Tunable Emission Research Articles

Tuneable Efficient White Emission of Sb3+/Mn2+ Co-Doped Lead-Free Perovskites for Single-Component White Light-Emitting Diodes.

Inorganic lead-free perovskite nanocrystals (NCs) with broadband self-trapped exciton (STEs) emission and low toxicity have shown enormous application prospects in the field of display and lighting. However, white light-emitting diodes (WLEDs) based on a single-component material with high photoluminescence quantum yield (PLQY) remain challenging. Here, we demonstrate a novel codoping strategy by introducing Sb3+/Mn2+ ions to achieve the tuneable dual emission in lead-free perovskite Cs3InCl6 NCs. The PLQY increases to 59.64% after doping with Sb3+. The codoped Cs3InCl6 NCs exhibit efficient white light emission due to the energy transfer channel from STEs to Mn2+ ions with PLQY of 51.38%. Density functional theory (DFT) calculations have been used to verify deeply the effects of Sb3+/Mn2+ doping. WLEDs based on Sb3+/Mn2+-codoped Cs3InCl6 NCs are explored with color rendering index of 85.5 and color coordinate of (0.398, 0.445), which have been successfully applied as photodetector lighting sources. This work provides a new perspective for designing novel lead-free perovskites to achieve single-component WLEDs.

Identification of Defect Origin and White-Light Emission Tuning of Chalcogenide Quantum Dots Through Pressure Engineering

Identification of Defect Origin and White-Light Emission Tuning of Chalcogenide Quantum Dots Through Pressure Engineering

The crystal structure, energy transfer and tunable luminescence properties of NaLaMgWO6:Tm3+, Eu3+ phosphors

A series of NaLaMgWO6:Tm3+, Eu3+ phosphors with color-tunable emission were successfully synthesized by the solid-state reaction method. The crystal structure, luminescence characteristics and energy transfer of NaLaMgWO6:Tm3+, Eu3+ phosphors have been studied. It is observed that Tm3+ singly doped phosphors exhibit intense blue emission at 484 nm, and Eu3+ singly doped phosphors emit red light at 621 nm. The phosphors co-doped with Tm3+, Eu3+ exhibit fluorescence spectra composed by the characteristic emission peaks of Tm3+ ions and Eu3+ ions. A tunable emission color from blue to red can be obtained by adjusting the ratio of the doping concentration of Tm3+/Eu3+, indicating a significant energy transfer from Tm3+ to Eu3+. The energy transfer mechanism between Tm3+→Eu3+ in the NaLaMgWO6:Tm3+, Eu3+ phosphors is proved to be a quadrupole-quadrupole interaction. These results show that NaLaMgWO6:Tm3+, Eu3+ phosphors may have a potential application in white light emitting diodes.

Layer‐By‐Layer Chiral Induction of Fluorene‐Based Metal–Organic Framework Films for Circularly Polarized Luminescence Sensing of Enantiomers

AbstractDeveloping films of chiral metal–organic frameworks (MOFs) with high circular polarization luminescence (CPL) is facing a great challenge for chiral sensing applications. Herein, a layer‐by‐layer chiral induction method is first reported to prepare enantiopure MOF films for CPL sensing. By layer‐by‐layer induction with the chiral inductor camphorsulfonic acid, fluorene‐based chiral MOF D/L‐ZnHF‐SO2 film (HF‐SO2 = 3,7‐Dibenzothiophenedicarboxylate, 5,5‐dioxide) with preferential growth orientation and homogeneous surface are prepared, which shows strong chiral feature and CPL with higher asymmetry factor of ±0.073. In addition, by mixed ligand approach, the isostructural fluorene ligand 9‐fluororenone‐2,7‐dicarboxylate is chosen to replace part of HF‐SO2 for preparing a series of chiral MOF films with tunable CPL emission. Furthermore, the prepared chiral MOF films with strong CPL performance are further utilized for enantiomers sensing. The CPL changes consisted with enantioselective adsorption results showed that D/L‐ZnHF‐SO2 film has good discrimination against chiral R/S‐phenylethylamine enantiomers, first reporting chiral MOF‐based candidates for the application in CPL sensing of enantiomers. This work provides a facile and effective approach for preparing chiral MOF films materials with high and tunable CPL performance, and also gives a new way to achieve CPL sensing of chiral enantiomers.

Water‐Soluble Fluorescent Polymer Dyes with Tunable Emission Spectra for Flow Cytometry Applications

AbstractThe application of spectrally unique, bright, and water‐soluble fluorescent dyes is indispensable for the analysis of biological systems. Multiparameter flow cytometry is a powerful tool for characterization of mixed cell populations. To discriminate the different cell populations, they are typically stained by a set of fluorescent reagents, e.g., antibody‐fluorophore conjugates. The number of parameters which can be studied simultaneously strongly depends on the availability of reagents which can be differentiated by their spectral properties. In this study a series of fluorescent polymer dyes was developed, that can be excited with a single violet laser (405 nm) but distinguished by their unique emission spectra. The polyfluorene‐based polymers can be used on their own, or in combination with covalently bound small‐molecule dyes to generate energy transfer constructs to red‐shift the emission wavelength based on Förster resonance energy transfer (FRET). The polymer dyes were utilized in a biological flow cytometry assay by conjugating several of them to antibodies, demonstrating their effectiveness as reagents. This report represents the first systematic investigation of structure–property relationships for this type of fluorescent dyes.

Water-Soluble Fluorescent Polymer Dyes with Tunable Emission Spectra for Flow Cytometry Applications.

The application of spectrally unique, bright, and water-soluble fluorescent dyes is indispensable for the analysis of biological systems. Multiparameter flow cytometry is a powerful tool for characterization of mixed cell populations. To discriminate the different cell populations, they are typically stained by a set of fluorescent reagents, e.g., antibody-fluorophore conjugates. The number of parameters which can be studied simultaneously strongly depends on the availability of reagents which can be differentiated by their spectral properties. In this study a series of fluorescent polymer dyes was developed, that can be excited with a single violet laser (405 nm) but distinguished by their unique emission spectra. The polyfluorene-based polymers can be used on their own, or in combination with covalently bound small-molecule dyes to generate energy transfer constructs to red-shift the emission wavelength based on Förster resonance energy transfer (FRET). The polymer dyes were utilized in a biological flow cytometry assay by conjugating several of them to antibodies, demonstrating their effectiveness as reagents. This report represents the first systematic investigation of structure-property relationships for this type of fluorescent dyes.

Ultrastability and color-tunability of CsPbI3 nanocrystals glass via doping CoBr2 and application in WLED

Extensive research has been conducted on all-inorganic CsPbI3 nanocrystals (NCs) due to their exceptional optical properties. In this study, we successfully prepared CoBr2-doped CsPbI3 NCs in Lithium-borosilicate using the conventional melting quenching approach. We investigated the optical characteristics of CsPbI3 NCs glass doped with varying amounts of CoBr2. Remarkably, the samples exhibited outstanding water and thermal stability and tunable emission ranging from 702 to 652 nm. Interestingly, the CsPbI3 NCs glasses doped with CoBr2 demonstrated significantly enhanced photoluminescence quantum yields (PLQYs), which increased from 8 % to 32 %. Furthermore, by mixing a red CsPbI3 NCs glass doped with 0.5 mol CoBr2 and a green CsPbBr3 under a blue LED chip, we effectively generated a WLED which achieved (0.3341, 0.3360) of chromaticity coordinate (CIE), 5775.35 K of a correlated color temperature (CCT) that close to positive white light (0.330, 0.330) and the color rendering index (CRI) 79.4. This study provides a new technique in the field of metal ion-doped perovskite NCs, providing a valuable reference for future research and demonstrating possible applications in LEDs.

Pulsed operation of perovskite LEDs: a study on the role of mobile ions

ABSTRACT Metal halide perovskite light-emitting diodes (PeLEDs) are a promising technology for energy-efficient and cost-effective lighting and displays, thanks to their tunable color emission, high brightness, color purity and low-temperature fabrication. However, the mixed ionic-electronic conductivity of perovskite materials presents unique challenges, as ionic defects can redistribute under operation, affecting the energy landscape and charge recombination mechanisms. Our drift-diffusion simulations establish a connection between the transient electroluminescence (TrEL) signals of PeLEDs under pulsed operation and the influence of mobile ions. We find that the TrEL plateau value’s dependence on the duty cycle and end-of-pulse overshoot can be explained by the time-varying distribution of ionic defects. The inclusion of mobile ions is crucial to understand the TrEL response. Moreover, the simulations highlight injection barriers at the perovskite/charge-transport layer interfaces, such as is the case for the hole transport layer in our example, as a significant source of non-radiative charge recombination. These findings contribute to the understanding of transient ionic processes in perovskite-based devices.

Organic Cocrystal Alloys: From Three Primary Colors to Continuously Tunable Emission and Applications on Optical Waveguides and Displays.

Multicolor luminescence of organic fluorescent materials is an essential part of lighting and optical communication. However, the conventional construction of a multicolor luminescence system based on integrating multiple organic fluorescent materials of a single emission band remains complicated and to be improved. Herein, organic alloys (OAs) capable of full-color emission are synthesized based on charge transfer (CT) cocrystals. By adjusting the molar ratio of electron donors, the emission color of the OAs can be conveniently and continuously regulated in a wide visible range from blue (CIE: 0.187, 0.277), to green (CIE: 0.301, 0.550), and to red (CIE: 0.561, 0.435). The OAs show analogous 1D morphology with smooth surface, allowing for full-color waveguides with low optical-loss coefficient. Impressively, full-color optical displays are easily achieved through the OAs system with continuous emission, which shows promising applications in the field of optical display and promotes the development of organic photonics.

Blue electroluminescence from homoleptic Ir(III) carbene phosphors and peripheral decorated multiple resonance boron emitters

Blue phosphors are indispensable in constructing organic light-emitting diodes (OLEDs). Herein, we reported two Ir(III) complexes, namely f-CN1 and f-CN2, with asymmetrically arranged benzo[d]imidazolylidenes, to which the peri-cyano substituent has concurrently induced both the selective aryl cyclometalation and emission tuning in giving one single blue Ir(III) phosphor. With the aforementioned ‘one stone for two birds’ tactics, these carbene complexes exhibited photoluminescent peak (λmax) at ∼472 nm and excellent quantum yields (83–100 %) in doped thin films. Consequently, the fabricated OLED devices delivered maximum external quantum efficiencies (EQEmax) of 23.6 % and 20.2 %, respectively. Furthermore, hyper-OLED devices with f-CN1 and multi-resonant TADF terminal emitter m-DiNBO displayed an EQEmax of 30.8 % with CIEx,y coordinates of (0.13, 0.10), together with impressive EQE of 26.9 % at practical brightness of 100 cd m−2.

Colorization strategy for carbon-based electrochromic devices: Achieving visible and mid-infrared regions modulation

Carbon-based materials exhibit unrivaled ability to modulate electromagnetic waves in the infrared band. However, the black appearance restricts the application in the visible light camouflage. This work combines color coatings (consisting mainly of pigments and thermochromic microcapsules) with carbon-based devices and overcomes the high absorption of the color coatings in the mid-infrared band. Ultimately, the obtained white carbon film (W-CNT) device exhibits tunable thermal emissivity from 0.453 to 0.833, maintains a residual modulation range up to 71.7%. In addition, the expansion of the coloration layer to thermochromic microcapsules enables the devices to independently modulate the visible and mid-infrared spectra, further expanding the applicability. We believe that the carbon-based device is valuable for a wide range of applications in camouflage and personal thermal management, which may provide some ideas for designing multispectral independent modulation devices.

Optically Anisotropic Films of Colloidal Nanocrystals/Photoluminescent Dye Doped Polymers

Semiconductor colloidal nanocrystals are attractive materials since they can be adapted to polymers to form hybrid materials and are compatible with many optical applications. Here, synthesis of CdSe/CdS nanorods (NRs) via hot injection method is carried out, followed by preparation of hybrid polymer films from polyethylene glycol monomethyl ether-block-poly(glycidyl methacrylate)-block-poly[2-(diethylamino)ethyl methacrylate] triblock copolymer (MPEG-b-PGMA-b-DEAEMA) at a liquid-air interface. The optical properties of the films are finely adjusted to form optically anisotropic (i.e. dual-color emissive) films by using dyes for the other emitter as desired. Thiazolo[5,4-d] thiazole (TTz)-based dye and 6-carboxy fluorescein were used for this purpose. Tunable emission of TTz dye from blue to green dependent on changing pH value resulted in blue-green emissive polymer films, while red emission of CdSe/CdS NRs caused red emissive films. Phase separation of these materials is achieved by the hexane-insoluble nature of MPEG-b-PGMA-b-DEAEMA and the high solubility of NRs in it. These dual emissive films are promising candidates for waveguides and optical sensors.

Active tuning of angular asymmetric thermal emission via carrier injection in metal-insulator-metal resonance gratings

We present a method to break the angular symmetry of infrared thermal emission using dynamic electrical control. An electrically tunable GaAs grating is designed to exhibit narrowband angular emission in the longwave infrared. The grating has GaAs stripes sandwiched between the top metallic contacts and the bottom reflector layer. The application of voltage across the GaAs allows for the change of the refractive index. Tuning one of the dielectric stripes within each unit cell enables symmetry-breaking index perturbation. The perturbed structure exhibits angular asymmetric thermal emission. We analyze our findings based on coupling coefficients and variational principle. Due to the reversible nature of the perturbation, this concept presents a route toward tunable asymmetric emission and directional ‘steering’ of thermal emission.

Triplet-triplet annihilation photon upconversion-mediated photochemical reactions.

Photon upconversion is a method for harnessing high-energy excited states from low-energy photons. Such photons, particularly in the red and near-infrared wavelength ranges, can penetrate tissue deeply and undergo less competitive absorption in coloured reaction media, enhancing the efficiency of large-scale reactions and in vivo phototherapy. Among various upconversion methodologies, the organic-based triplet-triplet annihilation upconversion (TTA-UC) stands out - demonstrating high upconversion efficiencies, requiring low excitation power densities and featuring tunable absorption and emission wavelengths. These factors contribute to improved photochemical reactions for fields such as photoredox catalysis, photoactivation, 3D printing and immunotherapy. In this Review, we explore concepts and design principles of organic TTA-UC-mediated photochemical reactions, highlighting notable advancements in the field, as well as identify challenges and propose potential solutions. This Review sheds light on the potential of organic TTA-UC to advance beyond the traditional photochemical reactions and paves the way for research in various fields and clinical applications.

Structurally diverse macrocycle co-crystals for solid-state luminescence modulation

Organic co-crystals offer an opportunity to fabricate organic functional materials. Traditional co-crystals are generally packed following the segregated or mixed stacking mode, leading to the lack of structural and functional diversity. Herein, we report three sets of macrocycle co-crystals with identical co-constitutions. The macrocycle co-crystals differ in the stoichiometric ratios (2:1, 1:1, and 2:3) of the constituents and molecular packing modes. The co-crystals are constructed using triangular pyrene-macrocycle and 1,2,4,5-tetracyanobenzene exploiting exo-wall charge-transfer interactions. Interestingly, the three co-crystals exhibit distinct, tunable emission properties. The corresponding emission peaks appear at 575, 602, and 635 nm, covering yellow via orange to red. The X-ray diffraction analyses and the density functional theory calculations reveal the superstructure-property relationships that is attributed to the formation of different ratios of charge-transfer transition states between the donor and acceptor motifs, resulting in red-shifted luminescence.

Research progress on Fe3+-activated near-infrared phosphor

Abstract Fe3+-activated near-infrared (NIR) luminescent materials have attracted widespread attention due to their tunable emission wavelength and extensive applications in various fields such as plant growth, food analysis, biomedical imaging, and night vision. Many excellent NIR materials have been developed by introducing non-toxic and environmentally friendly Fe3+ ions into different inorganic hosts. This article elucidates the luminescent properties of Fe3+ ions by combining the Tanabe–Sugano energy level diagram and the configuration coordinate model. The latest research progress on Fe3+-doped NIR luminescent materials is outlined, summarizing the luminescent characteristics of various Fe3+-doped materials, including emission wavelength, emission bandwidth, quantum efficiency, and thermal stability. Particularly, a detailed summary and analysis of the application areas of Fe3+-doped NIR luminescent materials are provided. Finally, the future prospects and challenges faced by Fe3+-doped NIR luminescent materials are presented. This review contributes to a deeper understanding of the luminescence mechanism of Fe3+ and the research progress of iron ion-doped luminescent materials, aiming to develop advanced Fe3+-activated NIR luminescent materials with enhanced performance and explore new application fields.

Large-Scale, Stretchable, Self-Protective, and Multifunctional Perovskite Luminescent Filament with Ultra-High Stability.

Lead halide perovskites possess great application potential in flexible displays and wearable optoelectronics owing to their prominent optoelectronic properties. However, the intrinsic instability upon moisture, heat, and ultraviolet (UV) light irradiation hinders their development and application. In this work, an ultra-stable CsPbX3 (X = Cl, Br, I) perovskite luminescent filament (PLF) with high stretchability (≈2400%) and luminescence performance (photoluminescence quantum yield (PLQY) of 24.5%, tunable emission spectrum, and high color purity) is introduced by a facile environmental-friendly wet-spinning technology via solvent extraction. Benefiting from the in situ encapsulation of the hydrophobic thermoplastic polyurethane (TPU) and the chelation of Lewis base CO in TPU with Lewis acid Pb2+, the CsPbBr3 PLF demonstrates ultra-high photoluminescence (PL) stability when stored in ambient air and high humidity circumstance, annealed at 50 °C, and dipped in water for 30 days, illuminated under ultraviolet light for 300 min, and immersed in organic solvents and solutions with pH of 1-13 for 5 min, respectively. Impressively, it retains 80% of its initial PL after being recycled five times. Overall, the CsPbX3 PLF demonstrates promising prospects in multifunctional applications, including organic dyes and tensile strain sensing, flexible pattern displays, secondary anti-counterfeiting, and hazard warning systems.

Tunable luminescent properties and structure of Sn2+-doped boroaluminate glasses

A series of novel Sn2+ doped boroaluminate glasses were prepared by the traditional melt quenching method in this work. Their glass network structure, luminescent properties, and mechanisms were studied in detail. The main framework of the glass network was dependent on the glass network former (B2O3) and intermediate (Al2O3), and was characterized by the 11B and 27Al NMR spectra. Broadband tunable blue-violet emissions ranging from 320 to 550 nm were realized by regulating the glass network structure through optical basicity. The quantitative relationship between optical basicity and emission/excitation peak positions and intensities, FWHM, and Stokes-Shift of this Sn2+-doped glass were revealed, according to which the luminescent properties of Sn2+ could be modulated and even predicted in the future. This work will enrich our understanding of the luminescent properties of Sn2+ ions and the variations of glass network structure, guiding the design of efficient and tunable luminescent boroaluminate glass.

Photoluminescent Bi-doped CsPbX3 (X: Br, I) perovskite quantum dots for optoelectronic devices

Perovskite quantum dots (PQDs) became a hot spot in recent years due to their amazing properties, such as the high photoluminescence quantum yield, tunable emission, and narrow bandwidth being important for their application in different optoelectronic devices. In this work, Bi-doped CsPbBr3 and Bi-doped CsPbI3 PQDs were synthesized through the hot-injection method and compared with pristine CsPbBr3 and CsPbI3 to analyze the effect of Bi and the halogen on their properties. In addition, all the samples were synthesized at 130°C, 150°C, and 170°C with the aim of analyzing the effect of the temperature. The results showed a wide range of the emission wavelength from around 500 nm (Bi-doped CsPbBr3) to 630 nm (Bi-doped CsPbI3) as a consequence of the effect of the halogen in “X” position and a slight blueshift in the main photoluminescence emission band after doping the pristine quantum dots with Bi.Graphical abstractImpact statementWe believe that the work in this article represents an important advance in the application of perovskite quantum dots in optoelectronics applications, such as in LEDs or lasers. We report here the synthesis and characterization of Bi-doped CsPbX3 perovskite quantum dots (PQDs), being X: Br and I. These Bi-doped PQDs show a wide range of the emission wavelength from around 500 nm (Bi-doped CsPbBr3) to 630 nm (Bi-doped CsPbI3) as a consequence of the effect of the halogen in “X” position and a slight blueshift in the main photoluminescence emission band after doping the pristine quantum dots with Bi. Therefore, they are good candidates to fabricate optoelectronic devices such as LEDs and lasers thanks to their high photoluminescence emission and their tunable emission.

Self-injection-locked optical parametric oscillator based on microcombs

Narrow-linewidth yet tunable laser oscillators are one of the most important tools for precision metrology, optical atomic clocks, sensing, and quantum computing. Commonly used tunable coherent oscillators are based on stimulated emission or stimulated Brillouin scattering; as a result, the operating wavelength band is limited by the gain media. Based on nonlinear optical gain, optical parametric oscillators (OPOs) enable coherent signal generation within the whole transparency window of the medium used. However, the demonstration of OPO-based Hertz-level linewidth and tunable oscillators has remained elusive. Here, we present a tunable coherent oscillator based on a multimode coherent OPO in a high-Q microresonator, i.e., a microcomb. Single-mode coherent oscillation is realized through self-injection locking (SIL) of one selected comb line. We achieve coarse tuning up to 20 nm and an intrinsic linewidth down to sub-Hertz level, which is three orders of magnitude lower than the pump. Furthermore, we demonstrate that this scheme results in the repetition rate stabilization of the microcomb. These results open exciting possibilities for generating tunable coherent radiation where stimulated emission materials are difficult to obtain, and the stabilization of microcomb sources beyond the limits imposed by the thermorefractive noise in the cavity.