcogenides are a class of IR NLO material with competitive features (good phase-matchability, very large SHG efficiency, wide transparency) desirable for practical applications.

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Section: Resultsmentioning

confidence: 99%

Hg-Based Infrared Nonlinear Optical Material KHg₄Ga₅Se₁₂ Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

et al. 2017

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“…We adopted a novel synthetic method and appropriate flux method, using binary selenides as the raw materials, regulating the selection and dose of the flux, and letting the flux participate in the reaction, and obtained a series of new compounds. In the past, relevant literature showed that ternary ZnGa 2 Se 4 reacts with flux, but only one case of KZn 4 Ga 5 Se 12 was obtained . Therefore, the former is more applicable for the A/Zn/Ga/Se system.…”

Section: Results and Discussionmentioning

confidence: 99%

“…The isostructural chalcogenides AZn 4 Ga 5 Se 12 (A = K, Rb, or Cs) show trigonal space group R 3 (No. 146) and belong to a huge family of A-II 4 -III 5 -Q 12 compounds (A = K–Cs; II = IIB and Mn; III = group 13; Q = chalcogen). ,,− This famliy has many remarkable structural features, such as rich element replaceability, great structural density, and co-occupation of bimetals. In the asymmetric unit, A, M, and Se occupy one, three, and four independent sites, respectively, among which both Zn and Ga atoms are arranged randomly at the three M sites.…”

Section: Results and Discussionmentioning

confidence: 99%

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AZn₄Ga₅Se₁₂ (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds

et al. 2021

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Despite the fact that nonlinear optical (NLO) crystals such as AgGaS 2 and AgGaSe 2 have been widely used in the infrared (IR) range due to their large second harmonic generation (SHG) coefficients and wide range of IR transparency windows, the small laser-induced damage threshold (LIDT) remains a great issue hindering their high-power applications. Herein, three noncentrosymmetric (NCS) chalcogenides AZn 4 Ga 5 Se 12 (A = K, Rb, or Cs) are successfully obtained through an appropriate flux method after the extensive design and synthesis of the A/Zn/Ga/Q system. Single-crystal X-ray diffraction data demonstrate that they adopt trigonal space group R3 (No. 146) with three-dimensional diamondlike frameworks composed of [M 9 Se 24 ] layers (M = Zn or Ga) stacking in the same direction and filled by charge-balancing A + cations. Noticeably, they all exhibit strong powder SHG responses (2.8−3.7 × AgGaS 2 ) and amazing LIDTs (19.2−23.4 × AgGaS 2 ). In addition, theoretical calculations are performed to further determine the relationship between NCS structures and NLO properties. This work provides effective solutions for overcoming the trade-off between strong SHG and high LIDT in IR-NLO materials.

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“…Compounds CsX II 4 In 5 Te 12 (X II = Mn, Zn, Cd) adopt the KCd 4 Ga 5 S 12 -structure type , and crystallize in the R 3 space group (Table ). Each metal atom (M) is disordered by X II and In atoms, with occupancies of 25–60% Mn, 32–53% Zn, and 36–49% Cd (Table S2, SI).…”

Section: Resultsmentioning

confidence: 99%

Strong Infrared NLO Tellurides with Multifunction: CsX^II₄In₅Te₁₂ (X^II = Mn, Zn, Cd)

et al. 2016

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Chalcogenides are the most promising mid- and far-infrared materials for nonlinear optical (NLO) applications. Yet, most of them are sulfides and selenides, and tellurides are still rare. Herein, we report three new KCd4Ga5S12-structure type NLO-active tellurides, CsX(II)4In5Te12 (X(II) = Mn, Zn, Cd), synthesized by solid-state reactions. The structure features a 3D diamond-like framework constructed by vertex-sharing asymmetric MTe4 tetrahedra that are stacked along the c-axis. CsCd4In5Te12 exhibits the strongest powder second-harmonic generation (SHG) intensity at 2050 nm (0.61 eV) among tellurides to date, 9 × benchmark AgGaS2 in the range of 46-74 μm particle size. The primary studies reveal the 1.42 eV direct band gap and high absorption coefficient in the visible spectral region for CsCd4In5Te12, suggesting it is a new potential solar cell absorber material. In addition, CsMn4In5Te12 also displays a spin-canted antiferromagnetic property below 50 K.

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Crystal structure and twinning of KCd₄Ga₅S¹² and some isotypic AB₄C₅X₁₂ compounds

Cited by 11 publications

References 18 publications

Hg-Based Infrared Nonlinear Optical Material KHg₄Ga₅Se₁₂ Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

Hg-Based Infrared Nonlinear Optical Material KHg₄Ga₅Se₁₂ Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

AZn₄Ga₅Se₁₂ (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds

Strong Infrared NLO Tellurides with Multifunction: CsX^II₄In₅Te₁₂ (X^II = Mn, Zn, Cd)

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Crystal structure and twinning of KCd4Ga5S12 and some isotypic AB4C5X12 compounds

Cited by 11 publications

References 18 publications

Hg-Based Infrared Nonlinear Optical Material KHg4Ga5Se12 Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

Hg-Based Infrared Nonlinear Optical Material KHg4Ga5Se12 Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

AZn4Ga5Se12 (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds

Strong Infrared NLO Tellurides with Multifunction: CsXII4In5Te12 (XII = Mn, Zn, Cd)

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Crystal structure and twinning of KCd₄Ga₅S¹² and some isotypic AB₄C₅X₁₂ compounds

Hg-Based Infrared Nonlinear Optical Material KHg₄Ga₅Se₁₂ Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

Hg-Based Infrared Nonlinear Optical Material KHg₄Ga₅Se₁₂ Exhibits Good Phase-Matchability and Exceptional Second Harmonic Generation Response

AZn₄Ga₅Se₁₂ (A = K, Rb, or Cs): Infrared Nonlinear Optical Materials with Simultaneous Large Second Harmonic Generation Responses and High Laser-Induced Damage Thresholds

Strong Infrared NLO Tellurides with Multifunction: CsX^II₄In₅Te₁₂ (X^II = Mn, Zn, Cd)