Eu3+‐doped glass as a color rendering index enhancer in phosphor‐in‐glass

A new method for improving color rendering index (CRI) and low correlated color temperature (CCT) in high‐power white‐light‐emitting diodes (WLEDs) is proposed. We used a configuration of phosphor‐in‐glass (PIG) and studied light output changes with the increment in concentration of yellow‐emitting Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) phosphor. The PIG was coupled on the top of blue‐light‐emitting diodes (LED) chip (465 nm). To compensate the lack of red emission in the phosphor, Eu³⁺‐doped tellurium glass with different europium content was employed as a red emitter. The suitable contents of YAG:Ce³⁺ and Eu³⁺ were 7.5 weight percent (wt%) and 3 mol percent (mol%), respectively. The CRI value went from 72 to 82, whereas the CCT was reduced from 24 933 to 6434 K. The proposed structure can improve CCT as well as CRI of WLEDs just by placing a glass on top.     

Deep‐red photoluminescence and long persistent luminescence in double perovstkite‐type La2MgGeO6:Mn4+

A novel non‐rare‐earth doped phosphor La₂MgGeO₆:Mn⁴⁺ (LMG:Mn⁴⁺) with near‐infrared (NIR) long persistent luminescence (LPL) was successfully synthesized by solid‐state reaction. The phosphors can be effectively excited using ultraviolet light, followed by a sharp deep‐red emission peaking at 708 nm, which is originated from ²E_g → ⁴A_2g transition of Mn⁴⁺ ions. The luminescent performance was analyzed by photoluminescence (PL) and photoluminescence excitation (PLE) spectra. The crystal field parameters were calculated to describe the environment of Mn⁴⁺ in LMG host. The LPL behaviors as well as the mechanisms were systematically discussed. This study suggests that the phosphors will broaden new horizons in designing and fabricating novel NIR long phosphorescent materials.     

The Investigations of the Pr,Gd, Si–N Doping,and Phosphor Curvature Effects on the Performances of YAG‐Based WLEDs

The effect of the phosphor curvature in the range 0.1766–0.2589 mm^?1 on the luminous efficacy of Y_2.95Al₅O₁₂:0.05Ce³⁺ (YAG)‐based white‐light‐emitting diodes (WLEDs) was investigated at the similar correlated color temperature (CCT) of ~6300 K by tuning the concentration of YAG phosphors in the phosphor layer ranging from 7.5 to 15 wt%. It was found that both the luminous efficacy and luminous power increased monotonically with the increasing curvature. The luminous efficacy (=82.4 lm/W) and luminous power (=297.85 mW) of the YAG‐based WLED at the preferable phosphor curvature of 0.2589 mm^?1 were 19.44% and 17.36%, respectively, higher than those at the curvature of 0.1766 mm^?1 under 350 mA. This finding reveals that the surface curvature of phosphor layers is a critical factor which cannot be ignored for the investigation of the light output of phosphor‐converted WLEDs. Moreover, the color rendering index (CRI) enhancement of YAG‐based WLED with substitution of Y_2.94Al₅O₁₂:0.05Ce³⁺, 0.01Pr³⁺ (YPrAG), Y_2.45Gd_0.5Al₅O₁₂:0.05Ce³⁺ (YGdAG), and Y_2.95Al_4.8Si_0.2O_11.8N_0.2:0.05Ce³⁺ (YAlSiON) for YAG were assessed under the same phosphor curvature of 0.2589 mm^?1 and the similar CCT ~6350 K. Taking the luminous efficacy, preparation cost of phosphors, and CRI into consideration, we suggest that the YGdAG is a preferable candidate for replacing the YAG for use in WLEDs among the four kinds of phosphors. Compared with the YAG (7.5 wt%)‐based WLED, the YGdAG (7 wt%)‐based WLED exhibited an improved CRI, less preparation cost of phosphors, and the acceptable reduction in luminous efficacy under 350 mA.     

Structure and Luminescence of New Red‐Emitting Materials‐Eu3+‐Doped Triple Orthovanadates NaALa(VO4)2 (A = Ca,Sr, Ba)

The new red‐emitting phosphors of Eu³⁺‐doped triple orthovanadates NaALa(VO₄)₂ (A = Ca, Sr, Ba) were prepared by the high‐temperature solid‐state reaction. The formation of single phase compound with isostructural structure of Ba₃(VO₄)₂ was verified through X‐ray diffraction (XRD) studies. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on doping level were investigated. The phosphor can be efficiently excited by near UV and blue light to realize an intense red luminescence (613 nm) corresponding to the electric dipole transition ⁵D₀→⁷F₂ of Eu³⁺ ions. Their potential applications as red‐emitting phosphors for solid‐state lighting were evaluated in comparison with the Eu³⁺‐doped lanthanum orthovanadate LaVO₄ and other reported references. The luminescence was discussed in detail on the base of the crystal structures. The luminescence thermal stability on temperature was investigated and the thermal activated energy was calculated. The phosphors can be suggested to be a potential red‐emitting phosphor for the application on white LEDs under irradiation of near‐UV or blue chips.     

Structure and Luminescence Characteristics of Eu3+‐Activated Trigonal Layered Perovskite Ba2La2ZnW2O12

Eu³⁺‐doped tungstate Ba₂La₂ZnW₂O₁₂ phosphors with perovskite‐structure were prepared by the high temperature solid‐state reaction. The X‐ray powder diffraction (XRD) patterns and structure refinements indicate that the phosphors crystalized in the trigonal layer‐perovskite. The luminescence properties of the phosphors were investigated such as photoluminescence (PL) excitation and emission spectra, decay lifetimes, and color coordinates. It was found that the pure host shows self‐activated emission excited by the UV light. Moreover, Ba₂La₂ZnW₂O₁₂ also shows scintillation characteristics under the X‐ray irradiation. The near‐UV and blue light can efficiently excite Eu³⁺‐doped Ba₂La₂ZnW₂O₁₂ phosphors inducing the strong orange–red luminescence. The optimal Eu³⁺ doping concentration in this host is 40 mol%. The luminescence spectra and the luminescence color of the phosphors strongly depend on the doping levels and excitation wavelength. The different luminescence features were discussed on the base of crystal structure. Eu³⁺ ions have two possible substitutions on A or B sites in this trigonal layered perovskite. The phosphor could act as a candidate for the potential application in near‐UV excited white‐LEDs lighting.     

Dy and Eu activated Ca3B2O6 phosphors for near ultraviolet‐based light‐emitting diodes

The Dy‐ and Eu‐activated Ca₃B₂O₆ phosphors were synthesized by a high‐temperature solid‐state reaction technique and their structural and luminescent properties were investigated. The phosphors are characterized by X‐ray diffraction, photoluminescence spectra, and Commission International de I'Eclairage (CIE) chromaticity coordinates. It is found that the charge compensator Na⁺ plays an important role in modifying the emission spectral profiles of Dy and Eu ions in the phosphors. The ratio of the emission located at the yellow wavelength portion to that located at the blue wavelength region of the Dy³⁺ ions can be apparently tuned by changing the Na⁺ content. The luminescence intensity of the phosphors can be enhanced with introducing Na⁺ ions as well. The emission colors of Dy/Eu codoped phosphors change from blue to white and successfully acquire the superior white light emission (x = 0.330, y = 0.329) by appropriately tuning the Na⁺/Dy³⁺ content and the excitation wavelength. The energy transfer process from Eu²⁺ to Dy³⁺ and Eu³⁺ occurs in the Dy/Eu codoped phosphors, providing a further approach to modify the emission spectral profile of the examined phosphors. The phosphors presented here have promising applications in the fields of light‐emitting diodes.     

Homogeneous Precipitation Synthesis and Low‐Voltage Cathodoluminescence of SnO2:Eu3+ Phosphors for Field Emission Displays

A reddish‐orange‐emitting SnO₂:Eu³⁺ phosphor for field emission displays (FEDs) was successfully synthesized via a homogeneous precipitation route using urea as a precipitant. The influences of the dopant concentration of Eu³⁺ and calcination temperature on optical properties were investigated. The low‐voltage field emission properties of the FED device prepared using the synthesized SnO₂:Eu³⁺ phosphors were reported. Under the UV light, SnO₂:Eu³⁺ phosphors display the strong orange–red emission peaked at 587, 591, and 597 nm due to the ⁵D₀→⁷F₁ magnetic dipole transition of Eu³⁺. The phosphor doped with 1.0 mol% Eu³⁺ possesses the highest photoluminescent (PL) intensity. Under the low‐voltage excitation of 300 V, the fabricated FED device exhibits the bright orange–red emission, high‐voltage brightness saturation, and high color purity, which has a potential application in low‐voltage full color FEDs.     

Novel Emitting‐Color Tunable Phosphors Ba3Y2(BO3)4:Ce3+,Tb3+ with Efficient Energy Transfer for Near‐UV Light‐Emitting Diodes

This work presents the ultraviolet–visible spectroscopic properties of Ba₃Y₂(BO₃)₄:Ce³⁺,Tb³⁺ phosphors prepared by a high‐temperature solid‐state reaction. Under ultraviolet light excitation, tunable emission from the blue to yellowish‐green region was obtained by changing the doping concentration of Tb³⁺ when the content of Ce³⁺ is fixed. The efficient energy transfer process between Ce³⁺ and Tb³⁺ ions was observed and confirmed in terms of corresponding excitation and emission spectra. In addition, the energy transfer mechanism between Ce³⁺ and Tb³⁺ was proved to be dipole–dipole interaction in Ba₃Y₂(BO₃)₄:Ce³⁺,Tb³⁺ phosphor. By utilizing the principle of energy transfer and appropriate tuning of Ce³⁺/Tb³⁺ contents, Ba₃Y(BO₃)₄:Ce³⁺,Tb³⁺ phosphors can have potential application as an UV‐convertible phosphor for near‐UV excited white light‐emitting diodes.     

Eu‐Doped β‐SiAlON Phosphors: Template‐Assistant Low Temperature Synthesis,Dual Band Emission,and High‐Thermal Stability

A hard template route has been successfully developed for synthesis of β‐SiAlON:Eu phosphors at low temperatures. The synthesis utilizes mesoporous silica (SBA‐15) skeleton as an active Si source, combined with the carbothermal reduction and nitridation method. It has been shown that the additional driving force from high surface area and porosity of SBA‐15 enables β‐SiAlON:Eu (with compositions of Si_6?zAl_z?xO_z+xN_8?z?x: xEu, x = 0.010–0.200 and z = 1.000) phosphors to be formed as a dominant phase at low temperature of 1400°C. The resultant β‐SiAlON:Eu phosphor powders exhibit a typical rod‐like morphology and a well dispersed state. By tailoring the Eu²⁺ concentration in the phosphors, a continuous change in emission band can be realized, that is a blue emission dominated for low Eu²⁺ concentrations and a green emission dominated for high Eu²⁺ doping concentrations. Furthermore, the resultant phosphors exhibit a small thermal quenching up to high temperature of 250°C. Therefore, the developed method is beneficial to synthesize LED phosphors of oxynitride systems at lower temperatures.     

Far‐Red‐Emitting BiOCl:Eu3+ Phosphor with Excellent Broadband NUV‐Excitation for White‐Light‐Emitting Diodes

Rare‐earth ion‐doped semiconducting phosphor has attracted extensive attention due to the ability to achieve efficient luminescence through the host sensitization. Here, we present a new type red‐emitting Eu³⁺ ‐doped BiOCl phosphors possessing a broad excitation band in the near‐ultraviolet (NUV) region. Experimental measurements and theoretical calculations confirm that Eu³⁺ ion dopants result in forming impurity energy level near valence band, and the excellent broadband NUV‐exciting ability of Eu³⁺ ion is due to the electronic transitions of BiOCl band gap. Moreover, the highest emission intensity of the phosphors is from the ⁵D₀ → ⁷F₄ transition of Eu³⁺ around 699 nm (far‐red) through whether host excitation or direct Eu³⁺ ions excitation, which lie in the particular structure of BiOCl crystals. Our results indicate that the Eu³⁺ ‐doped BiOCl crystals show great potential as red phosphors for white‐light‐emitting diodes.     

Photoluminescence Characteristics of a New Thiogallate‐Based Green‐Emitting Phosphor: MgGa2S4:Eu2+

A new thiogallate‐based green‐emitting phosphor, MgGa₂S₄:Eu²⁺, was first synthesized via a high‐temperature solid‐state reaction in a CS₂ atmosphere. We then investigated the structures and luminescent properties of the MgGa₂S₄:Eu²⁺ phosphors. The MgGa₂S₄:Eu²⁺ phosphors can be excited efficiently by UV–visible light in the wavelength range from 350 to 520 nm and they emit an intensely green light with emission bands peaking at 538 nm. The optimal concentration for Eu²⁺ in MgGa₂S₄ was found to be about 6 mol%, and the corresponding concentration quenching mechanism was the electric multipole–multipole interaction. The quenching temperature was calculated to be 402 K, and the Huang–Rhys factor was about 4. The energy barrier for thermal quenching was calculated to be 0.28 and 0.27 eV by the two types of the Arrhenius equations. The small variation in the color coordinates of MgGa₂S₄:Eu²⁺ under high temperatures indicates that the as‐synthesized phosphor has good color stability. Due to their broadband absorption in the 350–520 nm wavelength range, these phosphors may be able to fulfill the requirements for application in the development of Ga(In)N‐based white LEDs.     

Visible Quantum Cutting and Energy Transfer in Tb3+‐Doped KSr(Gd,Y)(PO4)2 Under VUV–UV Excitation

KSr(Gd,Y)(PO₄)₂: Tb³⁺ phosphors were synthesized using the high‐temperature solid‐state reaction method. The VUV–UV spectroscopic properties of these phosphors were studied. The results show that efficient energy transfer (ET) from Gd³⁺ to Tb³⁺ occurs in this system, and the ET efficiency increases with increasing of Tb³⁺ doping concentrations, which is evidenced that both the emission intensity and decay time of Gd³⁺ decreases with increasing Tb³⁺ doping concentrations. Visible quantum cutting via cross relaxation between the neighboring Tb³⁺ ions was observed in the high Tb³⁺ concentration doped sample. In addition, the emission color of KSr(Gd,Y)(PO₄)₂: Tb³⁺ phosphors can be tuned from blue to yellowish‐green by varying the doping concentration of Tb³⁺. Under 147 nm excitation, the sample KSrGd_0.5(PO₄)₂: 0.5Tb³⁺ exhibits the strongest emission, which is about 70% of the commercial green‐emitting phosphor Zn₂SiO₄: Mn²⁺ indicating the potential application of this phosphor for plasma display panels, Hg‐free lamps, and three‐dimensional displays.     

Regulation of Phosphor's Color Gamut Area Using Mesoporous Silicate Source—A New Paradigm for the Solid‐State Lighting Segment

The inception of phosphors provoked the need of highly efficient lighting sources for the conceivable next generation applications. In this regards, a striking characteristic material namely the mesoporous silica (MPS) and their series that are quite distinct to each other in their physical properties have been synthesized by adopting a cooperative self‐assemble strategy. Utilizing it, the development of high‐performance Sr_1?xCa_1?yEu_x+ySiO₄ phosphor was traversed using a simple wet‐solid phase process. Systematic investigations on morphological, structural, and few other physical properties were carried out. The derived results are intriguing with a crystal clear alteration in the phosphor morphology when MPS has been used as a silicate source. Subsequent luminescence studies displayed its efficient yellow‐emitting property covering the red spectral components, along with good thermal luminescence stability. Perhaps, the designed prototype LEDs yielded a color correlation temperature (CCT) < 5000 K and color rendering index (CRI) > 80. Therefore, it directs the way for the fabrication of potential warm white LEDs with a long‐lived emission efficacy and high thermal luminescence stability.     

A novel dazzling Eu3+‐doped whitlockite‐type phosphate red‐emitting phosphor for white light‐emitting diodes

A series of novel red‐emitting Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors were successfully synthesized using the high‐temperature solid‐state reaction method. The crystal structure, photoluminescence spectra, thermal stability, and quantum efficiency of the phosphors were investigated as a function of Eu³⁺ concentration. Detailed analysis of their structural properties revealed that all the phosphors could be assigned as whitlockite‐type β‐Ca₃(PO₄)₂ structures. Both the PL emission spectra and decay curves suggest that emission intensity is largely dependent on Eu³⁺ concentration, with no quenching as the Eu³⁺ concentration approaches 100%. A dominant red emission band centered at 611 nm indicates that Eu³⁺ occupies a low symmetry sites within the Ca₈ZnLa(PO₄)₇ host lattice, which was confirm by Judd‐Ofelt theory. Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors exhibited good color coordinates (0.6516, 0.3480), high color purity (~96.3%), and high quantum efficiency (~78%). Temperature‐dependent emission spectra showed that the phosphors possessed good thermal stability. A white light‐emitting diode (LED) device were fabricated by integrating a mixture of obtained phosphors, commercial green‐emitting and blue‐emitting phosphors into a near‐ultraviolet LED chip. The fabricated white LED device emits glaring white light with high color rendering index (83.9) and proper correlated color temperature (5570 K). These results demonstrate that the Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors are a promising candidate for solid‐state lighting.     

Orderly‐Layered Tetravalent Manganese‐Doped Strontium Aluminate Sr4Al14O25:Mn4+: An Efficient Red Phosphor for Warm White Light Emitting Diodes

Searching for an efficient non rare earth‐based oxide red phosphor, particularly excitable by light in the wavelength from 380 to 480 nm and unexcitable by green light, is essential for the development of warm white light emitting diodes (WLEDs). Here, we report a promising and orderly‐layered candidate: Sr₄Al₁₄O₂₅:Mn⁴⁺ with CIE color coordinates (0.722, 0.278). It has higher luminescence efficiency particularly upon blue excitation and is much cheaper than the commercial red phosphor 3.5MgO·0.5MgF₂·GeO₂:Mn⁴⁺ (MMG:Mn⁴⁺). In sharp contrast to Eu²⁺‐doped (oxy)nitrides, the phosphor can be synthesized by a standard solid‐state reaction at 1200°C in air. The effects of flux boron content, environment, and preparation temperature, sintering dwelling time as well as Mn concentration have been systematically investigated for establishing the optimal synthesis conditions. The low temperature emission spectra reveal that there are at least three types of Mn⁴⁺ ions in Sr₄Al₁₄O₂₅:Mn⁴⁺ due to the substitution for the distorted octahedral Al³⁺ sites. The AlO₆ layers where Mn⁴⁺ prefers to reside are well separated from one another by AlO₄ tetrahedra in one dimension parallel to axis a. This scenario can efficiently isolate Mn⁴⁺ ions from local perturbations, thereby enabling the high efficiency of luminescence. The energy transfer rates and mechanism are discussed.     

Phosphor‐in‐fluorescent‐glasses for high color rendering white light emitting diodes

Fluorescent glass frits were prepared and used to synthesize phosphor‐in‐fluorescent glass composites (PiFGs) to realize stable white light emitting diodes with high color‐rendering properties. Commercial red, green, and blue phosphors were co‐sintered and red phosphors were partially replaced by Eu³⁺ in glass frits. Phosphor‐in‐glass composites were placed on UV‐light emitting diodes (UV‐LEDs) to generate white light. Pure white light with a luminous efficacy=58.4 lm/W, general color rendering index R_a=87 and special color rendering index for strong red R₉=73 was realized with glass frits containing 7 mol% Eu₂O₃ and RGB ratio of 35:20:15. Luminous efficacy, R_a and R₉ increased as red phosphors were replaced by red‐fluorescent glass frits.     

2D photonic crystal layer assisted thiosilicate ceramic plate with red‐emitting film for high quality w‐LEDs

In this work, we have succeeded in obtaining high quality warm w‐light‐emitting‐diodes (LEDs) by adopting hybrid two‐dimensional (2D) structure of SiN_x photonic crystal layer (PCL) assisted cyan‐emitting ceramic‐plate thiosilicate SrLa₂Si₂S₈:Ce³⁺ with red‐emitting film SrLiAl₃N₄:Eu²⁺ phosphor on a 430 nm blue LED chip at 350 mA. 2D SiN_x PCL was capped with thiosilicate is because it can enhance the luminous efficacy and maintain the low correlated color temperature (CCT) and high color‐rendering index (CRI). High luminous efficacy (82.3 lm/W), high special CRI (R₉=75) as well as the low CCT (5431 K) of the optimal w‐LED was obtained due to the assistances of 2D SiN_x PCL and narrow‐band red‐emitting phosphor with the doping percentage at 10 wt%. The synthesis processes, structural analysis, optical properties and LED device performances were detailed investigated to find out the relationship between the optimum composition and good optical properties. Based on intriguing luminescence properties by the 2D SiN_x PCL and red‐emitting film phosphor introducing, we proclaim this method could also have high potential application in other phosphor‐converted w‐LEDs.     

Eu2+ activated NaBa3Si2O7F: A new efficient blue-emitting luminescent material for solid-state lighting and display

Exploring novel efficient phosphors for lighting and display has always been an important and meaningful work for researchers. Herein, a novel efficient blue-emitting phosphor, Eu²⁺ doped barium-containing silicate fluoride NaBa₃Si₂O₇F, was prepared by solid-state method. The phosphor can produce bright blue light peaked at 452 nm with full-width at half-maximum about 57 nm under near-UV light excitation, and it exhibits a high internal quantum yield about 76.23%. The temperature-dependent photoluminescence spectra show that this phosphor owns good thermal stability, and the emission intensity at 425 K is 67% of that at room temperature. The outstanding data of fabricated device demonstrate that the blue phosphor has large possibility of practical application for white light-emitting diode. Furthermore, the phosphor also possesses good cathodoluminescence properties under various accelerating voltage with different probe currents, indicating its potential application in field emission displays.     

Formation mechanism and optimized luminescence of Mn4+‐doped unequal dual‐alkaline hexafluorosilicate Li0.5Na1.5SiF6

A novel red phosphor Li_0.5Na_1.5SiF₆:Mn⁴⁺ (LNSF:Mn) based on the unequal dual‐alkaline hexafluorosilicate with superior optical performances has been synthesized via ion‐exchange between [MnF₆]^2? and [SiF₆]^2? at room temperature. The composition and the crystal structure of the as‐obtained phosphor LNSF:Mn were determined by energy‐dispersive x‐ray spectroscopy (EDS) and x‐ray diffraction (XRD), respectively. The formation mechanism of the red phosphor LNSF:Mn has been discussed in detail. The phosphor LNSF:Mn exhibits good chromaticity properties and a quantum yield (QY) of 96.1%, which are better than the identified fluorosilicate phosphors Na₂SiF₆:Mn⁴⁺ (NSF:Mn) and K₂SiF₆:Mn⁴⁺ (KSF:Mn). A broad and intense absorption in the blue and a bright emission in red‐shifted wavelengths make the phosphor LNSF:Mn a desired candidate for applications in warm white light‐emitting diodes.     

Effect of Rare Earth Doping on the Catalytic Activity of Copper‐Containing Hydrotalcites in Phenol Hydroxylation

The copper‐containing hydrotalcites (Cu‐HTLcs) are synthesized under microwave irradiation, the effect of rare earth elements (RE) on the synthesis of Cu‐HTLcs, wherein RE stands for rare earth elements, e.g., La, Y, Sm and Ce, is also investigated in the present work. The hydrotalcite structure of the synthesized samples is verified by XRD and FT‐IR. The results of their catalytic performances in phenol hydroxylation show that the doped rare earth elements can promote the catalytic activity of Cu‐HTLcs, exhibiting a good trend as follows: La>Y>Sm>Ce. XPS results show that the Cu⁺ species are produced after the interaction of La‐Cu‐HTLcs with H₂O₂. Combining with the catalytic test results, we propose a new mechanism about the generation of HO ^. radicals in phenol hydroxylation, it is assumed that HO‐Cu⁺‐OH species are first formed by the reduction of HO‐Cu²⁺‐OH located in hydrotalcites in the presence of H₂O₂, and then react with H₂O₂ to give rise to HO^. radicals.