The photosensitive effect of Ce on the precipitation of Ag nanoparticles induced by femtosecond laser in silicate glass

This paper studies the photosensitive effect of cerium oxide on the precipitation of Ag nanoparticles after femtosecond laser irradiating into silicate glass and successive annealing. Spectroscopy analysis and diffraction efficiency measurements show that the introduction of cerium oxide may increase the concentration of Ag atoms in the femtosecond laser-irradiated regions resulting from the photoreduction reaction Ce³⁺ + Ag⁺ \to Ce³⁺ + Ag⁰ via multiphoton excitation. These results promote the aggregation of Ag nanoparticles during the annealing process. It is also found that different concentrations of cerium oxide may influence the Ag nanoparticle precipitation in the corresponding glass.     

Luminescence studies on lanthanide ions (Eu, Dy and Tb) doped YAG:Ce nano-phosphors

Yttrium aluminum garnet nanoparticles both undoped and doped with lanthanide ions (Ce³⁺, Eu³⁺, Dy³⁺ and Tb³⁺) having average size around 30 (±3 nm) nm were prepared by glycine nitrate combustion method followed by annealing at a relatively low temperature of 800 °C. Increase in the annealing temperature has been found to improve the luminescence intensity and for 1200 °C heated samples there exists strong energy transfer from Tb³⁺ to Ce³⁺ ions in YAG:Ce(2%),Tb(2%) nanoparticles as revealed by luminescence studies. Co-doping the YAG:Ce nanoparticles with Eu³⁺ results in significant decrease in the emission intensity of both Ce³⁺ and Eu³⁺ ions and this has been attributed to the oxidation of Ce³⁺ to Ce⁴⁺ and reduction of Eu³⁺ to Eu²⁺ ions. Dy³⁺ co-doping did not have any effect on the Ce³⁺ emission as there is no energy transfer between Dy³⁺ and Ce³⁺ ions.     

敏化离子Ce3+对Er3+∶YAG的1.6μm波长激光性能的影响

测定了Ce³⁺,Er³⁺∶YAG中Ce³⁺离子的吸收截面.用从能级跃迁速率方程和激光传输方程推出的表达式计算了1.6μm波长激光的阈值能量(功率)和斜率效率.表明在Ce³⁺,Er³⁺∶YAG中,Ce³⁺对Er³⁺离子的激光性能影响与激活离子Er³⁺的浓度、晶棒大小有关.短晶棒或浓度低的晶体加入Ce³⁺可降低Er 关键词：     

Observation of green emission from Ce-doped gadolinium oxide nanoparticles

Green emission at around 500 nm is observed in Gd₂O₃:Ce³⁺ nanoparticles and the intensity is highly dependent on the concentration of Ce³⁺ in the nanoparticles. The luminescence of this emission displays both picosecond (ps) and millisecond (ms) lifetimes. The ms lifetime is over four orders of magnitude longer than typical luminescence lifetimes (10-40 ns) of Ce³⁺ in traditional Ce³⁺ doped phosphors and therefore likely originates from defect states. The picosecond lifetime is shorter than the typical Ce³⁺ value and is also likely due to defect or surface states. When the samples are annealed at 700 °C, this emission disappears possibly due to changes in the defect moieties or concentration. In addition, a blue emission at around 430 nm is observed in freshly prepared Gd₂O₃ undoped nanoparticles, which is attributed to the stabilizer, polyethylene glycol biscarboxymethyl ether. On aging, the undoped particles show similar emission to the doped particles with similar luminescence lifetimes. When Eu³⁺ ions are co-doped in Gd₂O₃:Ce nanoparticles, both the green emission and the emission at 612 nm from Eu³⁺ are observed.     

Space-selective co-precipitation of silver and gold nanoparticles in femtosecond laser pulses irradiated Ag, Au co-doped silicate glass

We report on space-selective co-precipitation of silver and gold nanoparticles in Ag⁺, Au³⁺ co-doped silicate glasses by irradiation of femtosecond laser pulses and subsequent annealing at high temperatures. The color of the irradiated area in the glass sample changed from yellow to red with the increase of the annealing temperature. The effects of average laser power and annealing temperature on precipitation of the nanoparticles were investigated. A reasonable mechanism was proposed to explain the observed phenomena.     

Ce3+ 掺杂高密度氧化物玻璃的闪烁性能研究

用高温熔融法制备了以SiO₂-B₂O₃-Al₂O₃-Gd₂O₃为基质系统Ce³⁺掺杂的玻璃样品, 测试样品的密度、紫外——可见透射光谱、紫外激发光谱和主要的闪烁性能, 并且把一部分闪烁性能和PbWO晶体及BGO晶体做比较. 着重研究了不同Ce³⁺掺杂浓度与Gd³⁺ 离子的含量对玻璃样品闪烁性能的影响规律. 结果表明: 玻璃样品具有较大的密度; 样品的X射线激发发射光谱发射峰位置都在390 nm左右, 当Ce³⁺ 离子的掺杂浓度为1.0 mol%(摩尔分数)、Gd₂O₃含量为15 mol%时, 玻璃样品的发光峰强度达到BGO晶体发光强度的90%; 同样验证了Ce³⁺ 离子具有浓度猝灭效应; Gd³⁺可以敏化Ce³⁺离子发光, 但是Gd³⁺离子到达一定浓度时, 反而会产生猝灭效应, 降低了Ce³⁺ 离子的发光. Ce³⁺ 离子掺杂SiO₂-B₂O₃-Al₂O₃-Gd₂O₃系统的闪烁玻璃有望替代闪烁晶体广泛应用于高能物理中.     

Effect of the valence state of ce ions on the phase stability and mechanical properties of the crystals of ZrO<Subscript>2</Subscript>-based solid solutions

The structure and mechanical properties of the crystals of solid solutions of zirconium dioxide, which are stabilized by yttrium and cerium oxides, have been studied. The electron paramagnetic resonance technique has been used to identify Ce³⁺ ions and to determine their relative concentration in the crystals. It is shown that the presence of Ce³⁺ ions in the crystals is the main factor responsible for their high fracture toughness. The annealings carried out during investigations, which lead to a decrease in the concentration of Ce³⁺ ions, show that a change in the valence state of cerium ions lowers the fracture toughness of the crystals.     

A novel scheme to acquire enhanced up-conversion emissions of Ho3+ and Yb3+ co-doped Sc2O3

A detailed investigation about the effect of Sc₂O₃: 1 mol%Ho³⁺/5 mol%Yb³⁺ co-doped with Ce⁴⁺ ions prepared by sol-gel methods was performed systematically. Under the excitation of 980 nm laser diode, both green emission (553 nm, ⁵F₄/⁵S₂→⁵I₈) and red emission (672 nm, ⁵F₅→⁵I₈) were both observed in the emission spectra of the samples, which were found to be two-photon process and sensitized by Yb³⁺ ions. With the increasing of Ce⁴⁺ ions, the up-conversion green emission intensity are increased by 6.52, 8.69, 10.85, 13.92 and 16.66 fold, corresponding to the Ce⁴⁺ ions concentrations from 5 mol% to 13 mol%, respectively. The number of photons are necessary to populate the upper emitting state decreases to 2 and the infrared absorption coefficient is reduced, when the Ce⁴⁺ ions concentration increase to 13 mol%. Ce⁴⁺ ions play an important role in tailoring the local crystal field around Ho³⁺ ions, lowering the highest phonon cut-off energy of matrix and reducing the infrared absorption coefficient, thus hindering the non-radiative processes, which contribute to the increased emission intensity. The excellent enhancement makes it a promising multifunctional optical luminescence material.     

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.     

Absorption and photoluminescence of YAG:Er3+, YAG:Ce3+, and YAG:Er3++Ce3+ crystals

We have studied absorption and luminescence spectra of yttrium-aluminum garnets doped with Er³⁺ and Ce³⁺ ions, as well as co-doped with Er³⁺+Ce³⁺ impurity ions. Luminescence of studied crystals was excited by cw laser radiation at the wavelengths 457 and 980 nm. We revealed obvious display of the energy transfer processes occurring in the impurity subsystem of a YAG: Er³⁺+Ce³⁺ crystal.     

Spatially selective modification of optical and magneto-optical properties in Fe- and Au-doped glasses irradiated with femtosecond-laser

The optical property and the magneto-optical response were space-selectively modified in transparent Fe³⁺- and Au³⁺-doped glasses by using infrared femtosecond- (fs-) laser irradiation and subsequent annealing. This irradiation process induces the precipitation of not only magnetic spinel-type Fe-oxide nanoparticles but also Au nanoparticles inside the glasses, which shows localized surface plasmon resonance absorption at the wavelengths larger than 500 nm. As the annealing time and the temperature increases, the position of the LSPR peaks exhibits red shifts, which is due to the growth of Au nanoparticles. Faraday rotation angles as a function of wavelength were measured, and the difference spectra exhibit distinct positive peaks, indicating that the coupling between the LSPR due to the Au nanoparticles and the diamagnetism of the matrix glass is effective. To decrease the coupling with the diamagnetic glass, a two-step annealing process (at 450 °C for 90 min and at 550 °C for 30 min) was carried out after irradiation with fs-laser. The preliminary annealing at the lower temperature contributes to the precipitation of ferrimagnetic magnetite nanoparticles. Au nanoparticles were subsequently grown by annealing at 550 °C. In this case, effective coupling between the LSPR and ferrimagnetic nanoparticles has significantly suppressed the intensity of the positive peak in the Faraday spectra compared with the single annealing process.     

Bridging between structure and optimum luminescence for nearly monodispersed Ce1−xGdxF3:Eu3+ nanoparticles

This work reports a systematic study on bridging between structure and optimum luminescence for Ce_1?xGd_xF₃:Eu³⁺ nanoparticles. It is found that all Ce_1?xGd_xF₃:Eu³⁺ nanoparticles were nearly monodispersed, showing average grain diameter of 30–35 nm. Regardless of the dopant level, all nanocrystals crystallized in a single hexagonal phase. With increasing Gd³⁺ content, the lattice dimension for Ce_1?xGd_xF₃:Eu³⁺ linearly decreased, which was followed by the highly distorted lattice symmetry surrounding Eu³⁺. The consequence of the structural modification is that the color purity was significantly improved. Furthermore, the excitation energy of Ce³⁺ in the ultraviolet range was efficiently transferred to Eu³⁺ ions via the sensitizer Gd³⁺, which significantly enhanced the red emission and showed a maximized quantum efficiency of 59.7%.     

Erratum to Formation and control of Au and Ag nanoparticles inside borate glasses using femtosecond laser and heat treatment

We report the spectroscopic properties of femtosecond laser-irradiated sodium-alumino-borate glass doped with silver and gold ions. We precipitated gold and silver nanoparticles by laser irradiation and annealing at 400°C for 30 min. The irradiation and annealing treatment produced different absorption and emission characteristics in Au³⁺ doped and Au³⁺, Ag⁺ codoped glasses, and the possible mechanisms of the observed results are discussed. The size of the nanoparticles was estimated by TEM and absorption band analysis.     

Thermoluminescence characteristics of rare-earth-doped LiCaBO3 phosphor

LiCaBO₃ was synthesized by high-temperature solid-state reaction. The influence of different rare earth dopants, i.e. Dy³⁺, Tb³⁺, Tm³⁺ and Ce³⁺, on thermoluminescence (TL) of LiCaBO₃ phosphor was discussed. We studied the TL properties and some dosimetric characteristics of Ce³⁺-activated LiCaBO₃ phosphor in detail. The effect of the concentration of Ce³⁺ on TL was investigated, the result of which showed that the optimum Ce³⁺ concentration was 1 mol%. The TL kinetic parameters of LiCaBO₃:0.01Ce³⁺ were studied by computer glow curve deconvolution (CGCD) method. The three-dimensional (3D) TL emission spectra were also studied, peaking at 431 and 474 nm due to the characteristic transition of Ce³⁺. We also studied the linearity, annealing condition, reproducibility, fading and different heating rate of the LiCaBO₃:0.01Ce³⁺ phosphor.     

Study of ESR spectra of Ce<Superscript>3+</Superscript> ions in polycrystalline Sr<Subscript>2</Subscript>B<Subscript>5</Subscript>O<Subscript>9</Subscript>Br

ESR spectra of Ce³⁺ ions in polycrystalline Sr₂B₅O₉Br were studied, and the two crystallographic positions of the Ce³⁺ ion in this compound were identified on the basis of the data obtained. The ESR spectrum of Ce³⁺ ions with local charge compensation contains a broad line indicating the existence of several types of charge compensation. ESR spectra of Ce³⁺ ions in samples activated additionally by K⁺ ions are similar to those of the regular Ce³⁺ centers, which indicates that the effect of the univalent cation on Ce³⁺ is negligible.     

The effect of codopants on spectral-kinetic characteristics of luminescence of scintillation glasses doped with terbium ions

The effect of Ce³⁺ and Pr³⁺ ions on spectral-kinetic characteristics of luminescence of lithium–phosphate–borate glasses is studied. It is shown that terbium ion luminescence caused by transitions from ⁵D₃ and ⁵D₄ multiplets to the ground 7FJ term is detected in samples containing Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺. It has been found that an increase in the concentration of cerium ions from 0.2 to 1 wt % leads to an increase in the intensity of main luminescence bands of terbium ions. In Tb³⁺/Pr³⁺ glasses, a decrease in the relative light yield is observed with an increase in the concentration of Pr³⁺ ions. Processes of energy transfer between Tb³⁺/Ce³⁺ and Tb³⁺/Pr³⁺ ions are discussed.     

Growth and characterization of cerium-substituted yttrium iron garnet single crystals for magneto-optical applications

This paper is concerned with the preparation and characterization of cerium-substituted yttrium iron garnets, which are known to be oxides having a large Faraday rotation effect. Using the improved flux method we successfully grew bulk single crystals of iron garnet doped with Ce³⁺ ions with maximum substitutions up to 0.349. Here we investigate different solution compositions for maximum Ce³⁺ substitution. The Faraday rotation and optical absorption spectra were measured in the near infrared region for different Ce³⁺ ion substituted iron garnets. The specific Faraday rotation of Ce_0.349Eu_0.195Y_2.456Fe₅O₁₂ was found to be 1430 deg/cm at a wavelength of 780 nm and –1280 deg/cm at 1150 nm. The Ce substitution prominently enhances the Faraday rotation effect, and Yb³⁺ and Eu³⁺ ions substituted for Y³⁺ in the dodecahedral sites of YIG can increase the concentration of Ce³⁺ ions, depressing the formation of nonmagnetic Ce⁴⁺ ions by charge compensation. Received: 24 January 2001 / Accepted: 2 March 2001 / Published online: 27 June 2001     

Cool white light emission on Ca3−(l+n)MgSi2O8:\mathrm{Ce}_{\mathrm{l}}^{3+}, \mathrm{Eu}_{n}^{2+} phosphors and analysis of energy transfer mechanism

Rare earth ions (Ce³⁺, Eu²⁺) activated Ca₃MgSi₂O₈ (CMSO) phosphors have been synthesized using solid-state reaction method in 95%N₂+5%H₂ reduction atmosphere at elevated temperatures by varying Eu²⁺ concentration from 0.0075 to 0.0300 at the fixed Ce_0.03 concentration to study their photoluminescence (PL) properties. An energy transfer occurs from Ce³⁺ to Eu²⁺ through a significant overlap of Eu²⁺ excitation spectrum with Ce³⁺ emission spectrum in CMSO, together with the systematic relative decrease and increase in emission bands of Ce³⁺ and Eu²⁺, respectively, have been observed. To support the phenomenon, diffuse reflectance spectra show various absorption levels corresponding to Ce³⁺, Eu²⁺, and/or mixture of both rare earth ions. An optimum emission was realized at 0.0150 of Eu²⁺ via. energy transfer from Ce³⁺ ion. By utilizing the principle of energy transfer, the critical distance (R _c ) between activator ions was found to be 18.64 Å. The CIE chromaticity coordinates measured on the Ca₃MgSi₂O₈:Ce³⁺, Eu²⁺ phosphors excited under ultraviolet (365 nm) source shows the values lie in cool white light region could be applied to solid state lighting.     

Temperature-dependent photoluminescence properties of (Y, Lu)3Al5O12:Ce phosphors for white LEDs applications

The effects of the excitation wavelength, Ce³⁺ concentration and chemical substitution on the thermal quenching of Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce³⁺) phosphors were investigated over a temperature range from 30 to 250 °C. The quenching behavior exhibits a complex dependence on the excitation wavelength and Ce³⁺ concentration, which can be attributed to temperature-dependent absorption strength of the different f-d absorption bands and thermally activated concentration quenching with or without energy migrations between Ce³⁺ ions, respectively. With increasing Lu³⁺content the luminescence of (Y, Lu)₃Al₅O₁₂:Ce³⁺ phosphors shows a pronounced blueshift, and simultaneously the temperature quenching is obviously improved due to a decrease in Stokes shift.     

Study of the growth of CeO2 nanoparticles onto titanate nanotubes

We report the study of the growth of CeO₂ nanoparticles on the external walls and Ce⁴⁺ intercalation within the titanate nanotubes. The materials were fully characterized by multiple techniques, such as: Raman spectroscopy, infrared spectroscopy (FTIR), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The ion exchange processes in the titanate nanotubes were carried out using different concentrations of Ce⁴⁺ in aqueous solution. Our results indicate that the growth of CeO₂ nanoparticles grown mediated by the hydrolysis in the colloidal species of Ce and the attachment onto the titanate nanotubes happened and get it strongly anchored to the titanate nanotube surface by a simple electrostatic interaction between the nanoparticles and titanate nanotubes, which can explain the small size and even distribution of nanoparticles on titanate supports. It was demonstrated that it is possible to control the amount and size of CeO₂ nanoparticles onto the nanotube surface, the species of the Ce ions intercalated between the layers of titanate nanotubes, and the materials could be tuned for using in specific catalysis in according with the amount of CeO₂ nanoparticles, their oxygen vacancies/defects and the types of Ce species (Ce⁴⁺ or Ce³⁺) present into the nanotubes.