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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(11), С. 7868 - 7874

Опубликована: Март 8, 2024

Sulfate crystals are often criticized for their low birefringence. The small anisotropic SO4 group is becoming the biggest bottleneck hindering application of sulfates in optical functional materials. In this study, we report a new method to significantly enhance birefringence sulfates. title compound increases recording 0.542@546 nm, which larger than that commercial birefringent crystal TiO2 ([email protected] nm). At infrared wavelength, Hg4(Te2O5)(SO4) can be up 0.400@1064 also much YVO4 (0.209@1064 addition, it has wide transparency range, high thermal stability, and excellent environmental making potential material. features novel two-dimensional layered structure composed [Hg4(Te2O5)]2+ layers separated by isolated (SO4)2– tetrahedra. This was designed introducing highly selective cation tellurite sulfate system. valence coordination cations connect with groups only, structure. steric repulsive action tetrahedra may regulate linear lone pair arranged way favors large proven theoretical calculations. PAWED studies showed originated from synergistic effect (Hg2O2)2–, (Te2O5)2–, units, contribution ratio 42.17, 37.92, 19.88%, respectively. Our work breaks limitation opens possibilities as crystals.

Язык: Английский

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A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation

Materials Horizons, Год журнала: 2024, Номер 11(7), С. 1704 - 1709

Опубликована: Янв. 1, 2024

For non-centrosymmetric (NCS) oxides intended for ultraviolet (UV) nonlinear optical (NLO) applications, achieving a wide band gap, large second harmonic generation (SHG) intensity, and sufficient birefringence to satisfy phase matching is significant challenge due their inherent incompatibility. To address this issue, study proposes strategy called framework-optimized structural transformation. Building upon centrosymmetric (CS) NaGa(SeO

Язык: Английский

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Rare-earth-based chalcogenides and their derivatives: an encouraging IR nonlinear optical material candidate

Chemical Science, Год журнала: 2024, Номер 15(16), С. 5869 - 5896

Опубликована: Янв. 1, 2024

With the continuous development of laser technology and increasing demand for lasers different frequencies in infrared (IR) spectrum, research on nonlinear optical (NLO) crystals has garnered growing attention. Currently, three main commercially available types borate materials each have their drawbacks, which limit applications various areas. Rare-earth (RE)-based chalcogenide compounds, characterized by unique f-electron configuration, strong positive charges, high coordination numbers RE cations, often exhibit distinctive responses. In field IR-NLO crystals, they a history spanning several decades, with interest. However, there is currently no comprehensive review summarizing analyzing these promising compounds. this review, we categorize 85 representative examples out more than 400 non-centrosymmetric (NCS) compounds into four classes based connection asymmetric building motifs: (1) RE-based chalcogenides containing tetrahedral motifs; (2) lone-pair-electron (3) [BS

Язык: Английский

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Pb₂(SeO₃)(SiF₆): the first selenite fluorosilicate with a wide bandgap and large birefringence achieved through perfluorinated group modification

Chemical Science, Год журнала: 2024, Номер 15(19), С. 7104 - 7110

Опубликована: Янв. 1, 2024

The first selenite fluorosilicate, Pb 2 (SeO 3 )(SiF 6 ), modified with perfluorinated groups, features a broad transparency range, large birefringence, high LIDT, and excellent environmental stability, marking it potential birefringent material.

Язык: Английский

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Highly Birefringent d⁰ Transition Metal Fluoroantimonite in the Mid Infrared Band: Order–Disorder Regulation by Cationic Size

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 24416 - 24424

Опубликована: Окт. 26, 2023

An unusual O/F ordered d0 transition metal fluoroantimonite, namely, K2SbMoO2F7, has been created by the cationic size effect of alkali metals. It features largest birefringence 0.220@550 nm among inorganic antimonites with a halogen element, which is an order magnitude larger than disordered A2SbMoO2F7 (A = Rb, Cs). These three new compounds exhibit two different structures, although all structures were made [SbMoO2F7]2- chains formed SbF5 square pyramids and MoO2F4 octahedrons. A transparent single crystal K2SbMoO2F7 dimensions 7.0 × 5.0 1.0 mm3 successfully grown aqueous solution volatilization method. The UV-vis-MIR transmission spectrum showed that can display excellent transmittance in range 0.5-5.0 μm 6.0-9.8 μm, indicating its application potential as birefringent material mid infrared band. This work offers fresh approach to design synthesis materials.

Язык: Английский

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Breaking Through the Trade‐Off Between Wide Band Gap and Large SHG Coefficient in Mercury‐Based Chalcogenides for IR Nonlinear Optical Application

Small, Год журнала: 2023, Номер 20(6)

Опубликована: Окт. 2, 2023

Abstract It is substantially challenging for non‐centrosymmetric (NCS) Hg‐based chalcogenides infrared nonlinear optical (IR‐NLO) applications to realize wide band gap ( E g > 3.0 eV) and sufficient phase‐matching (PM) second‐harmonic‐generation intensity d eff 1.0 × benchmark AgGaS 2 ) simultaneously due the inherent incompatibility. To address this issue, work presents a diagonal synergetic substitution strategy creating two new NCS quaternary chalcogenides, AEHgGeS 4 (AE = Sr Ba), based on centrosymmetric (CS) AEIn S . The derived displays excellent NLO properties such as (≈3.04–3.07 eV), large PM (≈2.2–3.0 ), ultra‐high laser‐induced damage threshold (≈14.8–15 suitable Δ n (≈0.19–0.24@2050 nm), making them highly promising candidates IR‐NLO applications. Importantly, second‐order are primarily attributed synergistic combination of tetrahedral [HgS ] [GeS functional primitives, supported by detailed theoretical calculations. This study reports first materials with well‐balanced comprehensive (i.e., eV puts forward design avenue construction more efficient candidates.

Язык: Английский

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Hg₃Se(SeO₃)(SO₄): A Mixed-Valent Selenium Compound with Mid-Infrared Transmittance Obtained by In Situ Reaction

Inorganic Chemistry, Год журнала: 2024, Номер 63(9), С. 4011 - 4016

Опубликована: Фев. 16, 2024

Exploring new material systems is a highly significant task in the field of inorganic chemistry. A mixed-valent selenium compound, Hg3Se(SeO3)(SO4), was successfully synthesized through situ reactions. This compound exhibits novel three-dimensional structure composed Hg3Se(SO4) layers bridged by SeO3 trigonal pyramids. It first containing (SeO3)2–, (SO4)2–, and Se2– simultaneously. In addition, Hg3Se(SeO3)(SO4) possesses wide bandgap (3.5 eV), moderate birefringence (Cal:0.064@546 nm, Exp:0.069@546 nm), high laser-induced damage threshold (23.35 MW cm–2), transmittance window (0.28–6.6 μm). Our work demonstrates that (+4, −2) selenite selenide can be potential optical materials for mid-infrared region.

Язык: Английский

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[(C₅H₆N₂)₂H](Sb₄F₁₃): A polyfluoroantimonite with strong second harmonic generation effect

Chemical Science, Год журнала: 2024, Номер 15(21), С. 8071 - 8079

Опубликована: Янв. 1, 2024

A universal synthesis method for polyfluoroantimonites has been developed. Polar [(C 5 H 6 N 2 ) H](Sb 4 F 13 was achieved by polyfluoroantimonite strategy. It features a strong SHG effect, large birefringence and high LIDT value.

Язык: Английский

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The first Hg-based oxychalcogenide Sr2HgGe2OS6: Achieving balanced IR nonlinear optical properties through synergistic cation and anion substitution

Materials Today Physics, Год журнала: 2024, Номер 44, С. 101442 - 101442

Опубликована: Апрель 17, 2024

Язык: Английский

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A Highly Optical Anisotropic Hybrid Perovskite for Efficient Manipulation of Light Polarization

Advanced Functional Materials, Год журнала: 2024, Номер 34(40)

Опубликована: Май 8, 2024

Abstract Optical anisotropic (e.g., birefringent) crystals can manipulate the polarization of light and thus are widely applied in modern optical fields. Common birefringent almost exclusively limited to inorganic oxides with small birefringence. Here, a new 1D hybrid halide perovskite PZPbCl 3 (PZ = phenazine) is reported, which consists perfectly parallel Pb–Cl chains PZ cations. Remarkably, polarized observations show that even crystal micrometer thickness modulate efficiently. Furthermore, exhibits exceptional birefringence up 0.65@546 nm, significantly larger than commercial oxide crystals. According first‐principles calculations polarizability anisotropy analyses, it found this mainly ascribed linear polymerization π ‐conjugated rings Due rich physical properties structural diversity perovskites, believed introduction excellent into perovskites will bring unprecedented opportunities future explorations polarization‐dependent functional materials.

Язык: Английский

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