RbPbPS₄: a promising IR nonlinear optical material achieved by lone-pair-cation-substitution-induced structure transformation

Inorganic Chemistry Frontiers, Год журнала: 2024, Номер 11(13), С. 3744 - 3754

Опубликована: Янв. 1, 2024

A novel excellent IR-NLO material RbPbPS 4 with superior comprehensive performances is provided, representing the first quaternary Pb-based chalcogenide breaks through incompatibility between a large E g and strong d eff .

Язык: Английский

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Exploring New Horizons in Mid-to-Far Infrared Nonlinear Optical Crystals: The Significant Potential of Trigonal Pyramidal [TeS₃]²⁻ Functional Units

Chemical Science, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

The [TeS 3 ] 2− unit with a SCALP disrupts tetrahedral symmetry, leading to the synthesis of Cu 10 Te 4 S 13 for first time. This material exhibits strong SHG (3.75 × AgGaS 2 ) and widest MFIR transparency (2.5–25 μm) reported NLO chalcogenides.

Язык: Английский

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A Giant Optically Anisotropic Phosphate Driven by Mixed Valence Mercury Units

Laser & Photonics Review, Год журнала: 2024, Номер unknown

Опубликована: Окт. 24, 2024

Abstract Phosphate crystals are known for their low birefringence, a result of the symmetrical tetrahedral structure PO 4 groups. Attempts to increase birefringence have traditionally involved incorporation highly anisotropic ions and Yet, majority modified phospates still exhibit value below 0.1, due counteracting effects elements within coordination. The present study has first time discovered novel birefringence‐active Hg I 2 II O 9 unit successfully constructed layered structure, which ingeniously prevents mutual cancellation effects. This synthesis (Te ) (HPO confirms effectiveness this strategy, yielding 0.444 at 546 nm, outperforms 99% phosphate surpasses that commercial counterparts like YVO (0.209@1064 nm) CaCO 3 (0.175@533 nm). Structural analysis PAWED calculations indicate significant is attributed synergistic interaction between (23.76%), HPO tetrahaedron (24.24%) TeO group (51.99%). breakthrough paves way phosphates meet demands modern technological advancements, expanding potential applications in field optics.

Язык: Английский

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Zero-Dimensional Oxyselenide Ba₁₂[(Ga₂OSe₅)₃(Si₂O₇)]: Enhanced Optical Anisotropy through Heteroanionic Engineering

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 11, 2025

The rational design of chalcogenides with exceptional optical properties remains a significant challenge. Here, we employ heteroanionic engineering to incorporate selenium into the celsian-type BaGa2Si2O8, synthesizing novel zero-dimensional oxyselenide, Ba12[(Ga2OSe5)3(Si2O7)]. It crystallizes in hexagonal space group P63/m and features isolated [Si2O7] [Ga2OSe5] clusters, balanced by Ba2+ cations. unit, reported for first time oxychalcogenides, marks structural breakthrough. compound exhibits wide bandgap (Eg = 3.14 eV), broad IR transmission (0.39-20.4 μm), high thermal stability (up 1100 K). Theoretical calculations reveal that 18-fold enhancement birefringence, increasing from 0.0038 0.068 at 1064 nm, compared its parent structure. This improvement is largely due role unit enhancing anisotropy. work highlights potential designing advanced birefringent materials, paving way functional crystals.

Язык: Английский

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Balanced IR Nonlinear Optical Performance Achieved by Cation–Anion Module Cosubstitution in V-Based Salt-Inclusion Oxychalcogenides

Chemistry of Materials, Год журнала: 2024, Номер unknown

Опубликована: Дек. 3, 2024

Oxychalcogenides have become notable contenders for infrared nonlinear optical (IR NLO) applications because of their diverse heteroanionic functional motifs. However, while the main group elements are well-explored these motifs, transition been less studied and lack high-performance materials. To address this gap, we investigated a series noncentrosymmetric [Ba4(Ba6S)][(VOxS4–x)6] (space group: P63), first V-based salt-inclusion oxychalcogenides demonstrating phase-matched IR-NLO properties. We achieved by cation–anion module cosubstitution in centrosymmetric structure [Ba4(Ba6Cl2)][(VO4)6] P63/m). The novel features isolated [VOxS4–x]3– units, charge-balanced Ba2+ cations, one-dimensional cationic chain [Ba6S]10+ octahedral units. Moreover, [Ba4(Ba6S)][(VO3S)6] exhibits properties including high second-harmonic-generation intensity (1.33 × AgGaS2@2900 nm), substantial laser-induced damage threshold (7.65 AgGaS2), broad IR cutoff edge (up to 11.2 μm), significant birefringence phase matching (Δn = 0.073@2900 nm). Structural analysis DFT calculations demonstrate that configuration [VO3S]3– units enhances NLO increases structural anisotropy. Our findings suggest promising class highlight as an effective approach creating crystals.

Язык: Английский

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Ag₂GeS₃: A Diamond‐Like Chalcogenide as an IR Nonlinear Optical Material with Outstanding Second‐Harmonic Generation Response

Advanced Optical Materials, Год журнала: 2024, Номер 12(27)

Опубликована: Июль 4, 2024

Abstract Diamond‐like (DL) metal chalcogenides have attracted significant attention in recent years because of their complex structural compositions and exceptional nonlinear optical (NLO) capabilities the infrared (IR) range. Despite notable advancements this field, there is still a lack systematic research on high‐performance simply composed IR‐NLO with DL structures. In study, insightful characteristics properties ternary Ag‐based chalcogenide Ag 2 GeS 3 are investigated for first time at both experimental theoretical levels. The compound belongs to non‐centrosymmetric Cmc 1 space group (No.36) displays 3D structure comprising highly oriented [AgS 4 ] [GeS tetrahedra. Due its distinct structure, may produce second harmonic generation (SHG) response (5.6 × AgGaS 2050 nm), biggest value reported among date, phase matchability IR range calculated birefringence Δ n = 0.09 nm. According calculations, combined impacts distorted NLO‐active motifs inside framework provide SHG tensor d 24 51.9 pm V −1 prospective uses field highlighted work.

Язык: Английский

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Strong Second‐Harmonic Generation Responses in Salt‐Inclusion Oxychalcogenides Enabled by the Highly Distorted Polyhedra with Mixed‐Anions

Advanced Optical Materials, Год журнала: 2025, Номер unknown

Опубликована: Фев. 18, 2025

Abstract Nonlinear optical (NLO) crystals demonstrate notable NLO effects, which are predominantly attributed to their anionic groups. However, the role of cations has long been overlooked. For first time, S 2− , Cl − and O successfully incorporated into two new salt‐inclusion oxychalcogenides, namely, [La 4 3 S][GaGeS 6 O] ( 1 ) 2 ][Ge ), characterized by highly distorted polarizable polycations Notably, they exhibit substantial second‐harmonic generation (SHG) intensities 2.7 3.8 × AgGaS @1700 nm, respectively. To best knowledge, latter represents highest value recorded for all oxychalcogenides constructed from tetrahedral structural units. Crystal structure analysis theoretical calculations reveal that units in host lattice polyhedral guest considerably contributed SHG coefficients. Furthermore, compounds display favorable laser‐induced damage thresholds (4.4 7.2 @1064 nm) along with expanded transparency windows. This finding underscores potential host–guest architectures multiple anions markedly enhancing coefficients, paves way development materials.

Язык: Английский

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Nonbonding Electron Inversion‐Driven Structural Engineering: Synergistic Enhancement of Linear and Nonlinear Optical Properties

Angewandte Chemie, Год журнала: 2025, Номер unknown

Опубликована: Апрель 29, 2025

Abstract The simultaneous optimization of large birefringence (Δn, a linear optical property) and strong second‐harmonic generation (SHG, nonlinear (NLO) in single crystal remains significant challenge due to the inherently distinct structural requirements for these properties. Although nonbonding electrons have been extensively studied oxides chalcogenides, research has predominantly focused on their role along polar axes, leaving influence axes tetrahedral stacking largely unexplored. Herein, we propose electron‐inversion strategy overcome phase‐matching limitations defect diamond‐like structures. By incorporating T2‐[Ga 4 S 10 ] supertetrahedral motifs, successfully synthesized [Ba Cl 2 ][CdGa (space group: I ), which exhibits 219% enhancement Δn compared nonphase‐matching parent structure Cd GaS . weakly bound electrons, governed by atomic potentials, demonstrate SHG responses under fields. compound not only achieves broad transmission range (0.28–18.6 µm) high laser‐induced damage threshold (40.1 × AgGaS ) but also optimally balances wide bandgap ( E g = 3.58 eV) response (1.4 representing one best‐performing Cd‐based materials date. This work introduces first design based electron‐driven structure–property relationships, providing critical insights rational high‐performance NLO materials.

Язык: Английский

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Design and Synthesis of Vanadium-Based Infrared Nlo Crystal K4cdv5o15br Through Aliovalent Substitution with Strongly Polarized Active Units

Опубликована: Янв. 1, 2025

Язык: Английский

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La₂Zn₃(SeO₃)₆: A UV Selenite Crystal with Second-Harmonic Generation and Large Birefringence

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 1, 2025

Inorganic selenites are promising candidates for nonlinear optical and birefringent crystals. However, that can effectively transmit in the UV region still relatively scarce. In this study, we successfully synthesized first Zn-based selenite with properties using a hydrothermal method by introducing Zn2+ La3+ ions, which cause blue shift compound's bandgap, into system. The compound crystallizes chiral space group P3112 presents unique three-dimensional structure composed of two-dimensional zinc layers bridged LaO10 polyhedra. Notably, possesses wide bandgap (5.0 eV), high birefringence (0.092 at 546 nm), excellent thermal stability (∼540 °C), broad transparency window (0.21-6 μm), apparent SHG efficiency (0.2 × KDP). Our work not only demonstrates great potential as crystals but also expands research scope materials.

Язык: Английский

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