Hafnium-Based Chiral 2D Organic–Inorganic Hybrid Metal Halides: Engineering Polarity and Nonlinear Optical Properties via Para-Substituent Effects

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 8, 2025

Two-dimensional (2D) organic–inorganic hybrid metal halides (OIMHs), characterized by noncentrosymmetric structures arising from the incorporation of chiral organic molecules that break inversion symmetry, have attracted significant attention. Particularly, chiral-polar 2D OIMHs offer a unique platform for multifunctional applications, as coexistence chirality and polarity enables simultaneous manifestation distinct properties such nonlinear optical (NLO) effects, circular dichroism (CD), ferroelectricity. In this study, we report first synthesis hafnium (Hf)-based OIMHs, achieved through strategic para-substituents on benzene ring components. By tuning substituents, successfully modulate crystal structures, resulting in both chiral-nonpolar systems. Our analysis structural properties, supported density functional theory calculations, demonstrates these materials can be systematically tuned, enabling adjustable band gaps CD UV range (200–280 nm). Notably, halogen substitution at para-position layer produces tunable ranging 4.33 to 4.48 eV, widest reported date OIMHs. Furthermore, exhibit enhanced NLO including remarkable 3.3-fold increase second-harmonic generation intensity compounds compared their counterparts. These findings position Hf-based promising candidates UV-region devices self-driven circularly polarized light detectors, offering new opportunities designing optoelectronic harnessing interplay between polarity.

Язык: Английский

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Bi-Based Metal Halide Perovskites and Their Photocatalytic Properties: A Review

Energy & Fuels, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Язык: Английский

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Effect of precursor concentration and annealing temperature on the optical properties of Cs2AgBiBr6 perovskite thin film

Deleted Journal, Год журнала: 2025, Номер 246(1)

Опубликована: Фев. 12, 2025

Язык: Английский

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Vacancy-Ordered Hybrid Two-Dimensional Bi(III) Iodides with (100)-Oriented Dion-Jacobson Perovskite-Related Structures

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Май 11, 2025

Two-dimensional (2D) hybrid iodide perovskites, (R-NH3)2MI4 and (H3N-R-NH3)MI4 (R = alkyl group; M divalent metal ion), are promising materials for optoelectronics. Traditionally, these compounds contain Pb2+ Sn2+ ions in the M-site; however, concerns over toxicity of instability have driven interest Bi3+ halide-based alternatives. This study reports two Dion-Jacobson type, vacancy-ordered 2D Bi-I perovskites: (H2DAC)Bi2/3□1/3I4, with vacancy every third site (H2DAP)BiBi1/2□1/2I3·(I3)1/2, second (H2DAC trans-1,4-diammoniumcyclohexane, H2DAP 1,5-diammoniumpentane, □ vacancy). The band gaps (H2DAC)Bi2/3□1/3I4 (H2DAP)Bi1/2□1/2I3·(I3)1/2 2.11 1.97 eV, respectively─both narrower than that Pb2+-based analogue (H2DAC)PbI4 (2.36 eV). These show a positive photoresponse under light exposure, highest response observed case (H2DAP)Bi1/2□1/2I3·(I3)1/2. enhancement is attributed to presence I3- ions, which not only cross-link perovskite layers stabilize cation its zigzag conformation but also contribute frontier orbitals. DFT calculations corroborate experimental results. Overall, this introduces an approach synthesizing Bi(III)-I may be further investigated as lead-free optoelectronic materials, including photovoltaics.

Язык: Английский

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Environmental‐Friendly Self‐Powered Polarization Photodetector Based on Lead‐Free Halide Double Perovskite Single Crystals with Asymmetric Contacts

Advanced Optical Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 16, 2025

Abstract 2D lead‐free halide double perovskites (HDPs) are distinguished by their low toxicity and superior stability, offering a promising avenue for environmentally friendly polarization photodetection due to intrinsic crystal anisotropy exceptional optoelectronic properties. However, the realization of self‐powered detection using these materials remains in its infancy requires further development. In this study, impressive is successfully achieved constructing HDP‐based asymmetric contact photodetectors (PDs), Ag/(BA) 2 CsAgBiBr 7 /C (BA = n‐butylamine). By leveraging potential difference from electrodes with varying work functions, PDs exhibit V oc 0.9 under illumination, facilitating at mode an detectivity 3.84 × 10¹⁰ Jones. Furthermore, combining perovskite (BA) , detectors realized photodetection, demonstrating ratio 1.35. This study insights construction detector employing domain perovskites, highlighting reliability future applications.

Язык: Английский

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Tri‐functionalized Cation Assisted Crystallization of 2D Chiral&Polar Hybrid Lead Iodide Showing Bulk Photovoltaic Effect for Self‐Powered Circularly Polarized Light Detection

Advanced Functional Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 26, 2025

Abstract Chiral organic–inorganic hybrid metal halides (OIHMHs) are such a promising family of chiral semiconductors to directly sense circularly polarized light (CPL) due inherent chiroptical activity, but face synthetic constraints shortage suitable building blocks that generate and 2D structures, which prerequisite for expected optoelectronic responses. Here, halogen interaction assisted crystallization pair OIHMHs, ( R / S ‐AMOL‐I) 2 PbI 4 1 ; AMOL‐I = 1‐amino‐4‐iodobutan‐2‐ol cation) is reported. In situ iodine substitution in the cation forms halogen‐halogen bond, favoring chiral&polar structure efficient chirality transfer. The polar produces significant bulk photovoltaic effect (0.48 V), serves as driving source self‐powered CPL detection. When exposed CPL, fabricated single crystal‐based device shows large response asymmetry factor (0.16) at zero bias. Moreover, prototypical broadband photo‐responses wavelength range 265–700 nm, attributed structure‐aroused pyroelectric effect. This study evidences how substituted group organic leads desired OIHMHs enable high‐sensitive detection, offering new insights design functional semiconductors.

Язык: Английский

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Optoelectronics of Lead‐Free Antimony‐ and Bismuth‐Based Metal Halides for Sensitive and Low‐Noise Photodetection

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Abstract Organic–inorganic hybrid halide perovskites have emerged as the most promising optoelectronic materials for next‐generation solution‐processed devices, primarily attributed to their distinctive properties such cost‐effectiveness, facile fabrication process, high light absorption coefficient, tunable bandgap, and relatively charge carrier mobility. Nevertheless, presence of Pb elements is inevitable in high‐performance perovskite posing environmental pollution concerns impeding commercialization. In this study, two novel non‐toxic bismuth‐ antimony‐based with environmentally conscious approaches are developed. Their structures been systematically characterized. Subsequently, photoconductive‐ photodiode‐type photodetectors designed fabricated. Notably, photodiode configuration exhibits exceptionally low dark current noise, superior detection sensitivity, fast response speed, good device stability. Owing these performance metrics, devices demonstrate great potential real applications. Furthermore, study furnishes a theoretical framework design perspectives semiconductor materials.

Язык: Английский

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A Three-Dimensional Lead Iodide Perovskite Analog Featuring Hydrogen-bonded Dual Monovalent Cations

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

A 3D perovskite analog is constructed by using hydrogen bond to reduce electrostatic repulsion of two monovalent cations. The study highlights the potential overcome cation selection limitations on novel perovskite-like materials.

Язык: Английский

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Enhanced Second‐Harmonic Generation in Quadratically Nonlinear Weyl Semimetal NbAs for Broadband Photodetection Applications

Advanced Functional Materials, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 18, 2024

Abstract Quadratically nonlinear photodetectors (QNPDs) typically focus on 2D materials with high second‐order polarizability, thereby severely disregarding bulk optical (NLO) crystals as these rely phase‐matching technology and achieving efficient QNPDs remains a significant challenge. Weyl semimetal have some signatures of inversion symmetry breaking, most notably NLO while the inability to balance low transmittance limits frequency conversion zero‐band gap absorption‐induced crystal. Herein, this study investigates an QNPD based NbAs designed strong second‐harmonic effect due its large refractive index (≈5.0), resulting in intense laser reflectivity 50% surface, which creates favorable environment for generation (SHG) without phase matching. The has rectification ratio exceeding 10 7 dark current 164 pA enhanced photoresponse 355‒1900 nm range, exhibiting maximum responsivity 4.1 mA W −1 detectivity 0.8 × Jones at 355 nm. improvement rate is 88% higher than that linear (001) photodetector. This opens new avenues designing by utilizing second harmonic crystals.

Язык: Английский

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