Bright Green Emission from Self-Trapped Excitons Triggered by Sb³⁺ Doping in Rb₄CdCl₆

Chemistry of Materials, Journal Year: 2022, Volume and Issue: 34(12), P. 5717 - 5725

Published: June 10, 2022

Sb3+ with stereochemically active lone pair 5s2 electrons is overwhelming in the doping engineering of luminescent metal halides, and it usually leads to extrinsic self-trapped excitons (STEs) tunable emissions. However, photoluminescence enhancement mechanism doped halides compared pristine host remains unclear. Herein, we into all-inorganic non-emissive Rb4CdCl6, realizing bright green emission peaking at 525 nm a quantum yield 70.2%. A comparison Raman spectra, as well Debye temperature, was utilized elucidate STEs mechanism, verifying that softens structural lattice. Thus, strong electron–phonon interactions enable highly efficient originating from Rb4CdCl6:Sb3+. This work demonstrates solid evidence emissions can be triggered by doping, design principle involved will guide future studies for emerging luminescence material exploration.

Language: Английский

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Highly Distorted Antimony(III) Chloride [Sb₂Cl₈]²⁻ Dimers for Near‐Infrared Luminescence up to 1070 nm

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 23, 2022

Zero-dimensional (0D) hybrid metal halides with unique compositional and structural tunability appear as an emerging class of luminescent materials, but near-infrared (NIR) emitters therein are largely unexplored to date. This study presents three novel 0D antimony chlorines edge-sharing [Sb2 Cl8 ]2- dimers, showing unusual room-temperature broadband NIR emission the maximum wavelength up 1070 nm. Photoluminescence studies density functional theory calculation demonstrate that emissions originate from highly localized excitons, confined dimers in these structures show low symmetry a large degree freedom. These expand range new materials halides.

Language: Английский

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Achieving Near‐unity Photoluminescence Quantum Yields in Organic‐Inorganic Hybrid Antimony (III) Chlorides with the [SbCl₅] Geometry

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(10)

Published: Jan. 9, 2023

Hybrid organic-inorganic antimony halides have attracted increasing attention due to the non-toxicity, stability, and high photoluminescence quantum yield (PLQY). To shed light on structural factors that contribute PLQY, five pairs of with general formula A2 SbCl5 Sb2 Cl8 are synthesized via two distinct methods characterized. The type adopts square pyramidal [SbCl5 ] geometry near-unity while seesaw dimmer [Sb2 PLQY≈0 %. Through combined data analysis literature, we found series generally has much longer Sb⋅⋅⋅Sb distances, leading more expressed lone SbIII . Additional including Sb-Cl distance stability chlorides may also affect PLQY. Our targeted synthesis correlated insights provide efficient tools precisely form highly emissive materials for optoelectronic applications.

Language: Английский

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Crystal-Liquid-Glass Transition and Near-Unity Photoluminescence Quantum Yield in Low Melting Point Hybrid Metal Halides

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(22), P. 12360 - 12369

Published: May 25, 2023

Hybrid metal halides (HMHs) are a class of materials that combine extraordinary photophysical properties and excellent processability. Their chemical variability allows for the solid-liquid transition toward melt-processable HMHs. Herein, we report design synthesis zero-dimensional HMHs [M(DMSO)6][SbCl6], where isolated octahedra [M(DMSO)6]3+ [SbCl6]3- alternatively aligned in crystal structure. The luminescent center enables photogeneration self-trapped excitons, resulting broadband photoluminescence with large Stokes shift nearly 100% quantum yield. Meanwhile, release DMSO ligands from is controlled by M-O coordination thus low melting point ∼90 °C achieved Interestingly, glass phase obtained melt quenching, sharp change colors compared to robust crystal-liquid-glass opens new avenue tailoring structural disorder optoelectronic performance organic-inorganic materials.

Language: Английский

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Temperature-Dependent Reversible Optical Properties of Mn-Based Organic–Inorganic Hybrid (C₈H₂₀N)₂MnCl₄ Metal Halides

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(4), P. 5487 - 5494

Published: Jan. 18, 2023

Organic-inorganic metal halides (OIMHs) have abundant optical properties and potential applications, such as light-emitting diodes, displays, solar cells, photodetectors. Herein, we report zero-dimensional Mn-based OIMH (C8H20N)2MnCl4 single crystals synthesized by a simple slow evaporation method, which exhibit intense green emission at 520 nm originating from 4T1-6A1 transition of Mn2+ ions. Large organic cations in the crystal structure result isolated [MnCl4]2- tetrahedrons, closest Mn-Mn distance reaches 9.07 Å, effectively inhibits migration excitation energy between adjacent centers, thus achieving high quantum yield (∼87%) long photoluminescence (PL) lifetime (3.42 ms). The different structural low temperatures are revealed temperature-dependent PL X-ray diffraction spectra. spectra lifetimes under heating cooling processes indicate that property transitions reversible 220/240 K. Our work provides promising strategy for building multifunctional optoelectronic materials insights into understanding convertible photophysical isomers halides.

Language: Английский

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The effect of solvent on the formation of low-dimensional metal halides and their self-trapped exciton emission

Chemical Engineering Journal, Journal Year: 2024, Volume and Issue: 486, P. 150257 - 150257

Published: March 8, 2024

Low-dimensional organic–inorganic hybrid metal halides, with broadband luminescence, have attracted much attention for optoelectronic applications due to their rich in structural diversity and solution processibility. However, it is still unclear about how the solvent molecules influence properties of processed low-dimensional halides. Here, we prepared five different antimony-based crystal structures, [SbCl6]3- as halide octahedron 4, 4-difluoropiperidine (DFPD+) organic cation, by using solvents: hydrochloric acid (HCl) aqueous four solvents (dimethylformamide (DMF), methanol (MeOH), acetonitrile (ACN) dimethylacetamide (DMAC)). We revealed relation between structures optical properties, found participation structure causes significant lattice distortions, which beneficial achieving self-trapped exciton (STE) emission. Among them, (DFPD)6SbCl9·2DMAC exhibits a remarkable photoluminescence (PL) quantum yield approximately 90 %. The STE dynamics were characterized femtosecond transient absorption time-resolved PL spectroscopies. Simultaneously, this study also provides new directions expanding application luminescent halides: addition UV-LEDs, efficient rapid detection or can be achieved raw materials, while realizing potential multi-level anti-counterfeiting.

Language: Английский

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Realizing High-Efficiency Yellow Emission of Organic Antimony Halides via Rational Structural Design

ACS Applied Materials & Interfaces, Journal Year: 2022, Volume and Issue: 14(40), P. 45611 - 45620

Published: Sept. 30, 2022

Zero-dimensional (0D) organic metal halides have captured extensive attention for their various structures and distinguished optical characteristics. However, achieving efficient emission through rational crystal structure design remains a great challenge, how the affects photophysical properties of 0D is currently unclear. Herein, regulation strategy in Sb(III)-based proposed to realize near-unity photoluminescence quantum yield (PLQY). Specifically, two compounds with different coordination configurations, namely, (C25H22P)2SbCl5 (C25H22P)SbCl4 (C25H22P+ = benzyltriphenylphosphonium), were successfully obtained by precisely controlling ratio initial raw materials. adopts an octahedral geometry shows highly broadband yellow PLQY 98.6%, while exhibits seesaw-shaped [SbCl4]- cluster does not emit light under photoexcitation. Theoretical calculations reveal that, rationally structure, indirect bandgap can be converted direct (C25H22P)2SbCl5, thus ultimately boosting intensity. Together outstanding stability high-performance white-light emitting diode (WLED) high luminous efficiency 31.2 lm W-1 demonstrated. Our findings provide novel regulate crystals, so as optimize luminescence halides.

Language: Английский

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Tunable Efficient White Emission in Holmium Doped Double Perovskites Cs₂KInCl₆ via Antimony Sensitization

Advanced Optical Materials, Journal Year: 2023, Volume and Issue: 11(10)

Published: March 12, 2023

Abstract Recently, ns 2 metal ions (such as Bi 3+ and Sb ) doped double perovskites have captured intense attention for their efficient emission, however, achieving tunable white light emission is always an enormous challenge. Herein, /Ho co‐doped Cs KInCl 6 are proposed, the photoluminescence results show that there two bands, one broad cyan band stems from self‐trapped exciton (STE) in [SbCl ] 3‐ octahedron, while another red derives f‐f transitions of Ho . The processes can act sensitizer to activate which due energy transfer channel STE As concentration increases, luminous color be modulated orange under 315 nm irradiation, even obtained with a quantum yield 90 ± 2% when energy‐transfer efficiency 50%. Finally, single compound white‐light emitting diodes fluorescent anti‐counterfeiting labels based on 0.5%Sb /60%Ho fabricated. This work provides effective strategy achieve lead‐free through lanthanide ion co‐doping.

Language: Английский

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Pseudo‐2D Layered Organic‐Inorganic Manganese Bromide with a Near‐Unity Photoluminescence Quantum Yield for White Light‐Emitting Diode and X‐Ray Scintillator

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 25, 2023

Abstract Eco‐friendly lead‐free organic–inorganic manganese halides (OIMHs) have attracted considerable attention in various optoelectronic applications because of their superior optical properties and flexible solution processibility. Herein, we report a novel pseudo‐2D layered OIMH (MTP) 2 MnBr 4 (MTP: methyltriphenylphosphonium), which exhibits intense green emission under UV/blue or X‐ray excitation, with near‐unity photoluminescence quantum yield, high resistance to thermal quenching (I 150 °C =84.1 %) good photochemical stability. These features enable as an efficient phosphor for blue‐converted white light‐emitting diodes, demonstrating commercial‐level luminous efficiency 101 lm W −1 wide color gamut 116 % NTSC. Moreover, these crystals showcase outstanding scintillation properties, delivering light yield 67000 photon MeV , detection limit 82.4 nGy s competitive spatial resolution 6.2 lp mm imaging. This work presents new avenue the exploration eco‐friendly luminescent OIMHs towards multifunctional applications.

Language: Английский

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Realizing Color‐Tunable and Time‐Dependent Ultralong Afterglow Emission in Antimony‐Doped CsCdCl₃ Metal Halide for Advanced Anti‐Counterfeiting and Information Encryption

Advanced Optical Materials, Journal Year: 2023, Volume and Issue: 11(14)

Published: April 23, 2023

Abstract Long afterglow luminescent materials have captured intense attention for their unique applications in biological imaging, photodynamic therapy, and optical anti‐counterfeiting. However, achieving highly efficient tunable ultralong emission all‐inorganic metal halides is an open challenge. Herein, Sb 3+ ‐doped hexagonal CsCdCl 3 halide reported via hydrothermal reaction. Upon photoabsorption, the as‐synthesized compounds exhibit dual‐emission bands with a photoluminescence quantum yield (PLQY) of 59.6%, which can be attributed to self‐trapped exciton out strong electron‐phonon coupling. After ceasing excitation 365 nm, bright longest duration lasting up 5000 s witnessed . More importantly, color‐tunable time‐dependent realized regulating doping concentration , should due trap electrons increase gradually under high concentration. Given this unusual characteristics, anti‐counterfeiting information encryption are constructed based on compounds. These findings not only help further understand mechanism halides, but also provide new strategy designing novel materials.

Language: Английский

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