Low-temperature wet chemical synthesis and photoluminescence properties of YVO4: Bi, Eu nanophosphors

YVO₄: Bi³⁺, Eu³⁺nanophosphors are prepared by the citrate-assisted low-temperature wet chemical synthesis. When the colloidal solution is aged at 60 °C, the crystalline YVO₄: Bi³⁺, Eu³⁺ nanorods are formed from the amorphous gel precursors, as confirmed by transmission electron microscopy and X-ray diffractometry (XRD). YVO₄: Bi³⁺, Eu³⁺ nanophosphors emit red through energy transfer from Bi³⁺ to Eu³⁺ under near-UV-light excitation. The emission intensity increases with increasing the fraction of the crystalline phase during aging. The excitation peak corresponding to Bi³⁺-V⁵⁺ charge transfer relative to those of O²⁻-V⁵⁺ and O²⁻-Eu³⁺ charge transfers gradually becomes strong until the completion of the crystallization, although the contents of individual Bi³⁺ and Eu³⁺ ions incorporated into YVO₄ keep constant. When the aging is continued after the completion of the crystallization, the content of incorporated Bi³⁺ gradually increases, and hence the emission intensity decreases as a result of the energy migration among Bi³⁺ ions. These results suggest that in addition to the fraction of the crystalline phase and the contents of incorporated Bi³⁺ and Eu³⁺ ions, the local chemical states around Bi³⁺ play significant roles in photoluminescence properties.     

Effects of the homogeneous Bi doping process on photoluminescence properties of YVO4:Bi,Eu nanophosphor

YVO₄:Bi³⁺,Eu³⁺ nanophosphors at a high Bi³⁺ concentration of 15 at% are synthesized from a Bi³⁺ source, nitrates of yttrium and europium(III), and sodium orthovanadate(V) by a low-temperature aqueous precipitation in the presence of citrate ions. When an ethylene glycol solution of bismuth(III) nitrate is used as a Bi³⁺ source, YVO₄:Bi³⁺,Eu³⁺ nanophosphors of ∼20 nm in size crystallize during aging at 85 °C without any by-products where the contents of Bi³⁺ and Eu³⁺ incorporated into crystalline YVO₄ are close to the respective nominal contents, as confirmed by transmission electron microscopy, X-ray diffractometry and X-ray fluorescent analysis. These nanophosphors show red emission corresponding to the f-f transition of Eu³⁺ under the excitation of Bi³⁺-V⁵⁺ charge transfer. When aging is continued after the completion of the crystallization, the photoluminescence intensity of nanophosphors reaches the constant value. This is the improved behavior in comparison to our previous work, where the photoluminescence intensity decreases after the prolonged aging because of the inhomogeneous doping of Bi³⁺ ions, and hence the concentration quenching.     

Kinetics of luminescence of interface defects and resonant Er ions in nanostructured SnO2:SiO2

Silica glass with SnO₂ nanocrystals and Er³⁺ ions are prepared by the sol-gel route and treatment above 1000 °C. Transmission electron microscopy evidences a homogeneous dispersion of nanoclusters 4-6 nm in size in the amorphous silica matrix. Photoluminescence spectra excited at 3.5 eV, outside erbium transitions, show an inhomogeneous spectral distribution of light emission from interface defects, in the range 1.9-2.4 eV, resonant with transitions of erbium ions. The analysis of kinetics and temperature dependence of luminescence allows to quantify the efficiency of the energy transfer channel between nanoclusters and erbium ions.     

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.     

Strong violet luminescence from ZnO nanocrystals grown by the low-temperature chemical solution deposition

The luminescence properties of zinc oxide (ZnO) nanocrystals grown from solution are reported. The ZnO nanocrystals were characterized by scanning electron microscopy, X-ray diffraction, cathodo- and photoluminescence (PL) spectroscopy. The ZnO nanocrystals have the same regular cone form with the average sizes of 100-500 nm. Apart from the near-band-edge emission around 381 nm and a weak yellow-orange band around 560-580 nm at 300 K, the PL spectra of the as-prepared ZnO nanocrystals under high-power laser excitation also showed a strong defect-induced violet emission peak in the range of 400 nm. The violet band intensity exhibits superlinear excitation power dependence while the UV emission intensity is saturated at high excitation laser power. With temperature raising the violet peak redshifts and its intensity increases displaying unconventional negative thermal quenching behavior, whereas intensity of the UV and yellow-orange bands decreases. The origin of the observed emission bands is discussed.     

Structural Change in Au^3＋-Doped BK7 Glass Irradiated by Femtosecond Laser

We report on structural change in an Au^3＋-doped BK7 glass irradiated by an infrared femtosecond laser at 800 nm. A grating structure is inscribed in the glass sample. The glass sample is then annealed at various temperatures. Structural change of the grating is observed by an optical microscope. Absorption spectra indicate that colour centres are induced after the laser irradiation, and they decrease with increasing annealing temperature. Au nanoparticles are precipitated at high temperatures （≥ 600℃）. The mechanisms of the phenomena are discussed.     

A new blue-emitting phosphor, SrZnO2:Pb, synthesized by the adipic acid templated sol-gel route

A new blue-emitting phosphor, Sr_1−xPb_xZnO₂, was prepared by a novel adipic acid templated sol-gel route. Photoluminescence and crystalline properties were investigated as functions of calcination temperatures and the Pb²⁺ doping levels. It was found that under UV excitation with a wavelength of 283 or 317 nm, the phosphors gave emission from 374 to 615 nm with a peak centered at 451 nm. This broad-band was composed of UV and the visible range was attributed to an impurity-trapped exciton-type emission. The maximum emission intensity of the Sr_1−xPb_xZnO₂ phosphors occurred at a Pb concentration of x=0.01. The decay time was observed to be ∼33 ms for the compound doped with 1 mol% Pb prepared at 1000 °C. Diffuse reflectance spectra revealed the characteristic absorption peaks and the bandgap energy of SrZnO₂ was found to be 3.4 eV. SEM analysis indicated that phosphor particles have an irregularly rounded morphology and the average particle size was found to be approximately 1 μm.     

Long lifetime and efficient emission from Er ions coupled to Si nanoclusters in Si-rich SiO2 layers

Reactive magnetron co-sputtering of two confocal SiO₂ and Er₂O₃ cathodes in argon-hydrogen plasma was used to deposit Er-doped Si-rich SiO₂ layers. The effects of the deposition conditions (such as RF power applied on each cathode and total plasma pressure) and annealing treatment (temperature and duration) on structural, compositional and photoluminescence (PL) properties of the layers were examined. It was found that a significant enhancement of both Er³⁺ PL intensity and emission lifetime up to 9 ms have been reached through monitoring of the conditions of both deposition process and annealing treatment. The effective absorption cross section and the fraction of Er ions coupled to Si clusters were analyzed. It was shown an increase of the fraction of Er³⁺ ions coupled to Si up to 11%.     

Waveguiding and photoluminescence in Er-doped Ta2O5 planar waveguides

The optimization of erbium-doped Ta₂O₅ thin film waveguides deposited by magnetron sputtering onto thermally oxidized silicon wafer is described. Optical constants of the film were determined by ellipsometry. For the slab waveguides, background losses below 0.4 dB/cm at 633 nm have been obtained before post-annealing. The samples, when pumped at 980 nm yielded a broad photoluminescence spectrum (FWHM∼50 nm) centred at 1534 nm, corresponding to ⁴I_13/2-⁴I_15/2 transition of Er³⁺ ion. The samples were annealed up to 600 °C and both photoluminescence power and fluorescence lifetime increase with post-annealing temperature and a fluorescence lifetime of 2.4 ms was achieved, yielding promising results for compact waveguide amplifiers.     

4-benzyl pyridinium dihydrogenmonophosphate C6H5CH2C5H4NHH2PO4 : Single-crystal structure and its conductivity in polycrystalline form

The salt 4-benzyl pyridinium dihydrogenmonophosphate is monoclinic P2₁/c with the following unit cell dimensions: ; ; ; and β=97.328(11). Also, , D_x=1.403, , F(000)=560; ; and R=0.0495 and R_w=0.0964 for 3733 independent reflections. The structure consists of infinite parallel two-dimensional planes built of H₂PO₄⁻ anions and C₆H₅CH₂C₅H₄NH⁺ cations mutually connected by strong O-H ?O and N-H ?O hydrogen bonding. There are no contacts other than the normal Van der Waals interactions between the layers. The conductivity relaxation parameters associated with some H⁺ conduction have been determined from an analysis of the spectrum measured in a wide temperature range.     

Encapsulation of strontium aluminate phosphors to enhance water resistance and luminescence

Strontium aluminate SrAl₂O₄:Eu²⁺,Dy³⁺ phosphors are chemically unstable against water or even moisture. To enhance the water resistance of the phosphors, an encapsulation was performed by direct surface reactions with phosphoric acid (H₃PO₄). The morphology, surface structure, surface element composition, water resistance, luminescence, and photoacoustic spectrum of the phosphors before and after encapsulation were discussed. Experimental results showed that phosphors were perfectly encapsulated by amorphous layers in nanoscale and crystalline layers in microscale under different conditions. The water resistance of phosphors was greatly enhanced by the two types of layer. More importantly, the amorphous layers enhanced the luminescence of phosphors markedly. The possible mechanism for the enhancements was also proposed.     

Spectral-kinetic characteristics of Pr luminescence in LiLuF4 host upon excitation in the UV-VUV range

Spectral-kinetic study of Pr³⁺ luminescence has been performed for LiLuF₄:Pr(0.1 mol%) single crystal upon the excitation within 5-12 eV range at T=8 K. The fine-structure of Pr³⁺ 4f ²→4f 5d excitation spectra is shown for LiLuF₄:Pr(0.1 mol%) to be affected by the efficient absorption transitions of Pr³⁺ ions into 4f 5d involving 4f ¹ core in the ground state. Favourable conditions have been revealed in LiLuF₄:Pr(0.1 mol%) for the transformation of UV-VUV excitation quanta into the visible range. Lightly doped LiLuF₄:Pr crystals are considered as the promising luminescent materials possessing the efficient Pr³⁺³P₀ visible emission upon UV-VUV excitation. The mechanism of energy transfer between Lu³⁺ host ion and Pr³⁺ impurity is discussed.     

Quantum efficiencies of near-infrared emission from Ni-doped glass-ceramics

A systematic method to evaluate potentials of Ni²⁺-doped transparent glass-ceramics as a new broadband optical gain media is presented. At first, near-infrared emission of various ceramics were investigated to explore the suitable crystalline phase to be grown in the glass-ceramics. The quantum efficiency of Ni²⁺ near-infrared emission estimated by the Struck-Fonger analysis was higher than 95% for spinel-type structure gallate crystals MgGa₂O₄ and LiGa₅O₈ at room temperature. Transparent glass-ceramics containing Ni²⁺:LiGa₅O₈ could be prepared and the quantum efficiency for the glass-ceramics was measured to be about 10%. This value shows a potential of Ni-doped transparent glass-ceramics as a broadband gain media.     

Quantum interference in the Raman scattering from the silicon nanostructures

We report here microscopic process involved in the photo-excited Fano interaction due to nonlinear process in the silicon nanostructures. Photo-excited Raman line-shapes are investigated to reveal the presence of nonlinear Fano interaction in the silicon nanostructures for three different sizes. The Fano interaction is found to be more prominent due to the phase matching between electronic and phonon Raman scatterings for smaller sized nanostructures. Phase matching is achieved by nonlinear process of two-wave mixing in the silicon nanostructures followed by the formation of electron-phonon bound state.     

Influence of the SiO thickness on the photoluminescence properties of Er-doped SiO/SiO2 multilayers

Er-doped SiO single layer and Er-doped SiO/SiO₂ multilayers with different SiO thicknesses were prepared by evaporation. In the as-deposited samples, the erbium ions exhibit a very weak photoluminescence emission at 1.54 μm. This luminescence is strongly enhanced after annealing treatments between 500 and 1050 °C, with an optimal annealing temperature which is dependent from the SiO thickness. For the SiO single layer, this optimal temperature is around 700 °C while it is shifted at highest temperature for the multilayers. The origin of the higher luminescence intensity in the SiO layer is also discussed.     

Effects of citric acid additive on photoluminescence properties of YAG:Ce nanoparticles synthesized by glycothermal reaction

We synthesize Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) nanoparticles in the presence of citric acid by glycothermal method. Fourier transform infrared absorption spectroscopy measurement indicates that the intensity of the peak corresponding to carboxyl groups coordinating to the nanoparticles increases with increasing amount of citric acid. At the same time, the primary particle diameter decreases from 10.2 to 4.0 nm. In addition, the internal quantum efficiency of the photoluminescence (PL) due to the 4f-5d transition of Ce³⁺ increases from 22.0% to 40.1% with increasing amount of citric acid. Two kinds of PL decay lifetimes, 16-26 and 72-112 ns, are detected for YAG:Ce³⁺ nanoparticles, whereas the micron sized YAG:Ce³⁺ bulk shows the lifetime of 57 ns. We discuss these phenomena from the aspects of the coordination of citric acid and the incorporation of Ce³⁺ ions into the nanoparticles.     

Soft X-ray excited optical luminescence studies of gold(I) complex with diphosphine and 4,4′-bipyridyl ligands

The luminescence of gold(I) complex [{-Ph₂P(CH₂)₂Ph₂-AuNC₅H₄C₅H₄NAu-}_x]^2x+ [CF₃CO₂⁻]_2x, in the solid state has been studied by soft X-ray excited optical luminescence and near-edge X-ray absorption fine structures at the C K-edge and we find that the origin of the luminescence is primarily from the 4,4′-bipyridine ligand facilitated by gold(I)-ligand interaction.     

Near-infrared emissions with widely different widths in two kinds of Er-doped oxide glasses with high refractive indices and low phonon energies

Er³⁺-doped alkali-barium-bismuth-tellurite (LKBBT) and alkali-barium-bismuth-gallate (LKBBG) glasses with high refractive indices and low phonon energies have been designed, fabricated, characterized and compared. Intense 1.53 μm emissions with widely different widths in the two kinds of glasses were observed and recorded under 980 nm diode laser excitation. The full-widths at half-maximum of the 1.53 μm emission bands in LKBBT and LKBBG glasses are 58 and 40 nm, and the lifetimes of them were measured to be 3.21 and 3.97 ms, respectively. The quantum efficiencies for the ⁴I_13/2 level in both glasses are almost 100%. The 1.53 μm broad and narrow emissions with high spontaneous emission probabilities and large emission cross-sections indicate that Er³⁺-doped LKBBT and LKBBG glasses are suitable materials in developing broadband optical amplifier and infrared laser, respectively.     

Temperature effect on porous silicon luminescence

A theoretical surface-state model of porousilicon luminescence is proposed. The temperature effect on the PhotoLuminescence (PL) spectrum for pillar and spherical structures is considered, and it is found that the effect is dependent on the doping concentration, the excitation strength, and the shape and dimensions of the Si microstructure. The doping concentration has an effect on the PL intensity at high temperatures and the excitation strength has an effect on the PL intensity at low temperatures. The variations of the PL intensity with temperature are different for the pillar and spherical structures. At low temperatures the PL intensity increases in the pillar structure, while in the spherical structure the PL intensity decreases as the temperature increases, at high temperatures the PL intensities have a maximum for both models. The temperature, at which the PL intensity reaches its maximum, depends on the doping concentration. The PL spectrum has a broader peak structure in the spherical structure than in the pillar structure. The theoretical results are in agreement with experimental results.     

Unusual luminescence of octahedrally coordinated divalent europium ion in Cs2MP2O7 (M=Ca, Sr)

The excitation and emission spectra of octahedrally coordinated europium ion (Eu²⁺) ions in Cs₂M²⁺P₂O₇ (M²⁺=Ca, Sr) are reported and discussed. The remarkable features of the Eu²⁺ luminescence in these phosphate materials include (a) very large Stokes shift of emission (∼1 eV), (b) high luminescence quenching temperature, and (c) unusually low energy of the emitted photons for Eu²⁺ luminescence in phosphate-based materials. The broad emission bands of Eu²⁺ in Cs₂CaP₂O₇ and Cs₂SrP₂O₇ peak at 607 and 563 nm, respectively. The Stokes shift, crystal field splitting, centroid shift and the red shift of the Eu²⁺ 4f⁶5d¹ electronic configuration have been estimated from the relevant optical data. The radiative lifetime of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is ∼1.2 μs. The nature of the Eu²⁺ emission in Cs₂M²⁺P₂O₇ is discussed and arguments are presented to associate the luminescence with an extreme case of normal 4f⁶5d¹→4f⁷[⁸S_7/2] emission.