A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency

Geng, Zi-Long; Tang, Hong-Xin; Fu, Rui-Biao; Ma, Zu-Ju; Wu, Xin-Tao

doi:10.1039/d3dt03071g

Cited by 3 publications

(1 citation statement)

References 43 publications

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“…Compounds with a short ultraviolet (UV) cutoff edge play an increasingly crucial role in scientific and technological applications for the capacity of providing short, strong, efficient, and stable laser sources. − To obtain NLO materials with short wavelengths, the selection of chemical elements is of great importance. Alkali/alkaline earth (A/AE) elements averting the d–d/f–f electron transition have long-term been recognized as powerful elements for a large band gap .…”

Section: Introductionmentioning

confidence: 99%

Centrosymmetric CaBaMF₈ and Noncentrosymmetric Li₂CaMF₈ (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

Yan,

Tang,

et al. 2024

Inorg. Chem.

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Zirconium/hafnium fluorides have recently been recognized as potential nonlinear optical (NLO) materials with short ultraviolet (UV) cutoff edges, which is significant in laser science and industry. The synthesis of noncentrosymmetric (NCS) materials based on centrosymmetric (CS) compounds by an isovalent cation substitution-oriented design is an emerging strategy in the NLO territory. Here, two isostructural and novel fluorides, CaBaMF8 (M = Zr (1), Hf (2)), have been synthesized through the combination of alkaline earth metals, zirconium/hafnium, and fluorine elements. They feature zero-dimensional and CS structures composed by an isolated MF8 (M = Zr, Hf) dodecahedron and dissociative Ca2+ and Ba2+ cations, and they display short UV cutoff edges (<200 nm) as well. Two three-dimensional fluorides Li2CaMF8 (M = Zr (3), Hf (4)) are obtained by replacing Ba with alkali metal Li atom, which not only represent phase-matchable second-harmonic-generation activities (0.36, 0.30× KH2PO4 (KDP)) at 1064 nm but also maintain short UV cutoff edges with high reflectance. This work has largely enriched the family of NCS zirconium/hafnium fluorides reaching the short UV region.

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Section: Introductionmentioning

confidence: 99%

Centrosymmetric CaBaMF₈ and Noncentrosymmetric Li₂CaMF₈ (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

Yan,

Tang,

et al. 2024

Inorg. Chem.

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A₃Sc(SO₄)₃ (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability

Geng,

Fu,

et al. 2024

Advanced Optical Materials

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Nonlinear optical (NLO) crystals that have the capability of achieving tunable lasers through frequency conversion are of great importance in solid‐state lasers. Herein, three new deep‐UV transparent alkali‐scandium sulfates with strong second‐harmonic generation (SHG) response and high thermal stability, A3Sc(SO4)3 (A = K, Rb, Cs), are successfully obtained. It is interesting that the slightly distorted [ScO6] octahedrons are in an ordered/oriented arrangement, which is in favor of the generation of SHG response. Especially, K3Sc(SO4)3 not only exhibits a strong phase‐matching SHG response of 1.6 × KDP, a short deep‐ultraviolet (deep‐UV) cutoff edge of 190 nm, a wide transparent window covering from the deep‐UV region to mid IR, a high laser‐induced damage threshold of 165 MW cm−2 and easy growth of large single crystal, but also behaves thermal stable up to 900 °C under an air atmosphere. Crystal structures and theoretical calculations reveal that their strong SHG responses mainly stem from the slightly distorted [ScO6] octahedron. This study highlights A3Sc(SO4)3 (A = K, Rb, Cs) as promising deep‐UV transparent NLO crystals and offers a new approach for the pursuit of high‐performance NLO crystals.

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K₁₅La₇(BO₃)₁₂: A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response

Bu,

Liu,

et al. 2024

Inorg. Chem.

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Nonlinear-optical (NLO) crystals capable of expanding the spectral regions of solid-state lasers are urgently needed by many high-technological applications. However, in the deep-ultraviolet (DUV) region, there are few crystals available, except KBe 2 BO 3 F 2 (KBBF), which still suffers from the layered growth habit and high toxicity for raw materials. Herein, through the use of rare-earth (RE) La 3+ to substitute Be 2+ cations, a novel KBBF-like borate without beryllium has been successfully synthesized. K 15 La 7 (BO 3 ) 12 (KLBO) crystallizes in the noncentrosymmetric space group Pn (No. 7) and features a three-dimensional framework composed of [La 12 B 7 O 78 ] ∞ layers, which are further linked together through interlayer [BO 3 ] groups. The property measurements show that KLBO not only possesses an ideal NLO performance including a short UV-cutoff edge (λ cutoff < 190 nm) and a remarkable second-harmonic-generation response (∼2.5 × KH 2 PO 4 ) with phase-matching ability, but also overcomes the layered habit of KBBF. Besides, theoretical calculations indicate that the good NLO performance is primarily attributed to the BO 3 units and LaO 8 polyhedra. These results demonstrate that KLBO has the potential to be a UV or DUV NLO crystal.U ltraviolet (UV) and deep-ultraviolet (DUV) coherent lights have numerous indispensable applications in lithography, laser micromachining, remote sensing, communications, biological monitoring, etc. 1−12 The most efficient method to generate short-wavelength lasers is through frequency conversion based on nonlinear-optical (NLO) crystals. Nevertheless, rationally designing a new UV or DUV NLO crystal with excellent comprehensive properties is highly challenging due to the stringent structural and performance requirements, 13−17 including (i) a noncentrosymmetric (NCS) structure, (ii) a wide transparent window to reach the UV or DUV range, (iii) a relatively large secondharmonic-generation (SHG) response [d eff ≥ d 36 (KDP) = 0.39 pm/V], and (iv) sufficient birefringence (0.05−0.10 at 1064 nm) to achieve phase matching (PM). After decades of continuous efforts, many high-performance NLO crystals, such as β-BaB 2 O 4 (β-BBO),

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A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency

Abstract: A new beryllium-free deep-UV transparent NLO crystal Li(H2O)2Sc(SO4)2 consists of distorted [LiO4], [SO4] tetrahedra and [ScO6] octahedra and exhibits a phase-matching SHG response of 0.7 × KDP and a deep-UV cutoff edge below 190 nm.

Cited by 3 publications

References 43 publications

Centrosymmetric CaBaMF₈ and Noncentrosymmetric Li₂CaMF₈ (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

Centrosymmetric CaBaMF₈ and Noncentrosymmetric Li₂CaMF₈ (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

A₃Sc(SO₄)₃ (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability

K₁₅La₇(BO₃)₁₂: A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response

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A lithium–scandium sulfate with second-harmonic generation response and deep-ultraviolet transparency

Abstract: A new beryllium-free deep-UV transparent NLO crystal Li(H2O)2Sc(SO4)2 consists of distorted [LiO4], [SO4] tetrahedra and [ScO6] octahedra and exhibits a phase-matching SHG response of 0.7 × KDP and a deep-UV cutoff edge below 190 nm.

Cited by 3 publications

References 43 publications

Centrosymmetric CaBaMF8 and Noncentrosymmetric Li2CaMF8 (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

Centrosymmetric CaBaMF8 and Noncentrosymmetric Li2CaMF8 (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

A3Sc(SO4)3 (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability

K15La7(BO3)12: A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response

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Centrosymmetric CaBaMF₈ and Noncentrosymmetric Li₂CaMF₈ (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

Centrosymmetric CaBaMF₈ and Noncentrosymmetric Li₂CaMF₈ (M = Zr, Hf): Dimension Variation and Nonlinear Optical Activity Resulting from an Isovalent Cation Substitution-Oriented Design

A₃Sc(SO₄)₃ (A = K, Rb, Cs): Three Deep‐Ultraviolet Transparent Alkali‐Scandium Sulfates with Strong Second‐Harmonic Generation Response and High Thermal Stability

K₁₅La₇(BO₃)₁₂: A KBBF-Like Nonlinear-Optical Material with a Short Cutoff Edge and a Strong Second-Harmonic-Generation Response