Effect of excitation wavelength (blue vs near UV) and dopant concentrations on afterglow and fast decay of persistent phosphor SrAl2O4:Eu2+,Dy3+

The persistent phosphor SrAl₂O₄:Eu²⁺,Dy³⁺ is the subject of numerous investigations. One often neglected aspect is that in this phosphor, as well as in Sr₄Al₁₄O₂₅:Eu²⁺,Dy³⁺, there are two different Sr²⁺ sites which can be occupied by the dopant Eu²⁺ ions. We first introduce a general scheme of possible energy transfers in these persistent phosphor materials including explicitly both europium ions. This scheme is used as a generic starting point to study experimentally specific pathways. We illustrate this application with the study of the effect of excitation wavelength (444 and 382 nm) on the afterglow of differently doped SrAl₂O₄:Eu²⁺,Dy³⁺ samples, as well as on the emission decay curves. With the same excitation intensity under 444 nm excitation, the resulting afterglow intensity is stronger than under near UV excitation. At 382 nm, Eu²⁺ ions on both Sr²⁺ sites in SrAl₂O₄ are excited, but at room temperature the blue emission is quenched, leading to a loss of photons. The observed effects can further be associated with the ratio of Eu²⁺ ions and trap states which are modulated by the concentrations of Eu²⁺ and Dy³⁺ in SrAl₂O₄, as well as by temperature. Increasing the nominal Dy³⁺ content from 0.1 mol% to 0.5 mol% with respect to Sr results in the doubling of the integrated afterglow intensity and confirms thus that Dy³⁺ ions are indeed involved in the trapping process. The concentration of trap states is much lower than the concentration of Eu²⁺ ions, as even with low excitation densities, a plateau of integrated afterglow intensity (corresponding to the total number of accessible traps) is reached. We postulate that an important fraction of excited Eu²⁺ ions can potentially transfer their energy to trap states. Once that all traps are filled or in a dynamical filling-depletion process under illumination (with thermal and/or optical depletion processes), for the remaining Eu²⁺ a “normal” steady-state emission is observed. The luminescence decay curves at 520 nm measured at 77 K show a mono-exponential decay with a common lifetime of about 1140 ns for all 5 samples under 437 nm excitation, while under 375 nm excitation, a feed process originating from the energy transfer between Eu²⁺ ions is demonstrated. Under 375 nm excitation, the non-exponential decay observed at 440 nm can be quantitatively associated to a Förster energy transfer process with R₀ = 1.58 (8) nm. For the overall understanding of the afterglow processes, it appears that one has to consider the individual contributions of all active ions on different lattice sites.     

Synthesis and luminescence properties of SrAleO4：Eue＋,Dy3＋ hollow microspheres via a solvothermal co-precipitation method

SrAl2O4:Eu2+,Dy3+ hollow microspheres were successfully prepared through a facile and mild solvothermal co-precipitation combining with a postcalcining process.The structure and particle morphology were investigated by X-ray diffraction(XRD),scanning and transmission electron microscopy(SEM and TEM)pictures,respectively.The mechanism for the formation of spherical SrAl2O4:Eu2+,Dy3+ phosphor was preliminary presented.After being irradiated with ultraviolet(UV)light,the spherical phosphor emitted long-lasting green phosphorescence.Both the photoluminescence(PL)spectra and luminance decay,compared with that of commercial bulky powders,revealed that the phosphors had efficient luminescent and long lasting properties.It was considered that the SrAl2O4:Eu2+,Dy3+ hollow microspheres had promising long-lasting phosphorescence with potential scale-dependent applications in photonic devices.     

Single-phase white-emitting and tunable color phosphor Na3Sc2(PO4)3:Eu2+,Dy3+: Synthesis,luminescence and energy transfer

A series of Eu²⁺/Dy³⁺ single doped and co-doped Na₃Sc₂(PO₄)₃ phosphors were synthesized by the high-temperature solid-state method, and their phase, morphology, and luminescence properties were characterized. Under the excitation of 370 nm, the Na₃Sc₂(PO₄)₃:Eu²⁺,Dy³⁺ phosphor can emit white light whose spectrum is composed of a broad emission band centered at 460 nm and the other three peaks at 483, 577, and 672 nm, respectively. There is energy transfer from Eu²⁺ to Dy³⁺ ion in Na₃Sc₂(PO₄)₃:Eu²⁺,Dy³⁺ phosphor due to the good overlap between the emission spectrum of Na₃Sc₂(PO₄)₃:Eu²⁺ and the excitation spectrum of Na₃Sc₂(PO₄)₃:Dy³⁺, which is further confirmed by the fluorescence lifetime decrease of Eu²⁺ ion with the increase of Dy³⁺ concentration. The process of energy transfer is via dipole–quadruple interaction which is confirmed by applying Dexter's theory. By increasing the Dy³⁺ concentration, the color coordinates of the Na₃Sc₂(PO₄)₃:0.01Eu²⁺,xDy³⁺ phosphors can be adjusted from blue to white, and then to yellow. The optimized concentration of Dy³⁺ ions is 4.0 mol%, beyond which the concentration quenching will take place. The Na₃Sc₂(PO₄)₃:Eu²⁺,Dy³⁺ phosphor shows fairly good resistance to thermal quenching behavior, of which the emission intensity at 423 K can maintain 90.3% of the initial value (298 K). These results suggest that the Na₃Sc₂(PO₄)₃:0.01Eu²⁺,xDy³⁺ phosphors have potential applications as the color-tunable or a single-phase white emitting phosphor in white LEDs.     

Synthesis of Long Afterglow Phosphors Doped B SrAl2O4:Eu2+, Dy3+ and Its Luminescent Properties

The long afterglow luminescent material SrAl₂O₄: Eu²⁺, Dy³⁺ was prepared by high temperature solid-state method. Effects of doped B on the luminescent properties of phosphors SrAl₂O₄: Eu²⁺, Dy³⁺ were investigated by means of excitation spectra, emission spectra and X-ray diffraction analysis. As the result, the addition of H₃BO₃ as flux promotes the growth of crystalline and reduces the synthesizing temperature, but the wavelength of emission peak of photoluminescent material did not change with the variation of H₃BO₃ content. The effect of Dy³⁺ concentration on the luminescent properties of material was investigated. It was found that the luminescence of phosphors prepared under the condition of the amount of H₃BO₃ 5% and the mole ratio of Eu/Dy = 1/7(Eu = 0.02 mole) had better luminescent property and longer afterglow time.     

Preparation and characterization of flower-like SrAIeO4：Eu^2＋,Dy^3＋ phosphors by sol-gel process

A flower-like Eu²⁺ and Dy³⁺ co-doped SrAl₂O₄ long-lasting phosphorescent (LLP) phosphor was synthesized via the inorganic- salt-based sol-gel method. The crystal structure, morphology and optical properties of the composite were characterized. X-ray diffraction diffusion (XRD) data and DSC-TG curves of the phosphor revealed that the SrAl₂O₄ crystallites have been formed after the precursor was calcined at 900 °C and to be single-phase SrAl₂O₄ at 1100 °C. The SEM photographs indicated that the sample exhibited a universal flower-like morphology with crystallite size of about 1-2 μm. After being irradiated with ultraviolet (UV) light, the flower-like phosphor emitted long-lasting green phosphorescence with an excitation peak at 365 nm and emission peak at 500 nm which was ascribed to the characteristic 5d-4f transition of Eu²⁺. Both the PL spectra and the luminance decay curve revealed that this phosphor exhibited efficient luminescence and long lasting properties.     

Preparation and properties of rare earth luminous fiber containing red organic fluorescent pigment

Rare earth luminous fiber was prepared by method of melt spinning. X-ray diffraction （XRD）, scanning electron micros-copy （SEM）, and fluorescence spectrophotometer as well as afterglow brightness tester were used to characterize the resulting sam-ples. Results from XRD and SEM demonstrated that the phase of SrA12O4：Eu2＋,Dy3＋in the fiber was not destroyed in the manufac-turing process and the as-formed luminous fiber consisted of irregular particles. Under ultraviolet excitation, the luminous fiber exhib-ited a yellow-green and orange-red emission band with a maximum at 520 nm and around 600 nm originating from SrAl2O4：Eu2＋, Dy3＋and red organic fluorescent pigments. The energy transfer process was further studied. Furthermore, the emission colors of lu-minous fibers could be tuned from yellow-green to orange-red easily by doping red organic fluorescent pigment, making the materials have potential application in many areas.     

A single-phase full-color phosphor Sr2Ca2La(PO4)3O:Eu2+,Tb3+,Mn2+: Photoluminescence and energy transfer

A single-phase full-color emitting phosphor Sr₂Ca₂La(PO₄)₃O:Eu²⁺,Tb³⁺,Mn²⁺ was synthesized by the high temperature solid-state method. The phase formation, luminescence properties, thermal stability, and energy transfer from Eu²⁺ to Tb³⁺ and Eu²⁺ to Mn²⁺ in Sr₂Ca₂La(PO₄)₃O were investigated in details. Tunable emission color from blue to blueish green or orange can be observed under 365 nm near-ultraviolet excitation based on the energy transfer from Eu²⁺ to Tb³⁺ or Mn²⁺ ions by varying the ratio of Eu²⁺/Tb³⁺ or Eu²⁺/Mn²⁺ ions. White light was obtained with chromaticity coordinates of (0.3558, 0.3500) in the Sr₂Ca₂La(PO₄)₃O:0.04Eu²⁺,0.08Tb³⁺,0.40Mn²⁺ phosphor, suggesting their potential applications in white light emitting diodes.     

Eu2＋ and Dy3＋ codoped （Ca,Sr）7（SiO3）6Cl2 highly efficient yellow phosphor

Eu2+ and Dy3+ codoped(Ca,Sr)7(SiO3)6Cl2 yellow phosphors were successfully synthesized by self-flux method. The structure, morphology and photoluminescence properties were investigated by X-ray diffraction(XRD), scanning electron microscopy(SEM) and photoluminescence spectra. The as-prepared phosphor showed a broad emission spectrum centered at 550 nm for Eu2+single-doped phosphor, while located at 548–544 nm for the Eu2+, Dy3+ codoped samples under excitation at 380 nm light. The emission intensity was greatly improved when Dy3+ was doped into the(Ca,Sr)7(SiO3)6Cl2:Eu2+ system. The composition-optimized sample with 3 mol.% of Dy3+ and constant 10 mol.% of Eu2+ exhibited a 220% PL enhancement compared to the phosphor with 10 mol.% Eu2+ single-doped. Meanwhile, it was found that the quantum efficiency of phosphor namely(Ca,Sr)7(SiO3)6Cl2:3 mol.% Dy3+, 10 mol.% Eu2+ could get up to 24.6%. The synthesized yellow-emitting(Ca,Sr)7(SiO3)6Cl2:Dy3+,Eu2+ is a promising candidate as high-efficiency yellow phosphor for NUV-excited white LEDs.     

Luminescent ionic lattice occupation and wide tunable emission spectra of La2MgZrO6:Bi3+,Eu3+ double perovskite phosphors for white light LED

La₂Mg_1-x/2Zr_1-x/2O₆:xBi³⁺(x=0.01-0.035,abbreviated as LMZ:Bi³⁺) and La_2-yMg_0.99Zr_0.99O₆:0.02Bi³⁺,yEu³⁺(y=0.1-0.11,abbreviated as LMZ:Bi³⁺,Eu³⁺) double-perovskite phosphors were prepared through high-temperature solid-phase method.The emission spectrum of LMZ:xBi³⁺(x=0.01-0.035)phosphors excited at 353 nm is asymmetric in the range be...     

Ln3+ (Ln = Eu,Dy) - doped Sr2CeO4 fine phosphor particles: Wet chemical preparation,energy transfer and tunable luminescence

The Sr₂CeO₄:Ln³⁺ (Ln = Eu, Dy) fine phosphor particles were prepared by a facile wet chemical approach, in which the consecutive hydrothermal-combustion reaction was performed. The doping of Ln³⁺ into Sr₂CeO₄ has little influence on the structure of host, and the as-prepared samples display well-crystallized spherical or elliptical shape with an average particle size at about 100–200 nm. For Eu³⁺ ions-doped Sr₂CeO₄, with the increase of Eu³⁺-doping concentration, the blue light emission band with the maximum at 468 nm originating from a Ce⁴⁺ → O²⁻ charge transfer of the host decreases obviously and the characteristic red light emission of Eu³⁺ (⁵D₀→⁷F₂ transition at 618 nm) is enhanced gradually. Simultaneously, the fluorescent lifetime of the broadband emission of Sr₂CeO₄ decreases with the doping of Eu³⁺, indicating an efficient energy transfer from the host to the doping Eu³⁺ ions. The energy transfer efficiency from the host to Eu³⁺ was investigated in detail, and the emitting color of Sr₂CeO₄:Eu³⁺ can be easily tuned from blue to red by varying the doping concentration of Eu³⁺ ions. Moreover, the luminescence of Dy³⁺-doped Sr₂CeO₄ was also studied. Similar energy transfer phenomenon can be observed, and the incorporation of Dy³⁺ into Sr₂CeO₄ host leads to the characteristic emission of ⁴F_9/2 → ⁶H_15/2 (488 nm, blue light) and ⁴F_9/2 → ⁶H_13/2 (574 nm, yellow light) of Dy³⁺. The Sr₂CeO₄:Ln³⁺ fine particles with tunable luminescence are quite beneficial for its potential applications in the optoelectronic fields.     

Plasmon-enhanced broad-band quantum-cutting of NaBaPO4:Eu2+,Er3+ phosphors with silver nano-particles

NaBaPO₄:Eu²⁺,Er³⁺ phosphors and Ag nano-particles (NPs) were prepared by the solid-state reaction and chemical reduction method, respectively. The fluorescence spectra and decay curves demonstrate the effective energy transfer from Eu²⁺ to Er³⁺ and the existence of three-photon quantum-cutting through two-step cross-relaxation of Er³⁺. The quantum-cutting emission is peaked at 1534 nm with a broad excitation band centered at 352 nm. Plasmon-enhanced quantum-cutting of NaBaPO₄:Eu²⁺,Er³⁺ phosphors was realized by decorating Ag NPs. The largest enhancement factor is 1.395. It is hopeful to improve the photovoltaic conversion efficiency of Ge solar cells by using this phosphor.     

Synthesis and characterization of needle-like BaAleO4：Eu,Dy phosphor via hydrothermal-homogeneous precipitation method

A needle-like Eu2+ and Dy3+ co-doped BaAl2O4 long-lasting phosphor was synthesized via a hydrothermal-homogeneous precipitation method assisted by cetyl trimethyl ammonium bromide(CTAB) as a template.The crystal structure,morphology and optical properties of the composites were characterized.XRD results showed that the single-phase BaAl2O4 was formed at 900 ℃ in an active carbon atmosphere,which was much lower than that prepared by traditional solid-state reaction method.Scanning electron microscopy(SEM) and transmission electron microscopy(TEM) observation revealed that the precursor had well-dispersed distribution and showed needle-like morphology with the average diameter of about 100 nm and the length up to 1 μm.The final product,BaAl2O4:Eu2+,Dy3+ phosphor,inherited the needle-like shape from precursor via adding the surfactant CTAB.After irradiation by ultraviolet radiation with 355 nm for 5 min,the phosphors emitted bluish green color long-lasting phosphorescence corresponding to the typical emission of Eu2+ ion.Both the photoluminescence spectra and luminance decay revealed that the phosphor had efficient luminescent and long-lasting properties.     

Luminescence properties of composite material Sr2MgSi2O7:Eu2+,Dy3+/light conversion agent with multilayer structure

In order to improve the red luminescent properties,Sr₂ MgSi₂ O₇:Eu²⁺,Dy³⁺was selected as a blue persistent luminescent donor phosphor,while light conversion agent was utilized to tune the persistent luminescent spectra from blue to red.Composite red luminescent material Sr₂ MgSi₂ O₇:Eu²⁺,Dy³⁺/light conversion agent(SMED/LCA) was fabricated with light conversion agent and Sr₂ M...     

Physicochemical properties of Li3Ba2La3(MoO4)8:Eu,Tb red-emitting phosphor for solid state white lamps

In this work,combustion synthesis was used for the first time to fabricate a phosphor material with red emission for applications in solid-state white-light lamps.We synthesized a material with emission wavelength at λ_em=617 nm,excited under long UV-blue wavelength based on Eu³⁺,Tb³⁺-activated molybdates Li₃Ba₂(La_1-x-yEu_xTb_y)₃(MoO₄)₈ with 0 ≤ x ≤1 and 0 ≤ y ≤ 1.A series of pow...     

Synthesis and optical characterization of Eu2+,Tb3+-codoped Sr3Y(PO4)3 green phosphors

A series of Eu~(2+),Tb~(3+)-codoped Sr_3 Y(PO_4)_3(SYP) green phosphors were synthesized by hightemperature solid-state reaction. Several techniques, such as X-ray diffraction, UV-vis spectrum,and photoluminescence spectrum, were used to investigate the obtained phosphors. The present study investigates in detail photoluminescence excitation and emission properties, energy transfer between the two dopants, and effects of doping ions on optical band gap. SYP:0.05 Eu2+ phosphor shows an intense and broad excitation band ranging from 220 to 400 nm and exhibits a bright green emission band with CIE chromaticity coordinates(0.189, 0.359) under 350 nm excitation. Green emission of SYP:0.03 Tb3+ is intensified by codoping with Eu~(2+), and energy transfer mechanism between them is demonstrated to be a dipole-dipole interaction. Upon 350 nm excitation, SYP:Eu~(2+),Tb~(3+) phosphors exhibits two dominating bands peaking at 466 and 545 nm, which are assigned to 4 f~65 d~1→4 f~7 transition of Eu~(2+) ions and ~5 D_4→~7 F_5 transition of Tb~(3+) ions, respectively. Optimal doping concentrations of Eu~(2+) and Tb~(3+) in the SYP host are 5 mol% and 15 mol%, respectively. Results indicate that SYP:Eu~(2+),Tb~(3+) phosphors are potentially used as green-emitting phosphors for white light-emitting diodes.     

Synthesis and luminescence characteristics of Li2Y4-xEux（WO4）7-y（MoO4）y red-emitting phosphor for white LED

Li2Y4-xEux（WO4）7-y（MoO4）y red-emitting phosphors were synthesized by solid state reaction and characterized by powder X-ray diffraction （XRD） and photoluminescence （PL） spectrum. The excitation spectra showed that the phosphors could be efficiently excited by near-UV light of 395 nm. When the relative molar ratio of Mo/W was 7：0, and the optimum doped concentration of Eu3＋was 2.8 mol, the phosphor showed strong red emission lines at 615 nm corresponding to the forced electric dipole 5D0→7F2 transition of Eu3＋. Compared with Na2Y2Eu2（MoO4）7 and K2Y2Eu2（MoO4）7, the fluorescence intensity of Li2Y1.2Eu2.8（MoO4）7 phosphor was the strongest. The CIE chromaticity coordinates of Li2Y1.2Eu2.8（MoO4）7 phosphor was calculated to be （0.66, 0.34）.     

Energy transfer,superior thermal stability and multi-color emitting properties of langbeinite-type solid-solution phosphor K_2Dy_(1.5-x)Eu_xTa_(0.5)(PO_4)_3

Langbeinite type compounds are a large kind of oxometallate with good flexibility structure.Herein,we synthesized a new langbeinite type compound K_2 Dy_(1.5)Ta_(0.5)(PO_4)_3,in which the Dy~(3+) and Ta~(5+) were blended to occupy the same crystallographic sites.Simultaneously,solid solutions of K_2 Dy_(1.5)_(-x)Eu_xTa_(0.5)(PO_4)_3(x=0-1.5) were prepared and their photoluminescence properties were investigated.Due to energy transfer from Dy~(3+) to Eu~(3+),both Dy~(3+) and Eu~(3+) characteristic emissions are observed under 393 nm light excitation.The emitting color of K_2 Dy_(1.5-x)Eu_xTa_(0.5)(PO_4)_3 turns from green through yellow to red by simply adjusting the Eu~(3+) concentration from 0 to 0.4.Moreover,K_2 Dy_(1.48)Eu_(0.02)Ta_(0.5)(PO_4)_3 phosphor possesses excellent fluorescence thermal stability and exhibits zero thermal quenching at 150 ℃.These results manifest that K_2 Dy_(1.5-x)Eu_xTa_(0.5)(PO_4)_3 solutions are promising multi-color emitting phosphors candidate for near-UV LED.     

Tunable luminescence in co-doped Zn3Al2Ge2O10:Cr3+ by controlling crystal field splitting and nephelauxetic effect

Ce³⁺/Dy³⁺/Tb³⁺/Eu³⁺/Mn²⁺ and Cr³⁺ ions co-doped Zn₃Al₂Ge₂O₁₀ phosphor were prepared by a high-temperature solid-state method. X-ray diffraction patterns prove the cubic phase structure of prepared Zn₃Al₂Ge₂O₁₀ phosphor. Emission, excitation spectra and decay curves confirm the tunable luminescence. Different degrees of the decrease of emission FWHM in Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,RE (RE = Ce³⁺, Dy³⁺, Tb³⁺, Eu³⁺) and Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Mn²⁺ are observed. The reason of variable FWHM is the effect of crystal field splitting and nephelauxetic effect, and the nephelauxetic effect is dominant. Therefore, the emission FWHM decreases with the increasing concentration of Mn²⁺/Tb³⁺/Eu³⁺ in Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺, and for Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Ce³⁺ and Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Dy³⁺, it is a constant. The variation of Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Tb³⁺ is more obvious than that of Zn₃Al₂Ge₂O₁₀:0.02Cr³⁺,Eu³⁺, because Tb³⁺ ion has smaller electronegativity. Thus, the tunable luminescence of Cr³⁺ can be realized by co-doping different ions. And these phosphors have potential applications in light-emitting diodes for plant growth.     

Site occupation and energy transfer in full color emitting phosphor Ba2Ca(BO3)2:Ce3+(K+),Eu2+,Mn2+

White light-emitting diodes (WLEDs) fabricated by single-phase full color emitting phosphor are an emerging solution for health lighting. The crystallographic site occupation of activators in a proper host lattice is crucial for sophisticated design of such phosphor. Here, we report a high quality white light-emitting phosphor Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ with spectral distribution covering whole visible region. Blue light emission originates from Ce³⁺ ions occupying preferentially Ba²⁺ site by controlling synthesis conditions. Green and red lights are obtained from Eu²⁺ occupying Ba²⁺ (and Ca²⁺) site and Mn²⁺ occupying Ca²⁺ site, respectively. In this triple-doped phosphor, strong red emission with a low concentration of Mn²⁺ is realized by the efficient energy transfer from Ce³⁺ and Eu²⁺ to Mn²⁺. Furthermore, high quality white light is accomplished by properly tuning the relative doping amount of Ce³⁺(K⁺)/Eu²⁺/Mn²⁺ based on efficient simultaneous energy transfer. The results indicate that Ba₂Ca(BO₃)₂:Ce³⁺(K⁺),Eu²⁺,Mn²⁺ is a promising white light-emitting phosphor in WLEDs application.     

Investigation on luminescence properties of Ln^3＋ doped Sr3EuMgSi2O8 （Ln=Dy, Er, Ho）

The luminescent properties of Sr2.97MgSi2O8:Eu2+0.01 phosphors were investigated with different Ln3+0.02(Ln3+:Dy3+,Er3+,Ho3+) co-dopants. The co-dopants had no influence on both the structure of the lattice and the position of the emission peak. However, the afterglow properties of samples were enhanced with different co-dopants. The afterglow duration of the Dy3+ co-doped sample was longer than that of the others. Furthermore, the co-doping samples had stronger thermoluminescence (TL) intensity and therefore longer afterglow duration. At last, the self-reduction of Eu3+→Eu2+ was observed in an silicate compound of Sr3-xMgSi2O8:xEu phosphor in air condition. This is the first time to show a blue long afterglow phosphor synthesized avoiding reducing atmosphere.