Energy transfer between Sm and Er in orthophosphate YPO4

The energy transfer between Sm³⁺ and Er³⁺ ions in yttrium orthophosphate is studied. This choice of ions is based on the possibility of quantum cutting processes and the host material is selected according to the position of the 5d bands of the Sm³⁺ ion. The Sm³⁺ and Er³⁺ doped and Sm³⁺, Er³⁺ co-doped YPO₄ have been synthesized. Spectroscopic studies were done in the ultraviolet and vacuum ultraviolet ranges. The energy transfer between Sm³⁺ and Er³⁺ is very efficient but it does not lead to Er³⁺ visible emission. Whatever the excitation wavelength, the emission of co-doped samples mainly occurs in the infrared range.     

Luminescence spectroscopy of Eu in Ca3Sc2Si3O12

Ca₃Sc₂Si₃O₁₂ doped with 1 mol% Eu³⁺ and having a cubic garnet structure was prepared by a solid state reaction. The low temperature luminescence spectrum shows no measurable ⁵D₀→⁷F₀ band, in agreement with the location of the lanthanide dopant in a site of D₂ symmetry, i.e. with a Ca²⁺ substitution. On the other hand, the spectrum is clearly dominated by the ⁵D₀→⁷F₄ band, which is significantly stronger than that for the other transitions originating from the ⁵D₀ level. This unusual behavior is explained on the basis of a model describing the distortion of the EuO₈ coordination polyhedron from a cubic geometry to the actual D₂ one.     

Energy transfer in Y3Al5O12:Ce, Pr and CaMoO4:Sm, Eu phosphors

Non-radiative energy transfers (ET) from Ce³⁺ to Pr³⁺ in Y₃Al₅O₁₂:Ce³⁺, Pr³⁺ and from Sm³⁺ to Eu³⁺ in CaMoO₄:Sm³⁺, Eu³⁺ are studied based on photoluminescence spectroscopy and fluorescence decay patterns. The result indicates an electric dipole-dipole interaction that governs ET in the LED phosphors. For Ce³⁺ concentration of 0.01 in YAG:Ce³⁺, Pr³⁺, the rate constant and critical distance are evaluated to be 4.5×10⁻³⁶ cm⁶ s⁻¹ and 0.81 nm, respectively. An increase in the red emission line of Pr³⁺ relative to the yellow emission band of Ce³⁺, on increasing Ce³⁺ concentration is observed. This behavior is attributed to the increase of spectral overlap integrals between Ce³⁺ emission and Pr³⁺ excitation due to the fact that the yellow band shifts to the red spectral side with increasing Ce³⁺ concentration. In CaMoO₄:Sm³⁺, Eu³⁺, Sm³⁺-Eu³⁺ transfer occurs from ⁴G_5/2 of Sm³⁺ to ⁵D₀ of Eu³⁺. The rate constant of 8.5×10⁻⁴⁰ cm⁶ s⁻¹ and the critical transfer distance of 0.89 nm are evaluated.     

Luminescence and EPR studies of Eu doped BaAl12O19 blue light emitting phosphors

Europium doped BaAl₁₂O₁₉ powder phosphors have been synthesized by combustion process within few minutes. The phosphors have been characterized by XRD, SEM, FT-IR, EPR and PL techniques. The EPR spectrum exhibits an intense resonance signal at g=1.96 characteristic of Eu²⁺ ions. In addition to this two weak resonance signals have been observed at g=2.28 and g=4.86. The population of the spin levels (N) for the resonance signal at g=1.96 is calculated as a function of temperature. By post-treating the phosphor at 1350 °C under a reducing atmosphere, it is observed that the population of spin levels has been increased five times. The excitation spectrum shows a peak at 326 nm with a shoulder at 290 nm. Upon excitation at 326 nm, the emission spectrum exhibits a well defined broad band with maximum at 444 nm emitting a blue light corresponding to 4f⁶5d→4f⁷ transition. The luminescence intensity also has been enhanced to 60% by post-treating the phosphor at 1350 °C under a reducing atmosphere.     

VUV sensitisation of Eu emission by Tb in Ba3Tb(PO4)3-Eu

The luminescence properties of Ba₃Tb_0.9Eu_0.1(PO₄)₃ and Ba₃Gd_0.9Eu_0.1(PO₄)₃ phosphors were studied for excitation over the 120-300 nm wavelength range. It is found that Tb³⁺, which exhibits a strong vacuum-ultraviolet (VUV) absorption band, provides sensitisation of Eu³⁺ emission in this host. This effect can be used to develop phosphors with enhanced conversion efficiency of the VUV radiation into visible light.     

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.     

PL and CL degradation and characteristics of SrAl2O4: Eu,Dy phosphors

Strontium aluminate phosphors are ideal for luminescent infrastructure materials. Their brightness and persistent glow time are much higher than previously used sulphide phosphors. Strontium aluminates prepared by the sol–gel and combustion methods are compared with commercially available strontium aluminate. High luminescent efficient SrAl₂O₄:Eu²⁺,Dy³⁺ pulsed laser deposited (PLD) thin films were also produced using the commercially available powder. Photoluminescence (PL) degradation studies showed that the phosphor intensity decreased about 20% over a period of 2 weeks under ultraviolet (UV) irradiation. Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) showed that cathodoluminescence (CL) degradation is due to the formation of SrO due to electron stimulated surface reactions. The light output mechanism of the phosphor is also discussed in more detail.     

Electronic energy relaxation and luminescence decay dynamics of Eu in Zn2SiO4:Eu phosphors

Electronic energy relaxation and decay dynamics of Eu³⁺ in Zn₂SiO₄:Eu³⁺ phosphors display evidence of intra-ion energy transfer from the ⁵D₁ to the ⁵D₀ manifold. The energy transfer timescale does not depend on Eu³⁺ concentration, or the addition of Mn²⁺ as a co-dopant and is estimated to be about 11 μs in Zn₂SiO₄. Evidence for intra-ion Eu³⁺ electronic energy transfer has also been observed in Eu-doped MgS as well as Eu³⁺ encapsulated in zeolite-Y. The energy transfer timescale in these other materials is shorter than in Zn₂SiO₄, most likely due to differences in Eu³⁺ surroundings or site symmetry.     

Combustion synthesis of Sr3MgSi2O8:Eu and Sr2MgSi2O7:Eu phosphors

Sr₃MgSi₂O₈:Eu²⁺ and Sr₂MgSi₂O₇:Eu²⁺ phosphors find uses in applications such as plasma display panel (PDP), solid-state lighting, longafter glow. Preparation of these phosphors by a modified combustion synthesis is described in this paper. As-prepared samples did not show photoluminescence. After reducing the samples at 900 °C, characteristic Eu²⁺ emission was observed. Preparation of these phosphors by using similar methods helped clarifying various results obtained for Sr₃MgSi₂O₈:Eu²⁺ by different investigators.     

Energy transfer between activators at different crystallographic sites in Sr3SiO5:Eu

A yellow phosphor, Sr₃SiO₅:Eu²⁺, was synthesized by a high temperature solid-state method. Sr₃SiO₅:Eu²⁺ exhibits a single yellow emission under the blue radiation excitation. However, Sr₃SiO₅:Eu²⁺ shows a two-peak emission under the ultraviolet radiation excitation when Eu²⁺ doping content is less than 0.01 mol. Moreover, the blue emission disappears and the yellow emission reaches the peak value when Eu²⁺ doping content is 0.01 mol. Namely, the energy transfer takes place between the Eu²⁺ activators, which is located at two different crystallographic sites in the Sr₃SiO₅. And the energy transfer mechanism is the dipole-dipole interaction.     

Enhanced photoluminescence of Sm/Bi co-doped Gd2O3 phosphors by combustion synthesis

Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ powders were prepared by a combustion method. Their structures were determined using X-ray diffraction. UV-visible absorption and photoluminescence spectra were investigated for Gd₂O₃:Sm³⁺ and Gd₂O₃:Sm³⁺,Bi³⁺ at different annealing temperatures and different doping concentrations. The emission spectra of all samples presented the characteristic emission narrow lines arising from the ⁴G_5/2→⁶H_J transitions (J=5/2, 7/2, and 9/2) of Sm³⁺ ions upon excitation with UV irradiation. The emission intensity of Sm³⁺ ions was largely enhanced with introducing Bi³⁺ ions into Gd₂O₃:Sm³⁺ and the maximum occurred at a Bi³⁺ concentration of 0.5 mol%. The relevant mechanisms were discussed with the sensitization theory by Dexter and the aggregation behavior of Bi³⁺ ions.     

Emission properties of Eu, Mn in MAl2Si2O8 (M=Sr, Ba)

The emission properties of Eu²⁺ and Mn²⁺ in monoclinic SrAl₂Si₂O₈ (M-SAS) and hexagonal BaAl₂Si₂O₈ (H-BAS), both of which have only one alkaline-earth site, were studied. The emission peaks of both Eu²⁺ (405 nm) and Mn²⁺ (564 nm) in SrAl₂Si₂O₈, are located at longer wavelengths, compared with those in H-BAS (373 nm for Eu²⁺ and 518 nm for Mn²⁺), because of the stronger crystal field strength at the Sr site. EPR spectra showed that the g values of Mn²⁺ are 4.5065 in M-SAS:Mn and 2.0247 in H-BAS:Mn. Magnetic measurements proved that Mn²⁺ was at high-spin state in both hosts. The large g value of Mn²⁺ in M-SAS was ascribed to the mixing of the first excitation state to the ground state, both of which have lower d orbital degeneracy due to the lower symmetry of Mn²⁺ site. The transfer efficiency from Eu²⁺ to Mn²⁺was about 10% in M-SAS, higher than that in H-BAS (5%). This was probably because Eu²⁺ emission overlaps the relatively low excitation level of Mn²⁺ in M-SAS. In order to obtain high transfer efficiency, it was necessary for the Eu²⁺ emission to overlap the lowest excitation level of Mn²⁺. The results obtained in this work may be helpful to design the new white or red phosphors for white-light emitting diode (w-LED) applications.     

Red, green and blue (RGB) emission doped Y3Al5O12 (YAG) phosphors prepared by non-hydrolytic sol-gel route

An evolutionary optimization process involving combination chemistry was employed in an attempt to develop Y₃Al₅O₁₂ (YAG). The combination chemistry process utilized here consisted the doping of the YAG host with appropriate amounts of red (R), green (G), and blue (B) dopants in a single layer, for use in tricolor white light. The doped YAG was acieved by means of the non-hydrolytic sol-gel route. Four samples were prepared, three of which were mono-doped samples containing 1.0% of a certain lanthanide (Eu³⁺, Tb³⁺, or Tm³⁺) ion, while the fourth contained the three ions. The samples were characterized by X-ray diffractometry and photoluminescence. The diffraction pattern of the mono-doped samples synthered at 800 °C for 16 h displayed peaks corresponding to the Y₃Al₅O₁₂ (YAG) phase, while the sample doped with the three ions revealed the presence of a mixture of Y₃Al₅O₁₂ (YAG) and Y₄Al₂O₉ (YAM) phases. The emission spectra of the three mono-doped YAG samples displayed the typical bands of the blue, green, and red emission of the corresponding lanthanide ions. As for the sample doped with the three lanthanide ions; it simultaneously emitted R, G and B lights. The green emission (546 nm) was more intense and narrow in relation to the red and blue emissions, which may be due to differences in the size of the three incorporated ions.     

Synthesis and Sm/Sm doping effects on photoluminescence properties of Sr4Al14O25

Complete and partial samarium reduction was achieved under strong reducing atmosphere by solid-state and combustion synthesis of Sr_3.96Sm_0.04Al₁₄O₂₅. Dependence of different fluxing agents on the formation of various strontium aluminates was examined. The samples were investigated by X-ray powder diffraction, temperature dependent luminescence decay and photoluminescence measurements. Excitation with UV radiation resulted in sharp and well resolved emission lines of samarium ions. Distinct temperature behavior for Sm²⁺ and Sm³⁺ were detected in the range of 100-500 K. Estimated emission thermal quenching values (TQ_1/2) for divalent samarium were approximately 270 K while for trivalent state around 660 K. Measured luminescence decay values of Sm²⁺ are substantially lower than for Sm³⁺,≈1.7 and ≈2.7 ms, respectively. The spectral feature of Sm²⁺ emission spectrum indicates that dopant occupies low symmetry site in Sr₄Al₁₄O₂₅ compound.     

Eu3+掺杂CaWO4红色荧光粉发光性质的浓度依赖关系研究

采用共沉淀法制备了不同Eu³⁺掺杂浓度的CaWO₄荧光粉材料.通过X射线衍射和场发射扫描电镜技术对样品的结构和形貌进行了表征.测量了各样品的激发光谱、发射光谱和荧光衰减曲线, 计算了各样品的部分Judd-Oflet (J-O)参数和^5D_0 (Eu³⁺)能级量子效率,以及荧光粉的色坐标, 讨论了样品电荷迁移带相对强度、J-O参数、量子效率与掺杂浓度的依赖关系.对Eu³⁺掺杂的CaWO₄ 发光材料的光致发光性质的研究表明,在CaWO₄: Eu³⁺中⁵D₀→⁷F₂跃迁的616~nm 红色发光能被394.5~nm和465~nm的激发光有效激发,具有近紫外(或蓝光)激发效率高和猝灭浓度大的优点, 有潜力成为高效的近紫外(或蓝光)激发白光发光二极管用红色荧光粉材料.     

Synthesis and luminescence properties of nanocrystalline Gd2O3:Eu by combustion process

The nanocrystalline Gd₂O₃:Eu³⁺ powders with cubic phase were prepared by a combustion method in the presence of urea and glycol. The effects of the annealing temperature on the crystallization and luminescence properties were studied. The results of XRD show pure phase can be obtained, the average crystallite size could be calculated as 7, 8, 15, and 23 nm for the precursor and samples annealed at 600, 700 and 800 °C, respectively, which coincided with the results from TEM images. The emission intensity, host absorption and charge transfer band intensity increased with increasing the temperature. The slightly broad emission peak at 610 nm for smaller particles can be observed. The ratio of host absorption to O²⁻-Eu³⁺ charge transfer band of smaller nanoparticles is much stronger compared with that for larger nanoparticles, furthermore, the luminescence lifetimes of nanoparticles increased with increasing particles size. The effects of doping concentration of Eu³⁺ on luminescence lifetimes and intensities were also discussed. The samples exhibited a higher quenching concentration of Eu³⁺, and luminescence lifetimes of nanoparticles are related to annealing temperature of samples and the doping concentration of Eu³⁺ ions.     

Photoluminescence of Eu in SrGa2S4

A photoluminescence (PL) study of the green-emitting SrGa₂S₄:Eu²⁺ phosphor is reported. Diffuse reflectance, excitation, and emission spectra were examined with the aim to enlarge the fundamental knowledge about the emission of the Eu²⁺ ion in this lattice. The thermal dependence of the radiative properties was investigated. In particular, the Stokes shift, the crystal field splitting and the activation energy of the thermal quenching were determined. By combining these results with the information presented in literature, we discussed the location of the Eu²⁺ levels relative to the valence and conduction bands of SrGa₂S₄.     

Investigation on Eu doped Sr2MgSi2O7 red-emitting phosphors for white-light-emitting diodes

In this work, we report the high temperature solid-state synthesis of red phosphors Sr₂MgSi₂O₇: Eu³⁺ with various Eu³⁺ concentrations. Their luminescent properties at room temperature are investigated. The X-ray diffraction patterns indicate that the red phosphors powder conforms to the tetragonal Sr₂MgSi₂O₇. Impurity structure appears when more than 20% Eu³⁺ is doped. The samples show a strong emission line at 615 nm and the intensity increases with the increase of Eu³⁺ concentration until concentration quenching occurs. Charge compensation assists in the reduction of the impurity structure and vacancies; hence the luminescent intensity is enhanced. The decay measurement indicates that the lifetime of Eu³⁺ emission is about 2-3 ms. Some of the Eu³⁺ can be reduced to Eu²⁺; this is also discussed.     

Effect of Eu,Tb codoping on the luminescent properties of Y2O3 nanorods

Red-emitting Y₂O₃:Eu³⁺ and green-emitting Y₂O₃:Tb³⁺ and Y₂O₃:Eu³⁺, Tb³⁺ nanorods were synthesized by hydrothermal method. Their structure and micromorphology have been analyzed by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM). The photoluminescence (PL) property of Y₂O₃:Eu³⁺,Tb³⁺ phosphor was investigated. In the same host (Y₂O₃), upon excitation with ultraviolet (UV) irradiation, it is shown that there are strong emissions at around 610 and 545 nm corresponding to the forced electric dipole ⁵D₀-⁷F₂ transition of Eu³⁺ and ⁵D₄-⁷F₅ transition of Tb³⁺, respectively. Different qualities of Eu³⁺and Tb³⁺ ions are induced into the Y₂O₃ lattice. From the excitation spectrum, we speculate that there exists energy transfer from Tb³⁺ to Eu³⁺ ions .The emission color of powders reveals regular change in the separation of light emission. These powders can meet with the request of optical display material for different colors or can be potentially used as labels for biological molecules.     

A white light emitting phosphor Sr1.5Ca0.5SiO4:Eu, Tb, Eu for LED-based near-UV chip: Preparation, characterization and luminescent mechanism

In this work, we report preparation, characterization and luminescent mechanism of a phosphor Sr_1.5Ca_0.5SiO₄:Eu³⁺,Tb³⁺,Eu²⁺ (SCS:ETE) for white-light emitting diode (W-LED)-based near-UV chip. Co-doped rare earth cations Eu³⁺, Tb³⁺ and Eu²⁺ as aggregated luminescent centers within the orthosilicate host in a controlled manner resulted in the white-light phosphors with tunable emission properties. Under the excitation of near-UV light (394 nm), the emission spectra of these phosphors exhibited three emission bands: one broad band in the blue area, a second band with sharp lines peaked in green (about 548 nm) and the third band in the orange-red region (588-720 nm). These bands originated from Eu²⁺ 5d→4f, Tb³⁺⁵D₄→⁷F_J and Eu³⁺⁵D₀→⁷F_J transitions, respectively, with comparable intensities, which in return resulted in white light emission. With anincrease of Tb³⁺ content, both broad Eu²⁺ emission and sharp Eu³⁺ emission increase. The former may be understood by the reduction mechanism due to the charge transfer process from Eu³⁺ to Tb³⁺, whereas the latter is attributed to the energy transfer process from Eu²⁺ to Tb³⁺. Tunable white-light emission resulted from the system of SCS:ETE as a result of the competition between these two processes when the Tb³⁺ concentration varies. It was found that the nominal composition Sr_1.5Ca_0.5SiO₄:1.0%Eu³⁺, 0.07%Tb³⁺ is the optimal composition for single-phased white-light phosphor. The CIE chromaticity calculation demonstrated its potential as white LED-based near-UV chip.