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.     

Highly Stable Red‐Emitting Sr2Si5N8:Eu2+ Phosphor with a Hydrophobic Surface

One of the biggest problems in white light‐emitting diodes (WLEDs) is the moisture‐induced degradation of phosphors. This paper proposes a simple and feasible surface modification method to solve it, whereby a hydrophobic surface layer is developed on the surface of the phosphors. The particular case of orange‐red‐emitting Sr₂Si₅N₈:Eu²⁺ (SSN) phosphor was investigated. The mechanism to develop the hydrophobic layer involves hydrolysis and polymerization of tetraethylorthosilicate (TEOS) and polydimethylsiloxane (PDMS). The experimental results showed that the surface layer of SSN phosphor was successfully modified to a hydrophobic nanolayer (8 nm) of amorphous silicon dioxide that contains CH₃ groups in the surface. This hydrophobic surface layer gives the modified phosphor superior stability in high‐pressure water steam conditions at 150°C.     

Photoluminescence Mechanism and Thermal Stability of Tb3+‐Doped Y4Si2O7N2 Green‐Emitting Phosphors

With solid‐state reaction method, series of Y₄Si₂O₇N₂:Tb³⁺ phosphors were prepared under the high‐temperature and high‐pressure conditions. The photoluminescence properties at room and high temperature were investigated. Two groups of emission lines have been observed, which are corresponding to Tb^{3+ 5}D₃ → ⁷F_J (J = 6, 5, 4, 3, 2) and ⁵D₄ → ⁷F_J (J = 6, 5, 4, 3) transitions. The physical mechanisms for excitation, emission, concentration quenching, and thermal quenching were investigated. The cross‐relaxation mechanism between the ⁵D₃ and ⁵D₄ emission was investigated and discussed. The Tb–Tb critical distance for cross‐relaxation was calculated to be ~13 Å. The optimum Tb³⁺ concentration in this phosphor is 15 mol%. The quadrupole–quadrupole interaction dominates the non‐radiative energy transfer between the Tb³⁺ luminescence centers and causes the concentration quenching. This phosphor shows high thermal stabilities that at 150°C the intensity remains 92% compared with that measured at room temperature. The present work suggests that this Tb³⁺‐doped Y₄Si₂O₇N₂ material is a kind of potential green‐emitting phosphor.     

Photoluminescence Properties of Heavily Eu3+‐Doped BaCa2In6O12 Phosphor for White‐Light‐Emitting Diodes

Heavily Eu³⁺‐doped BaCa₂In₆O₁₂ phosphors were prepared by conventional solid‐state reaction, and its structural properties were investigated by means of Rietveld refinement method using an X‐ray source. XRD patterns confirm the hexagonal phase of BaCa₂In₆O₁₂: Eu³⁺ phosphors. The obtained spectrum data indicate that the emission spectra of Ba_1?xEu_xCa₂In₆O₁₂ samples excited at 393 nm exhibit a series of shaped peaks assigned to the ⁵D_0,1,2,3 →⁷F_J (J = 0,1,2,3,4) transitions. Luminescence from the higher excited states, such as ⁵D₁, ⁵D₂, and ⁵D₃, were also observed even though the Eu³⁺ concentration was up to x = 0.4. More importantly, the Ba_1?xEu_xCa₂In₆O₁₂ phosphor still emits white luminescence, when the Eu³⁺ ion concentration is up to x = 0.07 before concentration quenching is observed, which shows that the phosphor is a promising single‐phase phosphor for near ultraviolet (NUV) light‐emitting diodes (LED). Furthermore, the temperature's impact on white luminescent properties was studied. Finally, a white‐light‐emitting diodes (W‐LEDs) fabricated with the Ba_0.95Eu_0.05Ca₂In₆O₁₂ phosphor incorporated with an encapsulant in ultraviolet LEDs (λ_max = 395 nm) is discussed.     

Synthesis of Y3Al5O12:Eu2+ Phosphor by a Facile Hydrogen Iodide‐AssistedSol–Gel Method

Pure yttrium aluminum garnet (YAG) phosphor doped with Eu²⁺ has been successfully synthesized by a facile sol–gel method. The use of hydrogen iodide aimed to get Eu²⁺ ions, confirmed by X‐ray absorption near‐edge structure (XANES) analysis. Nearly spherical and well dispersed particles were synthesized. The produced YAG:Eu²⁺ phosphor powder had a broad emission band in the range of 400–600 nm with a peak at 480 nm, attributed to the allowed 4f⁷–4f⁶5d¹ transition of electrons in Eu²⁺ ions. The proposed method could also be expanded to prepare many other Eu²⁺‐doped phosphors with a solution method.     

Synthesis and Persistent Luminescence Mechanism of a Novel Orange Emitting Persistent Phosphor Sr5(BO3)3Cl:Eu2+

A series of Eu²⁺‐doped Sr₅(BO₃)₃Cl phosphors were prepared successfully using a conventional solid‐state reaction method. The luminescent properties were studied systematically by utilizing photoluminescence spectra, decay curves, persistent luminescence spectra, and thermoluminescence glow curves. Energy transfer from host to emission center Eu²⁺ was affirmed. The orange persistent luminescence emission was observed for the first time. The optimal doping concentration of Eu²⁺ for persistent luminescence was experimentally to be approximately 0.5% and the orange persistent luminescence duration can persist about 15 min. On the basis of the experimental results, a model was constructed and the relevant mechanism of persistent luminescence was illustrated in detail. Two different ways of trapping the charge carriers were also discussed.     

A Novel Blue‐Emitting Phosphor of Eu2+‐Activated Magnesium Haloborate Mg3B7O13Cl

Eu²⁺‐doped magnesium haloborate Mg₃B₇O₁₃Cl was synthesized by the conventional high‐temperature solid‐state reaction. The phase formation was confirmed by X‐ray powder diffraction (XRD) measurements and structure refinement. The photoluminescence excitation and emission spectra, and decay curves were measured. Under the excitation of near‐UV light, Eu²⁺‐doped Mg₃B₇O₁₃Cl presents a narrow blue‐emitting band centered at 423 nm. The maximum absolute quantum efficiency (QE) of Mg₃B₇O₁₃Cl:Eu²⁺ phosphor was measured to be 80% excited at 385 nm light at 300 K. The thermal stability of the blue luminescence was evaluated by the luminescence decays as a function of temperature. The phosphor shows an excellent thermal stability on temperature quenching effects. Moreover, Mg₃B₇O₁₃Cl:Eu²⁺ phosphor shows scintillation characteristics excited by X‐ray irradiation at room temperature and presents a blue luminescence band with a fast lifetime of 600 ns.     

Temperature‐Sensitive Photoluminescence Property and Energy Transfer Mechanism in the Silicate Phosphor MgY4Si3O13: Eu3+

A red‐emitting phosphor MgY₄Si₃O₁₃:Eu³⁺ was synthesized by conventional solid‐state reaction for the first time. Photoluminescence spectra show that the phosphor can be efficiently excited by ultraviolet and blue light and exhibit an intense emission at 615 nm due to the dominant ⁵D₀→⁷F₂ electric dipole transition of Eu³⁺. The decay times of Eu³⁺ monitored at the different wavelengths present an interesting change trend. According to the results of XRD Rietveld refinement, in a unit cell, the number of Eu³⁺ is obtained to be 0.064 for 4f site and 0.294 for 6 h site. The remarkable preference occupancy for one site could be the leading reason of the abnormal change in decay times. The testing of thermal quenching indicates that the photoluminescence intensity of the phosphor is very sensitive to temperature and furthermore, the emission intensities from ⁵D₁→⁷F_J and ⁵D₀→⁷F_J show the different decay ratios with the increase in temperature. Based on the configurational coordinate diagram, an underlying mechanism is proposed and can explain the phenomenon reasonably. The mechanism could be helpful for the understanding of the energy transfer phenomenon among the various energy levels in the process of temperature change as reference.     

Structure and Photoluminescence of A Blue‐Green‐Emitting Phosphor for Near‐UV White LEDs

A series of phosphors Ca_12(0.97?x)Al₁₄O₃₂F₂: 0.03Ce³⁺, xTb³⁺ have been prepared by a hightemperature solid‐state reaction using boric acid as flux. These oxyfluorides crystallize in cubic structure, space group. Under the near ultraviolet excitation within wavelength range 310–390 nm, Ca_12(0.97?x)Al₁₄O₃₂F₂: 0.03Ce³⁺, xTb³⁺ phosphors exhibit an intense emission covering a broad band of 370–500 nm derived from the 5d→4f transitions of Ce³⁺ and a characteristic emission at 544 nm of Tb³⁺. The emission can be tuned from blue to green by altering the relative ratio of Ce³⁺ to Tb³⁺ in the composition. The energy‐transfer mechanism from Ce³⁺ to Tb³⁺ is investigated based on the site occupancy of the luminescence center in the crystal structure of the Ca₁₂Al₁₄O₃₂F₂ host. More importantly, when a certain amount of boric acid is added as flux in the synthesis, the fluorescence intensity of the phosphors increases about 65%. Because of its broad excitation and efficiently tunable blue to green luminescence, the Ca_12(0.97?x)Al₁₄O₃₂F₂: 0.03Ce³⁺, xTb³⁺ phosphors may find promising application as a near UV‐convertible phosphor for white‐light‐emitting diodes.     

Temperature‐Dependent Emission Spectra of Ca2Si5N8:Eu2+, Tm3+ Phosphor and its Afterglow Properties

The nitrides Ca₂Si₅N₈:0.5%Eu²⁺, x%Tm³⁺(x = 0, 0.5, 1, 2, 4) (CSN:0.5E, xT) phosphors were prepared via the high temperature solid‐sintering method using CaH₂ as calcium source. These phosphors exhibited strong orange long‐lasting phosphorescence (LLP) after turning off the activating light. Besides, the CSN:0.5E, 1T phosphor with an afterglow time of more than 200 min (0.32 mcd/m²). Furthermore, the temperature‐dependent emission spectra of CSN:0.5E, 1T were investigated from temperature 80–500 K and an anti‐quenching phenomenon that the emission intensities increased then decreased under excitation at increased temperature was found. Ultimate, the proposed mechanism on temperature dependence of luminescence was analyzed. This study provides a new perspective for the impact of temperature‐dependent problem as a consequence of heating processes in luminescent materials.     

草酸共沉淀法制备的Y2O3:Eu2+发光性能

采用草酸共沉淀法,利用草酸盐的自氧化还原,制得了以Y2O3为基质及Eu2 为发光中心的荧光粉Y2O3:Eu2 .该法煅烧温度低、操作简单,不需要外界置入任何还原性物质,可将高价阳离子Eu3 还原为Eu2 ,降低了反应的危险性和生产成本.对Y2O3:Eu2 的荧光性质进行了表征,并进一步探讨了Eu2 荧光发射主峰产生较大红移现象的原因,以及发光强度与煅烧温度和Eu2 含量的关系.     

Photoluminescence of Sr2P2O7:Sm3+ Phosphor as Reddish Orange Emission for White Light‐Emitting Diodes

A reddish orange emission Sr₂P₂O₇:Sm³⁺ phosphor is prepared by the solid‐state reaction method in air, and the crystal structure and luminescence properties of phosphors are investigated. Sr₂P₂O₇:Sm³⁺ phosphor shows Commission International de I'Eclairage (CIE) chromaticity coordinates (x = 0.5753, y = 0.4147). White light‐emitting diodes (W‐LEDs) fabricated using Sr₂P₂O₇:Sm³⁺ phosphor etc. show CIE chromaticity coordinates (x = 0.3471, y = 0.3124). These results indicate that Sr₂P₂O₇:Sm³⁺ phosphor could be a potential suitable reddish orange emitting phosphor candidate for W‐LEDs with excitation of a ~400 nm n‐UV LED chip.     

Decay Behavior in Ce3+‐doped La3Si6N11 and Lu3Al5O12 Phosphors

Ce³⁺‐activated light emitting diode (LED) phosphors have been extensively examined for photoluminescence, and have been the focus of many detailed structural studies. However, reports of the decay curves of Ce³⁺‐activated LED phosphors are rare. Although we have reported the decay behaviors of several Eu²⁺‐activated LED phosphors such as Sr₂SiO₄, Sr₂Si₅N₈, and CaAlSiN₃, we have never conducted an in‐depth study into the decay behavior for Ce³⁺‐activated LED phosphors. For this study, we investigated the decay curves of well‐known Ce³⁺‐activated LED phosphors such as La₃Si₆N₁₁ and Lu₃Al₅O₁₂. Similar to Eu²⁺‐activated LED phosphors, the decay behavior of Ce³⁺‐activated LED phosphors was sensitive to the Ce³⁺ concentration and to the detection wavelength. There was active nonradiative energy transfer between the Ce³⁺ activators located at different sites.     

Eu3+ luminescence in novel garnet-type Li5La3Nb2O12 ceramics

A novel Li₅La₃Nb₂O₁₂:Eu³⁺ phosphor was synthesized by the solid-state reaction at high temperature. The phase purity of products was checked by XRD. The emission spectrum is independent of the excitation wavelength and the ⁵D₀–⁷F₂ transition is the dominant one. In the excitation spectrum, there are some sharp peaks originating from the f–f transitions of Eu³⁺ and a broad band peaking at about 280 nm. The concentration dependence of emission intensity and decay curves of ⁵D₀–⁷F₂ transition were investigated. The temperature dependence of emission intensity and decay curves were also investigated in detail.     

A Novel Synthesis of Green Apatite‐Type Y5(SiO4)3N:Eu2+ Phosphor via SiC‐Assisted Sol–Gel Route

A green Y₅(SiO₄)₃N:Eu²⁺ phosphor has been successfully prepared by developing a new SiC reduction‐assisted sol–gel method. The valence state of Eu ions was identified with XPS analysis and the photoluminescence spectrum presents a Eu²⁺ typical broad green emission band. XRD analysis, photoluminescence and excitation measurement, and FTIR test were also carried out, to obtain crystal phase, light emitting, and chemical bonding results. The specific mechanism of SiC reductant in the synthetic process was studied in details. This novel method shows lower equipment requirements and is cost saving. The method can extend applications in synthesizing other silicon‐based oxynitrides.     

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.     

Particle Size and Crystal Phase Dependent Photoluminescence of La2Zr2O7:Eu3+ Nanoparticles

Herein, La₂Zr₂O₇:5% Eu³⁺ nanoparticles (NPs) with different sizes have been synthesized for the first time through a modified facile molten salt process using a single‐source complex precursor of La(OH)₃·ZrO(OH)₂:Eu(OH)₃·nH₂O. It was found that the concentration of the added ammonia to co‐precipitate the corresponding metallic ions to form the precursor can influence the final particle size of the fluorite La₂Zr₂O₇:5%Eu³⁺ NPs. Furthermore, the crystal phase of the La₂Zr₂O₇:5%Eu³⁺ NPs was transferred from fluorite to pyrochlore after thermal treatment at 1000°C. The relationship between photoluminescence (PL), quantum yield (QY), particles size and crystal phase has been further investigated through fluorescence decay, site symmetry, and Judd–Ofelt (J–O) analysis. Specifically, PLQY and lifetime increase with increasing particle size of the fluorite La₂Zr₂O₇:5%Eu³⁺ NPs. Additionally, crystal phase transfer from fluorite to pyrochlore resulted in large PLQY decrease and moderate lifetime increase in the La₂Zr₂O₇:5%Eu³⁺ NPs.     

白光LED用红色荧光粉的制备及发光性能

采用溶胶凝胶法(sol-gel)合成CaO-MgO-S iO2:Eu3+荧光粉,在近紫外393nm激发下发射出Eu3+的特征红色光谱,并研究了该方法中各种工艺条件(如:pH值,Eu3+的掺杂量等)对其影响。通过X射线粉末衍射、荧光光谱等分析其发光特性,表明Eu3+离子在CaO-MgO-S iO2:Eu3+基质中处于较低的对称格位,发射来源于5D0→7F2613nm为主的红光。     

SrAl2Si2O8:Eu2+蓝色荧光粉制备条件优化及助熔剂作用研究

采用高温固相法在弱还原气氛下制备SrAl<,2>Si<,2>O<,8>:Eu<,2+>系列荧光粉,研究了预烧温度、预烧时间、烧成温度和助熔剂用量对发光性能的影响;正交试验得出最佳制备条件为:经1050℃预烧180min,在1300℃,240min烧成,硼酸加入量6.0wt%.XRD分析表明,所制得样品属于单斜晶系.激发光谱位于220～400 nm,可拟合成四个峰,表观蜂值位于350nm;发射光谱位于370～600nm,可由406nm和441nm两峰拟合而成,表观峰值位于408nm.随着硼酸用量的增加,试样衍射峰半高宽变窄和强度增强,晶胞参数a、b、c和晶胞体积V减小,硼酸起到助熔剂和基质组分置换双重作用.     

Improved Photoluminescence Property of YBO3:Eu3+ Phosphor by Structure Tailoring

YBO₃:Eu³⁺ microspheres were synthesized by a hydrothermal method. Size and surface morphology of the spheres were tailored by ion‐adding. Phase identification, morphology observation, and photoluminescence (PL) performance of the YBO₃:Eu³⁺ microspheres were characterized byX‐ray diffraction (XRD), field‐emission scanning electron microscopy (FESEM), and PL spectrophotometer, respectively. Moderate particles with enlarged size and perfect surface were achieved by adding Li⁺ ion or/and Mg²⁺ ion. PL emissions of such YBO₃:Eu³⁺ phosphors were enhanced. Significantly improved PL intensity was achieved when 1% Li⁺ ion and 5% Mg²⁺ ion were added, which was nearly doubled compared with the reference sample.