Thermal Evolutions to Glass-Ceramics Bearing Calcium Tungstate Crystals in Borate Glasses Doped with Photoluminescent Eu3+ Ions

Thermal evolutions of calcium-tungstate-borate glasses were investigated for the development of luminescent glass-ceramics by using Eu³⁺ dopant in a borate glass matrix with calcium tungstate, which was expected to have a combined character of glass and ceramics. This study revealed that single-phase precipitation of CaWO₄ crystals in borate glass matrix was possible by heat-treatment at a temperature higher than glass transition temperature T_g for (100−x) (33CaO-67B₂O₃)−xCa₃WO₆ (x = 8−15 mol%). Additionally, the crystallization of CaWO₄ was found by Raman spectroscopy due to the formation of W=O double bondings of WO₄ tetrahedra in the pristine glass despite starting with the higher calcium content of Ca₃WO₆. Eu³⁺ ions were excluded from the CaWO₄ crystals and positioned in the borate glass phase as a stable site for them, which provided local environments in higher symmetry around Eu³⁺ ions.     

1D-Zigzag Eu3+/Tb3+ Coordination Chains as Luminescent Ratiometric Thermometers Endowed with Multicolor Emission

Two homometallic Coordination Polymers (CPs) with composition [Ln(hfac)₃bipy]_n (Ln³⁺ = Eu³⁺, 1, and Tb³⁺, 2; hfac = hexafluoroacetylacetonato, bipy = 4,4′-bipyridine) were used to develop a family of ratiometric luminescent thermometers containing Eu³⁺ and Tb³⁺ as red and green emitters, respectively. The thermometric properties of pure CPs and of their mixtures having an Eu³⁺/Tb³⁺ molar ratio of 1:1, 1:3, 1:5, and 1:10 (samples: Eu1Tb1, Eu1Tb3, Eu1Tb5, and Eu1Tb10) were studied in the 83–383 K temperature range. Irrespective of the chemical composition, we observed similar thermometric responses characterized by broad applicative temperature ranges (from 100 to 165 K wide), and high relative thermal sensitivity values (S_r), up to 2.40% K⁻¹, in the physiological temperature range (298–318 K). All samples showed emissions endowed with peculiar and continuous color variation from green (83 K) to red (383 K) that can be exploited to develop a colorimetric temperature indicator. At fixed temperature, the color of the emitted light can be tuned by varying composition and excitation wavelength.     

Synthesis of Green-Emitting (La,Gd)OBr:Tb3+ Phosphors

Green-emitting phosphors based on lanthanum-gadolinium oxybromide were synthesized in a single phase form by the conventional solid state reaction method, and photoluminescence properties of them were characterized. The excitation peak wavelength of (La_1-xGd_x)OBr:Tb³⁺ shifted to the shorter wavelength side with the increase in the crystal field around the Tb³⁺ ions by doping Gd³⁺ ions into the La³⁺ site, and, as a result, the green emission intensity was successfully enhanced. The maximum emission intensity was obtained for (La_0.95Gd_0.05)OBr:5%Tb³⁺, where the relative emission intensity was 45% of that of a commercial green-emitting LaPO₄:Ce³⁺,Tb³⁺ phosphor.     

Red-Emitting Hybrid Based on Eu3+-dbm Complex Anchored on Silica Nanoparticles Surface by Carboxylic Acid for Biomarker Application

Luminescent organic-inorganic hybrids containing lanthanides (Ln³⁺) have been prominent for applications such as luminescent bio-probes in biological assays. In this sense, a luminescent hybrid based on dense silica (SiO₂) nanospheres decorated with Eu³⁺ β–diketonate complexes using dibenzoylmethane (Hdbm) as a luminescent antenna was developed by using a hierarchical organization in four steps: (i) anchoring of 3-aminopropyltriethoxysilane (APTES) organosilane on the SiO₂ surface, (ii) formation of a carboxylic acid ligand, (iii) coordination of Eu³⁺ to the carboxylate groups and (iv) coordination of dbm⁻ to Eu³⁺. The hybrid structure was elucidated through the correlation of thermogravimetry, silicon nuclear magnetic resonance and photoluminescence. Results indicate that the carboxylic acid-Eu³⁺-dbm hybrid was formed on the surface of the particles with no detectable changes on their size or shape after all the four steps (average size of 32 ± 7 nm). A surface charge of −27.8 mV was achieved for the hybrid, assuring a stable suspension in aqueous media. The Eu³⁺ complex provides intense red luminescence, characteristic of Eu^{3+ 5}D₀→⁷F_J electronic transitions, with an intrinsic emission quantum yield of 38%, even in an aqueous suspension. Therefore, the correlation of luminescence, structure, particle morphology and fluorescence microscopy images make the hybrid promising for application in bioimaging.     

Structural and Photoluminescence Investigations of Tb3+/Eu3+ Co-Doped Silicate Sol-Gel Glass-Ceramics Containing CaF2 Nanocrystals

In this work, the series of Tb³⁺/Eu³⁺ co-doped xerogels and derivative glass-ceramics containing CaF₂ nanocrystals were prepared and characterized. The in situ formation of fluoride crystals was verified by an X-ray diffraction technique (XRD) and transmission electron microscopy (TEM). The studies of the Tb³⁺/Eu³⁺ energy transfer (ET) process were performed based on excitation and emission spectra along with luminescence decay analysis. According to emission spectra recorded under near-ultraviolet (NUV) excitation (351 nm, ⁷F₆ → ⁵L₉ transition of Tb³⁺), the mutual coexistence of the ⁵D₄ → ⁷F_J (J = 6–3) (Tb³⁺) and the ⁵D₀ → ⁷F_J (J = 0–4) (Eu³⁺) luminescence bands was clearly observed. The co-doping also resulted in gradual shortening of a lifetime from the ⁵D₄ state of Tb³⁺ ions, and the ET efficiencies were varied from η_ET = 11.9% (Tb³⁺:Eu³⁺ = 1:0.5) to η_ET = 22.9% (Tb³⁺:Eu³⁺ = 1:2) for xerogels, and from η_ET = 25.7% (Tb³⁺:Eu³⁺ = 1:0.5) up to η_ET = 67.4% (Tb³⁺:Eu³⁺ = 1:2) for glass-ceramics. Performed decay analysis from the ⁵D₀ (Eu³⁺) and the ⁵D₄ (Tb³⁺) state revealed a correlation with the change in Tb³⁺–Eu³⁺ and Eu³⁺–Eu³⁺ interionic distances resulting from both the variable Tb³⁺:Eu³⁺ molar ratio and their partial segregation in CaF₂ nanophase.     

Synthesis of New RE3+ Doped Li1+xTa1?xTixO3 (RE: Eu,Sm, Er,Tm, and Dy) Phosphors with Various Emission Colors

New phosphors with various emission colors for RE³⁺ doped Li_1+xTa_1−xTi_xO₃ (LTT) (RE: Eu, Sm, Er, Tm, and Dy) were synthesized by electric furnace at 1423 K for 15 h. The microstructure of the host material and the photoluminescence (PL) property were determined and compared to those of RE³⁺ doped Li_1+xNb_1−xTi_xO₃ (LNT)_. In the LTT phosphor, the highest PL intensity was achieved for the mixture composition Li_1.11Ta_0.89Ti_0.11O₃ with a LiTaO₃ structure, although it has an M-phase superstructure. In the LTT host material, the effective activators were Eu³⁺ and Sm³⁺ ions, in contrast to the LNT host material. Here, we discuss the relationship between PL property and the host material’s structure.     

Evidence for the involvement of more than one metal cation in the Schiff base deprotonation process during the photocycle of bacteriorhodopsin

The removal of metal cations inhibits the deprotonation process of the protonated Schiff base during the photocycle of bacteriorhodopsin. To understand the nature of the involvement of these cations, a spectroscopic and kinetic study was carried out on bacteriorhodopsin samples in which the native Ca²⁺ and Mg²⁺ were replaced by Eu³⁺, a luminescent cation. The decay of Eu³⁺ emission in bacteriorhodopsin can be fitted to a minimum of three decay components, which are assigned to Eu³⁺ emission from three different sites. This is supported by the response of the decay components to the presence of ²H₂O and to the changes in the Eu³⁺/bR molar ratio. The number of water molecules coordinated to Eu³⁺ in each site is determined from the change in its emission lifetime when ²H₂O replaces H₂O. Most of the emission originates from two “wet” sites of low crystal-field symmetry—e.g., surface sites. Protonated Schiff base deprotonation has no discernable effect on the emission decay of protein-bound Eu³⁺, suggesting an indirect involvement of metal cations in the deprotonation process. Adding Eu³⁺ to deionized bacteriorhodopsin increases the emission intensity of each Eu³⁺ site linearly, but the extent of the deprotonation (and color) changes sigmoidally. This suggests that if only the emitting Eu³⁺ ions cause the deprotonation and bacteriorhodopsin color change, ions in more than one site must be involved—e.g., by inducing protein conformation changes. The latter could allow deprotonation by the interaction between the protonated Schiff base and a positive field of cations either on the surface or within the protein.     

Red,Green, and Blue Photoluminescence of Ba2SiO4:M (M = Eu3+, Eu2+, Sr2+) Nanophosphors

Divalent europium doped barium orthosilicate is a very important phosphor for the production of light emitting diodes (LEDs), generally associated to the green emission color of micron-sized crystals synthesized by means of solid-state reactions. This work presents the combustion synthesis as an energy and time-saving preparation method for very small nano-sized Ba₂SiO₄ particles, flexibly doped to acquire different emission energies. The size of the resulting spherical nanoparticles (NPs) of the green emitting Ba₂SiO₄:Eu²⁺ was estimated to about 35 nm applying the Scherrer equation and further characterized with aid of atomic force microscopy (AFM) as well as scanning electron microscopy (SEM). This phosphor is able to build homogeneous luminescent suspensions and was successfully down-sized without changing the optical properties in comparison to the bulk phosphors. Besides the X-ray diffraction (XRD) analysis and the different types of microscopy, the samples were characterized by luminescence spectroscopy. Undoped Ba₂SiO₄ NPs are not luminescent, but show characteristic red emission of the ⁵D₀ → ⁷F_J (J = 0–4) electronic transitions when doped with Eu³⁺ ions. Moreover, these orthosilicate nanoparticles generate blue light at low temperatures due to impurity-trapped excitons, introduced by the partial substitution of the Ba²⁺ with Sr²⁺ ions in the Ba₂SiO₄ lattice causing a substantial distortion. A model for the temperature behavior of the defect luminescence as well as for their nature is provided, based on temperature-dependent luminescence spectra and lifetime measurements.     

Nonstoichiometric LaO0.65F1.7 Structure and Its Green Luminescence Property Doped with Bi3+ and Tb3+ Ions for Applying White UV LEDs

Red–green–blue phosphors excited by ultraviolet (UV) radiation for white light LEDs have received much attention to improve the efficiency, color rendering index (CRI), and chromatic stability. The spectral conversion of a rare-earth ion-doped nonstoichiometric LaO_0.65F_1.7 host was explored with structural analysis in this report. The nonstoichiometric structure of a LaO_0.65F_1.7 compound, synthesized by a solid-state reaction using La₂O₃ and excess NH₄F precursors, was analyzed by synchrotron X-ray powder diffraction. The crystallized LaO_0.65F_1.7 host, which had a tetragonal space group of P4/nmm, contained 9- and 10-coordinated La³⁺ sites. Optical materials composed of La_1−p−qBi_pTb_qO_0.65F_1.7 (p = 0 and 0.01; q = 0–0.2) were prepared at 1050 °C for 2 h, and the single phase of the obtained phosphors was indexed by X-ray diffraction analysis. The photoluminescence spectra of the energy transfer from Bi³⁺ to Tb³⁺ were obtained upon excitation at 286 nm in the nonstoichiometric host lattice. The desired Commission Internationale de l’Eclairage (CIE) values of the phosphors were calculated. The intense green La_0.89Bi_0.01Tb_0.1O_0.65F_1.7 phosphor with blue and red optical materials was fabricated on a 275 nm UV-LED chip, resulting in white light, and the internal quantum efficiency, CRI, correlated color temperature, and CIE of the pc LED were characterized.     

Crystal and Electronic Structures,Photoluminescence Properties of Eu2+-Doped Novel Oxynitride Ba4Si6O16-3x/2Nx

The crystal structure and the photoluminescence properties of novel green Ba_4-yEu_ySi₆O_16-3x/2N_x phosphors were investigated. The electronic structures of the Ba₄Si₆O₁₆ host were calculated by first principles pseudopotential method based on density functional theory. The results reveal that the top of the valence bands are dominated by O-2p states hybridized with Ba-6s and Si-3p states, while the conduction bands are mainly determined by Ba-6s states for the host, which is an insulator with a direct energy gap of 4.6 eV at Γ. A small amount of nitrogen can be incorporated into the host to replace oxygen and forms Ba_4-yEu_ySi₆O_16-3x/2N_x solid solutions crystallized in a monoclinic (space group P2₁/c, Z = 2) having the lattice parameters a = 12.4663(5) Å, b = 4.6829(2) Å, c = 13.9236(6) Å, and β = 93.61(1)°, with a maximum solubility of nitrogen at about x = 0.1. Ba₄Si₆O_16-3x/2N_x:Eu²⁺ exhibits efficient green emission centered at 515–525 nm varying with the Eu²⁺ concentration when excited under UV to 400 nm. Furthermore, the incorporation of nitrogen can slightly enhance the photoluminescence intensity. Excitation in the UV-blue spectral range (λ_exc = 375 nm), the absorption and quantum efficiency of Ba_4-yEu_ySi₆O_16-3x/2N_x (x = 0.1, y = 0.2) reach about 80% and 46%, respectively. Through further improvement of the thermal stability, novel green phosphor of Ba_4-yEu_ySi₆O_16-3x/2N_x is promising for application in white UV-LEDs.     

On the Superconductivity Suppression in Eu1−xPrxBa2Cu3O7−δ

This article reports on the non-trivial suppression of superconductivity in the Eu_1−xPr_xBCO cuprates. As non-magnetic Eu³⁺ ions are replaced by Pr³⁺ carrying a magnetic moment, spin-related superconductivity loss can be expected. The research shows that the superconductivity disappearance for x > 0.4 results from depletion of the carriers and their localization. The above conclusion was drawn by low-temperature X-ray diffraction analysis showing increased characteristic phonon frequencies with Pr content. This mechanism should promote electron–phonon coupling, at least for acoustic phonons. However, the inverse phenomenon was detected. Namely, there is a gradual deterioration of the optical phonons responsible for vibration of the Cu–O bonds with Pr increasing, as evidenced by Raman spectroscopy. Furthermore, the results of X-ray absorption spectroscopy precisely showed the location of the carriers for Pr-rich specimens. Finally, a schematic diagram for Eu_1−xPr_xBCO is proposed to consolidate the presented research.     

Role of Eu2+ and Dy3+ Concentration in the Persistent Luminescence of Sr2MgSi2O7 Glass-Ceramics

In this study, glass-ceramics based on Sr₂MgSi₂O₇ phosphor co-doped with Eu/Dy were obtained from the sintering and crystallisation of glass powders. The glasses were melted in a gas furnace to simulate an industrial process, and the dopant concentration was varied to optimise the luminescence persistence times. The doped parent glasses showed red emission under UV light excitation due to the doping of Eu³⁺ ions, while the corresponding glass-ceramics showed persistent blue emission corresponding to the presence of Eu²⁺ in the crystalline environment. The dopant concentration had a strong impact on the sintering/crystallisation kinetics affecting the final glass-ceramic microstructure. The microstructures and morphology of the crystals responsible for the blue emission were observed by scanning electron microscopy–cathodoluminescence. The composition of the crystallised phases and the distribution of rare-earth (RE) ions in the crystals and in the residual glassy phase were determined by X-ray diffraction and energy dispersive X-ray analysis. The emission and persistence of phosphorescence were studied by photoluminescence.     

Effect of Gd3+ Substitution on Thermoelectric Power Factor of Paramagnetic Co2+-Doped Calcium Molybdato-Tungstates

A series of Co²⁺-doped and Gd³⁺-co-doped calcium molybdato-tungstates, i.e., Ca_1−3x−yCo_{y x}Gd_2x(MoO₄)_1−3x(WO₄)_3x (CCGMWO), where 0 < x ≤ 0.2, y = 0.02 and represents vacancy, were successfully synthesized by high-temperature solid-state reaction method. XRD studies and diffuse reflectance UV–vis spectral analysis confirmed the formation of single, tetragonal scheelite-type phases with space group I4₁/a and a direct optical band gap above 3.5 eV. Magnetic and electrical measurements showed insulating behavior with n-type residual electrical conductivity, an almost perfect paramagnetic state with weak short-range ferromagnetic interactions, as well as an increase of spin contribution to the magnetic moment and an increase in the power factor with increasing gadolinium ions in the sample. Broadband dielectric spectroscopy measurements and dielectric analysis in the frequency representation showed a relatively high value of dielectric permittivity at low frequencies, characteristic of a space charge polarization and small values of both permittivity and loss tangent at higher frequencies.     

Fabricated Flexible Composite for a UV-LED Color Filter and Anti-Counterfeiting Application of Calcium Molybdate Phosphor Synthesized at Room Temperature

Crystalline CaMoO₄ and rare-earth-doped CaMoO₄:RE³⁺ (RE = Tb, Eu) phosphors were synthesized at room temperature using a co-precipitation method. The crystal structure of the synthesized powder was a tetragonal structure with a main diffraction peak (112) phase. When CaMoO₄ was excited at 295 nm, it showed a central peak of 498 nm and light emission in a wide range of 420 to 700 nm. Rare-earth-ion-doped CaMoO₄:Tb³⁺ was excited at 288 nm and a green light emission was observed at 544 nm, and CaMoO₄:Eu³⁺ was excited at 292 nm and a red light emission was observed at 613 nm. To take advantage of the light-emitting characteristics, a flexible composite was manufactured and a color filter that could be used for UV-LEDs was manufactured. In addition, it was suggested that an ink that could be checked only by UV light could be produced and applied to banknotes so as to prevent counterfeiting.     

Structure and Photoluminescence Properties of Dy3+ Doped Phosphor with Whitlockite Structure

Whitlockite has the advantages of a low sintering temperature, high stability, and a low fabrication cost, and it is widely used as the host for luminescent material. In this study, Ca_1.8Li_0.6La_0.6−x(PO₄)₂:xDy³⁺ phosphor was prepared by the high-temperature solid-state method, and its structure, composition, and luminescence properties were systematically studied. The results showed that a new whitlockite type matrix was prepared by replacing Ca²⁺ in whitlockite with monovalent and trivalent cations. The prepared phosphors belonged to a hexagonal crystal system with a particle size in the range of 5–20 μm. Under the excitation of 350 nm UV light, the samples emitted white light, and there were mainly two stronger emission peaks at 481 nm in the blue band and 573 nm in the yellow band, which correspond to the electron transitions at ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 of Dy³⁺, respectively. The optimal doping concentration of Dy³⁺ in Ca_1.8Li_0.6La_0.6(PO₄)₂ matrix was 0.03 (mol%). The main mechanism of concentration quenching in the sample was dipole–dipole energy transfer. When the temperature was 130 °C, the luminescence intensity of the samples was 78.7% of that at 30 °C, and their thermal quenching activation energy was 0.25 eV. The CIE coordinates of the sample at 30 °C were (0.2750, 0.3006), and their luminescent colors do not change with temperature. All the results indicate that Ca_1.8Li_0.6La_0.6−x(PO₄)₂:xDy³⁺ phosphor is a luminescent material with good luminescence performance and thermal stability, which shows a promising application in the field of LED display.     

Structural,Magnetic, Dielectric and Piezoelectric Properties of Multiferroic PbTi1−xFexO3−δ Ceramics

PbTi_1−xFe_xO_3−δ (x = 0, 0.3, 0.5, and 0.7) ceramics were prepared using the classical solid-state reaction method. The investigated system presented properties that were derived from composition, microstructure, and oxygen deficiency. The phase investigations indicated that all of the samples were well crystallized, and the formation of a cubic structure with small traces of impurities was promoted, in addition to a tetragonal structure, as Fe³⁺ concentration increased. The scanning electron microscopy (SEM) images for PbTi_1−xFe_xO_3−δ ceramics revealed microstructures that were inhomogeneous with an intergranular porosity. The dielectric permittivity increased systematically with Fe³⁺ concentration, increasing up to x = 0.7. A complex impedance analysis revealed the presence of multiple semicircles in the spectra, demonstrating a local electrical inhomogeneity due the different microstructures and amounts of oxygen vacancies distributed within the sample. The increase of the substitution with Fe³⁺ ions onto Ti⁴⁺ sites led to the improvement of the magnetic properties due to the gradual increase in the interactions between Fe³⁺ ions, which were mediated by the presence of oxygen vacancies. The PbTi_1−xFe_xO_3−δ became a multifunctional system with reasonable dielectric, piezoelectric, and magnetic characteristics, making it suitable for application in magnetoelectric devices.     

Enhancement of Y5−xPrxSb3−yMy (M = Sn,Pb) Electrodes for Lithium- and Sodium-Ion Batteries by Structure Disordering and CNTs Additives

The maximally disordered (MD) phases with the general formula Y_5−xPr_xSb_3−yM_y (M = Sn, Pb) are formed with partial substitution of Y by Pr and Sb by Sn or Pb in the binary Y₅Sb₃ compound. During the electrochemical lithiation and sodiation, the formation of Y_5-xPr_xSb_3-yM_yLi_z and Y_5−xPr_xSb_3−yM_yNa_z maximally disordered–high entropy intermetallic phases (MD-HEIP), as the result of insertion of Li/Na into octahedral voids, were observed. Carbon nanotubes (CNT) are an effective additive to improve the cycle stability of the Y_5−xPr_xSb_3−yM_y (M = Sn, Pb) anodes for lithium-ion (LIBs) and sodium-ion batteries (SIBs). Modification of Y_5−xPr_xSb_3−ySn_y alloys by carbon nanotubes allowed us to significantly increase the discharge capacity of both types of batteries, which reaches 280 mAh · g⁻¹ (for LIBs) and 160 mAh · g⁻¹ (for SIBs), respectively. For Y_5−xPrxSb_3−yPb_y alloys in which antimony is replaced by lead, these capacities are slightly smaller and are 270 mAh · g⁻¹ (for LIBs) and 155 mAh · g⁻¹ (for SIBs), respectively. Results show that structure disordering and CNT additives could increase the electrode capacities up to 30% for LIBs and up to 25% for SIBs.     

Features of the Preparation and Luminescence of Langmuir-Blodgett Films Based on the Tb(III) Complex with 3-Methyl-1-phenyl-4-stearoylpyrazol-5-one and 2,2′-Bipyridine

In this study, we investigated the effect of terbium ions (Tb³⁺⁾ on the subphases of the limiting area of the molecule for the complex compound (CC) TbL₃∙bipy (where HL is 3-methyl-1-phenyl-4-stearoylpyrazol-5-one and bipy is 2,2′-bipyridine). We examined the Langmuir monolayer and the change in the luminescence properties of TbL₃∙bipy-based Langmuir-Blodgett films (LBFs). The analysis of the compression isotherms, infrared, and luminescence spectra of TbL₃∙bipy LBFs was performed by varying the concentration of Tb³⁺ in the subphases. Our results demonstrate the partial dissociation of the CC at concentrations of C(Tb³⁺) < 5 × 10⁻⁴ M.     

Controlling energy transfer between multiple dopants within a single nanoparticle

Complex core-shell architectures are implemented within LaF₃ nanoparticles to allow for a tailored degree of energy transfer (ET) between different rare earth dopants. By constraining specific dopants to individual shells, their relative distance to one another can be carefully controlled. Core-shell LaF₃ nanoparticles doped with Tb³⁺ and Eu³⁺ and consisting of up to four layers were synthesized with an outer diameter of ≈10 nm. It is found that by varying the thicknesses of an undoped layer between a Tb³⁺-doped layer and a Eu³⁺-doped layer, the degree of ET can be engineered to allow for zero, partial, or total ET from a donor ion to an acceptor ion. More specifically, the ratio of the intensities of the 541-nm Tb³⁺ and 590 nm Eu³⁺ peaks was tailored from <0.2 to ≈2.4 without changing the overall composition of the particles but only by changing the internal structure. Further, the emission spectrum of a blend of singly doped nanoparticles is shown to be equivalent to the spectra of co-doped particles when a core-shell configuration that restricts ET is used. Beyond simply controlling ET, which can be limiting when designing materials for optical applications, this approach can be used to obtain truly engineered spectral features from nanoparticles and composites made from them. Further, it allows for a single excitation source to yield multiple discrete emissions from numerous lanthanide dopants that heretofore would have been quenched in a more conventional active optical material.