Target‐Driven Design of Deep‐UV Nonlinear Optical Materials via Interpretable Machine Learning

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(23)

Published: March 17, 2023

The development of a data-driven science paradigm is greatly revolutionizing the process materials discovery. Particularly, exploring novel nonlinear optical (NLO) with birefringent phase-matching ability to deep-ultraviolet (UV) region vital significance for field laser technologies. Herein, target-driven design framework combining high-throughput calculations (HTC), crystal structure prediction, and interpretable machine learning (ML) proposed accelerate discovery deep-UV NLO materials. Using dataset generated from HTC, an ML regression model predicting birefringence developed first time, which exhibits possibility achieving fast accurate prediction. Essentially, structures are adopted as only known input this establish close structure-property relationship mapping birefringence. Utilizing ML-predicted can affect shortest wavelength, full list potential chemical compositions based on efficient screening strategy identified. Further, eight good stability discovered show applications in region, owing their promising NLO-related properties. This study provides new insight into identify desired high performances broad space at low computational cost.

Language: Английский

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Rational Design of Novel Promising Infrared Nonlinear Optical Materials: Structural Chemistry and Balanced Performances

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: unknown

Published: Feb. 1, 2024

ConspectusSecond-order nonlinear optical (NLO) materials are currently a hot topic in modern solid-state chemistry and optics because they can produce coherent light by frequency conversion. Noncentrosymmetric (NCS) structure is not only the prerequisite for NLO but also challengeable issue tend to be centrosymmetric (CS) terms of thermodynamical stability. Among materials, an excellent infrared (IR) candidate should simultaneously meet several strict key conditions including large coefficient, high laser-induced damage threshold (LIDT), phase-matchable (PM) behavior, so on. Achieving balance between effect LIDT difficult, as have contradictory requirements chemical bonds. Considering urgent need high-power IR laser market drawbacks available ones, exploring new high-performance crystals necessary while challenging. In this Account, we first briefly introduce status advancement emphasize criteria candidate. Then, will five simple methods developed us discover practical candidates through understanding composition–structure–NLO performance relationship. (1) A rarely investigated system with compositions new-type crystals, namely, adducts containing S8 molecules, developed. Combining chairlike unit other units van der Waals forces has successfully obtained adducts. (2) The main trend that composition more diversified complex, expensive chemically active alkaline earth metals usually introduced counter cations. contrast, research on systems compositions, structures, low costs been continuously ignored. binary M2Q3 (M = Ga, In; Q S, Se) family rich acentric modifications systematically investigated, all exhibit strong SHG effects LIDTs. (3) We proposed concept inducing CS structures transformed NCS ones partial cation substitution design novel crystals. huge number database compared it attractive method apply parents obtain potential via partial-substitution-induced symmetry breaking. series chalcogenides performances way. (4) NLO-active rare (RE) chalcophosphates systematically, demonstrate wonderful comprehensive properties. (5) created mixed-anion applications, chalcogenide borates. Usually, compounds engender synergistic desired Our recent progress suggests borates although study still its infancy. Finally, state current problems give some perspectives their future development.

Language: Английский

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

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7868 - 7874

Published: March 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.

Language: Английский

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LaMg6Ga6S16: a chemical stable divalent lanthanide chalcogenide

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 5, 2024

Abstract Divalent lanthanide inorganic compounds can exhibit unique electronic configurations and physicochemical properties, yet their synthesis remains a great challenge because of the weak chemical stability. To best our knowledge, although several monoxides epitaxial thin films have been reported, there is no chemically stable crystalline divalent chalcogenide synthesized up to now. Herein, by using octahedra coupling tetrahedra single/double chains construct an octahedral crystal field, we La(II)-chalcogenide, LaMg 6 Ga S 16 . The nature La 2+ cations be identified X-ray photoelectron spectroscopy, absorption near-edge structure electron paramagnetic resonance, while stability confirmed differential thermal scanning, in-situ variable-temperature powder diffraction series solid-state reactions. Owing particular characteristics (5 d 1 ), displays ultrabroad-band green emission at 500 nm, which inaugural instance La(II)-based demonstrating luminescent properties. Furthermore, as crystallizes in non-centrosymmetric space group, P −6, it second-harmonic generation (SHG) active, possessing comparable SHG response with classical AgGaS 2 In consideration its wider band gap ( E g = 3.0 eV) higher laser-induced damage threshold (5×AgGaS also promising nonlinear optical material.

Language: Английский

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Rb₂CdSi₄S₁₀: novel [Si₄S₁₀] T2-supertetrahedra-contained infrared nonlinear optical material with large band gap

Materials Horizons, Journal Year: 2022, Volume and Issue: 10(2), P. 619 - 624

Published: Nov. 25, 2022

Infrared nonlinear optical (IR-NLO) materials with wide band gaps are important for generating high-power laser light modern technologies. Herein, a gap IR-NLO material, Rb2CdSi4S10, was rationally designed and fabricated by introducing NLO-active [Si4S10] T2-supertetrahedron (ST) into the quaternary sulfide system. The Rb2CdSi4S10 shows largest (4.23 eV) among chalcogenide reported, which results in high laser-induced damage threshold (LIDT) of ∼5 × AgGaS2 (AGS) at 1064 nm. At same time, it has moderate second-harmonic generation (SHG) response (0.6 AGS). Based on statistical analyses, is first compound to be discovered AI2BIICIV4QVI10 family, also Si-rich material T2-supertetrahedra. indicate that promising new T2-ST unit could used exploration excellent performances.

Language: Английский

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Zn₂HgP₂S₈: A Wide Bandgap Hg‐Based Infrared Nonlinear Optical Material with Large Second‐Harmonic Generation Response

Small, Journal Year: 2023, Volume and Issue: 19(46)

Published: July 20, 2023

Hg-based chalcogenides, as good candidates for the exploration of high-performance infrared (IR) nonlinear optical (NLO) materials, usually exhibit strong NLO effects, but narrow bandgaps. Herein, an unprecedented wide bandgap IR material Zn2 HgP2 S8 (ZHPS) with diamond-like structure is rationally designed and fabricated by a tetrahedron re-organization strategy aid property predictions. ZHPS exhibits 3.37 eV, which largest one among reported chalcogenide materials first breaks 3.0 eV "wall" in this system, resulting high laser-induced damage threshold (LIDT) ≈2.2 × AgGaS2 (AGS). Meanwhile, it shows large response (1.1 AGS), achieving balance between (≥3.0 eV) effect (≥1 AGS) excellent material. DFT calculations uncover that, compared to normal [HgS4 ]n , highly distorted ]d tetrahedral units are conducive generating bandgap, can be attributed s-p hybridization Hg─S bonding gives some insights into design chalcogenides properties based on tetrahedra.

Language: Английский

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Unbiased Screening of Novel Infrared Nonlinear Optical Materials with High Thermal Conductivity: Long‐neglected Nitrides and Popular Chalcogenides

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(16)

Published: Feb. 20, 2023

Traditional infrared (IR) nonlinear optical (NLO) materials such as AgGaS2 are crucial to key devices for solid-state lasers, however, low laser damage thresholds intrinsically hinder their practical application. Here, a robust strategy is proposed unbiased high-throughput screening of more than 140 000 explore novel IR NLO with high thermal conductivity and wide band gap which intrinsic threshold. Via our strategy, 106 compounds desired gaps, coefficients screened out, including 8 nitrides, 68 chalcogenides, in Sr2 SnS4 synthesized verify the reliability process. Remarkably, nitrides much higher that e.g., 5×AgGaS2 (5.13 W/m K) ZrZnN2 , indicating could be long-neglected system materials. This provides powerful tool searching conductivity.

Language: Английский

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Ga-based IR nonlinear optical materials: Synthesis, structures, and properties

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 502, P. 215617 - 215617

Published: Dec. 21, 2023

Language: Английский

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Na₃SiS₃F: A Wide Bandgap Fluorothiosilicate with Unique [SiS₃F] Unit and High Laser‐Induced Damage Threshold

Advanced Optical Materials, Journal Year: 2023, Volume and Issue: 11(16)

Published: May 17, 2023

Abstract The exploration of antilaser damage wide bandgap infrared (IR) nonlinear optical (NLO) materials is urgent but challenging. Herein, by introducing the idea fluorination into chalcogenides, a IR NLO material Na 3 SiS F with unprecedented [SiS F] tetrahedra designed and synthesized. shows 4.75 eV (the largest one in reported quaternary metal chalcogenides), resulting high laser induced threshold ≈5 × AgGaS 2 (AGS). Meanwhile, compound has moderate response (≈0.3 ×AGS) phase‐matching behavior, large birefringence (0.15@1064 nm), transparent region. introduction fluorine breaks structural symmetry broadens highest occupied molecular orbital‐lowest unoccupied orbital (HOMO‐LUMO) gap, polarizability anisotropy, hyperpolarizability Si–S tetrahedral unit. results indicate that promising for high‐power application open an avenue design new based on NLO‐active x 4− ] ( = 1, 2, 3) mixed anionic group.

Language: Английский

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Cd₂Nb₂Te₄O₁₅: A Novel Pseudo‐Aurivillius‐Type Tellurite with Unprecedented Nonlinear Optical Properties and Excellent Stability

Small, Journal Year: 2023, Volume and Issue: 19(39)

Published: May 28, 2023

Oxides are emerging candidates for mid-infrared (mid-IR) nonlinear optical (NLO) materials. However, their intrinsically weak second harmonic generation (SHG) effects hinder further development. A major design challenge is to increase the coefficient while maintaining broad mid-IR transmission and high laser-induced damage threshold (LIDT) of oxides. In this study, it reported on a polar NLO tellurite, Cd2 Nb2 Te4 O15 (CNTO), featuring pseudo-Aurivillius-type perovskite layered structure composed three types active groups, including CdO6 octahedra, NbO6 TeO4 seesaws. The uniform orientation distorted units induces giant SHG response that ≈31 times larger than KH2 PO4 , largest value among all metal tellurites. Additionally, CNTO exhibits large band gap (3.75 eV), wide transparency window (0.33-14.5 µm), superior birefringence (0.12@ 546 nm), LIDT (23 × AgGaS2 ), strong acid alkali resistance, indicating its potential as promising material.

Language: Английский

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