Tunable Emission Research Articles

Visualizing supramolecular assembly behavior, stimulus response, and solid state emission of higher-order Pt2+ aggregates.

Here, we present the first instance of a highly efficient red tetramer aggregate with tunable emission based on a cationic platinum(II) complex in conjunction with a silver cluster anion counterpart. This system exhibits multicolor emission response behaviors, which can be conveniently and directly detected through spectroscopic analysis, showcasing intriguing luminescence changes. The self-assembly of Pt⋯, π-π, and hydrogen bonding interactions not only enables an intriguing color adjustment from green to yellow emission, and eventually to red emission, but also demonstrates the co-existence of the monomer, excimer, and aggregation. These phenomena are further accompanied by well-defined nanostructures. The self-assembly process of these structures exhibits an isodesmic growth mechanism, which is dependent on temperature. In this regard, it exhibits potential applicability in multi-mode logic gates that rely on external stimuli such as concentration, solvent, and temperature. The sensitivity of the aggregates towards chemical stimuli combined with their exceptionally bright emission characteristics renders them suitable for diverse applications including solid-state lighting sensing mechanisms and anticounterfeiting measures. The multi-stimuli responsive phosphorescence and self-assembly behaviors of the cationic platinum(II) complex were substantiated by X-ray crystal structure determination, 1H NMR analysis spectroscopic investigations, computational calculations and scanning electron microscopy (SEM) studies.

Optimization of stacked Fabry-Perot cavities for VO2-based broadband adaptive thermal radiators

The performance of an adaptive thermal radiator (ATR) for temperature regulation depends on its ability to modulate spectral emissivity across a broad wavelength range. For a single cavity, we found that the tunable, thermal emissivity from 2-30 µm is maximized using a spacer material with low n and k, such as BaF2 . However, a single cavity produces a narrowband peak in the spectral emissivity. Stacking multiple cavities introduces additional resonances that create high-temperature spectral emissivity peaks. Here, we designed cavities composed of VO2 and BaF2 to have different resonant wavelengths to demonstrate a broadband response across the infrared spectrum out to ∼30 µm. In this work, we find that up to three cavities increases the tunable thermal emissivity with negligible changes from additional cavities.

Untypical tuneable emission activated by NIR radiation observed in gadolinium borate nanomaterials doped with Yb3+, Ho3+ and Ce3+ ions.

New luminescent nanoparticles with adjustable emission properties were synthesized via a hydrothermal method to investigate the effect of Ce3+ concentration on the tuneable emission properties of Yb3+/Ho3+ co-doped gadolinium borates. The synthesized samples' comprehensive structural and morphological analysis was conducted utilizing X-ray diffraction and transmission electron microscopy. To obtain highly crystalline nanoparticles GdBO3:Yb3+/Ho3+/Ce3+ characterized by intense and bright emission, they were annealed at 525°C and 925°C. Under the excitation of 972nm, the tunable yellow to green up-conversion (UC) emission was observed, while the Ce3+ concentration increased. This change correlated with a difference in the correlated color temperature from 4345K to 5442K, respectively. The untypical changes observed in the red-to-green (R/G) ratio, displaying a declining trend contrary to conventional expectations, allowed for the proposed mechanism for understanding their UC luminescence properties. The results obtained indicate that the Ce3+ doped GdBO3:Yb3+/Ho3+ nanoparticles demonstrate high application potential for anti-counterfeiting.

Tunable Blue-Light-Emitting Organic-Inorganic Zinc Halides with Thermally Activated Delayed Fluorescence and Room-Temperature Phosphorescence.

Hybrid metal halides have received great interests in the field of solid-state lighting technologies due to their diverse structures and excellent emission properties. In this work, we report the synthesis and characterization of four blue-emitting zero-dimensional hybrid metal halides, namely, (2HP)2ZnCl2, (2HP)2ZnBr2, (2TP)2ZnCl2, and (2TP)2ZnBr2 (2HP = 2-hydroxypyridine, 2TP = pyridine-2-thiol). By changing the ligands and halides, a remarkable increase in the photoluminescence quantum yield of (2HP)2ZnCl2 (44.7%) compared to (2TP)2ZnBr2 (1.8%) is realized. The 2HP series features excitation-dependent emission characteristics, whereas the 2TP series does not due to the effect of a different organic ligand. Utilizing time-resolved and temperature-dependent photoluminescence spectroscopies, all four compounds exhibit both thermally activated delayed fluorescence and room-temperature phosphorescence properties. These materials have excellent ambient and thermal stabilities and are solution-processable. Our work shows the importance of carefully incorporating organic ligands with the appropriate inorganic metal center to achieve tunable emission properties.

Simple synthesis of AgInS2/ZnS core/shell quantum dots with wide tunable emission wavelength for white light-emitting diodes

Phosphor with efficient and broad range emission is necessary for lighting applications. I-III-VI group quantum dots (QDs) have the advantages of non-toxic composition and large adjustable spectrum range, and have potential applications in the field of lighting. However, the efficient luminescence of these QDs at shorter wavelengths still needs further study, which is crucial for the development of high color rendering index white light LED devices (WLEDs). In this work, wide visible range emitting AgInS2/ZnS QDs with broad band and high luminous efficiency were obtained by altering the Ag/In ratios and Zn2+ inter-diffusion with cation of AgInS2. Photo-luminescent (PL) wavelength range of the obtained core-shell structured AgInS2/ZnS extended from 703 nm to 524 nm with high PL quantum yield (QY) and stability. The champion device based on the optimized AgInS2/ZnS QDs exhibits warm white light (correlated color temperature = 3652 K) characteristics with high color rendering index (CRI Ra) of 92.85 while maintaining excellent color stability under different driving currents. These properties are far superior to those of WLEDs with YAG phosphor.

Unlocking Full-Spectrum Brilliance: Dimensional Regulation in Lead-Free Metal Halides for Superior Photoluminescence.

Lead-free metal halides with tunable structures have emerged as a new class of optoelectronic materials. The arrangement of metal halide polyhedra defines their structural dimensionality and serves as a key factor influencing their optical properties. To investigate this, we synthesized four different antimony (Sb)-doped indium (In)-based metal halides, all of which possess zero-dimensional (0D) electronic structures but exhibit 3D, 2D, 1D, and 0D structural dimensionality at the molecular level. With a decreasing of structural dimensionality, their self-trapped exciton (STE) emission shows a red shift with peak position from 496 to 663 nm. We revealed that the red shift is caused by increased distortion of [SbCl6]3- octahedra as the structural dimensionality decreases, leading to lowered energy levels of STE and a corresponding red shift. The tunable STE emission makes these metal halides promising for anticounterfeiting and white LED applications. These findings provide a new strategy for tuning STE emission in lead-free metal halides.

Solution Processed Bilayer Metal Halide White Light Emitting Diodes.

Metal halide perovskites and perovskite-related organic metal halide hybrids (OMHHs) have recently emerged as a new class of luminescent materials for light emitting diodes (LEDs), owing to their unique and remarkable properties, including near-unity photoluminescence quantum efficiencies, highly tunable emission colors, and low temperature solution processing. While substantial progress has been made in developing monochromatic LEDs with electroluminescence across blue, green, red, and near-infrared regions, achieving highly efficient and stable white electroluminescence from a single LED remains a challenging and under-explored area. Here, a facile approach to generating white electroluminescence is reported by combining narrow sky-blue emission from metal halide perovskites and broadband orange/red emission from zero-dimensional (0D) OMHHs. For the proof of concept, utilizing TPPcarz+ passivated two-dimensional (2D) CsPbBr3 nanoplatelets (NPLs) as sky blue emitter and 0D TPPcarzSbBr4 as orange/red emitter (TPPcarz+ = triphenyl (9-phenyl-9H-carbazol-3-yl) phosphonium), white LEDs (WLEDs) with a solution processed bilayer structure have been fabricated to exhibit a peak external quantum efficiency (EQE) of 4.8% and luminance of 1507 cd m-2 at the Commission Internationale de L'Eclairage (CIE) coordinate of (0.32, 0.35). This work opens a new pathway for creating highly efficient and stable WLEDs using metal halide perovskites and related materials.

Self‐reduction triggered color tuning of Eu3+‐doped aluminosilicate glass for solid‐state white illumination

AbstractRare earth‐doped transparent glass, boasting high transmittance and excellent luminescent properties, holds great potential in the field of all‐inorganic solid‐state white illumination. Currently reported single‐structure solid‐state white lighting usually has the problems of low color rendering index (CRI) and high correlated color temperature (CCT) due to the lacking of red light emission. In this work, a novel single‐structure MgO–Al2O3–SiO2–Eu2O3 (MAS: Eu) glass with color tuning was prepared by the simple glass melting process. Interestingly, the prepared Eu3+‐doped aluminosilicate glass possessed a unique capability to achieve color emission under different excitation wavelengths. The reason for this was attributed to the good self‐reduction capability of the MAS glass, which effectively reduced Eu3+ to Eu2+ under an air atmosphere. Meanwhile, only by regulating the Eu3+ doping concentration, the MAS glass also achieved a tunable emission from blue to white to red light under 380 nm excitation. The acquisition of white light was realized through the multispectral emission of blue–green light emitted by Eu2+ and orange–red light emitted by Eu3+. Remarkably, the single‐structure MAS glass doped with 8 wt.% Eu3+ successfully achieved high‐quality white light and high thermal stability, exhibiting a high CRI of 86, a low CCT of 2761 K, good chromaticity parameters of (0.407 and 0.3192), and the emission intensity at 423 K remains above 86.35% that of room temperature. Meanwhile, the doped Eu3+ exceeded 12 wt.%, without any observable concentration quenching. Moreover, the MAS: Eu glass showed a high transmittance of 90 and a moderate thermal conductivity of 1.45 W/mK (epoxy resin ∼0.17 W/mK). These results would dramatically inspire the development of high‐quality solid‐state white lighting applications.

Current Context of Designing Phototheranostic Cyclometalated Iridium (III) Complexes to Open a New Avenue in Cancer Therapy.

Photo-induced chemotherapy offers the best option for the selective treatment of cancer among all the prevailing modalities. Iridium (III) complexes, flourished with excellent photophysical and photochemical properties, have been considered to be superior for undergoing photo-responsive cancer therapy. Large Stokes shift, long-lived triplet excited state, photostability, and tuneable emission have rendered its excellence as a phototheranostic agent. In particular, the cyclometalated Ir (III) complexes and their respective nanoparticles have made a strong niche in the arena of cancer therapy. In recent years, Ir (III) based complexes have shown promising utilities as both imaging and therapeutic agents as well. Therefore, this review summarises the recent advances in the strategic designing of cyclometalated Ir(III) complexes to augment their phototheranostic applications in precision medicine.

Precise Regulation Strategy for Fluorescence Wavelength of Aggregation-Induced Emission Carbon Dots.

Aggregation-induced emission (AIE) carbon dot (CDs) in solid state with tunable multicolor emissions have sparked significant interest in multidimensional anti-counterfeiting. However, the realization of solid-state fluorescence (SSF) by AIE effect and the regulation of fluorescence wavelength in solid state is a great challenge. In order to solve this dilemma, the AIE method to prepare multi-color solid-state CDs with fluorescence wavelengths ranging from bright blue to red emission is employed. Specifically, by using thiosalicylic acid and carbonyl hydrazine as precursors, the fluorescence wavelength can be accurately adjusted by varying the reaction temperature from 150 to 230°C or changing the molar ratio of the precursors from 1:1 to 1:2. Structural analysis and theoretical calculations consistently indicate that increasing the sp2 domains or doping with graphite nitrogen both cause a redshift in the fluorescence wavelength of CDs in the solid state. Moreover, with the multi-dimensional and adjustable fluorescence wavelength, the application of AIE CDs in the fields of multi-anti-counterfeiting encryption, ink printing, and screen printing is demonstrated. All in all, this work opens up a new way for preparing solid-state multi-color CDs using AIE effect, and further proposes an innovative strategy for controlling fluorescence wavelengths.

Beating the Odds with Binuclear N‐Heterocyclic Carbene Metallacycles: A Practical and Efficient Full‐Color Tunable Fluorescence System

AbstractAchieving full‐color emission with just two emitters presents a significant challenge. Two N‐heterocyclic carbene metallacycles (NHC‐M; M ═ Ag, Au) featuring a tetraphenylethene core, combining covalent and coordination bonds are synthesized to restrict rotation within the NHC‐M‐BC (BC = bicyclic) metallacycles and greatly enhanced their quantum yields. The enhancement is accomplished by adjusting the CH3CN/H2O solvent mixture, allowing emission tuning from blue to green for NHC‐Ag‐BC. Further diversification of the emission spectrum, including access to high‐quality white light (CIE coordinates 0.33, 0.34), is facilitated through the addition of sulforhodamine B via fluorescence resonance energy transfer (FRET). The compatibility of NHC‐Ag‐BC with agarose gel extends its applicability to UV‐LEDs chromic coatings, as well as information encryption and anti‐counterfeiting materials. The results underscore the viability of dual‐fluorophore systems for achieving full‐color emission and highlight the potential for developing versatile, multi‐colored functional materials.

Chromatic tuning of upconversion emission upon dual infrared wavelength co-excitation in Er3+ doped Ba3Lu4O9 phosphor

Emission color change of the upconversion luminescence materials is often required for applications in optical anti-counterfeiting, laser lighting, and 3D displays. In this work, we developed a new route for chromatic tuning of upconversion emission upon two wavelength co-excitation by changing excitation power density. The proposed route was used for Er3+ single-doped Ba3Lu4O9 phosphor which was derived from a traditional solid-state reaction. The crystal structure of the obtained Ba3Lu4O9:Er3+ phosphor was characterized by X-ray diffraction and Rietveld refinement modeling. Under individual excitation of 980 or 1550 nm, it was found that the luminescence intensity ratio of red to green changes slightly with respectively increasing excitation power density (working current of the laser) of 980 or 1550 nm laser. However, upon both 980 and 1550 nm co-excitation at the same time and by adjusting the excitation power density of one laser amongst the two lasers, the luminescence intensity ratio of red to green changes greatly with increasing excitation power density. The change of luminescence intensity ratio of red to green implies the upconversion emission color tuning. The mechanism for the color tuning was discovered. It was found that with changing excitation power density the ratio of red to green changed greatly when the phosphor was irradiated by 980 and 1550 together, but the ratio of red to green changed slightly when the phosphor was irradiated individually by 980 or 1550. It is proved that it is feasible to turn color by the method of two infrared wavelengths excitation.

Tunable double emission of Sb3+/Mn2+ doping stabilized organic-inorganic hybrid zinc-based halides

Low-dimensional organic-inorganic hybrid metal halides (OIHMHs) have attracted much attention lately in contrast to all-inorganic metal halides because of their excellent photophysical properties and tunable emission wavelengths. Zn-based metal halides have the following advantages: simplicity of synthesis, wide bandgap, and excellent chemical stability. Therefore, they are well-suited as host materials for photoluminescence by cation ion doping. We have successfully synthesized intrinsically non-emissive 0D (PPZ)ZnCl4 [PPZ (1-phenylpiperazine) = C10H14N2], and by mono/co-doping with Mn2+ and Sb3+, interesting luminescence phenomena have been produced. Single-doped Mn2+ / Sb3+ shows distinctive green and single orange emission, respectively. However, the co-doped Mn2+ and Sb3+ appeared as dynamic double emission peaks at 530nm and 670nm. Therefore, the co-doped crystals showed luminescence from two different luminescence centers ([MnCl4]2- and [SbCl4]-). We used DFT to calculate the DOS (density of states) of co-doped crystals, which results in energy transfer between Mn2+ and Sb3+. All of the above samples showed high stability after being left for two months. In addition, two different luminescence centers can be produced by the adjustment of the excitation of the co-doped (PPZ)ZnCl4: Sb0.12Mn0.08 samples, which is a distinguishable and obvious photoluminescence phenomenon having great potential preparation of advanced anti-counterfeiting materials in the future.

Tunable emission and energy transfer of Tb3+/Eu3+ co-doped single-phase Sr2MgSi2O7 glass-ceramics

In this work, the Tb3+/Eu3+ co-doped 30SrO-10MgO-50SiO2-5TiO2-5B2O3-1Tb2O3-xEu2O3 (x = 0-2.5 mol% at 0.5 intervals) glasses were prepared by the melt-quenching method, and the single-phase Sr2MgSi2O7 glass-ceramics were obtained after heat treatment. The structural and fluorescence performance of the glasses and glass-ceramics were examined using DSC, XRD, SEM, FTIR, and photoluminescence spectra, and the energy transfer process between Tb3+ and Eu3+ was systematically investigated. With increasing Eu2O3 contents, the thermal stability of the glasses is enhanced and the density of both the glasses and the glass-ceramics rises. The XRD and SEM results reveal the precipitation of the irregular spherical Sr2MgSi2O7 microcrystals with a grain size roughly within 0.5-1 μm. Under 376 nm excitation, the overall emission intensity and lifetime of Eu3+ ions increase with increasing Eu2O3 contents, and the energy transfer efficiency reaches 58.74% from 31.07%. According to the Dexter model, the energy transfer process between the Tb3+ and Eu3+ is dominated by the quadrupole-quadrupole interactions. By varying the Eu2O3 contents, all the glass-ceramics exhibit higher color purity (82.06-96.27%), and their chromaticity coordinates shift from yellowish green towards reddish orange, which is potentially promising for w-LEDs.

Blue lasers using low-toxicity colloidal quantum dots.

Blue lasers play a pivotal role in laser-based display, printing, manufacturing, data recording and medical technologies. Colloidal quantum dots (QDs) are solution-grown materials with strong, tunable emission covering the whole visible spectrum, but the development of QD lasers has largely relied on Cd-containing red-emitting QDs, with technologically viable blue QD lasers remaining out of reach. Here we report on the realization of tunable and robust lasing using low-toxicity blue-emitting ZnSe-ZnS core-shell QDs that are compact in size yet still feature suppressed Auger recombination and long optical gain lifetime approaching 1 ns. These characteristics allow us to handle the blue QDs like laser dyes for liquid-state amplified spontaneous emission and lasing. The blue QD laser is operated under quasi-continuous-wave excitation by solid-state nanosecond lasers. A Littrow-configuration cavity enables narrow linewidth (<0.2 nm), wavelength-tunable, coherent and stable laser outputs without circulating the solution. These results indicate the promise of ZnSe-ZnS QDs to fill the 'blue gap' of QD lasers and to replace less stable blue laser dyes for a multitude of applications.

Influence of crystal field inhomogeneities on the spontaneous and laser tuning emission of a Nd3+-doped Li2O-BaO-Al2O3-P2O5 glass

The present work focuses on the spectroscopic and laser properties of Nd3+ in a Li2O-BaO-Al2O3-P2O5 aluminophosphate glass which includes Judd-Ofelt calculation, stimulated emission cross-section of the 4F3/2→4I11/2 emission laser transition, lifetime of the 4F3/2 state and quantum efficiency. Site-selective laser spectroscopy and stimulated emission under selective excitation has been performed to determine the crystal field inhomogeneity at the Nd3+ site together with its broadening effect on the spontaneous and laser emissions. However, a much narrowed laser emission has been achieved by using an intracavity tilting plate which acts as a tunable optical filter to adjust the laser wavelength.

Recent Advances of Organic Cocrystals in Emerging Cutting-Edge Properties and Applications.

Organic cocrystals, representing one type of new functional materials, have gathered significant interest in various engineering areas. Owing to their diverse stacking modes, rich intermolecular interactions and abundant functional components, the physicochemical properties of organic cocrystals can be tailored to meet different requirements and exhibit novel characteristics. The past few years have witnessed the rapid development of organic cocrystals in both fundamental characteristics and various applications. Beyond the typical properties like ambipolarity, emission tuning ability, ferroelectricity, etc. that are previously well demonstrated, many novel, impressive and cutting-edge properties and applications of cocrystals are also emerged and advanced recently. Especially during the nearest five years, photothermal conversion, room-temperature phosphorescence, thermally activated delay fluorescence, circularly polarized luminescence, organic solid-state lasers, near-infrared sensing, photocatalysis, batteries, and stimuli responses have been reported. In this review, these new properties are carefully summarized. Besides, some neoteric architecture and methodologies, such as host-guest structures and machine learning-based screening, are introduced. Finally, the potential future developments and expectations for organic cocrystals are discussed for further investigations on multiple functions and applications.

Mono-/multi-fluorination of 1,8-naphthalimides for developing AIE/AIEE fluorophores with tuning emission wavelength

Aggregation-induced emission/aggregation-induced emission enhancement (AIE/AIEE) luminogens provides amount of highly emissive materials in density states for versatile applications. Most of the AIE/AIEEgens were designed with the multiply rotation unit, in which the additional rotation units not only extend the molecular structure but also suffer from low atom economy. Herein, a fluorination strategy was introduced to construct ten AIE/AIEEgens with 1∼3 fluorine (F) atoms at different position of phenyl ring at previous developed AIEgen, 4-phenyl-1,8-naphthalimide, which can output tuning emissive wavelength and high quantum yields in both aqueous solutions and solids. In these compounds, five AIEgens with ortho-F atom and five AIEEgens without ortho-F atom were obtained. All compounds show bright blue emissions centered at 430–485 nm in aqueous solutions and wide emissions covering visible region in solid states. We calculated the ratio of quantum yields between their aqueous solution and THF solution (Φwater/ΦTHF). The AIE luminogens show the higher ratios between 10.19 and 24.89 and the AIEEgens show the lower ratios between 1.89 and 6.40. This strategy based on changing the substituent positions of F atoms provides an efficient and convenient method for construction of novel AIE-active materials with variable photophysical properties in density states.

Activatable red/near-infrared aqueous organic phosphorescence probes for improved time-resolved bioimaging

Abstract Organic red/near-infrared (NIR) room-temperature phosphorescence (RTP) holds significant potential for autofluorescence-free bioimaging and biosensing due to its prolonged persistent luminescence and exceptional penetrability. However, achieving activatable red/NIR organic RTP probes with tunable emission in aqueous solution remains a formidable challenge. Here we report on aqueous organic RTP probes with red/NIR phosphorescence intensity and lifetime amplification. These probes consist of supramolecular assemblies comprising macrocyclic cucurbit[8]uril and amine-containing alkyl-bridged pyridiniums, exhibiting viscosity-activatable phosphorescence with enhanced quantum yield (up to 20%) and lifetime. Notably, by utilizing this activatable organic RTP probe, we successfully achieve two-photon imaging of lysosomal viscosity and millisecond scale time-resolved cell imaging. Moreover, intravital phosphorescence imaging using RTP probe enable the monitoring of viscosity variations in inflammatory mice, demonstrating a significantly improved signal-to-background ratio compared to fluorescence imaging. This activatable red/NIR supramolecular platform facilitates versatile high-resolution phosphorescence imaging for in vivo tracking of specific biomarkers and physiological events.

Lantern-Shaped Structure Induced by Racemic Ligands in Red-Light-Emitting Metal Halide with Near 100 % Quantum Yield and Multiple-Stimulus Response.

Organic-inorganic metal halides (OIMHs) have become a research hotspot in recent years due to their excellent luminescent properties and tunable emission wavelengths. However, the development of efficient red-light-emitting OIMHs remains a significant challenge. This work reports three Mn-based OIMHs derived from 1-methyl-1,2,3,4-tetrahydroisoquinoline hydrobromide: racemic one (Rac-TBM) and chiral ones (R-TBM and S-TBM). As a result of the synergism of chiral organic ligands inducing a unique lantern-shaped hybrid structure containing both tetrahedra and octahedra, Rac-TBM exhibits red-light emission with near-unity luminescence quantum yield. In comparison, the chiral counterparts R/S-TBM display strong green emission and circularly polarized luminescence (CPL) with a glum value up to ±2.5×10-2. Interestingly, a mixture of R- and S-TBM can transform into Rac-TBM, successfully achieving a sensitive and reversible switch between red light of octahedra and green light of tetrahedra under external stimuli. The outstanding luminescent properties allow Rac-TBM to be utilized not only for X-ray radioluminescence with a detection limit down to 46.29 nGys-1, but also for advanced information encryption systems to achieve leak-proof decryption.