LiRE(SO<sub>4</sub>)<sub>2</sub>(RE = Y, Gd, Eu): noncentrosymmetric chiral rare-earth sulfates with very large band gaps

Cho, Sunghwan; Ok, Kang Min

doi:10.1039/d2qm00983h

Cited by 10 publications

(8 citation statements)

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“…Nonlinear optical (NLO) crystals have garnered significant attention due to their crucial role in advancing laser science and technology. [1][2][3][4][5][6][7] The conversion of laser frequency can be achieved through various up-and down-conversion processes in NLO crystals, such as second-order harmonic generation (SHG), sum frequency generation (SFG), difference frequency generation (DFG), optical parametric oscillation (OPO), and optical parametric amplification (OPA). 8 Over the past few decades, several promising deep-ultraviolet (DUV), ultravioletvisible (UV-Vis), and infrared (IR) crystals have been discovered and extensively researched, such as KBe 2 BO 3 F 2 (KBBF), 9 LiB 3 O 5 (LBO), 10 b-BaB 2 O 4 (b-BBO), 11 KH 2 PO 4 (KDP), 12 KTiOPO 4 (KTP), 13 AgGaS 2 (AGS), 14 AgGaSe 2 (AGSe) 15 and ZnGeP 2 (ZGP).…”

Section: Introductionmentioning

confidence: 99%

Nitrides: a promising class of nonlinear optical material candidates

Zhao,

Lin,

Tian

et al. 2023

Mater. Chem. Front.

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Section: Introductionmentioning

confidence: 99%

Nitrides: a promising class of nonlinear optical material candidates

Zhao,

Lin,

Tian

et al. 2023

Mater. Chem. Front.

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“…50 The 3D title NRY compound is structurally closely related to the earlier reported noncentrosymmetric (NCS) LiY(SO 4 ) 2 compound. 51 Both compounds are composed of a YO 8 dodecahedron and SO 4 tetrahedra with isolated alkali metals. The reported LiY(SO 4 ) 2 compound has been crystallized in nonpolar NCS helical structures due to the influence of the smaller cation Li + .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Deep-Ultraviolet Bialkali–Rare Earth Metal Anhydrous Sulfate Birefringent Crystal

Zhao,

Song,

et al. 2024

Inorg. Chem.

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Birefringence is an important linear optical property of anisotropic crystals that plays a significant role in regulating light polarization. A new bialkali–rare earth metal sulfate, NaRbY2(SO4)4 compound, consisting of non-π-conjugated alkali metals and rare earth metal-centered dodecahedral YO8 has been synthesized. The structure analysis suggests that the three-dimensional (3D) structure of the compound is found to be attributable to the combination of dodecahedral YO8 and tetrahedral SO4 groups with Na+ and Rb+ located in the cavities. The ultraviolet, visible, and near-infrared (UV–vis–NIR) spectra reveal that the compound exhibits transparency at a wavelength of less than 200 nm. The observed birefringence of the compound is 0.045@550 nm, which is comparatively larger than that of most deep-ultraviolet (DUV) birefringent crystals. The birefringence mainly originated from the YO8 dodecahedron, which is suggested by first-principles calculations. This research work can provide a useful perspective to explore new DUV sulfates with excellent birefringence.

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“…Sulfate crystals are receiving increasing attention in the research of optoelectronic functional materials due to their tetrahedral building unit, wide optical band gap, short UV cutoff edge, and easy crystal growth. , The long overlooked SO 4 tetrahedron has been found to be a good type of functional unit used in nonlinear optical materials. , However, the highly symmetrical SO 4 groups often result in a low birefringence of sulfates, such as LiNH 4 SO 4 (0.0078@532 nm) and LiKSO 4 (0.00025@546 nm) . Such a small birefringence prevents many sulfates from achieving phase matching by a direct second-harmonic generation process, hindering the application of sulfate crystals. , …”

Section: Introductionmentioning

confidence: 99%

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

Li,

Hu,

et al. 2024

J. Am. Chem. Soc.

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Sulfate crystals are often criticized for their low birefringence. The small anisotropic SO 4 group is becoming the biggest bottleneck hindering the application of sulfates in optical functional materials. In this study, we report a new method to significantly enhance the birefringence of sulfates. The title compound increases the birefringence recording of sulfates to 0.542@546 nm, which is significantly larger than that of the commercial birefringent crystal of TiO 2 (0.306@546.1 nm). At the infrared wavelength, the birefringence of Hg 4 (Te 2 O 5 )(SO 4 ) can be up to 0.400@1064 nm, which is also much larger than the infrared birefringent crystal of YVO 4 (0.209@1064 nm). In addition, it also has a wide transparency range, high thermal stability, and excellent environmental stability, making it a potential birefringent material. Hg 4 (Te 2 O 5 )(SO 4 ) features a novel two-dimensional layered structure composed of [Hg 4 (Te 2 O 5 )] 2+ layers separated by isolated (SO 4 ) 2− tetrahedra. This compound was designed by introducing a highly selective cation in a tellurite sulfate system. The low valence low coordination cations connect with tellurite groups only, making the sulfate isolated in the structure. The steric repulsive action of the isolated SO 4 tetrahedra may regulate the linear and lone pair groups arranged in a way that favors large birefringence. This method can be proven by theoretical calculations. PAWED studies showed that the large birefringence originated from the synergistic effect of (Hg 2 O 2 ) 2− , (Te 2 O 5 ) 2− , and (SO 4 ) 2− units, with a contribution ratio of 42.17, 37.92, and 19.88%, respectively. Our work breaks the limitation of low birefringence in sulfates and opens up new possibilities for their application as birefringent crystals.

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LiRE(SO₄)₂(RE = Y, Gd, Eu): noncentrosymmetric chiral rare-earth sulfates with very large band gaps

Abstract: Syntheses, structure determinations, and linear/nonlinear optical properties of novel noncentrosymmetric chiral sulfate materials, LiRE(SO4)2 (RE = Y, Gd, and Eu), exhibiting very short UV-cutoff edges are presented.

Cited by 10 publications

References 42 publications

Nitrides: a promising class of nonlinear optical material candidates

Nitrides: a promising class of nonlinear optical material candidates

Deep-Ultraviolet Bialkali–Rare Earth Metal Anhydrous Sulfate Birefringent Crystal

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

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LiRE(SO4)2(RE = Y, Gd, Eu): noncentrosymmetric chiral rare-earth sulfates with very large band gaps

Abstract: Syntheses, structure determinations, and linear/nonlinear optical properties of novel noncentrosymmetric chiral sulfate materials, LiRE(SO4)2 (RE = Y, Gd, and Eu), exhibiting very short UV-cutoff edges are presented.

Cited by 10 publications

References 42 publications

Nitrides: a promising class of nonlinear optical material candidates

Nitrides: a promising class of nonlinear optical material candidates

Deep-Ultraviolet Bialkali–Rare Earth Metal Anhydrous Sulfate Birefringent Crystal

Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

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LiRE(SO₄)₂(RE = Y, Gd, Eu): noncentrosymmetric chiral rare-earth sulfates with very large band gaps

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation