Characterization of CdSe and CdSe/CdS core/shell nanoclusters synthesized in aqueous solution

CdSe nanoclusters overcoated with CdS shell were prepared with macapoacetic acid as stabilizer. The optical properties of CdSe nanoclusters and the influence of CdS shell on the electronic structures of CdSe cores were studied by optical absorption, photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopies. Based on PL and PLE results and the theoretical calculation on fine structure of bandedge exciton, a model of formation of excimer within the small clusters was proposed to explain the large Stokes shift of luminescence from absorption edge observed in PL results. (C) 2000 Elsevier Science B.V. All rights reserved.

Pressure behavior of deep centers in ZnSxTe1-x alloys

We have measured photoluminescence of ZnSxTe1-x alloys (x > 0.7) at 300 K and under hydrostatic pressure up to 7 GPa. The spectra contain only a broad emission band under excitation of the 406.7 nm line. Its pressure coefficients are 47, 62 and 45 meV/GPa for x = 0.98, 0.92 and 0.79 samples, which are about 26%, 7% and 38% smaller than that of the band gap in the corresponding alloys. The Stokes shifts between emission and absorption of the bands were calculated by fitting the pressure dependence of the emission intensity, being 0.29, 0.48 and 0.13 eV for the three samples, respectively. The small pressure coefficient and large Stokes shift indicate that the emission band observed in our samples may correspond to the Te isoelectronic center in the ZnSxTe1-x alloy.

Experimental study of the U-238(S-36,3-5n)(269-271)Hs reaction leading to the observation of (270)Hs

The deformed doubly magic nucleus (270)Hs has so far only been observed as the four-neutron (4n) evaporation residue of the reaction Mg-26+Cm-248, where a maximum cross section of 3 pb was measured. Theoretical studies on the formation of (270)Hs in the 4n evaporation channel of fusion reactions with different entrance channel asymmetry in the framework of a two-parameter Smoluchowski equation predict that the reactions Ca-48+Ra-226 and S-36+U-238 result in higher cross sections due to lower reaction Q values, in contrast to simple arguments based on the reaction asymmetry, which predict opposite trends. Calculations using HIVAP predict cross sections for the reaction S-36+U-238 that are similar to those of the Mg-26+Cm-248 reaction. Here, we report on the first measurement of evaporation residues formed in the complete nuclear fusion reaction S-36+U-238 and the observation of (270)Hs, which is produced in the 4n evaporation channel, with a measured cross section of 0.8(-0.7)(+2.6) pb at 51-MeV excitation energy. The one-event cross-section limits (68% confidence level) for the 3n, 4n, and 5n evaporation channels at 39-MeV excitation energy are 2.9 pb, while the cross-section limits of the 3n and 5n channel at 51 MeV are 1.5 pb. This is significantly lower than the 5n cross section of the Mg-26+Cm-248 reaction at similar excitation energy.

Rational Design, Synthesis, and Optical Properties of Film-Forming, Near-Infrared Absorbing, and Fluorescent Chiromophores with Multidonors and Large Heterocyclic Acceptors

A new series of film-forming, low-bandgap chromophores (1a,b and 2a,b) were rationally designed with aid of a computational study., and then synthesized and characterized. To realize absorption and emission above the 1000 nm wavelength, the molecular design focuses on lowering the LUMO level by fusing common heterocyclic units into a large conjugated core that acts an electron acceptor and increasing the charge transfer by attaching the multiple electron-donating groups at the appropriate positions of the acceptor core. The chromophores have bandgap levels of 1.27-0.71 eV, and accordingly absorb at 746-1003 nm and emit at 1035-1290 nm in solution. By design, the relatively high molecular weight (up to 2400 g mol(-1)) and non-coplanar structure allow these near-infrared (NIR) chromophores to be readily spin-coated as uniform thin films and doped with other organic semiconductors for potential device applications. Doping with [6,6]-phenyl-C-61 butyric acid methyl ester leads to a red shift in the absorption on]), for la and 2a. An interesting NIR electrochromism was found for 2a, with absorption being turned on at 1034 nm when electrochemically switched (at 1000 mV) from its neutral state to a radical cation state. Furthermore, a large Stokes shift (256-318 nm) is also unique for this multidonor-acceptor type of chromophore.

N-Methyl-N-Allylpyrrolidinium Based Ionic Liquids for Solvent-Free Dye-Sensitized Solar Cells

We prepared four new ionic liquids consisting of N-methyl-N-allylpyrrolidinium cation in conjunction with anions including iodide, nitrate, thiocyanate, and dicyanamide, respectively, and measured their physical properties of density, viscosity, and conductivity. Owing to the relatively lower melting point of electroactive N-methyl-N-allylpyrrolidinium iodide, in combination with three other nonelectroactive ionic liquids, we could construct solvent-free electrolytes possessing high iodide concentrations for dye-sensitized solar cells. We correlated temperature-dependent electrolyte viscosity with molar conductivity and triiodide mobility through applying an empirical Walden's rule and a modified Stokes-Einstein equation, respectively. We have further found that these anions (nitrate, thiocyanate, and dicyanamide) have different influences on surface states and electron transport in the mesoporous titania film, resulting in different photovoltages and photocurrents of dye-sensitized solar cells.

Syntheses of Ag, PbSe, and PbTe nanocrystals and their binary self-assembly exploration at low size-ratio

Nanocrystals of Ag, PbSe, and PbTe were prepared via a high-temperature organic solution approach, respectively. Using a size-selection technique, the size-distribution of each set of nanocrystals could be fine-tuned and finally monodisperse products were achieved. Superlattice structure of binary self-assemblies in low size-ratio were also explored and characterized by transmission electron microscopy. It is realized that a success of achieving binary self-assembly pattern is greatly dependent on several key factors including particle size-distributions, relative concentrations of both components, as well as the size-ratios between Ag and PbSe (or PbTe) nanocrystals.

Mesoscopic simulation of the impregnating process of unidirectional fibrous preform in resin transfer molding

The resin transfer molding has gained popularity in the preparation of fiber-reinforced polymer-matrix composites because of its high efficiency and low pollution. The non-uniform inter-tow and intra-tow flows are regarded as the reason of void formation in RTM. According to the process characteristics, the axisymmetric model was developed to study the interaction between the flow in the inter-tow space and that in the intra-tow space. The flow behavior inside the fiber tows was formulated using Brinkman's equation, while that in the open space around the fiber tows was formulated by Stokes' equation. The volume of fluid (VOF) method was applied to track the flow front, and the effects of filling velocity, resin viscosity, inter-tow dimension and intra-tow permeability on fluid pressure and flow front were analyzed. The results show that the flow front difference between the inter-tow and intra-tow becomes larger with the decrease of intra-tow permeability, as well as the increase of filling velocity and inter-tow dimension.

A new luminescent material: Li2CaSiO4 : Eu2+

In our study, the Eu2+ doped Li2CaSiO4 phosphors were initially synthesized by high temperature solid state method, and their luminescent properties were also investigated. Eu2+ ions occupied 8-coordinatid distorted dodecahedral Ca sites, leading to strong crystal field splitting. The strong crystal field splitting made the broad excitation band extending from UV to visible region. In addition, the high concentration of Li+ ions in the structure constrained the distortion of the emission centers, then resulted in a small stokes shift, similar to 1100 cm(-1). Under excitation, the Li2CaSiO4:Eu2+ phosphors emitted bluish green light with peak of 480 nm, FWHM of 31 nm and color coordination of (0.06, 0.44). The Eu2+ doped Li2CaSiO4 phosphor would be suitable for bluish green phosphor of white LEDs due to its excellent excitation profile and chromaticity.

Tunable photoluminescence in sol-gel derived silica xerogels

Silica xerogels prepared by sol-gel method show blue emission under UV excitation with a smaller Stokes shift. The luminescent properties have been investigated under various preparation conditions and compositions. The silica xerogels show similar luminescent properties when using C2H5OH and N,N-dimethylformamide (DMF) as solvents, which are very different from those when using dimethylsulfoxide (DMSO) as solvent, i.e., a red shift of excitation and emission has been observed in the latter case. The emission intensity of the silica xerogels also depends on the water content and pH of the starting reaction solution. The introduction of organic group (-CH3) in the silica xerogel modifies the network structure and further changes their luminescence properties. Heat treatment results in the decomposition of the organic (-SiCH3) groups, which eliminates the old luminescent centers and produces new luminescent centers in longer wavelength simultaneously. (C) 2000 Elsevier Science B.V. All rights reserved.

Encapsulation of Eu(TTA)(3) into MCM-41 mesoporous molecular sieve by sol-gel method

The rare earth complex Eu(TTA)(3) was successfully encapsulated into MCM-41 mesoporous molecular sieve by the addition of the complex into the sol-gel mixture for the synthesis of MCM-41 mesoporous material under microwave radiation. The as-synthesized MCM-41-hosted Eu(TTA)(3) mesophase was confirmed to possess hexagonally ordered mesostructure and a uniform crystal. size of about 30 nm with XRD and HRTEM techniques. Moreover, the IR spectrum, photoluminescence effect and fluorescence lifetime of the Eu(TTA)(3)/MCM-41 hybrid were also studied. An increase in Stokes' shift and no change in luminescence lifetime were observed to the resultant mesophase in comparison with Eu(TTA)(3) in ethanol solution.

Eu(TTA)_3/MCM-41介孔复合体的溶胶凝胶法组装

利用溶胶 凝胶法将稀土配合物Eu(TTA) 3 组装到MCM 41介孔分子筛的孔道中 ,并初步认定客体分子Eu(TTA) 3 是以加合物形式包裹于表面活性剂胶束中。该法制得的介孔复合体Eu(TTA) 3/MCM 41,用XRD、HRTEM技术证实具有短程有序的、规整的六方介孔结构和大小分布均匀的纳米晶粒。对其光致发光和荧光寿命的研究发现 :与乙醇溶液中相比 ,Eu3 +的荧光寿命没有发生改变 ,但Stokes位移却明显增大 ;复合体中 ,能量是从主体MCM 41传递到客体Eu(TTA) 3 上。

Diffusion-limited kinetics modeling of one-step polyimide formation

A diffusion-limited kinetic model was developed to describe the imidization of one-step polythioetherimide formation based on an endgroup diffusion model. The changes of conversion and viscosity during the imidization were monitored with thermogravimetric analysis and dynamic stress rheometry, respectively. It was observed that the imidization rate began to decelerate after a fast early stage, whereas the viscosity in the system increased dramatically after a period of low value. Amic acid and imide formations concurrently take place in the one-step polyimide formation, but the formation of amic acid is much slower than that of imide and is the rate-limiting step of imidization. When a second-order kinetic model was used to describe the imidization, the effect of viscosity on the diffusion resistance of reactive groups needed to be included. In order to predict the change of viscosity during the imidization, the Lipshitz-Macosko model was modified and introduced into the diffusion-limited kinetic model by the Stokes-Einstein equation. The comparison of the modeled results with experimental data indicated that the diffusion-limited kinetic model and the modified Lipshitz-Macosko model were able to efficiently predict the changes of conversion and viscosity with temperature and time during the one-step polythioetherimide formation. (C) 2001 John Wiley & Sons, Inc.

Luminescence of unusual bismuth in barium berates BaB8O13 : Bi)

The luminescence of unusual divalent bismuth (Bi2+) in BaB8O13 is reported. The emission band with maximum peak at 592 nm corresponds to the P-2(3/2)-->P-2(1/2) transition of Bi2+ in the matrix and the excitation spectrum with two bands peaked at 470 and 580 nm respectively corresponds to two split crystal-field levels of P-2(3/2) state. The small Stokes shift (similar to 350 cm(-1)) reflects the rigid structure of the host for the Bi2+ ions.

Structure, luminescence and magnetic properties of AgLnW(2)O(8) (Ln = Eu, Gd, Tb and Dy) compounds

Four new compounds AgLnW(2)O(8) (Ln = Eu, Gd, Tb and Dy) are prepared by solid-state reactions. They crystallize with a scheelite-related monoclinic symmetry. Infrared (IR) spectra show complicated absorption transitions in the region of 1000-400 cm(-1) that are similar to those of AgLnMo(2)O(8). Broad excitation and emission bands of the tungstate group are observed in AgGdW2O8 and AgTbW2O8 with a large Stokes shift, 12 573 and 12 387 cm(-1), respectively. Excitation and emission spectra of AgLnW(2)O(8) (Ln = Eu, Gd and Tb) show that energy transfer from the tungstate to EU3+, Gd3+ and Tb3+ occurs and that Eu3+ ions occupy a single crystallographic site with the C-2 Site symmetry. (C) 1997 Elsevier Science Ltd. All rights reserved.