Luminescence Applications Research Articles

Anisotropic Fluorescence Surface Quenching of Quantum Dot-in-Rods on Silver Nanopatterned Film

Semiconductor quantum dot-in-rods (QDIRs) have served in the broad applications such as luminescent applications, sensor technology, quantum information processing, due to their polarized emission and polarized absorption characteristics. The localized surface plasmon resonance (LSPR) characteristics of the noble metal nanostructures can regulate the fluorescence intensity by controlling the radiation and non-radiation channels of fluorescent substances. However, the reports on the fluorescence surface quenching of QDIRs by plasmonic nanoparticles (NPs) are very rare. Herein, we propose a new method to realize QDIRs orientation, as well as the fluorescence intensity can be regulated. The effect of Ag nanopatterned film on the fluorescence surface quenching of QDIRs is discussed from both theoretical and experimental perspectives. Generally, the direct combination of Ag nanopatterned film and QDIRs results in 75% fluorescence surface quenching. Through FDTD simulation, we further analyzed the modulation of fluorescence intensity of the dipole source by the Ag nanopatterned film. This work will be useful for the development of QDIRs in the future.

Dy3+ ions in fluorophosphate glasses for luminescent white light applications

Abstract In this study, a series of fluorophosphate (FP) glasses, activated with Dy3+ ions and displaying concentration dependence, have been prepared and analysed for their suitability in luminescent white light applications. The melt quenching method was utilized to fabricate a set of FP glasses, doped with Dy3+ ions and possessing the composition of (60 − x) P2O5 + 10MgO + 10ZnO + 10BiF3 + 10KF + xDy2O3, where x ranges from 0.1 to 2.0 mol%. The structural properties of the samples were analysed using x-ray diffraction (XRD), scanning electron microscope (SEM), Fourier transform infrared (FTIR), and Raman spectroscopy while the optical properties of the samples were studied using absorption and emission spectra. The amorphous nature of the FP glasses was confirmed through SEM analysis and XRD profiles. Moreover, the presence of elements in their composition was verified using EDX. The FTIR spectra of the FP glasses exhibited vibration bands consistent with the characteristic phosphate groups, which was further supported by Raman analysis. The absorption spectra were used to calculate oscillator strengths (f exp & f cal) and Judd–Ofelt (JO) parameters Ω λ (λ = 2, 4, 6). The values of Ω λ (λ = 2, 4, 6) followed this order: Ω6 > Ω2 > Ω4. The emission spectra displayed three prominent transitions in the UV–visible region: (4F9/2 → 6H15/2) blue, (4F9/2 → 6H13/2) yellow, and (4F9/2 → 6H11/2) red. The peak at 553 nm (4F9/2 → 6H13/2) was the most intense and dominant. Radiative characteristics were evaluated from the emission spectra through the employment of JO intensity parameters and refractive indices. The Y/B intensity ratio values were greater than 1, indicating the high covalency of Dy3+ ions. The colour coordinates (x, y) and correlated colour temperature values of CIE 1931 were situated in the cool white region. The comprehensive analysis suggests that these glasses have the potential to become highly favourable candidates as luminescent components for solid-state white light emitting instruments.

Systematic long-term investigation on Cu2ZnCdS4 wide band gap semiconducting materials for optics and luminescence applications

Copper Zinc Cadmium Sulfide (Cu2ZnCdS4) semiconducting material compound synthesized using a new economic beneficial route. Copper sulfate, zinc sulfate, cadmium sulfate and thiourea salt solutions were utilized for Cu2ZnCdS4 compound formation. Basic characteristics like pH value, electrical conductivity, concentration measurements were investigated for several hundred samples. Optics transmittance was investigated by UV – Vis spectrophotometer within the 350 to 950 nm range. Photo luminescence measurement was examined by using photo–fluorometer. Optic properties of Cu2ZnCdS4 compound were investigated through photo-calorimeter measurements including mixed wavelength bands. The real time investigated noteworthy results from several hundred samples are presented and discussed.

Spectral characteristics and luminescence applications of Eu3+-activated fluorosilicate Na2MgGd2[SiO3]4F2

This work reports the luminescence spectra and application of novel Eu3+-doped Na2MgGd2[SiO3]4F2 phosphor. The X-ray powder diffraction confirmed the pure phase formation of the samples with the monoclinic space group P21/c (No:14). The phosphors demonstrated efficient red emission at 613 nm from the electric dipole transitions 5D0→7F2. The optimal doping concentration was found to be approximately 25 mol%. Na2MgGd2[SiO3]4F2:0.25Eu3+ exhibits a high quantum efficiency (QE) of 57 % with excellent thermal stability and pure chromaticity. Red- and the white light-emitting diode devices were packaged using InGaN chips and Na2MgGd2[SiO3]4F2:0.25Eu3+. The fabricated WLED has CIE coordinates of (x = 0.33, y = 0.34), which are very close to the white point in the National Television System Committee (x = 0.33, y = 0.33). The color rendering index (CRI, Ra) and correlated color temperature (CCT) of the WLED are 91 and 4400 K, respectively. The results show that as a red luminescent phosphor, it is a potential candidate for the preparation of near-UV/blue InGaN-based WLEDs.

Discrete Macrocyclic Polymer Hosts-Induced Cascade Luminescence Enhancement and Application in Bioimaging.

The integration of polymers, supramolecular macrocycles and aggregation-induced emission (AIE) molecules provides numerous possibilities for constructing various functional supramolecular systems. Herein, we constructed supramolecular assembled systems based on discrete macrocyclic polymer hosts via the cooperation of hydra-headed macrocycles containing two or three pillar[5]arene units (defined as P2, P3), the block polymer F127 and AIE molecules (alkyl-cyano modified tetraphenylethene, alkyl-triazole-cyano modified 9,10-distyrylanthracene, defined as TPE-(CN)4 and DSA-(TACN)2). Compared with the binary assembly between hydra-headed hosts or F127 and AIE molecules, cascaded supramolecular assembly-induced emission enhancement (SAIEE) in aqueous solution was achieved in discrete macrocyclic polymer-based supramolecular assembled systems. Considering the cascaded SAIEE performance, we have successfully applied discrete macrocyclic polymer-based supramolecular assembled systems to bioimaging and constructed an artificial light-harvesting system (LHs) to explore more potential applications. The supramolecular assembly form of discrete macrocyclic polymers hosts and AIE molecules proposed in this work provides new inspiration for the construction and application of high-performance supramolecular luminescent systems.

ALd of Metal Fluorides–Potential Applications and Current State

AbstractMetal fluoride thin films are important materials in a multitude of applications. Currently, they are mostly used in optics, but their potential in energy harvesting and storage is recognized as well. Atomic layer deposition (ALD) is an advanced thin film deposition method that has an ever‐increasing role in microelectronics. The assets of ALD are its capability to produce uniform, stoichiometric, and pure films with precise thickness control even on top of complicated structures, such as high aspect ratio trenches. These characteristics can be beneficial in applications of metal fluoride thin films but so far ALD of metal fluorides has remained much less studied and used than ALD of metal oxides, nitrides, sulfides, and pure metals. This review aims to motivate research on ALD of metal fluorides by surveying potential applications for ALD metal fluoride thin films and coatings. The basics of luminescent applications, antireflection coatings, and lithium‐ion batteries will be discussed. Next, the fundamentals of ALD will be presented followed by a comprehensive summary of the metal fluoride ALD processes published so far.

Near-Infrared Persistent Luminescence of CaTiO3:Cr,Y for Imaging of Bone Implants Using Red-Light Illumination Instead of X-ray.

Near-infrared (NIR) persistent luminescence (PersL) materials have unique optical properties with promising applications in bioimaging and anticounterfeiting. However, their development is currently hindered by poor red-light-exciting ability. In this study, CaTiO3:Cr0.001,Y0.02 (CTCY) was synthesized with 650 nm-excited 772 nm NIR PersL. The Y3+ doping in the Ca2+ lattice plays a key role in the PersL property. A charge compensation mechanism was proposed, in which Cr3+ in the Ti4+ lattice was stabilized by Y3+-doping while oxygen vacancies were generated to store the excitation energy at the same time. A thermal ionization mechanism might elucidate the red-light-excited NIR PersL of CTCY, which benefits from the perovskite structure of CaTiO3. CTCY has 120 times more intense red-light-excited PersL than Zn3Ga2Ge2O10:Cr. Its potential applications in luminescence anticounterfeiting and bioimaging were demonstrated using a visible/NIR dual-channel PersL flower painting and a CTCY-labeled bone screw for in situ reactivable PersL imaging using red light illumination instead of X-ray, respectively. This study not only provides a new NIR PersL material but also will add to our understanding in developing other potential red-light- or even NIR-activable PersL materials with perovskite-like structures.

Luminescence Applications in Ore Geology, Mining, and Industry

Luminescence Applications in Ore Geology, Mining, and Industry

Luminescence Applications in Petrology

Luminescence Applications in Petrology

A 2-D coordination polymer based on 3-(2-pyridyl)-5-(4-chlorophenyl)-1,2,4-triazine ligands and lead(II) bromide: synthesis, structure, luminescent properties, and application in organic light-emitting diodes

The combination of PbBr2 with 3-(2-pyridyl)-5-(4-chlorophenyl)-1,2,4-triazine (PCPT) results in a 2-D Pb(II) coordination polymer, denoted as [Pb9(PCPT)4Br18] n . This compound has been identified and studied through CHN analysis, FT-IR, and 1H NMR spectroscopy, in addition to detailed analysis using single-crystal X-ray diffraction techniques. Considering the primary and secondary Pb–N and Pb–Br bonds, Pb1 and Pb2 exhibit hemidirected pentagonal bipyramidal geometries, whereas Pb3, Pb4, and Pb5 demonstrate holodirected octahedral geometries. The 2-D structure transitions into a 3-D arrangement due to the presence of non-covalent C–H…Br and π…π stacking interactions. The interactions highlighted above enhance the structural stability and support the transfer of charge and energy between metal centers, positioning the polymer as a potential candidate for luminescence applications. Analysis of the electro-optical characteristics of this compound indicates its suitability as a luminescent material for incorporating into organic light-emitting diodes.

Facile fac- to mer-configuration transformation in tricyano Ru(II) complexes: Synthesis, luminescence, and potential application as chemical tracers for water flooding

Two mononuclear tricyanoruthenium(II) compounds fac-(PPh4)[RuII(dpq)(CN)3(PPh3)] (1a), fac-(PPh4)[RuII(Ph2Phen)(CN)3(PPh3)] (2a) have been prepared from the reactions of (PPh4)2[RuII(PPh3)2(CN)4] with pyrazino[2,3-f][1,10]phenanthroline (dpq) and 4,7-diphenyl-1,10-phenanthroline (Ph2Phen) in DMF, respectively. Metathesis of 1a/2a with excess NaPF6 in MeOH afforded fac-Na[RuII(dpq)(CN)3(PPh3)] (1b) and fac-Na[RuII(Ph2Phen)(CN)3(PPh3)] (2b), respectively where the coordination geometries around the Ru(II) centers are retained. However, treatment of 1a with [Zn(cyclam)]Cl2 or [Zn(cyclen)]Cl2 afforded the trinuclear heterobimetallic complexes [Zn(cyclam){mer-RuII(dpq)(CN)3(PPh3)}2] (3) and mer-[RuII(dpq)(CN)3(PPh3)][Zn(cyclen){mer-RuII(dpq)(CN)3(PPh3)}] (4), respectively. The crystal structures of 1a, 1b, 2a, 3, and 4 have been determined by X-ray crystallography. It is clearly shown that the coordination geometries of Ru(II) centers are changed from fac- to mer-configuration upon coordination with Zn2+ complexes. It is noteworthy that in 4 the coordination geometry in the anionic Ru moiety is also changed, although it is not linked to the Zn2+ moiety. The luminescence properties of these compounds have been investigated in detail. Both 1a and 1b exhibit strong solvatochromism as those related complexes. 1b is soluble in H2O and the luminescent detection limit can reach 0.01 mM in H2O. Upon loading 1b onto nano SiO2, the luminescence of 1b@SiO2 is remarkably enhanced and the luminescent detection limit can reach 0.1 µM.

Structural and spectroscopic features of single-phase Dy3+ activated BiYWO6 phosphor for luminescent device applications

Structural and spectroscopic features of single-phase Dy3+ activated BiYWO6 phosphor for luminescent device applications

Hydroxyl-driven construction of dual-emitting CsPbBr3/EuWO4(OH) composite for radiometric thermometer and information encryption applications

Self-assembled inorganic metal halide perovskite composites with high emitting efficiency, tunable multimode emission and stimuli-responsive luminescence demonstrated great potential in diversified luminescence applications. Here, a novel CsPbBr3/EuWO4(OH) composite was successfully prepared through the surface adsorption of Pb2+ ions on hydroxylated EuWO4(OH) microsheets and subsequent nucleation of CsPbBr3 peroviskite quantum dots (PQDs) by the anti-solvent crystallization in CsBr containing N,N-dimethylformamide (DMF) solution. Due to the distinct fluorescent thermochromic switching properties of temperature-insensitive Eu3+ and sensitive CsPbBr3 PQDs emitting centers, the resultant CsPbBr3/EuWO4(OH) composite exhibits excellent ratiometric temperature sensing performance. The CsPbBr3/EuWO4(OH) thermometer based on the fluorescence intensity ratio (FIR) technique originating from emissions of Eu3+ to CsPbBr3 PQDs was then explored with a high temperature sensitivity (Sr) of 5.8 % ℃−1 at 54 ℃. In addition, a high-security-level information encryption scheme was proposed by utilizing the excitation-wavelength-dependent switchable fluorescence of CsPbBr3/EuWO4(OH) composite. This study provides a simple and feasible strategy for assembling dual-emission CsPbBr3/EuWO4(OH) composite, showing potential applications in optical ratiometric thermometry and information encryption fields.

Warm white light emitting thermally stable Dy3+ activated antimony fluoroborate glasses for n-UV based white LEDs

A transparent series of trivalent dysprosium (Dy3+) ions activated calcium antimony fluoroborate glass samples (CAFB) were synthesized by the aid of the melt quenching process. The thermogravimetric, structural, and spectroscopic characterizations were evaluated and investigated in detail. Thermogravimetric analysis was performed to determine the glass transition temperature Tg and crystallization temperature (Tc) of the prepared host CAFB glass. Raman Spectroscopy and Fourier transform infrared (FT-IR) analyzed the structural orientation as well as bonding formation in the prepared CAFB host and CAFBDy1.0 glass matrix. Furthermore, the optical absorption spectra exhibit various absorption peaks between the n-UV to NIR region (350 to 2000 nm). Under the different n-UV excitation wavelengths, photoluminescence (PL) spectra reflect three foremost emission centres located around 482, 575, and 663 nm in the Dy3+: CAFB glasses. The observed colour coordinates of the prepared CAFBDy glasses were marked in the standard white area of the CIE chart under different n-UV excitation wavelengths. Moreover, temperature-dependent PL (TDPL) studies demonstrate that these glass samples have significant thermal stability and also a large activation energy. Hence, the above-mentioned results prove the versatility of the CAFBDy glasses to make them potential candidates for usage in luminescent device applications.

Tunable multi-peak emission solid-state fluorescent carbon dots: Luminescence regulation mechanism and application in single-component-based LEDs

The design of solid-state fluorescent carbon dots (CDs) with multi-peak emission has become an urgent challenge to be solved with the in-depth research of CDs in LEDs. Here, one- and two-component solid-state white light CDs are synthesized by microwave-assisted hydrothermal method using the biological pollutant cyanobacteria, respectively. The solid-state fluorescence quantum yield of the one-component CDs was as high as 41.8 %, and the solid-state fluorescence mechanism of CDs is discussed to be mainly attributed to the self-quenching-resistant feature of “core-shell” structure and the reabsorption/RET-induced long-wavelength red light emission, and attenuation of the short emission wavelength. For two-component white light CDs, blue- and red-light CDs are obtained by simple dialysis separation, realizing the fluorescence tunability. The different origins of their multi-peak emission are discussed: core, edge and surface states. The synthesis yields of CDs are up to 62 %, enabling stable gram-scale production. The white- and red-light CDs are used as phosphors to fabricate fluorescent films and cold, pure, and warm white- and red-light LEDs with good resistance to photobleaching and temperature stability and CRI of 84.4, 85.7 and 61.5.

Multiple wavelengths excitation of NaYF4:Tm/Er microcrystals for multicolor anti-counterfeiting and temperature sensing

Multicolor luminescence and optical thermometry hold charming potential applications in many fields, which are likely to be achieved in one rationally designed unit. Herein, a triple-wavelength (980 nm, 1550 nm and 808 nm) responsive upconversion microcrystal, using Er3+ ions as sensitizers, is proposed, which can generate tunable emission color from red to yellow and then to green. The modulated population route and energy transfer process of Er3+ are perceived to be the reason for tunable luminescence color upon excitation-wavelength. In addition, based on thermally coupled energy levels (TCLs), i.e., 2H11/2/4S3/2 and non-thermally coupled energy levels (NTCLs), i.e., 2H11/2/4F9/2 of Er3+ ions, the temperature-dependent upconversion properties were investigated. The maximum relative sensing sensitivity (Sr) of NaYF4:0.5%Tm/20%Er was found to be 1.373 % K−1 at 313 K, outperforming the majority of the same type thermometers. The results indicate that the NaYF4:0.5%Tm/20%Er microcrystals serve as a promising candidate for multicolor anticounterfeiting and optical thermometry applications.

Substitution of europium (III) in hydroxyapatite lattice for luminescence applications: Integrating experimental and theoretical insights

Europium(III) (Eu3+/Eu(III)) substitution in the hydroxyapatite (HAp) lattice imparts luminescence properties, enabling its application in diagnostics and bioimaging. Despite numerous experimental studies, there has been a lack of comprehensive discussion on the substitution behavior and local structural stability of Eu3+ within HAp. In this study, experimental and first-principles investigations were integrated to explore and understand the substitution of Eu3+ in HAp. Optimization of various HAp models revealed the dependency of Eu3+ substitution site on the charge compensation mechanism. Eu3+ prefers the Ca(2) site when OH is converted to O and the Ca(1) site in the presence of a Ca vacancy. Phonon calculations showed that temperature influences charge compensation and site preference, favoring OH to O compensation and Eu3+ in Ca(2) at higher temperatures and Ca vacancy and Eu3+ in Ca(1) at lower temperatures. Electronic structure simulations explained that the luminescence in Eu(III)-substituted HAp primarily arises from charge transfer between Eu3+ and O atoms, supported by experimental photoluminescence measurements. Correspondence between simulations and experimental photoluminescence data emphasizes the reliability of the computational approach in this study. The integration of insights from experimental and simulation results enhances the understanding of substitution of Eu3+ in the HAp lattice, providing valuable guidance for designing and optimizing HAp-based luminescent and optical materials.

Modulating Visible-Light Driven NIR Lanthanide Polymer Photocatalysis for Amplification Detection of Exosomal Proteins and Cancer Diagnosis.

Near-infrared (NIR) luminescent lanthanide materials hold great promise for bioanalysis, as they have anti-interference properties. The approach of efficient luminescence is sensitization through a reasonable chromophore to overcome the obstacle of the aqueous phase. The involvement of the surfactant motif is an innovative strategy to arrange the amphiphilic groups to be regularly distributed near the polymer to form a closed sensitized space. Herein, a lanthanide polymer (TCPP-PEI70K-FITC@Yb/SDBS) is designed in which the meso-tetra(4-carboxyphenyl)porphine (TCPP) ligand serves as both a sensitizer and photocatalytic switch. The surfactant sodium dodecyl benzenesulfonate (SDBS) wraps the photosensitive polymers to form a hydrophobic layer, which augments the light-harvesting ability and expedites its photocatalysis. TCPP-PEI70K-FITC@Yb/SDBS is subsequently applied as an amplified photocatalysis toolbox for universally regulating the generation of reactive oxygen species (ROS). Boosting 3,3',5,5'-tetramethylbenzidine (TMB) oxidation to produce blue products, a dual-mode biosensor is fabricated for improving the diagnosis of programmed death ligand-1-positive (PDL1) cancer exosomes. Exosomes were captured by Fe3O4 modified by the PDL1 aptamer, enabling replacement of alkaline phosphatase (ALP)-labeled multiple hybridized chains; then, the isolated ALP triggered a hydrolysis reaction to block the generation of oxTMB. Detection sensitivity improves by 1 order of magnitude through SDBS modulation, down to 104 particles/mL. The sensor performed well clinically in distinguishing cancer patients from healthy individuals, expanding physiological applications of near-infrared lanthanide luminescence.

High-contrast tricolor-tunable solid luminescent AIE-active Au(I) isocyanide complexes based on thermo- and mechanochromism

Breaking through the limitations of traditional luminescent materials, integrating the charming aggregation-induced emission (AIE) characteristics, high-contrast mechanochromism and thermochromism into one molecule is of great significance to make stimuli-responsive materials more intelligent. Herein, two Au(I) isocyanide complexes with short alkoxyl chains (C2 and C3) in the solid state are designed and synthesized, the length of the alkoxyl chain exerts significant impacts on molecular arrangement. Both C2 and C3 exhibit obvious AIE properties, the green luminescent aggregate of C2 and C3 is result from J-aggregation while the orange luminescent aggregate of C3 is result from the formation of aurophilic bonds, which supported by the single crystal X-ray analysis. Moreover, C2 and C3 not only display red-shifted mechanochromism (20 nm and 26 nm), but also exhibit gradual blue-shifted thermochromism. A tricolored luminescent switch application was demonstrated using C3 as a multi-stimuli responsive material. This molecular design strategy provides a new avenue for efficient luminescent materials with AIE and multi-stimuli responsive properties.

Dimethylamine Copper(I) Halide Single Crystals: Structure, Physical Properties, and Scintillation Performance.

Hybrid copper(I) halides have garnered a significant amount of attention as potential substitutes in luminescence and scintillation applications. Herein, we report the discovery and crystal growth of new zero-dimensional compounds, (C2H8N)3Cu2I5 and (C2H8N)4Cu2Br6. The bromide and iodide have a triclinic structure with space group P1̅ and an orthorhombic structure with space group Pnma, respectively. (C2H8N)3Cu2I5 exhibits cyan emission peaking at 504 nm with a photoluminescence quantum yield (PLQY) of 34.79%, while (C2H8N)4Cu2Br6 shows yellowish-green emission peaking at 537 nm with a PLQY of 38.45%. The temperature-dependent photoluminescence data of both compounds were fitted to theoretical models, revealing that nonradiative intermediate states significantly affect thermal quenching and antiquenching. Electron-phonon interactions, the origin of emission line width broadening and peak shifting, were also investigated via fittings. The scintillation properties of (C2H8N)3Cu2I5 were evaluated, and an X-ray imaging device was successfully fabricated using (C2H8N)3Cu2I5. This work demonstrates the potentiality of copper halides in lighting and X-ray imaging applications.