Highly Anisotropic Second-Order Nonlinear Optical Effects in the Chiral Lead-Free Perovskite Spiral Microplates

Nano Letters, Год журнала: 2023, Номер 23(2), С. 606 - 613

Опубликована: Янв. 9, 2023

Chiral metal halide perovskites with intrinsic asymmetric structures have drawn increased research interest for the application of second-order nonlinear optics (NLO). However, designing chiral features a large NLO coefficient, high laser-induced damage thresholds (LDT), and environmental friendliness remains major challenge. Herein, we synthesized two hybrid bismuth halides: (R/S-MBA)4Bi2Br10 spiral structure microplates, templated by (R/S)-methylbenzylamine (R/S-MBA). The as-grown lead-free perovskite microplates exhibit recorded second harmonic generation (SHG) effect effective coefficient (deff) 11.9 pm V-1 LDT up to 59.2 mJ cm-2. More importantly, twisted screw show competitive circular polarization sensitivity at 1200 nm an anisotropy factor (gSHG-CD) 0.58, which is about 3 times higher than that reported Pb-based perovskites. These findings provide new platform design multifunctional photonic applications.

Язык: Английский

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Chiral Hybrid Germanium(II) Halide with Strong Nonlinear Chiroptical Properties

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(41)

Опубликована: Авг. 23, 2023

Due to the pronounced anisotropic response circularly polarized light, chiral hybrid organic-inorganic metal halides have been regarded as promising candidates for application in nonlinear chiroptics, especially second-harmonic generation circular dichroism (SHG-CD) effect. However, designing novel lead-free with large anisotropy factors and high laser-induced damage thresholds (LDT) of SHG-CD remains challenging. Herein, we develop first germanium halide, (R/S-NEA)3 Ge2 I7 ⋅H2 O (R/S-NGI), systematically investigated its linear chiroptical properties. S-NGI R-NGI exhibit (gSHG-CD ) 0.45 0.48, respectively, along a LDT 38.46 GW/cm2 ; these were highest values among reported halides. Moreover, effective second-order optical coefficient could reach up 0.86 pm/V, which was 2.9 times higher than that commercial Y-cut quartz. Our findings facilitate new avenue toward halides, their implementation applications.

Язык: Английский

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Efficient Red-Emissive Circularly Polarized Electroluminescence Enabled by Quasi-2D Perovskite with Chiral Spacer Cation

ACS Nano, Год журнала: 2023, Номер 17(8), С. 7830 - 7836

Опубликована: Апрель 11, 2023

Perovskites are promising environmentally sustainable materials for circularly polarized electroluminescence (CPEL). While another chiral nonemissive layer is required the developed perovskite-based CPEL, we report herein a highly efficient based on single of quasi-2D perovskite with achiral phenethylammonium iodide (PEAI) and S/R-1-(1-naphthyl)ethylammonium (S/R-NEAI) as dual spacer cations. The was further passivated by carbazole-functionalized phosphonium. as-fabricated film exhibits not only circular dichroism (CD) signal but also prominent luminescence (CPL) activity maximum photoluminescence dissymmetry factor (glum) ∼2.1 × 10-3. More importantly, efficient, spin-polarized light-emitting diode (LED) fabricated in situ peak external quantum efficiency 3.7% (gEL) ∼4.0

Язык: Английский

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Free Halogen Substitution of Chiral Hybrid Metal Halides for Activating the Linear and Nonlinear Chiroptical Properties

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(49), С. 26833 - 26842

Опубликована: Дек. 1, 2023

Halogen substitution has been proven as an effective approach to the band gap engineering and optoelectronic modulation of organic–inorganic hybrid metal halide (OIHMH) materials. Various high-performance mixed OIHMH film materials have primarily obtained through coordinated halogens in their inorganic octahedra. Herein, we propose a new strategy free halogen outside octahedra for constructing single crystals with chiral structures, resulting boost linear nonlinear chiroptical properties. The from DMA4[InCl6]Cl (DMA = dimethylammonium) DMA4[InCl6]Br facile antisolvent vaporization method produces centimeter-scale high thermal stability along quantum yield photoluminescence, conspicuous circularly polarized luminescence, greatly enhanced second harmonic generation (SHG). In particular, crystal features intrinsic structure, exhibiting significant SHG circular dichroism (SHG-CD) response highest reported anisotropy factor (gSHG-CD) 1.56 among enhancements both properties are directly attributed octahedral distortion. by confine introduced within sites lattice, thereby ensuring compositions successful employment such may broaden horizon regulation structures

Язык: Английский

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Two-Dimensional Hybrid Dion–Jacobson Germanium Halide Perovskites

Chemistry of Materials, Год журнала: 2023, Номер 35(8), С. 3265 - 3275

Опубликована: Апрель 5, 2023

Hybrid two-dimensional (2D) halide perovskites have emerged as an important class of high-performance semiconductors because their excellent physical properties and structural diversity. Here, we report a new family hybrid 2D Ge-based that the Dion–Jacobson structure type, with general formula A(MA)n–1GenX3n+1, where A = 2-(aminomethyl)pyridinium (2AMPY), 3-(aminomethyl)pyridinium (3AMPY), 4-(aminomethyl)pyridinium (4AMPY), or 4-(aminomethyl)piperidinium (4AMP), X Br I, n 1 2. Single-crystal X-ray diffraction shows most bromide structures are centrosymmetric, whereas iodide analogues all non-centrosymmetric. The optical band gaps effectively regulated by level octahedral distortion corresponding [GeX6], larger corresponds to gap. These compounds exhibit relatively weak photoluminescence, which can be observed at low temperatures. All good second-harmonic generation (SHG) responses, highest reaching 0.53 × AgGaS2 for (4AMPY)GeI4, particle-dependent SHG has been investigated. First-principles calculations in agreement experimental results. Furthermore, layer transformation achieved from (100)- (110)-oriented configuration mixing halides, is rare example. results showcase versatility diversity employing asymmetric dication Ge2+ metal achieve active non-centrosymmetric materials, providing strategies design lead-free alternatives interesting photophysical properties.

Язык: Английский

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Resonant Second Harmonic Generation in Proline Hybrid Lead Halide Perovskites

Advanced Optical Materials, Год журнала: 2023, Номер 11(8)

Опубликована: Фев. 8, 2023

Abstract Chiral hybrid organic−inorganic perovskites (HOIPs) with intrinsic noncentrosymmetry have shown great potentials for chiroptoelectronic applications including second‐order nonlinear optics (NLO). Ideal NLO materials should simultaneously feature a large coefficient, wide optical transparency, high laser damage threshold, and physicochemical stability. However, the development of applicable has been largely restricted due to their strict requirement on structural noncentrosymmetry. Here, chiral amino acids abundant in nature adopted synthesize lead halide ( D ‐/ L ‐Pro)PbI 3 ·H 2 O (Pro = Proline) resonance enhanced second‐harmonic generation (SHG). Their crystals balanced performances transparent region, polarization ratio. This work demonstrates promise naturally construction metal next optoelectronic materials.

Язык: Английский

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Reversible tri-state structural transitions of hybrid copper(i) bromides toward tunable multiple emissions

Inorganic Chemistry Frontiers, Год журнала: 2023, Номер 11(1), С. 156 - 163

Опубликована: Окт. 17, 2023

Synthetic control and tri-state structural transitions (112 ↔ 224 246) of three hybrid copper bromides with different coordination geometries, which exhibit tunable optical property, are fristly discovered investigated in halides.

Язык: Английский

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Boosted Second Harmonic Generation of a Chiral Hybrid Lead Halide Resonant to Charge Transfer Exciton from Metal Halide Octahedra to Ligand

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(19)

Опубликована: Март 12, 2024

Abstract Chiral hybrid organic–inorganic metal halides (HOMHs) offer an ideal platform for the advancement of second‐order nonlinear optical (NLO) materials owing to their inherent noncentrosymmetric structures. The enhancement nonlinearity chiral HOMHs could be achieved by matching free exciton and/or self‐trapped energy levels with desired NLO frequencies. However, current scarcity resonance modes and low ratio hamper further improvements performance. Herein, we propose a new resonant channel charge transfer (CT) excited states from halide polyhedra organic ligand boost HOMHs. model lead (C 7 H 10 N)PbBr 3 N=1‐ethylpyridinium) exhibits drastically enhanced second harmonic generation in deep CT energy, intensity up 111.0 times that KDP 10.9 urea. effective coefficient has been determined as high ~40.2 pm V −1 , balanced large polarization laser damage threshold. This work highlights contribution ligands construction enhancing coefficients halides, thus provides guidelines designing advanced photonic applications.

Язык: Английский

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1D Tin(II)‐Based Chiral Hybrid Perovskite Single Crystals with Extremely Distorted Inorganic Chains for Second Harmonic Generation

Advanced Optical Materials, Год журнала: 2024, Номер 12(17)

Опубликована: Фев. 17, 2024

Abstract The organic–inorganic hybrid metal halides with chiral structures have attracted great attentions in the field of optoelectronic functional materials, especially for nonlinear optics. To date, second harmonic generation (SHG) properties several classes different ions been reported. However, SHG‐active tin(II)‐based materials are rarely explored, hindering deep understandings relationship between their and SHG properties. Herein, Sn 2+ successfully introduced into perovskites, four new species perovskites ( R / S ‐α‐PEA)SnX 3 (X = Cl Br, PEA phenylethylammonium) obtained. as‐grown crystals P 2 1 space group, highly distorted [SnX 6 ] octahedral units forming 1D chain lattice, due to effect stereochemically active lone pair 5s electrons . Such an response ≈1.4× Y‐cut α‐quartz ‐α‐PEA)SnBr ≈0.9× ‐α‐PEA)SnCl at 1020 nm excitation, high polarization ratio signals as well wide bandgaps transparency windows meanwhile. This work opens up a platform discovering more novel superior optical future.

Язык: Английский

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Magneto‐chiral Nonlinear Optical Effect with Large Anisotropic Response in Two‐Dimensional Halide Perovskite

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Март 28, 2024

Abstract The chiral organic–inorganic halide perovskites (OIHPs) are vital candidates for superior nonlinear optical (NLO) effects associated with circularly polarized (CP) light. NLO in materials often couples magnetic dipole (MD) transition, as well the conventional electric (ED) transition. However, importance of MD transition process OIHPs has not yet been recognized. Here, circular probe analysis second harmonic generation dichroism (SHG‐CD) provides direct evidence that contribution leads to a large anisotropic response CP lights OIHPs, (R‐/S‐MBACl) 2 PbI 4 . thin films exhibit great sensitivity over wide wavelength range, and g‐value reaches up 1.57 at where is maximized. Furthermore, it also effective light generator, outputting CP‐SHG maximum g‐factor 1.76 upon stimulation linearly This study deepens understanding relation between chirality magneto‐optical effect, such an efficient discrimination signal highly applicable chirality‐based sensor communication devices.

Язык: Английский

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