Sol-gel synthesis and characterization of SiO2@CaWO4, SiO2@CaWO4 : Eu3+/Tb3+ core-shell structured spherical particles

Nanocrystalline CaWO4 and Eu3+ (Tb3+)-doped CaWO4 phosphor layers were coated on non-aggregated, monodisperse and spherical SiO2 particles by the Pechini sol-gel method, resulting in the formation of SiO2@CaWO4, SiO2@CaWO4:Eu3+/Tb3+, core-shell structured particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), photoluminescence (PL), low-voltage cathodoluminescence (CL), time-resolved PL spectra and lifetimes were used to characterize the core-shell structured materials. Both XRD and FT-IR indicate that CaWO4 layers have been successfully coated on the SiO2 particles, which can be further verified by the FESEM and TEM images. The PL and CL demonstrate that the SiO2@CaWO4 sample exhibits blue emission band WO42- with a maximum at 420 nm (lifetime = 12.8 mu s) originated from the 4 groups, while SiO2@CaWO4:Eu3+ and SiO2@CaWO4:Tb3+ show additional red emission dominated by 614 nm (Eu3+:D-5(0)-F-7(2) transition, lifetime = 1.04 ms) and green emission at 544 nm (Tb3+:D-5(4)-F-7(5) transition, lifetime = 1.38 ms), respectively.

Sol-gel synthesis and photoluminescence properties of spherical SiO2@LaPO4 : Ce3+/Tb3+ particles with a core-shell structure

LaPO4: Ce3+ and LaPO4: Ce3+, Tb3+ phosphor layers have been deposited successfully on monodispersed and spherical SiO2 particles of different sizes ( 300, 500, 900 and 1200 nm) through a sol - gel process, resulting in the formation of core - shell structured SiO2@ LaPO4: Ce3+/ Tb3+ particles. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microcopy (SEM), transmission electron microscopy (TEM), and general and time-resolved photoluminescence (PL) spectra as well as lifetimes were used to characterize the resulting SiO2@ LaPO4: Ce3+/ Tb3+ samples. The XRD results demonstrate that the LaPO4: Ce3+, Tb3+ layers begin to crystallize on the SiO2 templates after annealing at 700 degrees C, and the crystallinity increases on raising the annealing temperature. The obtained core - shell phosphors have perfectly spherical shape with a narrow size distribution, non-agglomeration, and a smooth surface. The doped rare-earth ions show their characteristic emission in the core - shell phosphors, i.e. Ce3+ 5d - 4f and Tb3+5D4 - F-7(J) (J = 6 - 3) transitions, respectively. The PL intensity of the Tb3+ increased on increasing the annealing temperature and the SiO2 core particle size.

Fabrication and optical properties of core-shell structured spherical SiO2@GdVO4 : Eu3+ phosphor via sol-gel process

Europium-doped nanocrystalline GdVO4 phosphor layers were coated on the surface of preformed submicron silica spheres by sol-gel method. The resulted SiO2@Gd0.95Eu0.05VO4 core-shell particles were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (FESEM), energy-dispersive X-ray spectra (EDS), transmission electron microscopy (TEM), photoluminescence (PL) spectra, low voltage cathodoluminescence (CL), time resolved PL spectra and kinetic decays. The XRD results demonstrate that the Gd0.95Eu0.05VO4 layers begin to crystallize on the SiO2 spheres after annealing at 600 C and the crystallinity increases with raising the annealing temperature. The obtained core-shell phosphors have spherical shape, narrow size distribution (average size ca. 600 nm), non-agglomeration. The thickness of the Gd0.95Eu0.05VO4 shells on the SiO2 cores could be easily tailored by varying the number of deposition cycles (50 nm for four deposition cycles). PL and CL show that the emissions are dominated by D-5(0)-F-7(2) transition of Eu3+ (618 nm, red).

Electrochemical growth and characterization of polyoxometalate-containing monolayers and multilayers on alkanethiol monolayers self-assembled on gold electrodes

A general strategy has been developed for fabrication of ultrathin monolayer and multilayer composite films composed of nearly all kinds of polyoxometalates (POMs), including isopolyanions (IPAs), and heteropolyanions (HPAs). It involves stepwise adsorption between the anionic POMs and a cationic polymer on alkanethiol (cysteamine and 3-mercaptopropionic acid) self-assembled monolayers (SAMs) based on electrostatic interaction. Here a Keggin-type HPA SiMo11VO405- was chosen as a main representative to elucidate, in detail, the fabrication and characterization of the as-prepared composite films. A novel electrochemical growth method we developed for film formation involves cyclic potential sweeps over a suitable potential range in modifier solutions. It was comparatively studied with a commonly used method of immersion growth, i.e., alternately dipping a substrate into modifier solutions. Growth processes and structural characteristics of the composite films are characterized in detail by cyclic voltammetry, UV-vis spectroscopy (UV-vis), X-ray photoelectron spectroscopy (XPS), micro-Fourier transform infrared reflection-absorption spectroscopy (FTIR-RA), and electrochemical quartz crystal microbalance (EQCM). The electrochemical growth is proven to be more advantageous than the immersion growth. The composite films exhibit well-defined surface waves characteristic of the HPAs' redox reactions. In addition, the composite films by the electrochemical growth show a uniform structure and an excellent stability. Ion motions accompanying the redox processes of SiMo11VO405- in multilayer films are examined by in situ time-resolved EQCM and some results are first reported. The strategy used here has been successfully popularized to IPAs as well as other HPAs no matter what structure and composition they have.

Effect of water on the electrochemical oxidation process of biliverdin in dimethylformamide

A systematic study has been made for the electrochemical oxidation reaction of biliverdin (BV) in pure dimethylformamide (DMF) and in DMF - H2O mixed solvent by in situ time resolved spectroelectrochemical and cyclic voltametric techniques. The experiments show that not only the oxidation of BV is promoted, the reaction mechanism is also changed from a ECEC to a ECCECC process by the introduction of water into DMF.

LIFETIMES OF RYDBERG LEVELS IN THE PERTURBED 6SNP 3P2 SERIES OF YTTERBIUM-I

Using three-step laser excitation in an atomic beam and a time-resolved spectroscopy technique, we measured both the lifetimes of the Rydberg levels of Yb I belonging to the perturbed series 6nsp 3P2 and the lifetimes of the perturbing 4f(13)5d(2)6s 3P2, 1D2 levels. An expected shortening has been observed for the lifetimes of those levels which are strongly mixed with the perturbers.

Arc Root Motions In An Argon-Hydrogen Direct-Current Plasma Torch At Reduced Pressure

Arc root motions in generating dc argon-hydrogen plasma at reduced pressure are optically observed using a high-speed video camera. The time resolved angular position of the arc root attachment point is measured and analysed. The arc root movement is characterized as a chaotic and jumping motion along the circular direction on the anode surface.

Ultrafast electronic excitation in CaF2 crystals

A new pump and probe experimental system was developed, the pump pulse duration of which is stretched and is much longer than that of the probe pulse. Using this system, time-resolved electronic excitation processes and damage mechanisms in CaF2 crystals were studied. The measured reflectivity of the probe pulse begins to increase at the peak of the pump pulse and increases rapidly in the latter half of the pump pulse, when the pump pulse duration is stretched to 580fs. Our experimental results indicate that both multiphoton ionization and impact ionization play important roles in the generation of conduction band electrons, at least they do so when the pump pulse durations are equal to or longer than 580fs.

Mechanisms of femtosecond laser-induced breakdown and damage in MgO

Single-shot laser damage threshold of MgO for 40-986 fs, 800 nm laser pulses is reported. The pump-probe measurements with femtosecond pulses were carried out to investigate the time-resolved electronic excitation processes. A theoretical model including conduction band electrons (CBE) production and laser energy deposition was applied to discuss the roles of multiphoton ionization (MPI) and avalanche ionization in femtosecond laser-induced dielectric breakdown. The results indicate that avalanche ionization plays the dominant role in the femtosecond laser-induced breakdown in MgO near the damage threshold. (c) 2005 Elsevier B.V. All rights reserved.

飞秒强激光场中大尺寸氩团簇爆炸机理的实验研究

By using time-of-flight spectroscopy, the ionization and explosion of large argon clusters ( (n) over bar = 3 x 10(3) - 3 x 10(6)) in the intense femtosecond pulsed laser field (60 fs,2 x 10(16) W/cm(2)) has been studied, and the dependence of average energy of ions emitted from argon clusters on the gas backing pressure has been measured. By comparing the average ion energies obtained with two different supersonic conical nozzles and considering the Hagena's scaling law of clusters, we have found that the average ion energy is determined by the cluster size when the laser parameters are kept unchanged. The experimental results indicated that when the cluster size is less than 3 x 10(5) atoms per cluster, the Coulomb repulsion force is the dominating factor in the expansion mechanism. Beyond this size, for 3 x 10(5) < (n) over barn < 3 x 10(6), the expansion is the result of the combined effect of both the Coulomb repulsion force and the hydrodynamic force, and the latter will play the dominating role for increasing cluster size.

飞秒激光作用下全向高反膜破坏的激发过程

设计和制备了全向高反膜SiO2／TiO2，研究了它在不同脉冲宽度、不同脉冲能量的飞秒激光作用下的破坏阈值和烧蚀深度．利用发展的抽运．探针方法，研究了抽运脉冲作用下材料中导带电子的超快激发和能量沉积过程，建立并求解了飞秒激光激发材料和材料的激发对抽运光自身反作用的耦合动力学模型．模型较好地揭示了材料破坏的激发过程．

飞秒激光作用下透明介质材料的反射率演化

利用800nm抽运和400nm探针技术，测量了CaF2和MgO的时间分辨反射率，研究了材料的电子激发和弛豫超快动力学过程。采用耦合动力学模型，探讨了飞秒激光对透明介质材料的激发，以及材料的激发对抽运激光在材料中的传输、分布和反射特性的影响。根据这个理论模型计算了时间分辨反射率的演化，计算结果和实验结果相吻合。研究表明，多光子电离（MPI）和碰撞电离（II）在介质材料的导带电子激发中起着重要的作用。

时间分辨的X射线衍射

详细论述了时间分辨X射线衍射探测原子动态过程和生物大分子瞬态结构的各种方法。介绍了多种超快X射线脉冲光源及其在材料和生化领域中的研究进展状况。材料方面：在皮秒时间尺度探测到了晶格间距毫埃的微小变化；在亚皮秒的时间尺度直接观测到晶体的超快熔化过程和晶体内的相干声子散射；生物化学方面：采用时间分辨X射线劳厄衍射方法探测了蛋白质大分子结构的变化和功能之间的关系；精确描述了有机分子在光作用下形态发生改变时分子键角的扭转角度，从结构上揭示了其动态机理。

Energy transfer between silicon-oxygen-related defects and Yb3+ in transparent glass ceramics containing Ba2TiSi2O 8 nanocrystals

We report on the conversion of near-ultraviolet radiation of 250-350 nm into near-infrared emission of 970-1100 nm in Yb3+-doped transparent glass ceramics containing Ba2TiSi2O8 nanocrystals due to the energy transfer from the silicon-oxygen-related defects to Yb3+ ions. Efficient Yb3+ emission (F-2(5/2)-> F-2(7/2)) was detected under the excitation of defects absorption at 314 nm. The occurrence of energy transfer is proven by both steady state and time-resolved emission spectra, respectively, at 15 K. The Yb2O3 concentration dependent energy transfer efficiency has also been evaluated, and the maximum value is 65% for 8 mol % Yb2O3 doped glass ceramic. These materials are promising for the enhancement of photovoltaic conversion efficiency of silicon solar cells via spectra modification.

Ultrafast dynamics in ZnO thin films irradiated by femtosecond lasers

The damage morphologies, threshold fluences in ZnO films were studied with femtosecond laser pulses. Time-resolved reflectivity and transmissivity have been measured by the pump-probe technique at different pump fluences and wavelengths. The results indicate that two-phase transition is the dominant damage mechanism, which is similar to that in narrow band gap semiconductors. The estimated energy loss rate of conduction electrons is 1.5 eV/ps. (c) 2005 Elsevier Ltd. All rights reserved.