Micropowder Ca2YMgScSi3O12:Ce Silicate Garnet as an Efficient Light Converter for White LEDs

This work is dedicated to the crystallization and luminescent properties of a prospective Ca₂YMgScSi₃O₁₂:Ce (CYMSSG:Ce) micropowder (MP) phosphor converter (pc) for a white light–emitting LED (WLED). The set of MP samples was obtained by conventional solid-phase synthesis using different amounts of B₂O₃ flux in the 1–5 mole percentage range. The luminescent properties of the CYMSSG:Ce MPs were investigated at different Ce³⁺ concentrations in the 1–5 atomic percentage range. The formation of several Ce³⁺ multicenters in the CYMSSG:Ce MPs was detected in the emission and excitation spectra as well as the decay kinetics of the Ce³⁺ luminescence. The creation of the Ce³⁺ multicenters in CYMSSG:Ce garnet results from: (i) the substitution by the Ce³⁺ ions of the heterovalent Ca²⁺ and Y³⁺ cations in the dodecahedral position of the garnet host; (ii) the inhomogeneous local environment of the Ce³⁺ ions when the octahedral positions of the garnet are replaced by heterovalent Mg²⁺ and Sc³⁺ cations and the tetrahedral positions are replaced by Si⁴⁺ cations. The presence of Ce³⁺ multicenters significantly enhances the Ce³⁺ emission band in the red range in comparison with conventional YAG:Ce phosphor. Prototypes of the WLEDs were also created in this work by using CYMSSG:Ce MP films as phosphor converters. Furthermore, the dependence of the photoconversion properties on the layer thickness of the CYMSSG:Ce MP was studied as well. The changes in the MP layer thickness enable the tuning of the white light thons from cold white/daylight to neutral white. The obtained results are encouraging and can be useful for the development of a novel generation of pcs for WLEDs.     

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.     

Tunable Luminescence and Energy Transfer of Sr3B2O6:Ce3+, Sm3+ Phosphors with Potential Anti-Counterfeiting Applications

Sm³⁺ and Ce³⁺ singly doped and Sm³⁺ and Ce³⁺ co-doped Sr₃B₂O₆ phosphors are prepared via a high-temperature solid-state reaction method. The crystal structure and phase purity are characterized by X-ray diffraction (XRD) analyses. The Sm³⁺-doped sample displays an emission in the orange-red region, with the strongest emission line at about 648 nm and possessing a good luminescence thermal stability between 78 and 500 K. With the increase in the Sm³⁺ content, the concentration quenching is observed due to the cross-relaxation (CR) processes among the Sm³⁺ ions. Upon 340 nm excitation, the Ce³⁺-doped phosphor presents a broad emission band in the blue region with a maximum at about 420 nm, which overlaps well with the ⁶H_5/2 → ⁶P_3/2 excitation line of Sm³⁺ and implies the possible energy transfer from Ce³⁺ to Sm³⁺. The spectral and decay measurements of the Ce³⁺ and Sm³⁺ co-doped samples are conducted and the Inokuti–Hirayama (I-H) model is adopted to analyze the luminescence decay dynamics of the donor Ce³⁺. Owing to the evident sensitization of the Sm³⁺ by the Ce³⁺ ions, the co-doped samples exhibit color variation under different wavelength excitations, endowing them with potential applications in optical anti-counterfeiting.     

Synthesis,Characterization and Biodistribution of GdF3:Tb3+@RB Nanocomposites

Herein we report the development of a nanocomposite for X-ray-induced photodynamic therapy (X-PDT) and computed tomography (CT) based on PEG-capped GdF₃:Tb³⁺ scintillating nanoparticles conjugated with Rose Bengal photosensitizer via electrostatic interactions. Scintillating GdF₃:Tb³⁺ nanoparticles were synthesized by a facile and cost-effective wet chemical precipitation method. All synthesized nanoparticles had an elongated “spindle-like” clustered morphology with an orthorhombic structure. The structure, particle size, and morphology were determined by transmission electron microscopy (TEM), X-ray diffraction (XRD), and dynamic light scattering (DLS) analysis. The presence of a polyethylene glycol (PEG) coating and Rose Bengal conjugates was proved by Fourier-transform infrared spectroscopy (FTIR), thermogravimetric analysis (TG), and ultraviolet–visible (UV-vis) analysis. Upon X-ray irradiation of the colloidal PEG-capped GdF₃:Tb³⁺–Rose Bengal nanocomposite solution, an efficient fluorescent resonant energy transfer between scintillating nanoparticles and Rose Bengal was detected. The biodistribution of the synthesized nanoparticles in mice after intravenous administration was studied by in vivo CT imaging.     

The pH Value Control of Morphology and Luminescence Properties of Gd2O2S: Tb3+ Phosphors

Developing rare-earth doped oxysulfide phosphors with diverse morphologies has significant value in many research fields such as in displays, medical diagnosis, and information storage. All of the time, phosphors with spherical morphology have been developed in most of the related literatures. Herein, by simply adjusting the pH values of the reaction solution, Gd₂O₂S:Tb³⁺ phosphors with various morphologies (sphere-like, sheet-like, cuboid-like, flat square-like, rod-like) were synthesized. The XRD patterns showed that phosphors with all morphologies are pure hexagonal phase of Gd₂O₂S. The atomic resolution structural analysis by transmission electron microscopy revealed the crystal growth model of the phosphors with different morphology. With the morphological change, the band gap energy of Gd₂O₂S:Tb³⁺ crystal changed from 3.76 eV to 4.28 eV, followed by different luminescence performance. The samples with sphere-like and cuboid-like microstructures exhibit stronger cathodoluminescence intensity than commercial product by comparison. Moreover, luminescence of Gd₂O₂S:Tb³⁺ phosphors have different emission performance excited by UV light radiation and an electron beam, which when excited by UV light is biased towards yellow, and while excited by an electron beam is biased towards cyan. This finding provides a simple but effective method to achieve rare-earth doped oxysulfide phosphors with diversified and tunable luminescence properties through morphology control.     

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.     

Down-Shifting in the YAM: Ce3+ + Yb3+ System for Solar Cells

In this work, we investigate Ce³⁺ to Yb³⁺ energy transfer in Y₄Al₂O₉ (YAM) for potential application in solar spectrum down-converting layers for photovoltaic devices. Photoluminescence properties set, of 10 samples, of the YAM host activated with Ce³⁺ and Yb³⁺ with varying concentrations are presented, and the Ce³⁺ to Yb³⁺ energy transfer is proven. Measurement of highly non-exponential luminescence decays of Ce³⁺ 5d band allowed for the calculation of maximal theoretical quantum efficiency, of the expected down-conversion process, equal to 123%. Measurements of Yb³⁺ emission intensity, in the function of excitation power, confirmed the predominantly single-photon downshifting character of Ce³⁺ to Yb³⁺ energy transfer. Favorable location of the Ce³⁺ 5d bands in YAM makes this system a great candidate for down-converting, and down-shifting, luminescent layers for photovoltaics.     

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.     

Temperature Dependence of Absorption and Energy Transfer Efficiency of Er3+/Yb3+/P5+ Co-Doped Silica Fiber Core Glasses

A high phosphorus Er³⁺/Yb³⁺ co-doped silica (EYPS) fiber core glass was prepared using the sol-gel method combined with high-temperature sintering. The absorption spectra, emission spectra, and fluorescence decay curves were measured and compared in temperatures ranging from 300 to 480 K. Compared to 915 and 97x nm, the absorption cross-section at ~940 nm (~0.173 pm²) demonstrates a weaker temperature dependence. Hence, the 940 nm pump mechanism is favorable for achieving a high-power laser output at 1.5 μm. Additionally, the double-exponential fluorescence decay of Yb³⁺ ions and the emission intensity ratio of I_1018nm/I_1534nm were measured to evaluate the energy transfer efficiency from Yb³⁺ ions to Er³⁺ ions. Through the external heating and active quantum defect heating methods, the emission intensity ratios of I_1018nm/I_1534nm increase by 30.6% and 709.1%, respectively, from ~300 to ~480 K. The results indicate that the temperature rises significantly reduce the efficiency of the energy transfer from the Yb³⁺ to the Er³⁺ ions.     

Energy Structure and Luminescence of CeF3 Crystals

The results of the calculation of the energy band structure and luminescent research of CeF₃ crystals are presented. The existence of two 5d1 and 5d2 subbands of the conduction band genetically derived from 5d states of Ce³⁺ ions with different effective electron masses of 4.9 m_e and 0.9 m_e, respectively, is revealed. The large electron effective mass in the 5d1 subband facilitates the localization of electronic excitations forming the 4f-5d cerium Frenkel self-trapped excitons responsible for the CeF₃ luminescence. The structure of the excitation spectra of the exciton luminescence peaked at 290 nm, and the defect luminescence at 340 nm confirms the aforementioned calculated features of the conduction band of CeF₃ crystals. The peculiarities of the excitation spectra of the luminescence of CaF₂:Ce crystals dependent on the cerium concentration are considered with respect to the phase formation possibility of CeF₃.     

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 and Characterization of Li2MgGeO4:Ho3+

In this work, the synthesis and characterization of Li₂MgGeO₄:Ho³⁺ ceramics were reported. The X-ray diffraction measurements revealed that the studied ceramics belong to the monoclinic Li₂MgGeO₄. Luminescence properties were analyzed in the visible spectral range. Green and red emission bands correspondent to the ⁵F₄,⁵S₂→⁵I₈ and ⁵F₅→⁵I₈ transitions of Ho³⁺ were observed, and their intensities were significantly dependent on activator concentration. Luminescence spectra were also measured under direct excitation of holmium ions or ceramic matrix. Holmium ions were inserted in crystal lattice Li₂MgGeO₄, giving broad blue emission and characteristic 4f-4f luminescent transitions of rare earths under the selective excitation of the ceramic matrix. The presence of the energy transfer process between the host lattice and Ho³⁺ ions was suggested.     

Combustion Synthesis and Photoluminescence Properties of Red-Emitting CaAlSiN3:Eu2+ Phosphor for White-LEDs

A combustion synthesis method has been developed for synthesis of Eu²⁺ doped CaAlSiN₃ phosphor and its photoluminescence properties were investigated. Ca, Al, Si, and Eu₂O₃ powders were used as the Ca, Al, Si and Eu sources. The addition of NaN₃, NH₄Cl and Si₃N₄ powders was found to increase significantly the product yield. These powders were mixed and pressed into a compact, which was then wrapped up with an igniting agent (i.e., Mg+Fe₃O₄). The compact was ignited by electrical heating under a N₂ pressure of ≤1.0 MPa. Effects of these experimental parameters on the product yield were investigated and a reaction mechanism was proposed. The synthesized CaAlSiN₃:Eu²⁺ phosphor absorbs light in the region of 200–600 nm and shows a broad band emission in the region of 500–800 nm due to the 4f⁶5d¹ → 4f⁷ transition of Eu²⁺. The sample doped with Eu²⁺ at the optimized molar ratio of 0.04 is efficiently excited by the blue light (460 nm) and generates emission peaking at ~650 nm with peak emission intensity ~106% of a commercially available phosphor, YAG:Ce³⁺(P46-Y3).The internal quantum efficiency of the synthesized phosphor was measured to be 71%, compared to 69% of the YAG:Ce³⁺ (P46-Y3).     

Surface Characterization and Photoluminescence Properties of Ce3+,Eu Co-Doped SrF2 Nanophosphor

SrF₂:Eu,Ce³⁺ nanophosphors were successfully synthesized by the hydrothermal method during down-shifting investigations for solar cell applications. The phosphors were characterized by X-ray diffraction (XRD), scanning Auger nanoprobe, time of flight-secondary ion mass spectrometry (TOF-SIMS), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) spectroscopy. XRD showed that the crystallite size calculated with Scherrer’s equation was in the nanometre scale. XPS confirmed the formation of the matrix and the presence of the dopants in the SrF₂ host. The PL of the nanophosphor samples were studied using different excitation sources. The phenomenon of energy transfer from Ce³⁺ to Eu²⁺ has been demonstrated.     

Energy Transfer Studies in Tb3+-Yb3+ Co-Doped Phosphate Glasses

Detailed optical properties of Tb³⁺-Yb³⁺ co-doped phosphate glasses were performed based on their emission spectra and decay measurements. Under blue excitation of Tb³⁺ at 488 nm, the intensity of Yb³⁺ emissions gradually enhanced upon increasing the Yb³⁺ content until 1 mol% indicated an energy transfer from Tb³⁺ to Yb³⁺. Otherwise, under near infrared excitation of Yb³⁺ at 980 nm, these glasses exhibit intense green luminescence, which led to cooperative sensitization of the ⁵D₄ level of Tb³⁺ ions. A cooperative energy transfer mechanism was proposed on the basis of the study on the influence of Yb³⁺ concentration on up-conversion emission intensity, as well as the dependence of this up-conversion intensity on near infrared excitation power. Moreover, the temporal evolution of the up-conversion emissions have been studied, which was in positive agreement with a theoretical model of cooperative up-conversion luminescence that showed a temporal emission curve with rise and decay times of the involved levels.     

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.     

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.     

Optical Properties of Mg,Fe, Co-Doped Near-Stoichiometric LiTaO3 Single Crystals

Mg, Fe co-doped near-stoichiometric lithium tantalite (SLT) single crystals were grown by employing the zone-leveling Czochralski (ZLCz) technique. The optical properties, holographic parameters, as well as the composition of the grown crystals were measured. It was found that the Li/Ta ratio decreased with the doping of Mg and Fe ions. A red shift was observed in absorption spectrum for the Mg, Fe co-doped crystals compared to the undoped and Mg-doped ones. The effect of the iron ions (Fe²⁺ and Fe³⁺) was further discussed based on the specified absorption bands. Moreover, the occupation mechanism for the defects was discussed by using the IR absorption spectrum, which was attributed to the Fe_Ta³⁻ defects in the highly Fe-doped crystal. In addition, the holographic parameters were also found to be improved with a higher Fe/Ta ratio in the crystals.     

Ultrasonic Spray Pyrolysis Synthesis and Photoluminescence of LuAG:Ce Thin Films

LuAG:Ce (Lu₃Al₅O₁₂:Ce) is one of the most important color converters in white lighting industry. Especially, LuAG:Ce film attracts more attention due to the outstanding advantages, such as the efficient heat dissipation, the saving of rare earth, and so on. Here, LuAG:Ce film on sapphire was successfully prepared by the ultrasonic spray pyrolysis process. The phase, microstructure and photoluminescence of LuAG:Ce films were investigated. LuAG:Ce films had a thickness of around 5 μm, which were well crystallized at 1000 °C in air atmosphere to form the typical garnet structure. Under the protection of CO atmosphere, increasing the annealing temperature greatly enhanced the photoluminescence performance. After annealing at 1500 °C for 5 h in CO atmosphere, 3.0 mol.% Ce³⁺ doped LuAG:Ce film exhibited the highest emission and excitation intensity. The emission intensity of 3.0 mol.% Ce³⁺ doped LuAG:Ce film annealed at 1500 °C in CO atmosphere increased up to five times, when compared with the best LuAG:Ce film annealed at 1000 °C in air atmosphere. The effects of Ce³⁺ doping concentration on the photoluminescence were also examined. As the Ce³⁺ doping concentration increased from 0.2 mol.% to 7.0 mol.%, the color of LuAG:Ce films changed from yellowish green to greenish yellow. When coupling the 3.0 mol.% Ce³⁺ doped LuAG:Ce film with a 0.5 W 450 nm blue laser, the formed device successfully emitted white light.