Luminescence Behavior Research Articles

Room Temperature Phase Transition and Luminescence Behavior of a Novel Metal‐Free Ionic Crystal [C7H16NO][ClO4

AbstractMetal‐free ionic crystals have attracted tremendous attention for their environmental friendliness, biocompatibility, easy fabrication and structural variability. Herein, a metal‐free ionic crystal [C7H16NO][ClO4] ([C7H16NO]=1‐methyl‐4‐piperidinemethanol) with a dielectric transition at room temperature was designed and constructed. Differential scanning calorimetry (DSC) proved that there exists a reversible phase transition near room temperature at 304 K, accompanied with switchable dielectric behaviors between the low and high dielectric states. The single crystal structure show that the mechanism of such structural phase transition mainly results from the dynamic motion of perchlorate anions. The compound is further shown to exhibit remarkable luminescent properties, characterized by a prolonged lifetime of 18.6 ns. This work offers valuable insights into the construction of room temperature phase‐transition ionic crystals involved with dielectric switching and blue luminescence properties.

Luminescence and Transport Behavior in Incommensurately Modulated CaGd2(MoO4)4:Yb/Er.

The phenomenon of thermal quenching of luminescence can significantly compromise the efficiency of luminescent materials, a process accompanied by the generation of substantial phonon populations. While plenty of models for elucidating this behavior have been proposed, the crucial role of phonon transport has largely been neglected, particularly in the enigmatic incommensurate scheelite structure with good luminescence performance. In this study, we delve into the thermal quenching dynamics of the near-infrared emission in the incommensurately modulated CaGd2(MoO4)4:Yb/Er system. Our comprehensive investigation reveals distinct evolutionary patterns in electrical conductivity, luminescence intensity, thermal conductivity, and Raman scattering at varying temperature regimes. Notably, we have determined that thermally induced ion migration, occurring above ∼300 °C, serves as a pivotal trigger for the activation of all phonons and the enhancement of phonon-defect scattering within this incommensurate framework. This phenomenon not only diminishes the thermal conductivity but also accelerates the multiphonon relaxation of the Er3+ emission levels, culminating in a marked thermal quenching of luminescence. This work illuminates the thermal quenching mechanism of luminescence by focusing on phonon scattering dynamics, providing critical insights for the design of thermally robust near-infrared luminescent materials, which are essential for the advancement of optical amplification systems.

Glass-ceramic materials: influence of fluoride nanocrystals on emission properties of lanthanide ions

In this work, the oxyfluoride glass-ceramic materials containing LaF3 nanocrystals, prepared by using the sol-gel method, were described. The influence of fluoride nanocrystals on the photoluminescence properties of selected lanthanide ions was determined. The experimental results obtained for nano-glass-ceramics were compared to the precursor xerogels. Those Ln3+-doped sol-gel materials with dispersed LaF3 nanocrystals exhibit several visible emission bands. It was observed that heat-treatment process caused the elongation of the lifetimes of the 5D0 state from τ = 0.22 ms to τ1 = 0.79 ms, τ2 = 9.76 ms (for Eu3+-doped materials) and of the 4F9/2 state from τ = 0.027 ms to τ1 = 0.034 ms, τ2 = 1.731 ms (for Dy3+‑doped materials). The performed studies clearly revealed that luminescence behaviour also depends on an activator concentration and a distribution of energy levels of lanthanide ions.

Unveiling the radiant secrets: Delving into luminescent behaviors of rare earth-infused strontium cerate

Unveiling the radiant secrets: Delving into luminescent behaviors of rare earth-infused strontium cerate

AIE-active fluorescence emitters containing tetraphenylethylene and α-cyanostilbene with mechanochromism and photo-responsive behaviors

Aggregation induced emission luminogens (AIEgens) as one of the optimal alternatives for designing stimuli-responsive fluorophores for real-life applications have sparked much current interest in smart materials design. Herein, the “Star molecules” in AIEgens of α-cyanostilbene and Tetraphenylethylene (TPE) derivatives were constructed into one molecular, namely DC-TPE-tBu and DC-TPE-CN. Both compounds exhibited significant AIE properties. Moreover, the two compounds could change their luminescent colors and intensities under the stimulation of external mechanical force and UV light, showing excellent mechanochromic luminescent (MCL) and remarkable photo-responsive behaviors, respectively. The stimuli responsive mechanisms were investigated by powder X-Ray diffractometer (PXRD) spectra and density functional theory calculations (DFT). The MLC behaviors were associated with the crystalline-to-amorphous transitions after mechanical grinding. These remarkable features make them suitable for the application of mechano/photo-sensors. The studies provide a useful strategy for developing AIE-active functional materials.

Unusual Manganese Luminescence Channels in Low Doped MgAl2O4

We have done the rigorous characterizing of the Mn-doped MgAl2O4 (Mn = 0, 0.02, 0.04, 0.1 wt.%) single crystals and the comprehensive analysis of their optical properties theoretically supported by the Modified Crystal Field Theory to obtain the most complete picture, to date, of the diverse absorption and luminescence behavior of MgAl2O4:Mn spinels. The study has focused on exploring the formation and coexistence of multivalent states of Mn and identifying the conditions needed for activating luminescence channels. We found that Mn takes the charge state +2, +3 and +4 and occupies both tetrahedral and octahedral positions. Six luminescence channels related to Mn ions were identified for the first time. Two channels activate the luminescence at 520 nm: intra-atomic transitions in tetrahedral coordinated Mn2+ ions under VIS-excitation and a recombination Mn3+→Mn2+→Mn3+ process involving Mn3+ in tetrahedral positions under X-ray. Mn3+ in tetrahedrons and octahedrons activate luminescence channels at 733 and 926 nm under UV-C and VIS excitations. Two distinct processes involving Mn3+ and Mn4+ ions in octahedrons result in the luminescence at 651 nm. The first is an intra-atomic transition in the Mn4+ occurring under VIS-excitation. The second appears through a charge transfer Mn3+→Mn4+→Mn3+ in the octahedrons under UV-B-excitation.

In Situ Reversible and Robust Mechano-Responsive Ultralong Phosphorescence of Polyurethane Elastomer.

Though mechano-responsive luminescent materials obtained much attention, most of their responses are non-reversible, let alone in situ reversible. Here, the study presents a new strategy to push through this limitation for their applications, which relies on the reversible mechano-responsive (MR) hydrogen bonding interactions and polymer chain orientation among a doped polyurethane (PU) elastomer. The radiative and nonradiative transitions inside these phosphorescent triphenylene-based aromatic secondary amines (TpNP and TpNPO) doped in the PU matrix can be accordingly modulated by these MR variations, including the PU chains orientation and the interactions between emitters and PU, respectively. Surprisingly, the intensities, quantum yields, and even lifetimes of their ultralong phosphorescence correlate well with the stress of PU, showing triple mechano-enhancement with a small threshold value of 7.9MPa. Importantly, these in situ and rapidly reversible MR phosphorescences possess excellent repeatability, which is still displayed even after >500 cycles of loading/unloading. Based on such a robust and highly sensitive MR afterglow, these PU materials have been demonstrated applications with no interruption of background in several fields, including micro-crack detection, material damage prediction, limb movement monitoring, and information encryption. This work provides new insights for developing innovative ultralong phosphorescence materials with improved luminescence and reversible mechano-responsive behavior.

Rod‐Like Microcrystal Scintillators Based on Organic–Inorganic Hybrid Copper Halides for X‐Ray Imaging

AbstractCopper‐based organic–inorganic hybrid halides (OIHHs) have garnered significant interest in X‐ray imaging due to their flexible structural adjustability, efficient light emission, strong X‐ray absorption, etc. Herein, four copper‐based OIHH crystals composed of the same organic ligands (isopropyl triphenylphosphonium cations, IPP+) and inorganic parts (Cu2I42−) are synthesized by varying the ratios of raw materials and types of reaction solvents. Although these crystals share identical structures, they exhibit different luminescent behaviors (blue, green, white, and yellow) attributed to vacancy defects originating from CuI. Notably, the novel copper‐based OIHH (CP2) with green emission shows the best luminescence efficiency (99.54%) and excellent scintillation performance (50675 photons MeV−1). The traditional technology of scintillation screens mixing scintillator powders and polymers often results in light scattering due to powder aggregation and inhomogeneity. To address this challenge, the dispersant polyvinyl pyrrolidone is introduced to prepare uniform rod‐like microcrystals of CP2. The scintillation screen based on CP2 microcrystals achieves a high spatial resolution of 16–18 lp mm−1, surpassing the resolution of most copper‐based OIHH scintillators. Furthermore, it is imaging capabilities are validated using a commercial X‐ray flat panel detector, demonstrating imaging performance comparable to that of commercial scintillators.

Reversible photochromism and photoluminescence modulation in (K,Na)NbO3‐based ceramics via oxygen vacancy regulation

AbstractMost of the optical behaviors in photoelectric multifunctional ceramics strongly depend on the addition of rare‐earth elements. However, the limited species of rare‐earth cations available as luminescence centers restrict the further development of photoelectric devices. Additionally, introducing the large atomic‐radii elements usually dramatically deteriorates the piezoelectric properties. Herein, the novel photochromism and luminescence modulation properties have been realized in CuO‐doped [(K0.43Na0.57)0.94Li0.06][(Nb0.94Sb0.06)0.95Ta0.05]O3 (KNLNST) piezoelectric ceramics which show intense sensitivity to visible‐light irradiation. As a strategy for regulating oxygen vacancy concentrations in piezoelectric ceramics, different CuO amounts are doped to generate color centers for photochromism. The photoluminescence phenomenon exhibiting green emission under 375 nm excitation is observed in KNLNST piezoelectric ceramics, which is most commonly realized via rare‐earth doping in luminescent materials. KNLNST–0.3CuO ceramics with the highest oxygen vacancy concentration achieve a reversible luminescence modulation of 46.9% by altering light irradiation and thermal stimulus. Moreover, a hand‐rewritable optical information test demonstrates exceptional reproducibility and fatigue durability. This research displays the controllable photochromism and luminescence behaviors in ceramics via regulating oxygen vacancy concentration by CuO “hard” doping. The lead‐free high performance photoelectric ceramics fulfill the demands of potential applications in anti‐counterfeiting and optical storage devices.

Dynamic Phosphorescence/Fluorescence Switching in Hybrid Metal Halides Toward Time‐Resolved Multi‐Level Anti‐Counterfeiting

AbstractHybrid metal halides (HMHs) with time‐resolved luminescence behavior promise to be a breakthrough in multi‐level anti‐counterfeiting, but controlling the dynamic switching between phosphorescence and fluorescence is extremely challenging. Herein, an array of 0D HMHs is constructed by screening the π‐conjugated ligand with room‐temperature phosphorescence (RTP). Compared to the organic chromophore, (ETPP)2ZrCl6 possesses a misaligned stacking and rigid structure, contributing to an improved phosphorescence quantum yield (ΦP = 27.50%) and an extended phosphorescence lifetime (τ = 0.6234 s), as the intervening of inorganic unit [ZrCl6]2− suppresses the energy losses caused by nonradiative relaxation and prompts the intersystem crossover (ISC) process. Not only that, the interplay of phosphorescence‐fluorescence dual‐mode emission can be intelligently controlled by doping the active metal Te4+, resulting in a dynamic switching between RTP phosphorescence and self‐trapped exciton (STE) fluorescence. DFT calculations reveal the governing origins of RTP‐STE from the intermolecular ISC channels and spin‐orbit coupling (SOC) coefficients. These precise images into periodic pixelated arrays enable the multi‐level anti‐counterfeiting and information encryption. This work proposes a fluorescence‐phosphorescence co‐modulating strategy under the premise of dissecting the structural origins for optimizing RTP phosphorescence, which paves the way for designing high‐security‐level anti‐counterfeiting materials.

Unconventional Luminescence Polymer with Color-Tunability based on Solvent-Induced Electrostatic Potential Distribution of Fluorophore.

Tuning full-color emission of polymers holds significant promise. However, preparing unconventional luminescence polymers with color-tunability in dilute solution and understanding the relationship between non-covalent interactions and luminescent behavior remains a great challenge. We report two emitters (P1 and P2) incorporating tetracoordinate boron. The P1 with non-conjugated D-π-A structure, exhibited red delayed fluorescence at 645 nm with quantum yield of 9.15 % in aggregates. Notably, the emission wavelength of P1 can be tuned from 418 to 588 nm at different solvent. Similarly, the emission wavelength of P2 can also be adjusted by manipulating the interactions between the solvent and fluorophore. Experimental characterization and theoretical calculations indicate that the B←N bond and electronic interactions between solvent and fluorophore significantly regulate the equilibrium the electrostatic potential (ESP) and the intramolecular O⋅⋅⋅O interactions of P1, thereby modulating its emission wavelength. Additionally, these polymers showed excellent potential in fluoride ions detection. This work provides new insights into the complex effects of intermolecular interactions on luminescent properties.

Eu(III) complexes derived from 2-quinolinecarbohydrazide Schiff base ligand, relations between structure and luminescence properties

A series of Eu(III) complexes were obtained following the template condensation of 2-quinolinecarbohydrazide and 2,6-diacetylpyridine, namely: [Eu(H2pbqh)(NO3)3]·MeOH (1), [Eu(Hpqh)(NO3)3]·2MeCN (2), [Eu(H2pbqh)(SCN2)(MeOH)2](SCN) (3) and [Eu2(pbqh)2(NO3)2(H2O)2]·2.5MeOH (4). The structures of complexes and a new H2pbqh ligand (N',N'''-((1E,1′E)-pyridine-2,6-diylbis(ethan-1-yl-1-ylidene))bis(quinoline-2- carbohydrazides)) were elucidated by single-crystal X-ray diffraction. H2pbqh coordinate pentadentate ONNNO and forms mononuclear complexes 1 and 3. The bis-deprotonated ligand pbqh2- act as hexadentate/bridging mode generates the binuclear complex in 4. The partially condensed ligand Hpqh, tetradentate ONNO, was recorded in complex 2. The crystallographic results reveals that the coordinated H2pbqh/Hpqh ligands and Eu3+ cation form a planar structure in these complexes and nitrate anions coordinate chelate, completing the coordination sphere of Eu3+. The solid state photoluminescent emission was investigated highlighting the nitrate complexes 1 and 2 that exhibit red intense luminescence (λmax = 618 nm). Moreover, the computational calculations reveal different pathways of energy transfer from ligand to Eu3+ electronic states explaining the luminescent behavior.

Nitrogen doping of cuprous oxide films: A surface science perspective

Nitrogen doping of Cu2O films grown on Au(111) and Pt(111) supports was explored by a variety of surface-science techniques, including electron-diffraction, X-ray photoelectron-spectroscopy (XPS), scanning tunneling microscopy and photoluminescence spectroscopy (PL). The films were prepared by Cu vapor deposition and high-pressure oxidation at 50 mbar O2. Nitrogen was inserted by adding N2 to the reactive gas or via sputter doping. Only the latter resulted in a clear N1s signal in XPS, compatible with the insertion of N-atoms at O substitutional sites. The N-doping caused an overall degradation of the oxide lattice and suppressed the formation of the (√3×√3)R30° surface reconstruction observed on pristine Cu2O(111). Moreover, the oxide Fermi level shifted from the valence-band top into the band gap, indicative for a reduced p-type conductivity of the sample upon doping. The N-dopants featured low thermal stability and largely desorbed at around 500 K, leaving behind a pronounced 850 nm PL peak due to O vacancy emission. Our findings indicate that the N-atoms initially occupy O substitutional sites but get removed easily at moderate temperature, casting doubts whether N-doping is a suitable pathway to improve the conductance and luminescence behavior of Cu2O.

Advancing understanding of composition–structure–luminescent properties in laser glass through machine learnings

AbstractRare‐earth (RE)‐doped laser glasses meet urgent needs in national security and scientific fields, and their optimization has garnered extensive attention. However, the design of these laser glasses often relies excessively on trial‐and‐error experimentation, leading to significant costs and a lack of scientific guidance. Herein, we propose an integrated method that combines structural descriptors determined from molecular dynamics simulations, a self‐constructed luminescent database, and a machine learning algorithm to establish the composition–structure–luminescent property (CSLP) relationship. Using an Nd3+‐doped commercial silicate laser glass system as an example, the effectiveness of this approach has been demonstrated. The developed CSLP model enables highly accurate predictions of spectral properties, achieving a determination coefficient (R2) greater than 0.94, based on eight structural descriptors. The importance of different structural descriptors on spectral characteristics is ranked and thoroughly discussed, revealing an intrinsic relationship between the first and second coordination shells around RE ions and luminescent behaviors. Furthermore, the generic structural descriptors identified in the CSLP model can be extrapolated to other systems involving different network formers (e.g., silicate and phosphate) and modifier cations (e.g., Li, Na, K, Ba, and Ca). This capability facilitates the design of laser glasses tailored to specific targets, such as large emission cross‐sections, extended lifetimes, or reduced quenching effects.

Green florescent carbon dots synthesized from various household green wastes for detection of parathion methyl pesticide

The purpose of the current study was to examine the use of green household wastes, such as lemon peel, bottle gourd peel (BG), culinary banana peel, and sugarcane bagasse, as a source for synthesizing carbon dots (C-dots) and to determine how the composition of the material affected the functional characteristics of the C-dots and its interaction behaviour for detection of pesticide. The synthesized C-dots showed green fluorescence with varying particle sizes and red shifting fluorescence with more than 100 nm Stokes shift, indicating time and excitation dependent luminescence behaviour. C-dots produced from bottle gourd (BG) peel had a positive impact on the functional characteristics with a maximum emission of 514 nm and excitation of 410 nm. The SAED and TEM pattern confirmed its amorphous structure. The hydronium ion diameter and the quantum yield were 0.99 nm and 3.1 % respectively. Contributing towards food safety, the synthesized C-dots from BG showed significant behaviour in the detection of parathion methyl (MP) like organophosphorus pesticide (OP) as it conjugated with iron and 1 ppm of parathion methyl, which exhibited “Turn-Off-On” fluorescence behaviour with noticeable changed in intensity and act as a promising qualitative tool for detection of parathion methyl in real sample. The intensity of FL and concentration of OP is directly proportional which is established by the investigated OP in vegetable, fruit and water samples. The significance of iron and MP-OP was also investigated in the presence of other metal ions and pesticides and showed that the C-dots synthesized probe solution was reliable and sensitive towards the detection of MP-OP in real samples.

Trace element analysis and luminescence behavior of quartz in pegmatites of the Tørdal Region, Norway

This publication presents a study on the mineral chemistry and luminescence properties of quartz samples from pegmatites of the Tørdal region in Norway. A total of 12 samples were analyzed using Secondary Ion Mass Spectrometry (SIMS), Electron Paramagnetic Resonance Spectroscopy (EPR), and Cathodoluminescence (CL) to gain insights into their trace element concentration and distribution as well as their luminescence behavior. The samples are characterized by different Cl emissions at 450 nm, 500 nm 650 nm and an additional shoulder at 390 nm, which is only partially visible due to the absorption of the glass optics. Of these luminescence bands, the 500 nm band is the most dominant in most samples and it is characterized by an initial blue-green luminescence, which is not stable under electron irradiation. Moreover, it is characterized by a heterogeneous distribution within the samples. This luminescence can be mostly assigned to [AlO4/M+]0 defects, with charge compensation mostly achieved by Li+. Analyses by EPR spectroscopy prove the dominance of structurally bound Al, Li, and Ti ions in the investigated samples. Further analyses using SIMS mapping demonstrate that Na and K are mainly bound to micro fractures or inclusions, suggesting a limited role in the compensation of the luminescence centers. Additionally, the SIMS mappings show that some samples contain Al-rich clusters of 10 to 20 μm in diameter, whereas other trace elements are characterized by a homogeneous distribution. These clusters correspond to bright luminescence areas in size and shape and could potentially indicate H+ compensated [AlO4/M+]0 defects.

The luminescent behaviors and J-O theory analysis of red phosphor Ca1-xGeO3:xEu3+

The luminescent material Eu3+-doped CaGeO3 has been synthesized using a high-temperature solid-state reaction technique. The crystal structure was analyzed using X-ray diffraction (XRD). The results showed that the samples belonged to the triclinic crystal system with the space group P1̅. The luminescent properties including photoluminescence excitation (PLE), Photoluminescence emission (PL) spectra, and lifetime, thermal stability, and diffuse reflectance spectroscopy (DRS) have been investigated. Under near-ultraviolet excitation at 390 nm, the phosphor emits red light with the highest intensity around 611 nm, which is dominated by the 5D0→7F2 electric dipole transitions. It indicates that Eu3+ is in the inversion center of the crystal. The concentration quenching occurs at about 6 % doping from the concentration-dependent luminescence behavior. The energy transfer mechanism was analyzed to be mainly the energy transfer between neighboring ions. The thermal stability was 82.16 % at 423 K. The chromaticity coordinates are in the red area and the color purity approaches 99 %. Furthermore, the J-O theoretical results are used to confirm the experimental result. It suggests that Ca1-xGeO3:xEu3+ is an effective red luminescent material for illumination and backlight display applications.

Multistimuli Luminescence and Anthelmintic Activity of Zn(II) Complexes Based on 1H-Benzimidazole-2-yl Hydrazone Ligands

Three novel Zn(II) mononuclear complexes with the general formula ZnL2Cl2 (L = 2-(4-R-phenylmethylene)benzimidazol-2-hydrazines; R-H (1), R-CH3 (2), and R-OCH3 (3)) were synthesized and fully characterized by various means. These complexes demonstrate excitation-dependent emission, which is detected by a change in the emission color (from blue to green) upon an increase in the excitation wavelength. Moreover complex 1 shows reversible mechanochromic luminescence behavior due to the reversible loss of solvated methanol molecules upon the intense grinding of crystals. In addition, 1 exhibits vapochromic properties, which originate from the adsorption methanol vapor on the crystal surface. The strengthening of anthelmintic activity at the transition from free hydrazones to zinc-based complexes is shown.

Tunable Emission and Structural Insights of 6-Arylvinyl-2,4-bis(2'-hydroxyphenyl)pyrimidines and Their O∧N∧O-Chelated Boron Complexes.

In this study, we present the synthesis and photophysical characteristics of a novel series of 6-arylvinyl-2,4-bis(2'-hydroxyphenyl)pyrimidines. These compounds exhibit nonemissive properties attributed to the potential occurrence of a excited-state intramolecular proton transfer process from the OH groups to the nitrogen atoms of the pyrimidine ring. The introduction of an acid for protonation of the pyrimidine ring results in a significant enhancement of the fluorescence response, easily perceptible to the naked eye. Notably, these molecules serve as intriguing rigid O∧N∧O ligands for boron chelation. The incorporation of boron atoms promotes structural planarity, increases rigidity, and successfully restores fluorescence in both solution and the solid state. Moreover, the photoluminescence was found to be strongly influenced by the nature of the end groups on the arylvinylene fragment, allowing for the modulation of the emission color and covering the optical spectrum from blue to red. Strong emission solvatochromism was observed in various solvents, a finding that supports the formation of intramolecular charge-separated emitting states, particularly when terminal electron-donating groups are present in the structure. X-ray diffraction analysis enables the determination of inter- and intramolecular interactions, as well as molecular packing structures, aiding in the rationalization of distinct luminescent behaviors in the solid state. All experimental findings are elucidated through extensive density functional theory (DFT) and time-dependent DFT calculations.

The role of spacer heteroatomic fragment in spectroscopic and luminescent behaviour of phenyl-substituted phthalocyanine complexes

Peripheral phenyl-substituted metal phthalocyanines with thio and oxa substitution in the spacer bridge fragment were obtained in the work. Spectroscopic properties were studied for the obtained complexes, and the main patterns of behavior and characteristics change depending on the solvent and the nature of the spacer atom. It is shown that the replacement of an oxygen atom in the bridge fragment of a peripheral substituent with a sulfur atom leads to a change in the values of the fluorescence quantum yields. It was revealed that the presence of a spacer fragment is one of the key factors that strongly influence both the solubility of phthalocyanine complexes and their aggregation behavior in various solvents.