Luminescence of Eu<Superscript>3+</Superscript> rare-earth ions in Lu<Subscript>2</Subscript>O<Subscript>3</Subscript> nanospheres

The kinetics of luminescence of Eu³⁺ ions in Lu₂O₃:Eu nanospheres with diameters of 100–270 nm and a small standard deviation of the size distribution <15% has been studied. A sharp decrease in the decay time of luminescence of Eu³⁺ ions in the red range with an increase in the diameter of nanospheres has been attributed to the appearance of a photon mode accelerating spontaneous luminescence, which is confirmed by the calculation of ranges of existence of whispering-gallery modes in studied nanospheres.     

Concentration quenching anomalies of activated Y<Subscript>2</Subscript>SiO<Subscript>5</Subscript>:Pr<Superscript>3+</Superscript> nanocrystal luminescence

For the fist time in Y₂SiO₅:Pr³⁺ nanocrystals, the ordered stage in the ¹ D ₂ luminescence decay curves for Pr³⁺ ions has been observed at anomalously low doped ion concentration (0.5 at %). This effect is caused by preferred location of the activator ions in the near-surface layer of the nanocrystal that provides the relaxation of elastic tension arising due to the difference of ionic radii of Pr³⁺ and Y³⁺ ions. Concentration quenching of Pr³⁺ luminescence is caused by the cooperative cross-relaxation.     

Spectral properties of Nd<Superscript>3+</Superscript> ions in samples of transparent Y<Subscript>2</Subscript>O<Subscript>3</Subscript> ceramics

The spectral and luminescent characteristics of samples of Y₂O₃:Nd³⁺ ceramics obtained from different precursors under different preparation conditions (the concentration of an HfO₂ compacting additive, the temperature and time of synthesis) are studied at 300 and 77 K. It is shown that the spectral positions of absorption and luminescence lines of ceramics correspond to those of a Y₂O₃:Nd³⁺ single crystal. At the same time, the absorption and luminescence spectra show an inhomogeneous broadening, characteristic of disordered crystals and glass. The energies of the ⁴ I _9/2 and ⁴ F _3/2 Stark states of the Nd³⁺ ion are calculated. The calculation results nearly coincide with the data from the literature for the Y₂O₃:Nd³⁺ single crystal and transparent ceramics. Samples containing the compacting additive show additional lines, whose intensities correlate with its concentration and the method of preparation of Y₂O₃:Nd³⁺ ultradispersed powders. It is assumed that these lines are related to the fact that either Nd³⁺ ions enter the composition of the HfO₂ compacting additive or Hf⁴⁺ ions are present in the nearest environment of Nd³⁺ ions at the boundaries of granules enriched with HfO₂.     

Investigation of luminescence spectra of the Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> and Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Ce single-crystal films

The luminescence spectra of single-crystal films and bulk crystals of yttrium-aluminum garnet Y₃Al₅O₁₂ and Ce³⁺-activated Y₃Al₅O₁₂ were investigated. It was shown that the room-temperature luminescence intensity of the Ce³⁺-free single-crystal Y₃Al₅O₁₂ film was considerably lower than that of the bulk crystals, while the luminescence intensity of the Ce³⁺ ions in the Y₃Al₅O₁₂:Ce films was considerably higher than that one for the corresponding bulk crystal.     

Luminescence and scintillation properties of Y<Subscript>3</Subscript>A<Subscript>l5</Subscript>O<Subscript>12</Subscript>:Ce single crystals and single-crystal films

Luminescence and scintillation properties of Y₃A_l5O₁₂:Ce single crystals grown from the melt by the Czochralski and horizontal directed crystallization methods in various gas media and Y₃A_l5O₁₂:Ce single-crystal films grown by liquid-phase epitaxy from a melt solution based on a PbO-B₂O₃ flux have been comparatively analyzed. The strong dependence of scintillation properties of Y₃A_l5O₁₂:Ce single crystals on their growth conditions and concentrations of Y_Al antisite defects and vacancy defects has been established. Vacancy defects are involved in Ce³⁺ ion emission excitation as the centers of intrinsic UV luminescence and trapping centers. It has been shown that Y₃A_l5O₁₂:Ce single-crystal films are characterized by faster scintillation decay kinetics than single crystals and a lower content of slow components in Ce³⁺ ion luminescence decay during high-energy excitation due to the absence of Y_Al antisite defects in them and low concentration of vacancy defects. At the same time, the light yield of Y₃A_l5O₁₂:Ce single-crystal films is comparable to that of single crystals grown by directed crystallization due to the quenching effect of the Pb²⁺ ion impurity as a flux component and is slightly lower (∼25%) than the light yield of single crystals grown by the Czochralski method.     

Red,Yellow, Blue and Green Emission from Eu<Superscript>3+</Superscript>, Dy<Superscript>3+</Superscript> and Bi<Superscript>3+</Superscript> Doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>nano-Phosphors

Rare earth elements (RE = Eu³⁺& Dy³⁺)and Bi³⁺ doped Y₂O₃ nanoparticles were synthesized by urea hydrolysis method in ethylene glycol, which acts as reaction medium as well as a capping agent, at a low temperature of 140 °C,followed by calcination of the obtained product. Transmission electron microscope (TEM) images reveals that ovoid shaped Y₂O₃ nanoparticles of around 22–24 nm size range were obtained in this method. The respective RE and Bi³⁺ doped Y₂O₃ precursor nanoparticles when heated at 600 and 750 °C, retains the same shape as that of the as-synthesized Y₂O₃ precursor samples. From EDAX spectra, the incorporation of RE ions into the host has been studied. XRD pattern reveals the crystalline nature of the heated nanoparticles and indicate the absence of any impurity phase other than cubic Y₂O₃.However, the as-synthesized nanoparticles were highly amorphous without the presence of any sharp XRD peaks. Photoluminescence study suggests that the synthesized samples could be used as red (Eu³⁺), yellow (Dy³⁺), blue and green (Bi³⁺)emitting phosphors.     

The influence of the specific surface of grains on the luminescence properties of Nd<Superscript>3+</Superscript>-doped Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript> nanopowders

Nd³⁺:Y₃Al₅O₁₂ (Nd:YAG) powders were prepared by the Pechini method in the temperature range of 800 to 1400 °C. The pure garnet phase of the obtained materials was confirmed by XRD studies. The size of the grains was controlled by the annealing temperature of the samples. Their morphologies were investigated by TEM and porosity measurements (BET). The effect of annealing temperature on the morphology and luminescence properties of Nd:YAG nanocrystallites was studied, and the results were compared to the properties of a Nd:YAG single crystal. A significant enhancement of the ⁴F_3/2→⁴I_9/2/⁴F_3/2→⁴I_11/2 intensity ratio with decreasing grain size was observed. It was found that the decay times of the Nd³⁺ luminescence depends on the specific surface and is significantly longer for well crystallized nanocrystalline grains than for single crystals having the same concentration of Nd³⁺ ions. The role of crystallinity and specific surface on the radiative processes is analyzed. PACS 78.55.-m; 78.20.Ci; 78.67.Bf; 78.68.+m     

Photolumiscent Properties of Nanorods and Nanoplates Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript>

Nanorods and nanoplates of Y₂O₃:Eu³⁺ powders were synthesized through the thermal decomposition of the Y(OH)₃ precursors using a microwave-hydrothermal method in a very short reaction time. These powders were analyzed by X-ray diffraction, field emission scanning electron microscopy, Fourrier transform Raman, as well as photoluminescence measurements. Based on these results, these materials presented nanoplates and nanorods morphologies. The broad emission band between 300 and 440 nm ascribed to the photoluminescence of Y₂O₃ matrix shifts as the procedure used in the microwave-hydrothermal assisted method changes in the Y₂O₃:Eu³⁺ samples. The presence of Eu³⁺ and the hydrothermal treatment time are responsible for the band shifts in Y₂O₃:Eu³⁺ powders, since in the pure Y₂O₃ matrix this behavior was not observed. Y₂O₃:Eu³⁺ powders also show the characteristic Eu³⁺ emission lines at 580, 591, 610, 651 and 695 nm, when excited at 393 nm. The most intense band at 610 nm is responsible for the Eu³⁺ red emission in these materials, and the Eu³⁺ lifetime for this transition presented a slight increase as the time used in the microwave-hydrothermal assisted method increases.     

Color Change Upconversion Mechanism of Y<Subscript>6</Subscript>O<Subscript>5</Subscript>F<Subscript>8</Subscript>: Er<Superscript>3+</Superscript>/Yb<Superscript>3+</Superscript> Microtubes by Using Time-Resolve Spectra

The mechanism of the upconversion processes in Y₆O₅F₈: 2%Er³⁺/X%Yb³⁺ (X = 3, 10, 20) microtubes has been explored. The luminescent properties of the as prepared sample is investigated by utilizing up- /downconversion, decay and time resolve spectra. The results indicate that the red and green emission are clearly competitive depending on the Yb³⁺ concentration. High Yb³⁺ concentration induces the enhancement of the energy-back-transfer (EBT), process, which leads to the quenching of green emission and enhances the red emission. So it is possible to utilize the temporal evolutions of emission bands to deeply understand the color change UC mechanisms.     

Morphology-dependent luminescence behavior of Y<Subscript>2-x</Subscript>Gd<Subscript>x</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> thin-film phosphors grown by a laser ablation

Y_2-xGd_xO₃:Eu³⁺ luminescent thin films have been grown on Al₂O₃(0001) substrates using pulsed laser deposition. Films grown under different deposition conditions have been characterized using microstructural and luminescence measurements. The crystallinity, surface morphology and photoluminescence (PL) of the films are highly dependent on the amount of Gd present. The photoluminescence (PL) brightness data obtained from Y_2-xGd_xO₃:Eu³⁺ films grown under optimized conditions have indicated that Al₂O₃(0001) is one of the most promising substrates for the growth of high-quality Y_2-xGd_xO₃:Eu³⁺ thin-film red phosphors. In particular, the incorporation of Gd into the Y₂O₃ lattice could induce a remarkable increase of PL. The highest emission intensity was observed with Y_1.35Gd_0.60Eu_0.05O₃, whose brightness was increased by a factor of 3.1 in comparison with that of Y₂O₃:Eu³⁺ films. This phosphor may be promising for application in flat-panel displays. PACS 78.20.-e; 78.55.-m; 78.66.-w     

Synthesis and characterization of mono-dispersed Y<Subscript>3</Subscript>Al<Subscript>5</Subscript>O<Subscript>12</Subscript>:Er<Superscript>3+</Superscript>-coated SiO<Subscript>2</Subscript> nanoparticles by co-precipitation process

In this paper, a facile co-precipitation process for preparing mono-dispersed core–shell structure nanoparticles is reported. The 110 nm SiO₂ cores coated with an yttrium aluminum garnet (Y₃Al₅O₁₂) layer doped with Er³⁺ were synthesized and the influence of the concentration ratio of [urea]/[metal ions] on the final product was investigated. The structure and morphology of samples were characterized by the X-ray powder diffraction, Fourier transform IR spectroscopy and transmission electron microscopy, respectively. The results indicate that a layer of well-crystallized garnet Y₃Al₅O₁₂:Er³⁺ were successfully coated on the silica particles with the thickness of 20 nm. The near infrared and upconversion luminescent spectra of the SiO₂@Y₃Al₅O₁₂:Er³⁺ powders further confirm that a Y₃Al₅O₁₂:Er³⁺ coating layer has formed on the surface of silica spherical particles.     

Synthesis and luminescent properties of Eu<Superscript>3+</Superscript>- and Eu<Superscript>2+</Superscript>-activated sodium pyrophosphate Na<Subscript>4</Subscript>P<Subscript>2</Subscript>O<Subscript>7</Subscript>

The luminescent properties of Eu³⁺ and Eu²⁺ ions in sodium pyrophosphate, Na₄P₂O₇, have been studied. The excitation spectrum of the Eu³⁺ emission in Na₄P₂O₇ consists of several sets of bands in the range 280–535 nm due to 4f–4f transitions of Eu³⁺ ions and a broad band with a maximum at about 240 nm interpreted to be due to a charge transfer (CT) transition from oxygen 2p states to empty states of the Eu³⁺ 4f⁶-configuration. Although the CT band energy is large enough, the quantum efficiency (η) of the Eu³⁺ emission in Na₄P₂O₇ under CT excitation was estimated to be very low (η ≤ 0.01). In terms of a configurational coordinate model, this fact is interpreted as a result of the high efficiency of a radiationless relaxation from the CT state to the ⁷F₀ ground state of Eu³⁺ ions occupying sodium sites in Na₄P₂O₇. A strong reducing agent is required in order to stabilize Eu²⁺ ions in Na₄P₂O₇ during the synthesis. Several nonequivalent Eu²⁺ luminescence centers in Na₄P₂O₇ were found.     

Optical and fluorescent properties of Y<Subscript>2</Subscript>O<Subscript>3</Subscript> sol–gel planar waveguides containing Tb<Superscript>3+</Superscript> doped nanocrystals

Terbium doped Y₂O₃ planar waveguides were fabricated by sol–gel process and dip-coating using yttrium acetate as precursor. Two different doping modes were compared, i.e. introduction in the sol of dispersed Tb³⁺ions from dissolved Tb(NO₃)₃, or of nanoparticles of Tb₂O₃ or [Y₂O₃:50% Tb] from an alcoholic suspension. The chemical and nanostructural properties were analyzed by infrared spectroscopy, transmission electron microscopy and X-ray diffraction. The Tb³⁺ fluorescence properties were studied as a function of temperature and atmosphere of the thermal treatments, and of the Tb³⁺ concentration. The fluorescence properties are discussed in relation to the quenching mechanisms induced by Tb⁴⁺ transformation, residual OH groups, and crystallites size and structure. Optical propagation losses of the Tb doped Y₂O₃ planar waveguides related to the doping modes and Tb³⁺ concentration are presented. Doping sol–gel films by nanoparticles is shown to be a valuable alternative to the conventional doping from dissolved terbium salt. PACS 81.21.Fw; 84.40.Az; 78.67.Bf     

Spectral properties of a Nd<Superscript>3+</Superscript>-doped Li<Subscript>3</Subscript>Ba<Subscript>2</Subscript>Gd<Subscript>3</Subscript>(MoO<Subscript>4</Subscript>)<Subscript>8</Subscript> crystal

The spectral properties of a promising laser material, ternary molybdate Li₃Ba₂Gd₃(MoO₄)₈:Nd³⁺, are studied (i.e., its optical absorption spectra, luminescence spectra, kinetic of luminescence decay, and temperature dependence of luminescence). Luminescence of the crystalline matrix is detected, and the temperature dependence of its intensity and reabsorption by neodymium are investigated.     

Correction of the band gap of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Submicron samples of Y₂O₃:Eu³⁺ phosphor with elevated photoluminescence (PL) efficiency and activator concentration of 9 at % obtained by the sol–gel method were investigated by diffuse reflection spectroscopy and PL spectroscopy. It is found that the diffuse reflection spectrum in the vicinity of the fundamental absorption edge (<300 nm) is distorted by the superposition of the PL of Eu³⁺ ions, as a result of which the calculated value of optical band gap E _g of the Y₂O₃ matrix is overestimated. An algorithm for eliminating the PL influence on the absorption edge is proposed, and the correct E _g values are found to be 4.61 ± 0.12 and 4.50 ± 0.12 eV for annealing at 700 and 1300°C, respectively.     

Luminescence characteristics of the Pr<Superscript>3+</Superscript> ion in SrB<Subscript>4</Subscript>O<Subscript>7</Subscript> and SrB<Subscript>6</Subscript>O<Subscript>10</Subscript>

Spectral and kinetic characteristics of the luminescence and luminescence excitation spectra of polycrystalline SrB₄O₇:Pr (1%) and SrB₆O₁₀:Pr (1%) samples are studied at 150–170 K. The samples show an intense luminescence band in the vicinity of 405 nm (¹ S ₀→¹ I ₆ transitions of Pr³⁺) and shorter wavelength bands also assigned to transitions from the ¹ S ₀ level. The main luminescence decay constant is ～2×10^?7 s. The excitation spectra of the ¹ S ₀ luminescence in these crystals are significantly different. The SrB₄O₇:Pr crystal shows three well-resolved bands at 6.14, 6.55, and 6.91 eV in the region of the 4f ²→4f ¹5d transitions and a complex structure in the region of interband transitions (7.1–20 eV), whereas the SrB₆O₁₀:Pr crystal shows a weakly structured band at 6.31 eV and no excitation in the region of the interband transitions. The physical mechanisms that may be responsible for the observed features of the spectra are discussed.     

Eu<Superscript>3+</Superscript> As a Luminescent Probe for Studying the Structure of R<Subscript>2</Subscript>O<Subscript>3</Subscript> Materials (R = Y,Eu, and Gd)

Spectra of Eu³⁺ in various dielectric matrices (Gd₂O₃:Eu³⁺, Y₂O₃:Eu³⁺, Eu₂O₃, and mSiO₂/Gd₂O₃:Eu³⁺ mesoporous particles) are studied by local cathodoluminescence. The results allowed identification of the local environment of Er³⁺ ions in amorphous samples and detection of the monoclinic Eu₂O₃ phase impurity in samples with yttrium oxide. The cathodoluminescence spectra of chemically pure Y₂O₃, Eu₂O₃, and Gd₂O₃ are recorded. Conclusions about the structural features of the materials are made and confirmed by other methods (XRD and EPMA).     

Spectroscopy of NaLa(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> and NaGd(MoO<Subscript>4</Subscript>)<Subscript>2</Subscript>: Tm<Superscript>3+</Superscript> crystals as advanced laser materials

Single crystals of double sodium-containing lanthanum and gadolinium molybdates doped with Tm³⁺ ions were synthesized by the Czochralski method. The spectroscopic properties of these crystals were investigated from the viewpoint of their use as active media in diode-pumped lasers. The polarized spectra of absorption on the ³ H ₄ and ³ F ₄ levels and the polarized spectra of luminescence due to the ³ F ₄-³ H ₆ laser transition were recorded, and the lifetimes of the ³ H ₄ and ³ F ₄ excited states of the Tm³⁺ ions were determined. The luminescence cross sections were calculated using the Füchtbauer-Ladenburg formula. The simulation of the decay curve of the ³ H ₄ excited state according to the Golubov-Konobeev-Sakun method revealed that, in the crystals under investigation, the interaction between Tm³⁺ ions predominantly occurs through the dipole-dipole mechanism.     

Luminescence excitation in reactive molecular CO + O<Subscript>2</Subscript> collisions on the surface of Y<Subscript>2</Subscript>O<Subscript>3</Subscript>-Eu

It is shown that the CO + O₂ → CO₂ catalytic reaction on the surface of Y₂O₃-Eu may lead to electronic excitation of Eu³⁺ luminescence centers due to the chemical energy release. The luminescence observed allows one to study the interaction between molecular particles of ultralow (thermal) energies with surface by optical methods.     

Electron paramagnetic resonance of Ce<Superscript>3+</Superscript> and Nd<Superscript>3+</Superscript> impurity ions in YBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>6.13</Subscript>

The electron paramagnetic resonance (EPR) spectra of Ce³⁺ and Nd³⁺ impurity ions in unoriented powders of the YBa₂Cu₃O_6.13 compound are observed and interpreted for the first time. It is demonstrated that, upon long-term storage of the samples at room temperature, the EPR signals of these ions are masked by the spectral line (with the g factor of approximately 2) associated with the intrinsic magnetic centers due to the significant increase in its intensity.