The silicon effect on the regioselectivity of the Tsuji-Trost reaction. Experimental and theoretical approaches

Regioselectivity of the Tsuji-Trost reaction on allyl acetates and carbonates substituted with silyl groups at the olefinic moiety has been analyzed. Silicon atom in the central carbon atom increases the stability of the intermediate π-allylpalladium cation with respect to the isomeric π-allylpalladium cation featuring the silicon in a terminal carbon atom.     

In situ observation of NaBi(WO4)2 dendrite growth and the study on microstructure of solidification

The dendrite growth process of transparent NaBi(WO₄)₂ with small prandtl and high melting point was studied by using the in-situ observation system. According to the dynamic images and detailed information, there are two kinds of restriction effect on the dendrite growth, the competition between arms and branches and the convection in the melt. The dendrite growth rate was time dependent, and the rate of arm growth reached the maximum 5.8 mm/s in the diffusive-advective region and rapidly decreased in the diffusive-convective region. The growth rate of branch had the same change trends as the arm’s. Based on the EPMA-EDS data of solidification structure of quenched NaBi(WO₄)₂ melt, it was found that there were component differences from stoichiometric concentration in the melt near the interface during the growth process. Supported by the National Natural Science Foundation of China (Grant No. 50331040) and the Innovation Funds from Shanghai Institute of Ceramics, Chinese Academy of Sciences (Grant No. SCX0623)     

X-ray photoelectron spectroscopy characterization of oxidated Si particles formed by pulsed ion-beam ablation

X-ray photoelectron spectroscopy (XPS) is used to probe oxidation states of Si species in particles deposited using a pulsed ion-beam evaporation method. The effects of He ambient gas, ion beam intensity and post-treatments on the oxides composition and oxygen content have been studied. It is found that presence of He ambient gas led to a profound oxidation of Si species as compared to that prepared in vacuum at the same ion-beam ablation energy, i.e. both increase of SiO₂ component and oxygen concentration in the oxides coverage. The deposition in He also resulted in an increase of oxygen concentration even under lower ablation intensity, but a higher Si suboxides concentration. It is revealed that the reaction between Si and O was controlled by the ion beam intensity (temperature of Si plasma) and the gas ambient (collision probability of Si and O species). The difference in structure of oxide layers for samples obtained under various conditions is discussed based on the results of XPS analyses.     

Synthesis and magnetic properties of multilayer Ni/Cu and NiFe/Cu nanowires

Highly ordered composite nanowires with multilayer Ni/Cu and NiFe/Cu have been fabricated by pulsed electrodeposition into nanoporous alumina membrane. The diameter of wires can be easily varied by pore size of alumina, ranging from 30 to 100 nm. The applied potential and the duration of each potential square pulse determine the thickness of the metal layers. The nanowires have been characterized by transmission electron microscopy (TEM), magnetic force microscopy (MFM), and vibrating sample magnetometer (VSM) measurements. The MFM images indicate that every ferromagnetic layer separated by Cu layer was present as single isolated domain-like magnet. This technique has potential use in the measurement and application of magnetic nanodevices.     

Microstructure array on Si and SiOx generated by micro-contact printing, wet chemical etching and reactive ion etching

A method, combining micro-contact printing (μCP), wet chemical etching and reactive ion etching (RIE), is reported to fabricate microstructures on Si and SiOx. Positive and negative structures were generated based on different stamps used for μCP. The reproducibility of the obtained microstructures shows the methodology reported herein could be useful in Micro-Electro-Mechanical Systems (MEMS), optical and biological sensing applications.     

57Fe Mössbauer spectroscopic study of (25−x)MnO–xZnO–15Fe2O3–60B2O3 glasses

The ⁵⁷Fe Mössbauer technique has been used to investigate the effect of zinc oxide substitution in (25???x)MnO–xZnO–15Fe₂O₃–60B₂O₃ glass system (x?=?0, 5, 10, 15 and 20 mol% of ZnO ). Mössbauer absorption spectra for all the samples recorded at room temperature suggest the existence of the two paramagnetic quadrupole doublets. The observed variations in hyperfine parameters have been explained on the basis of cations distribution and exchange interaction at the lattice sites and it is concluded that B–B interaction increases while the metal–metal interaction decreases due to replacement of manganese oxide by zinc oxide. These results suggest that the present glass system exhibits a paramagnetic behaviour that changes towards the weak paramagnetic when manganese oxide was replaced with zinc oxide.     

排列形状及阵列数目对纳米导线阵列场发射性能的影响

为了进一步研究纳米导线阵列的排列形状以及阵列数目对其场发射行为的影响，利用镜像悬浮球模型对正方形以及六边形排列的纳米导线阵列的场发射行为进行计算与模拟，近似的得到纳米导线阵列的场发射增强因子满足如下的变化趋势：β=h/ρ(1/1+W)+1/2(1/1+W)²+3,其中h为纳米导线的高度，ρ为纳米导线的半径，W是以R为自变量的函数，R为纳米导线阵列的间距.结果显示纳米导线阵列的排列形状对其场发射性能的影响较小，而阵列间距则是影响场发射性能的关键因素：当R<R₀时，场发射增强因子随着阵列间距的减小而急剧减小；当R>R₀时，场发射增强因子基本不变，其中R₀为导线阵列场发射的最佳间距.进一步研究表明改变纳米导线阵列的数目基本不会改变阵列的场发射性能随间距的变化趋势，但是随着阵列数目的增加，R₀会有一定程度的减小，场发射增强因子也会降低. 关键词： 纳米导线 场发射 增强因子 阵列数目     

The electronic structure of the interface between thin conjugated oligomer films and inorganic substrates with different work function

In this work, a comparison of the interfacial electronic properties between a semiconducting oligomer and a variety of substrates with different properties—metal, semiconductor and oxide layers—is reported. The interface formation was studied by X-ray and Ultraviolet photoelectron spectroscopies (XPS, UPS). High purity oligomer films with thickness up to 10 nm were prepared by stepwise evaporation on the clean substrates under ultrahigh vacuum (UHV) conditions. Analysis of the oligomer and substrate related XPS spectra clarified the interfacial chemistry and band bending in the semiconducting materials. The valence band structure and the interfacial dipoles were determined by UPS. The barriers for hole injection were measured at the interfaces of the organic film with all substrates. The interfacial energy band diagrams were deduced in all cases from the combination of XPS and UPS results. Emphasis was given on the influence of the substrate work function (eΦ) on the electronic properties of these interfaces.     

Electrolytical production of Ni + Mo + Si composite coatings with enhanced content of Si

Ni + Mo + Si composite coatings were prepared by co-deposition of nickel with molybdenum and silicon powders from a nickel solution in which Mo and Si particles were suspended by stirring. The layers have been deposited on a carbon steel substrate (St3S) under galvanostatic conditions. The content of Si in deposited layers was about 2-5 wt.% depending on deposition current density and the value of electric charge. For comparison Ni + Mo composite coatings were obtained under analogous current conditions. Composite coatings of enhanced Si content (15 wt.%) were deposited from an electrolyte in which 40 g/dm³ of Si covered with electroless plated nickel was dispersed. Deposition current density was equal 0.1 A/cm² and the value of electric charge Q = 500 C/cm². The thickness of the coatings was about 100-300 μm depending on their kind, electric charge and the deposition current density. Surface and cross-section morphology were investigated by scanning electron microscope (SEM). All deposited coatings are characterized by great, developed surface area. No internal stresses causing their cracking were observed. Chemical composition of the layers was determined by X-ray fluorescence spectroscopy (XRF) method and quantitative X-ray analysis (QXRD). It was stated, that the content of molybdenum and silicon in Ni + Mo + Si coatings depends on deposition current density and the amount of the powder in bath. The results of structural investigation of the obtained layers by the X-ray diffraction (XRD) method show, that they consist in crystalline Mo or Mo and Si phases built into Ni matrix. Moreover, Ni + Mo + Si composite coatings were modified by thermal treatment. It has been found that the thermal treatment of Ni + Mo + Si composite coatings caused that the new phases (NiSi, Mo₂Ni₃Si and Ni₆Mo₆C_1.06) were obtained.     

Fabrication and characterization of sputtered titanium dioxide films

TiO₂ thin films were prepared under various conditions by using a reactive RF sputtering technique. The structural, optical and electrical characteristics of the films have been investigated. All as-deposited films were amorphous. After annealing at T > 673 K, the crystallinity of the observed tetragonal anatase phase appeared improved. The optical band gap, determined by using Tauc plot, has been found to amount to 3.38 ± 0.03 and 3.21 ± 0.03 eV for the direct and indirect transition, respectively. Also the complex optical constants for the wavelength range 300-2500 nm are reported. Using the two-point probe technique, the dark resistivity has been measured as a function of the film thickness, d. The resistivity, ρ, of the samples has been found to decrease markedly with increasing thickness, but only for d < 100 nm. The behaviour of ρd versus d was found to fit properly with the Fuchs and Sondheimer relation with parameters ρ_o = 4.95 × 10⁶ Ω cm and mean free path, l = 310 ± 2 nm. The log ρ versus 1/T curves show three distinct regions with values for the activation energy of 0.03 ± 0.01, 0.17 ± 0.01 and 0.50 ± 0.02 eV, respectively.