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.     

Synthesis, characterization and optical spectroscopy of Eu doped titanate nanotubes

The synthesis of Eu³⁺ doped titania nanotubes was carried out via a hydrothermal method. X-ray diffraction and transmission electron microscope analyses showed that the nanotubes were formed by rolling multilayered titania structure with a length of up to 100 nm. The Eu³⁺-doped nanotubes exhibited strong emission lines associated with the ⁵D₀→⁷F_J (with J from 1 to 4) transition of Eu³⁺ and the differences between the luminescence properties of the precursor powders and the nanotubes were studied at low temperature.     

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.     

Ultrashort-laser-pulse-induced persistent spectral hole burning of Eu(3+) in sodium borate glasses

We have observed persistent spectral hole burning (PSHB) in Eu(3+) -doped sodium borate glasses irradiated with near-IR femtosecond laser pulses. As-prepared glasses, i.e., glasses melted in air, do not show PSHB even at low temperatures (~77K) , but room-temperature PSHB occurs in the irradiated glasses. The exposure to IR radiation causes both the reduction of Eu(3+) to Eu(2+) and the formation of intrinsic defects. We propose that the photoinduced redistribution of electric charges between Eu(3+) to Eu(2+) is responsible for the occurrence of PSHB.     

Room-temperature persistent spectral hole burning of Eu(3+) in sodium aluminosilicate glasses

Persistent spectral hole burning has been observed at 77 K, 180 K, and room temperature for Eu(3+) in sodium aluminosilicate glass melted under a reducing atmosphere. In particular, room-temperature persistent spectral hole burning is reported for the first time to our knowledge in Eu(3+) -doped materials. The persistent hole is accompanied by no antiholes and lasts for 1 h at least. The thermal stability of the hole is greater than that of a persistent hole burned for Eu(3+) in sodium aluminosilicate glass melted in air.     

An efficient and stable green phosphor SrBaSiO:Eu for light-emitting diodes

Eu²⁺-activated strontium–barium silicate, SrBaSiO₄:Eu²⁺, which is an intermediate phase between Sr₂SiO₄ and Ba₂SiO₄, was synthesized by a solid-state reaction. The synthesized phosphor was efficiently excited by a broad spectral range of near UV between 300 and 450 nm, and exhibited a strong and wide green emission. As the doped Eu²⁺ concentration increased from 0.005 to 0.18 (molar ratio), the emission wavelength shifted from 509 to 521 nm, and this red-shift phenomenon was discussed through a band-gap model. The concentration quenching mechanism was calculated to be a dipole–quadrupole interaction. It showed good thermal stability with T_1/2 of 170 °C and high internal quantum efficiency (78%). A green LED was fabricated with SrBaSiO₄:Eu²⁺and a 395 nm-emitting InGaN chip and it showed a superior current tolerant property. All the results indicate that this phosphor is a good candidate as green component in fabrication of phosphor-converted white LEDs.     

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.     

Effect of cation mixing on luminescence of Eu in SrCl2

SrCl₂ forms solid solutions of various compositions with BaCl₂ and CaCl₂. Orthorhombic and tetragonal phases are also known to occur in the SrCl₂-CaCl₂ system. Though efficient emission of Eu²⁺ in SrCl₂ and CaCl₂ is known, there are no reports available on Eu²⁺ luminescence in the solid solutions and other phases. Investigations on these lines were carried out and the results are presented in this paper. Very intense emission comparable to that of the commercial lamp phosphors was observed for the solid solutions while the intensities for the orthorhombic and tetragonal phases are an order of magnitude smaller. Emission wavelengths do not vary much while excitation spectra for the solid solutions are much enhanced in the near UV region (350-400 nm). It is suggested that these results will be significant for developing phosphors with near UV excitations needed in applications such as solid state lighting.     

Some studies of BF2 and B+F implanted Silicon

Ion-implanted shallow junctions have been investigated using BE₂ (molecular ions) by the anodic oxidation method coupled with a four-point probe technique. BF₂ ions were implanted through screen oxide at doses of 3–5 × 10¹⁵ ions/cm² and energies of 25 and 45 keV which is equivalent to 5.6 keV and 10 keV of boron ions. The effect of energy, dose and annealing temperature on shallow junctions is presented in this paper. The shallow junctions in the range of 0.19 μm to 0.47 μm were fabricated.

The effect of fluorine on sheet resistivity of boron implanted silicon at various doses, treated with two-step and three-step annealing, is also presented for comparison in the paper.     

Luminescence of BaBr2:Eu under hydrostatic pressure

Luminescence spectra of BaBr₂:Eu²⁺ have been measured under pressures up to 27 GPa at room temperature. In the low-pressure range a red-shift of the 5d-4f transition of −225 cm⁻¹/GPa is observed. From 3 to 10 GPa a phase mixture of the original orthorhombic phase and the high-pressure monoclinic phase gives rise to two luminescence bands. Above 10 GPa the crystal is completely transformed to its high-pressure phase where two different Eu²⁺ sites exist of which, however, only one 5d-4f transition is detected. This transition exhibits a red-shift of −200 cm⁻¹/GPa. The shifts are compared with other literature data.     

Novel room temperature ionic liquid for fluorescence enhancement of Eu and Tb

The newly prepared ionic liquid, 1-butyl-3-methylimidazolium benzoate, ([bmim][BA]), was found to enhance the fluorescence of Eu³⁺ and Tb³⁺. The fluorescence enhancement resulted from a sensitization of the lanthanide fluorescence by the benzoate anion of the ionic liquid, [bmim][BA], and a reduction in the non-radiative channels in the non-aqueous environment provided by the ionic liquid. However, the fluorescence enhancement of the lanthanides in the ionic liquid was limited due to the operation of the inner filter effect, which resulted from the strong absorption of the benzoate. The inner filter effect was minimized by observing the Eu³⁺ fluorescence using a front face geometry and also by diluting the lanthanide-[bmim][BA] system, using another ionic liquid, 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([bmim][Tf₂N]), as a solvent. In the case of Tb³⁺, the emission from the lanthanide was masked by the strong emission from the ionic liquid in the region 450-580 nm. The long lived Tb³⁺ emission was therefore observed using delayed gated detection, where an appropriate delay was used to discriminate against the short lived emission from the ionic liquid. The large fluorescence enhancement due to ligand sensitized fluorescence observed with [bmim][BA] diluted in [bmim][Tf₂N], leads to nanomolar detection of the lanthanides. This is, to the best of our knowledge, the first report of an ionic liquid being employed for ligand sensitized fluorescence enhancement of lanthanides.     

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.     

Thermoluminescence spectroscopy of Eu and Mn doped BaMgAl10O17

Thermoluminescence (TL) studies of Eu²⁺ and Mn²⁺ doped BaMgAl₁₀O₁₇ (BAM) are reported and discussed. The TL spectra that are measured after irradiation with ultraviolet (120-) show a series of TL peaks between 100 and . The TL spectra are similar for BAM with the two dopants, which suggest that the shallow traps are typical for the BAM host lattice. Using the Hoogstraaten analysis trap depths between 0.1 and are determined. A model is proposed based on thermally activated recombination in local TL centres (not via the conduction band). Further support for this model is obtained from the observation that the TL signal is strongest for excitation around the band edge of BAM . Upon heating the samples in air all low temperature TL peaks decrease in intensity. In addition a new peak appears in the TL spectrum, which is connected with a deeper trap and also a partial oxidation of Eu²⁺ to Eu³⁺ is observed. The luminescence efficiency is lower and the UV induced degradation is faster after annealing in air. These results indicate that the shallow traps are related to oxygen vacancies. The shallow traps do not have a negative influence on performance (efficiency and degradation) of BAM as a lighting phosphor. The luminescence efficiency and stability are strongly influenced by the formation of Eu³⁺ and a deeper trap during annealing in air. Subsequent annealing in a reducing atmosphere restores the original properties.     

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.     

Influence of high hydrostatic pressure on Eu-luminescence in KMgF3:Eu crystal

Spectroscopic investigations are presented of KMgF₃:Eu²⁺ crystal under high hydrostatic pressure from ambient to 310 kbar. The sample was excited by 30 ps pulses generated by optical parametric generator (OPG) system with wavelength controlled between 210 and 325 nm. The Grüneisen parameters of individual phonons are obtained from the pressure shift of the Eu²⁺ emission related to the ⁶P_7/2→⁸S_7/2 transition accompanied by phonon sideband. The luminescence decays exponentially for the pressure below 135 kbar with lifetime of 3.30 ms and slightly nonexponential above 135 kbar, while the average decay time is nearly independent of the pressure. The results obtained for KMgF₃:Eu²⁺ are compared with those for LiBaF₃:Eu²⁺ in which the ⁶P_7/2→⁸S_7/2 emission is replaced by the broadband emission of the 4f⁶5d¹→4f⁷ transition at high hydrostatic pressure.     

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.     

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.     

Blue light emission from Eu ions in sol-gel-derived Al2O3-SiO2 glasses

Blue light-emitting glasses were successfully prepared by doping Eu²⁺ ions in the system Al₂O₃-SiO₂. The Al₂O₃-SiO₂ glasses doped with Eu³⁺ ions were synthesized using a sol-gel method, followed by heating in hydrogen gas atmosphere to reduce into the Eu²⁺ ions. The obtained glasses exhibited emission spectra with peak at ∼450 nm due to 4f⁶5d→4f⁷ (⁸S_7/2) transition, the intensities of which strongly changed depending on their glass composition and heating conditions. The emission quantum efficiency of 48% was achieved by heating the glass with the ratio of Al³⁺ to Eu³⁺ at about 6 at 1000 °C in hydrogen gas atmosphere. It was found that the Al₂O₃-SiO₂ glasses were appropriate not only for homogeneously doping the Eu³⁺ ions in glass structure but also reducing to Eu²⁺ ions, resulting in enhanced blue light-emission properties.     

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.