Luminescence Color Research Articles

Time Division Colorful Multiplexing Based on Carbon Nanodots with Modifiable Colors and Lifetimes.

Optical multiplexing technology plays a crucial role in various fields such as data storage, anti-counterfeiting, and time-resolved biological imaging. Nevertheless, employing single-wavelength phosphorescence for multiplexing often results in spectral overlap among the emission peaks of various channels, which can precipitate crosstalk and misinterpretation in the information-decoding process, thereby compromising the integrity and precision of the encrypted data. This paper proposes a time-divided colorful multiplexing technology based on phosphorescent carbon nanodots with different colors and lifetimes. Using different luminescence colors to symbolize varying information levels helps achieve multitiered information encryption and storage. By modulation of the lifetime and the emission wavelength, intricate information can be encoded, thereby enhancing the intricacy and security of the encryption mechanism. By assigning different data bits to each color, more information can be encoded in the same physical space. This method enables higher-density information storage and fortifies encryption, ensuring the compactness and security of information.

Full colour luminescence tuning including white light from a mixed lanthanide activated metal-organic complex

In an attempt, metal–organic compounds of rare earth ions with 2,6-pyridinedicarboxylic acid (H2pydc) were synthesized and characterized. This paper summarizes the synthesis, characterization, and multicolour luminescence behaviour of a europium and terbium co-doped metal–organic compound (MOC) of formula [Y1.972Eu0.013Tb0.014(pydcH)6]·3H2O, 1 {H2pydc = 2,6-pyridinedicarboxylic acid}. The synthesis was performed by simple solvent evaporation method. We have also synthesized a pure yttrium based compound [Y2(pydcH)6]·3H2O, 1a following a similar procedure. The powder XRD patterns indicated that 1 and 1a were new materials; the patterns being entirely consistent with the simulated XRD pattern generated based on the structure of pure Eu compound determined using the single-crystal XRD. Compound 1 was well characterized by SEM, IR, TGA, EDX, and EDX elemental mapping analysis. Compound 1 showed different colour upon the variation of the excitation wavelength from 260 nm to 385 nm.

Highly Selective Protic-Solvent-Mediated Organic-Inorganic Hybrid Cuprous Bromides Achieving Structural Transformation.

The potential application of stimuli-responsive hybrid copper halides in information storage and switch devices has generated significant interest. However, their transformation mechanism needs to be further studied deeply. Herein, two zero-dimensional (0D) organic-inorganic hybrids, namely, (TBA)CuBr2 (1) with linear [CuBr2]- units and (TBA)2Cu4Br6 (2) with [Cu4Br6]2- clusters (TBA+ = (C4H9)4N+), are synthesized using simple solvent evaporation approaches. Interestingly, upon exposure to distinct protic solvents, such as methanol, ethanol, ethylene glycol, or hot water, 1 undergoes a transformation into 2 with varying degrees of transition, accompanied by a change in luminescence color from cyan to orange (or mixed color) under high-energy emission (e.g., 254 nm) excitation. Hot water can trigger 1 to completely transform into 2 because of its large contact angle difference in the solvents. Furthermore, 2 can be converted back to 1 through a simple solid-state mechanochemical reaction. Additionally, the structure of 2 remains unchanged even after immersion in 80 °C H2O for 168 h due to the dense organic framework. This study provides valuable insights for exploring reversible structural transformation materials in the 0D metal halide system.

Ratiometric visualization fluorescence temperature sensing based on dual-lanthanide metal-organic frameworks

High-performance optical temperature sensors play an important role in various fields, and lanthanide metal-organic frameworks (Ln-MOFs) are expected to be luminescent temperature sensors due to their distinctive luminescent properties. Herein, a new three-dimensional (3D) Ln-MOF [Tb(TCA)(Phen)]·DEF (1) (H3TCA = 4,4′,4′'-nitrilotribenzoic acid, Phen = 1,10-phenanthroline, DEF= N, N-diethylformamide) is constructed with a rtl topology based on {Tb2(COO)4} secondary building units (SBUs). Meanwhile, dual-lanthanide Ln-MOFs [TbxEu1-x(TCA)(Phen)]·DEF (2-6) are also synthesized by varying the ratio of Tb3+: Eu3+ in the reaction mixture, which can be applied in practical LED applications originating from their visual luminescent color changes. Among them, 4 is an efficient ratiometric fluorescent thermometer over a wide temperature range from 283 to 393 K and has a large relative sensitivity Sr of 4.2407 % K−1 at 393 K with good repeatability. Furthermore, the emission color of 4 gradually changes from yellow (283 K) to orange-red (393 K) as temperature increases for visual colorimetric temperature measurements, which attributed to the energy transfer between Tb3+ and Eu3+ ions.

Phenyl Derivatives Modulate the Luminescent Properties and Stability of CzBTM-Type Radicals

The distinctive electron structures of luminescent radicals offer considerable potential for a diverse array of applications. Up to now, the luminescent properties of radicals have been modulated through the introduction of electron-donating substituents, predominantly derivatives of carbazole and polyaromatic amines with more and more complicated structures and redshifted luminescent spectra. Herein, four kinds of (N-carbazolyl)bis(2,4,6-tirchlorophenyl)-methyl (CzBTM) radicals, Ph2CzBTM, Mes2CzBTM, Ph2PyIDBTM, and Mes2PyIDBTM, were synthesized and characterized by introducing simple phenyl and 2,4,6-trimethylphenyl groups to CzBTM and PyIDBTM. These radicals exhibit rare blueshifted emission spectra compared to their parent radicals. Furthermore, modifications to CzBTM significantly enhanced the photoluminescence quantum yields (PLQYs), with a highest PLQY of 21% for Mes2CzBTM among CzBTM-type radicals. Additionally, the molecular structures, photophysical properties of molecular orbitals, and stability of the four radicals were systematically investigated. This study provides a novel strategy for tuning the luminescent color of radicals to shorter wavelengths and improving thermostability.

The optical temperature sensing performance of Bi3+, Sm3+ co-doped CaWO4 phosphors

CaWO4 phosphors with fixed Bi3+ doping concentration and varied Sm3+ doping concentration have been prepared for this study. XRD analysis showed that the samples were scheelite in structure. The FE-SEM images revealed that the samples appeared to be the form of micrometer spheres. The results of the experiments analysed show that the luminescence of Bi3+ has a significant thermal quenching trend, while the tendency of the luminescence of Sm3+ to be thermally quenched is slower, resulting in an increase in the FIR of Sm3+ to Bi3+ with increasing temperature. Using this FIR to represent temperature gives a high relative sensitivity. The maximum relative sensitivity of the phosphor prepared in this experiment was 3.56 % K-1 (CaWO4: 5 mol% Bi3+, 0.1 mol% Sm3+, 303 K). As the temperature increases, we observe that the luminescence colour of CaWO4: Bi3+, Sm3+ changed. This makes it possible to be able to estimate the temperature change using the colour change. Temperature cycling tests showed that the FIR repeatability of the samples was very well. In conclusion, CaWO4: Bi3+, Sm3+ phosphors have promising applications in optical temperature sensing technology.

Chromic soft crystals based on luminescent platinum(II) complexes.

Platinum(II) complexes of square-planar geometry are interesting from a crystal engineering viewpoint because they exhibit strong luminescence based on the self-assembly of molecular units. The luminescence color changes in response to gentle stimuli, such as vapor exposure or weak mechanical forces. Both the molecular and the crystal designs for soft crystals are critical to effectively generate the chromic luminescence phenomenon of Pt(II) complexes. In this topical review, strategies for fabricating chromic luminescent Pt(II) complexes are described from a crystal design perspective, focusing on the structural regulation of Pt(II) complexes that exhibit assembly-induced luminescence via metal-metal interactions and structural control of anionic Pt(II) complexes using cations. The research progress on the evolution of various chromic luminescence properties of Pt(II) complexes, including the studies conducted by our group, are presented here along with the latest research outcomes, and an overview of the frontiers and future potential of this research field is provided.

Precise Regulation the Multiemission Based on Soft Double Salt for Information Encryption.

Manipulation of multiemissive luminophores is meaningful for exploring luminescent materials. Herein, we report a soft double salt assembly strategy that could result in well-organized nanostructures and different luminescence based on multiple weak intermolecular interactions thanks to the existence of electrostatic attraction between the anionic and cationic platinum(II) complexes. The cationic complexes B1 and B2 can coassemble with anionic complex A, respectively, and the emission switches from monomeric and excimeric emission to the triplet metal-metal-to-ligand charge transfer (3MMLCT) along with morphology changes from 0-dimensional (0-D) nanospheres to 3-dimensional (3-D) nanostructures. It is demonstrated that an isodesmic growth mechanism is adopted during the spontaneous self-assembly process, and the relative negative ΔG values make the anionic and cationic complex molecules prefer to form aggregates based on π-π stacking, Pt···Pt interactions, and electrostatic interactions. The coassembly strategy between anionic and cationic complexes endows them with multicolor luminescent and apparent color as optical materials for advanced information encryption.

Enhancement of Excimer Formation Ability by Modulating the Length of Side-Chains in Polyhedral Oligomeric Silsesquioxane (POSS) and Application for Fluorescence Sensors for Metal Cations

Abstract Polyhedral oligomeric silsesquioxane (POSS) is a molecule with an inorganic cubic structure and organic side-chains and has attracted great attention for its application to luminescent materials by modifying luminophores. In this study, pyrenes-integrated POSSs with various lengths of side-chains were synthesized and the effect of the length on luminescent properties was evaluated. In optical measurements, highly efficient excimer emission was observed under dilute solution conditions. The higher value of the intensity ratio of the excimer emission to the monomer one was detected in the shortest side-chains. It is likely that the shorter side-chains of POSS lead to more efficient intramolecular interaction. Interestingly, we also found that the luminescence color was changed in response to metal cations in the dilute solutions. From the mechanistic study, metal cations such as Cu2+ can accelerate hydrolysis at the linker moiety. As a result, highly-sensitive luminescent sensors were obtained. These data represent that POSS can work as a reaction field where chemical reactions are accelerated through the accumulation of reactive species.

Multi-color and multi-mode luminescence tuning in persistent phosphors by trap engineering

Conventional persistent luminescent phosphors face a significant challenge in developing a single material for multi-color anti-counterfeiting. In this study, a wide range of Cr3+ activated gallium germanate-based persistent phosphors are successfully synthesized using high-temperature solid phase approach. By incorporating Cr3+ and Er3+ as dual emitting centers, and utilizing Yb3+ as a sensitizer and electron traps, the resulting phosphors exhibit an exceptional combination of photoluminescence, up-conversion luminescence, persistent luminescence, photo/thermo-stimulated luminescence, followed by photo-stimulated persistent luminescence in a single material system. Beyond its multi-mode emissions, the luminescence color output can be conveniently controlled by adjusting annealing time, Yb3+ ion doping concentration, excitation wavelength, or excitation power. A systematic study of trap distribution related to PersL has been conducted by regulating annealing temperature, time, doping concentration and type. The responding multi-mode luminescent mechanisms are also proposed. Particularly, these phosphors demonstrated outstanding performance as security labels in advanced anti-counterfeiting applications. This research holds the potential to inspire the design and development of more intricate luminescence anti-counterfeiting materials and technologies.

Site occupancy and tunable luminescence of Eu2+ and Eu3+ coactivated KCaY (PO4)2:Eu phosphors.

Utilizing the structure characteristic of KCaY (PO4)2 crystal, the site distribution of Eu2+ in KCaY (PO4)2:Eu phosphor coactivated with Eu2+ and Eu3+ ions is tuned. Upon 393-nm excitation, the as-prepared phosphor exhibits a broadband emission of Eu2+ peaked at ~ 475 nm and a typical red emission of Eu3+ with a strong 5D0-7F1 emission at ~ 591 nm. The luminescence color of the phosphor can be adjusted from blue to green, white, yellow, and red. The increasing concentration of Sr2+ and Eu2+ results in a blue shifting of Eu2+ emission. The increasing concentration of Eu3+ results in a red shifting of Eu2+ emission and an enhanced red emission of Eu3+. The luminescence behaviors of the phosphors are analyzed in terms of the site distribution of Eu2+ and Eu3+. A single-phase white light emitting was achieved in KCaY (PO4)2:Eu phosphor upon UV and NUV light excitation, indicating that the phosphor has potential application in white lighting.

36‐1: Invited Paper: Submicron Narrow‐Band Phosphors in Luminescent Color Filters & Next Generation MiniLED and MicroLED Displays

Both phosphors and quantum dots are currently used in liquid crystal displays (LCDs), with GE's KSF narrow red phosphor demonstrating the best possible red color point, reliability, and efficiency. Next generation miniLED and microLED based displays require excellent color quality (gamut) and high brightness which will require color conversion materials with high EQE and narrow emission peaks. Here we describe recent advancements in submicron narrow‐band phosphors which are being implemented in next‐generation miniLED displays, and being considered for enabling full‐color microLED and luminescent color filter displays of the future due to their excellent optical performance and robust nature.

Upconversion luminescence and temperature sensing properties of Tm3+, Yb3+, and Ho3+ doped 12CaO·7Al2O3 single crystals

Tm3+, Yb3+, and Ho3+ doped 12CaO·7Al2O3 (C12A7) single crystal exhibiting white light emission has been successfully prepared by the Czochralski method. Under 980 nm excitation, the emission peaks were observed at 475 nm, 550 nm, 653 nm, and 660 nm. As the temperature increased from 403 K to 623 K, the upconversion luminescence color of the Tm3+/Yb3+/Ho3+/C12A7 crystal changed from white to green and exhibited large temperature dependence. In the temperature range of 403K-623 K, the absolute sensitivity (SA) value of the thermal coupling levels (TCLs) fluorescence intensity ratio (FIR, I700/I800) was 1.48×10−5K−1, and the relative sensitivity (SR) value was 7.13×10−3%K−1. The non-thermal coupling levels (NTCLs) FIR (I800/I870) had an SA value of 0.026K−1 and an SR value of 0.014%K−1, which achieved a significant increase in temperature sensitivity compared to the former. It provides a strategy to achieve accurate sensitivity of FIR technology. Rare earth (RE) ions doped C12A7 single crystal material has good research and application prospects in the field of temperature sensing and optoelectronics.

Dynamic modulation of multicolor upconversion luminescence of Er3+ via excitation pulse width.

Lanthanide-doped upconversion (UC) luminescent materials display multicolor emissions, making them ideal for a variety of applications, such as multi-channel biological imaging, fluorescence encryption, anti-counterfeiting, and 3D display. Manipulating the UC emissions of the luminescent materials with a fixed composition is crucial for their applications. Herein, we propose a facile strategy to achieve pulse-width-dependent multicolor UC emissions in NaYF4:Yb/Er/Tm nanocrystals. Upon excitation with a 980nm continuous-wave laser diode, Er3+ ions in NaYF4:20%Yb,15%Er,1%Tm nanocrystals exhibited UC emissions with a red-to-green (R/G) ratio of 11.3. Nevertheless, by employing a 980nm pulse laser with pulse widths from 0.1 to 10ms, the UC R/G ratio can be easily adjusted from 0.9 to 11.3, resulting in continuous and remarkable color transformation from green, yellow, orange, to red. By virtue of the dynamic luminescence color variation of these NaYF4:20%Yb,15%Er,1%Tm nanocrystals, we demonstrated their potential applications in the areas of anti-counterfeiting and information encryption. These findings provide deep insights into the excited-state dynamics and energy transfer of Er3+ in NaYF4:Yb/Er/Tm nanocrystals upon 980nm pulse excitation, which may pave the way for designing multicolor UC materials toward versatile applications.

Construction of the Red‐Green‐Blue Luminescence Conversion System Based on Donor‐Acceptor Dyes Exchange with Diels‐Alder Dynamic Covalent Bonds

AbstractThe construction of full‐color fluorescence systems has received widespread attention because of their applications in lighting materials, optoelectronic materials, and fluorescent probes. However, for the full‐color luminescence system based on trichromatic materials, there are no connections between materials of different luminescent colors. Herein, A new donor‐acceptor dye with red fluorescence was synthesized. The dye displays excellent optical properties of short half‐peak width and strong fluorescence emission. An effective energy transfer process from the dansyl donor to the acceptor was observed with a transfer efficiency of 81 %. Further, dyes with green and blue fluorescence were introduced to construct a full‐spectrum fluorescent system. Through exchange reactions of Diels‐Alder dynamic covalent bonds, red, green, and blue luminescence can be converted. This work provides a new idea for the design of full‐color fluorescent materials.

Utilizing a water-stable terbium (III) metal-organic framework for luminescent sensing of nitroimidazole antibiotics

A new 3D terbium (III)-based metal–organic framework, [Tb(TDC)(µ2-CH3COO)(H2O)] (Tb-MOF, H2TDC = 2,5-thiophenedicar-boxylic acid), was obtained with Tb3+ ions as metal source and TDC ligands as the auxiliary ligand through self-assemble mode. The Tb-MOF features a 3D network constructed by bridging a 2D wave-like network connected by TDC ligands with monodentate coordination mode, which results in the formation of a 3D net framework. The luminescent properties and sensing antibiotics experiments were extensively investigated for the Tb-MOF. Remarkably, the Tb-MOF exhibits a substantial quantum yield (QY) at 55.0 % and an average photoluminescence lifetime of 534 µs. Furthermore, the Tb-MOF shows selective luminescence quenching for nitroimidazole antibiotics, including metronidazole (MDZ), dimetridazole (DTZ), and ornidazole (ODZ), with a particularly strong response for MDZ (Ksv = 5.49 × 104 M−1, LOD value is 7.9 × 10−5 M). Finally, the Tb-MOF enables a simple and convenient test paper that allows luminescent color changes to be observed with the naked eye for detecting MDZ.

Multidimension‐Regulated Dynamic Timing Control Over Multicolor Emission of Host–Guest Assemblies for Information Encryption and Advanced Anti‐Counterfeiting

AbstractDynamical control over molecular luminescence, especially in a time‐dependent manner, holds great promise for the development of smart luminescent materials for anti‐counterfeiting and preventing information leakage. Herein, a series of self‐assembled systems are reported using pillar[5]arene (DMP[5]) and spiropyran derivatives (SP‐C4‐Py). The assemblies rely on the time‐encoded locking and unlocking ring‐switching and fluorescence resonance energy transfer (FRET) units for information camouflage and multilevel encryption. DMP[5] with cyan solid fluorescence color acts as the host and energy transfer (EnT) donor, while photochromic SP‐C4‐Py with the ring‐opened and closed isomers acts as guest and EnT acceptor. When irradiated, the assemblies undergo a time‐dependent luminescence color change ranging from cyan to yellow to red through a FRET process. The molar ratio of host and guest in the assembly systems affects the FRET efficiency, and the power of the irradiation source influences the isomerization degree and rate of SP‐C4‐Py, allowing for precise control over the fluorescent color transition time. The combination of molecular composition and external stimuli governs the kinetics of color change, resulting in a difference in the appearance time of a specific fluorescent color pre‐designed as correct authorized information. By combining these diverse assembles in one label, information encryption and dynamic information identification are achieved in the dimensions of time, ratio, and light power. This time‐dependent feature offers the assembly materials with a multilevel security and provides new possibilities for anti‐counterfeiting and blocking information leakage.

Excellent Color Purity and Luminescence Thermometry Performance in Germanate Tellurite Glass Doped with Eu3+ and Tb3+

Germanate tellurite glasses doped with Eu3+ and Tb3+ were synthesized by the conventional melt-quenching method. There is no indication of the energy transfer between dopant ions in this host, but the co-dopants exhibit excellent color purity of 100% for Eu3+ and 80% for Tb3+. The co-doped glass exhibits yellow luminescence. The quantum yield of the Eu3+ emission is equal to 23% under 395 nm excitation. The thermal quenching of Eu3+ and Tb3+ luminescence occurs at different temperature ranges, which enables the thermal sensing properties of the material. The relative fluorescence intensity ratio (FIR) sensitivity of 0.16% K−1 was recorded in the wide range of temperatures spanning from −193 °C up to 0 °C. The temperature dependence of the decay times was also studied. The lifetime-based temperature sensitivity was determined to be 0.95% K−1 at 250 °C for Tb3+5D3 level emission and 0.3% K−1 at 225 °C for Eu3+5D1 level emission.

Hybrid Water-Harvesting Channels Delivering Wide-Range and Supersensitive Passive Fluorescence Humidity Sensors.

The development of optical humidity detection has been of considerable interest in highly integrated wearable electronics and packaged equipment. However, improving their capacities for color recognition at ultralow humidity and response-recovery rate remains a significant challenge. Herein, we propose a type of hybrid water-harvesting channel to construct brand-new passive fluorescence humidity sensors (PFHSs). Specifically, the hybrid water-harvesting channels involve porous metal-organic frameworks and a hydrophilic poly(acrylic acid) network that can capture water vapors from the ambient environment even at ultralow humidity, into which polar-responsive aggregation-induced emission molecules are doped to impart humidity-sensitive luminescence colors. As a result, the PFHSs exhibit clearly defined fluorescence signals within 0-98% RH coupling with desirable performances such as a fast response rate, precise quantitative feedback, and durable reversibility. Given the flexible processability of this system, we further upgrade the porous structure via electrostatic spinning to furnish a kind of Nano-PFHSs, demonstrating an impressive response time (<100 ms). Finally, we validate the promising applications of these sensors in electronic humidity monitoring and successfully fabricate a portable and rapid humidity indicator card.

Thermosensitive chameleon films based on polystyrene doped with complexes of europium(III) and terbium(III)

New complexes of Eu(III) and Tb(III) tris(β-diketonates) with Lewis bases were synthesized. The spin-coating technique was used to produce composite films consisting of polystyrene (PS) polymer doped with mixtures of Eu(III) and Tb(III) complexes with different ratio of luminophores. An increase in the content of the Tb(III) complexes in the 5 %Eu x%Tb films intensifies emission of both the Tb3+ and Eu3+ ions due to occurring intermolecular energy transfer and leads to a significant increase in photostability of the material (the loss of luminescence intensity ratio did not exceed 0.5 %/hour). These photostable films were characterized as potential luminescent temperature sensors. The temperature sensitivity of their luminescence intensity and lifetime was investigated in the range of 298–383 K. The maximum absolute sensitivity of the films reaches 6.00 µs/K and exceeds that of all known lanthanide-containing thermal sensors designed for measuring physiological temperatures. In combination with changeable luminescence colors of the films, such a sensitivity makes these materials promising colorimetric thermal sensors for in situ temperature measurements.