Correlation of photoluminescence of (Y, Ln)VO4:Eu (Ln=Gd and La) phosphors with their crystal structures

We have studied the photoluminescence (PL) of (Y, Ln)VO₄:Eu³⁺ (Ln=La and Gd) phosphors and the correlation of the PL of those phosphor with their crystal structure. It is found that (Y, Gd)VO₄:Eu³⁺ phosphors have the same crystal structure as YVO₄:Eu³⁺, which is tetragonal with a little different lattice parameters. In the case of (Y, La)VO₄:Eu³⁺ phosphors, however, the gradual change from tetragonal to monoclinic structure of host lattice was observed as the amount of La ion increased. To investigate the PL property of (Y, Ln)VO₄:Eu³⁺ (Ln=La and Gd) phosphors, vacuum ultraviolet (VUV) and ultraviolet (UV) excitation were used. The favorable crystal structure for the PL intensity of orthovanadate phosphor under 147 and 254 nm excitation was tetragonal containing Gd ion and under 365 nm excitation was monoclinic containing La ion which might have the lowest site symmetry for Eu³⁺ ion.     

Probing of surface Eu ions present in ZnO:Eu nanoparticles by covering ZnO:Eu core with Y2O3 shell: Luminescence study

Eu³⁺ doped ZnO nanoparticles are known to have significance extent of surface Eu³⁺ ions due to a large difference in ionic radii. Effect of such Eu³⁺ ions on the luminescence properties of ZnO:Eu nanoparticles has been understood from the luminescence studies of ZnO:Eu nanoparticles covered with Y₂O₃ shell. Based on the asymmetric ratio of luminescence and extent of energy transfer, it is established that when ZnO:Eu nanoparticles are covered with Y₂O₃ shell, a part of Eu³⁺ ions present with ZnO:Eu core migrate to Y₂O₃ shell and occupy Y³⁺ lattice positions.     

Effect of Sr substitution on photoluminescent properties of BaAl2O4:Eu, Dy

Phosphor material BaAl₂O₄:Eu²⁺, Dy³⁺ with varying compositions of Sr substitution were prepared by the solid-state synthesis method. The phosphor compositions were characterized for their phase and crystallinity by XRD, SEM and TEM. Photoluminescence (PL) properties were investigated measuring PL and decay time for varying Ba/Sr compositions. The PL results show the blue shift in the luminescence properties in Sr substituted BaAl₂O₄:Eu²⁺, Dy³⁺ compared to parent BaAl₂O₄:Eu²⁺, Dy³⁺. It is probably due to the influence of 5d electron states of Eu²⁺ in the crystal field because of atomic size variation causing crystal defects. Dy³⁺ ion doping in the phosphor generates deep traps, which results in long afterglow phosphorescence.     

Optical properties of (ZnO)0.5(P2O5)0.5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Binary (ZnO)_0.5(P₂O₅)_0.5 glasses doped with Eu₂O₃ and nanoparticles of Gd₂O₃:Eu were prepared by conventional melt-quench method and their luminescence properties were compared. Undoped (ZnO)_0.5(P₂O₅)_0.5 glass is characterized by a luminescent defect centre (similar to L-centre present in Na₂O-SiO₂ glasses) with emission around 324 nm and having an excited state lifetime of 18 ns. Such defect centres can transfer the energy to Eu³⁺ ions leading to improved Eu³⁺ luminescence from such glasses. Based on the decay curves corresponding to the ⁵D₀ level of Eu³⁺ ions in both Gd₂O₃:Eu nanoparticles incorporated as well as Eu₂O₃ incorporated glasses, a significant clustering of Eu³⁺ ions taking place with the latter sample is confirmed. From the lifetime studies of the excited state of L-centre emission from (ZnO)_0.5(P₂O₅)_0.5 glass doped with Gd₂O₃:Eu nanoparticles, it is established that there exists weak energy transfer from L-centres to Eu³⁺ ions. Poor energy transfer from the defect centres to Eu³⁺ ions in Gd₂O₃:Eu nanoparticles doped (ZnO)_0.5(P₂O₅)_0.5 glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between luminescent centre and Eu³⁺ ions.     

Photoluminescence and gamma-ray irradiation of SrAl2O4:Euand Y2O3:Eu phosphors

Y₂O₃:Eu³⁺ phosphor is a very attractive material for use as a red phosphor in many fields. SrAl₂O₄:Eu²⁺ belongs to long lasting phosphor (LLP) and it is a useful bluish-green luminescence material, which can also be a promising candidate as a simple and easy-to-use radiation detection element for visual display of two dimensional radiation distributions. In the present study, both these two kinds of phosphors were synthesized using high temperature solid state reactions. In our work, the influence of gamma-ray irradiation on the properties of these two kinds of phosphors was studied by comparing photoluminescence, brightness and the decay curve of unirradiated and gamma-ray-irradiated samples. Conclusions from the present work can be briefly summarized as follows. In irradiated samples, the brightness is decreased without sensible change in the wavelength distribution of the luminescence spectrum and in the decay kinetic upon gamma exposure. Moreover, the emission due to Eu³⁺→Eu²⁺ conversion in Y₂O₃:Eu³⁺ phosphors was not observed in our sample after irradiation to high exposure. Also the brightness of SrAl₂O₄:Eu²⁺ phosphor turned out to decrease after the exposition to ionizing radiation while the luminescence wavelength distribution remained unchanged. The reason for the effect of gamma-ray irradiation on the properties of phosphors is also discussed in the paper.     

Novel red phosphors for solid state lighting; the system BixLn1−xVO4; Eu/Sm (Ln=Y, Gd)

Solid solutions of vanadates of formula Bi_xLn_1−xVO₄ (Ln=Y, Gd) doped with Eu³⁺ or Sm³⁺ ions have been synthesized by solid-state reactions. Intense red/orange-red luminescence is obtained in these samples on excitation in the broad charge-transfer band in the near UV. The excitation in the Eu³⁺ levels leads to much less intense red emission. These materials could find applications as red phosphors for solid-state white lighting devices utilizing GaN-based excitation in the near UV.     

An efficient co-doping of Eu and Er in CaAl2O4 aluminate phosphor

CaAl₂O₄:Eu²⁺ co-doped with varying concentrations of Er³⁺ was prepared by solid-state reaction method. Prepared materials with 1 mol% Eu²⁺ and 2-10 mol% of Er³⁺ were investigated for their photoluminescence properties. Phase, morphology and crystalline structure were investigated by powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Broad band UV-excited luminescence was observed for CaAl₂O₄:Eu²⁺, Er³⁺ in the blue region (λ_max=440 nm) due to transitions from 4f⁶5d¹ to the 4f⁷ configuration of the Eu²⁺ ion. The Er³⁺ ion co-doping generates deep traps, which results in longer decay time for phosphorescence.     

VUV excited luminescence of MGdF4:Eu (M=Na, K, NH4)

Eu³⁺-doped NaGdF₄, KGdF₄ and NH₄GdF₄ phosphors with little oxygen contamination have been synthesized by hydrothermal technique. The emission spectra show that the doped Eu³⁺ ions are located in noncentrosymmetric sites in the three compounds. The two-photon emission has been observed in NaGdF₄:Eu³⁺ and KGdF₄:Eu³⁺ compounds under VUV excitation from the ground states to higher ⁶G_J excited states of Gd³⁺ ions, while in Eu³⁺-doped NH₄GdF₄, emissions from ⁵D_1,2,3 excited states of Eu³⁺ cannot be detected in the luminescence spectra.     

Luminescent properties of (Y,Gd)BO3:Bi,RE (RE=Eu, Tb) phosphor under VUV/UV excitation

Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors were prepared and their luminescent properties under vacuum ultraviolet (VUV)/UV excitation were investigated. Strong red emission for (Y,Gd)BO₃:Bi³⁺,Eu³⁺ and strong green emission for (Y,Gd)BO₃:Bi³⁺,Tb³⁺ are observed under VUV excitation from 147 to 200 nm with a much broader excitation region than that of single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃ phosphor. Strong emissions are also observed under UV excitation around 265 nm where as nearly no luminescence is observed for single Eu³⁺-doped or Tb³⁺-doped (Y,Gd)BO₃. The luminescence enhancement of Bi³⁺- and RE³⁺-co-doped (Y,Gd)BO₃ phosphors is due to energy transfer from Bi³⁺ ion to Eu³⁺ or Tb³⁺ ion not only in the VUV region but also in the UV region. Besides, host sensitization competition between Bi³⁺ and Eu³⁺ or Tb³⁺ is also observed. The investigated phosphors may be preferable for devices with a VUV light 147-200 nm as an excitation source such as PDP or mercury-free fluorescent lamp.     

Concentration quenching of Eu in SrO·Al2O3:Eu phosphor

The luminescence of Eu²⁺ in alkaline earth aluminates of the type SrO·Al₂O₃ has been studied. In SrO·Al₂O₃:Eu²⁺ phosphor, green Eu²⁺ luminescence is observed from Eu²⁺ on the two different strontium sites present in the lattice. Their concentration quenching processes of the two inequivalent Eu²⁺ ions are investigated, respectively, and the corresponding concentration quenching mechanism is verified as dipole-dipole interaction. The value of the critical transfer distance is calculated.     

On the luminescence of bismuth aluminate (Bi2Al4O9)

The luminescence of Eu³⁺ and Tb³⁺ in Bi₂Al₄O₉ is reported. It is shown that the Bi³⁺ excitation energy does not migrate through the lattice. The Cr³⁺ ion shows 704.5 nm line emission in this host lattice.     

Synthesis, structure and luminescence properties of Y(V,P)O4:Eu,Bi phosphors

YVO₄:Eu³⁺-based red-emitting phosphors with the compositions of Y_0.95−xVO₄:0.05Eu³⁺,xBi³⁺ (x=0.01, 0.03, 0.05, 0.07 and 0.09) and Y_0.90(V_1−zP_z)O₄:0.05Eu³⁺,0.05Bi³⁺ (z=0, 0.1, 0.3, 0.5, 0.7, 0.9 and 1.0) were synthesized by the high temperature solid-state method. The as-prepared phosphors have the similar tetragonal phase structure and their morphologies varied with the relative content ratio of V to P. The photoluminescence spectra for the as-synthesized phosphors show that a dominant red emission line at around 619 nm, which is due to the Eu³⁺ electric dipole transition of ⁵D₀-⁷F₂, is observed under different excitation wavelengths (254 and 365 nm). Further, the emission intensities of ⁵D₀-⁷F₂ transition upon 365 nm excitation increase sharply owing to the Bi³⁺ doping. Energy transfer process, luminescent lifetime and quantum efficiency for the selected Y_0.90(V_1−yP_y)O₄:0.05Eu³⁺,xBi³⁺phosphors were also studied in detail.     

Spherical shape with fast decaying property of solvothermally grown (Y,Gd)BO3:Eu nanophosphor

Monodispersed spherical (Y,Gd)BO₃:Eu³⁺ phosphors have been fabricated by a solvothermal method. Each particle is composed of crystalline hexagonal phase primary nanoparticles (∼10 nm in diameter), leading to an abnormal energy-dependent decay behavior, as compared to a micron scale phosphor prepared by the conventional solid-state reaction method. The faster luminescence decay excited under a specific wavelength region making the resultant phosphor suitable for the up-coming display devices, such as 3-dimensional (3D) imaging.     

Luminescence studies on ZnO-P2O5 glasses doped with Gd2O3:Eu nanoparticles and Eu2O3

Zinc phosphate glasses doped with Gd₂O₃:Eu nanoparticles and Eu₂O₃ were prepared by conventional melt-quench method and characterized for their luminescence properties. Binary ZnO-P₂O₅ glass is characterized by an intrinsic defect centre emission around 324 nm. Strong energy transfer from these defect centres to Eu³⁺ ions has been observed when Eu₂O₃ is incorporated in ZnO-P₂O₅ glasses. Lack of energy transfer from these defect centres to Eu³⁺ in Gd₂O₃:Eu nanoparticles doped ZnO-P₂O₅ glass has been attributed to effective shielding of Eu³⁺ ions from the luminescence centre by Gd-O-P type of linkages, leading to an increased distance between the luminescent centre and Eu³⁺ ions. Both doped and undoped glasses have the same glass transition temperature, suggesting that the phosphate network is not significantly affected by the Gd₂O₃:Eu nanoparticles or Eu₂O₃ incorporation.     

New red phosphors BaZr(BO3)2 and SrAl2B2O7 doped with Eu for PDP applications

Vacuum ultraviolet (VUV) excitation and photoluminescence (PL) characteristics of Eu³⁺ ion doped borate phosphors; BaZr(BO₃)₂:Eu³⁺ and SrAl₂B₂O₇:Eu³⁺ are studied. The excitation spectra show strong absorption in the VUV region with the absorption band edge at ca. 200 nm for BaZr(BO₃)₂:Eu³⁺ and 183 nm for SrAl₂B₂O₇:Eu³⁺, respectively, which ensures the efficient absorption of the Xe plasma emission lines. In BaZr(BO₃)₂:Eu³⁺, the charge transfer band of Eu³⁺ does not appear strongly in the excitation spectrum, which can be enhanced by co-doping Al³⁺ ion into the BaZr(BO₃)₂ lattices. The luminescence intensity of BaZr(BO₃)₂:Eu³⁺ is also increased by Al³⁺ incorporation into the lattices. The PL spectra show the strongest emission at 615 nm corresponding to the electric dipole ⁵D₀→⁷F₂ transition of Eu³⁺ in both BaZr(BO₃)₂ and SrAl₂B₂O₇, similar to that in YAl₃(BO₃)₄, which results in a good color purity for display applications.     

The temperature‐sensitive luminescence of (Y,Gd)VO4:Bi3+,Eu3+ and its application for stealth anti‐counterfeiting

Anti‐counterfeiting technologies are desired to protect products far away from the violation of dummy, fake and shoddy goods. The phosphor of (Y,Gd)VO₄:Bi³⁺,Eu³⁺ was synthesized for the application of this purpose. Its photoluminescence was investigated by exciting with different wavelengths at variant temperatures. Wide emission color ranged from green through yellow to orange was tuned up by tailor‐ing Bi³⁺ and Eu³⁺ concentrations. The temperature dependent luminescence and wavelength selective excitation of (Y,Gd)VO₄:Bi³⁺,Eu³⁺ were observed, which provide different encryptions in anti‐counterfeiting. To verify the feasibility in application, two anti‐counterfeiting patterns were fabricated practically and excellent performance was obtained. Moreover, the physical mechanisms for the different phenomena of luminescence were elucidated from excitation spectra combining with the configuration coordinate model. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The luminescent properties of CaYBO4:Ln(Ln=Eu, Tb) under UV-VUV range

The luminescent properties of CaYBO₄:Ln(Ln=Eu³⁺, Tb³⁺) were investigated under ultraviolet (UV) and vacuum ultraviolet (VUV) region. The CT band of Eu³⁺ at about 245 nm blue-shifted to 230 nm in VUV excitation spectrum; the band with the maximum at 183 nm was considered as the host lattice absorption. For the sample of CaYBO₄:0.08Tb³⁺, the bands at about 235 and 263 nm were assigned to the f-d transitions of Tb³⁺ and the CT band of Tb³⁺ was calculated according to Jφrgensen's theory. Under UV and VUV excitation, the main emission of Eu³⁺ corresponding to the ⁵D₀-⁷F₂ transition located at about 610 nm and two intense emission of Tb³⁺ from the ⁵D₄-⁷F₅ transition had been observed at about 542 and 552 nm, respectively. With the incorporation of Gd³⁺ into the host lattice of CaYBO₄, the luminescence of Tb³⁺ was enhanced while that of Eu³⁺ was decreased because of their different excitation mechanism.     

Self-assembled CaMoO4 and CaMoO4:Eu hierarchical superstructures: Facile sonochemical route synthesis and tunable luminescent properties

Tetragonal CaMoO₄ and CaMoO₄:Eu³⁺ with various novel three-dimensional (3D) hierarchical architectures were successfully synthesized via a facile, efficient sonochemistry process in the absence of any surfactant or template. XRD, EDS, FE-SEM, and photoluminescence (PL) were employed to characterize the as-obtained products. It was found that morphology modulation could be easily realized by changing pH value of the precursor. The pH value of the precursor not only affected the substructures of the hierarchical structures, but also determined the size distributions of the final products. The formation mechanism for different hierarchical architectures was proposed on the basis of time-dependent experiments. The luminescence spectra showed that CaMoO₄:Eu³⁺ phosphors can be effectively excited by the near ultraviolet (UV) (396 nm) and blue (466 nm) light, and exhibited strong red emission around 615 nm, which was attributed to the Eu³⁺⁵D₀→⁷F₂ transition. Compared with Y₂O₃:Eu³⁺ phosphor, CaMoO₄:Eu³⁺ is much more stable, efficient and suitable, therefore, this phosphors could be a promising red component for possible applications in the field of LEDs.     

Preparation and optical properties of Ag enwrapped Y2O3:Eu nanoparticles in solution and in powders

Ag enwrapped Y₂O₃:Eu³⁺ nanoparticles were prepared by a wet chemistry method, which was dispersed in liquid (glycol) or dried to powders. Their luminescence properties were studied in comparison to those in the un-enwrapped ones. The results demonstrated that in glycol the ⁵D₀-⁷F₂ transitions for Ag enwrapped Y₂O₃:Eu³⁺ nanoparticles became stronger than that for un-enwrapped ones, while the excitation charge transfer band shifted blue. On the contrary, the ⁵D₀-⁷F₂ transitions in Ag enwrapped Y₂O₃:Eu³⁺ powders became weaker than those in the un-enwrapped ones. It was suggested that in liquid the Ag shells thinly deposited in the surface of Y₂O₃:Eu³⁺ and insulated the Y₂O₃:Eu³⁺ from the liquid, which contained large organic vibration modes. As a result, the surface nonradiative energy transfer from Eu³⁺ to the organic modes decreased, and emission intensity of ⁵D₀-⁷F₂ increased. In the Y₂O₃:Eu³⁺ powders, the Ag shells absorbed the excitation light, leading to the decrease in excitation density and the intensity of ⁵D₀-⁷F₂.     

A novel blue-emitting long-lasting proyphosphate phosphor Sr2P2O7:Eu,Y

By introducing the Y³⁺ into Sr₂P₂O₇:Eu²⁺, we successfully prepared a kind of new phosphor with blue long-lasting phosphorescence by the high-temperature solid-state reaction method. In this paper, the properties of Sr₂P₂O₇:Eu²⁺,Y³⁺ were investigated utilizing XRD, photoluminescence, luminescence decay, long-lasting phosphorescence and thermoluminescence (TL) spectra. The phosphor emitted blue light that was related to the 4f⁶5d¹-⁸S_7/2 transition of Eu²⁺. The bright blue phosphorescence could be observed by naked eyes even 8 h after the excitation source was removed. Two TL peaks at 317 and 378 K related to two types of defects appeared in the TL spectrum. By analyzing the TL curve the depths of traps were calculated to be 0.61 and 0.66 eV. Also, the mechanism of LLP was discussed in this report.