铀表面初始氧化行为的电子能量损失谱研究

利用俄歇电子能谱仪获取了表面清洁的铀及其在氧化过程中的电子能量损失谱(EELS)，研究这些电子能量损失谱线显示：清洁表面铀的等离子损失的实验值与理论值较为符合；随着氧化程度的加剧，体等离子体(BP)、表面等离子体(SP)以及价带间跃迁所造成的电子能量损失峰发生了明显的连续偏移和强度的变化，表明室温下清洁表面铀暴露微量纯氧后，在铀表面上发生了U→UO→UO2初始氧化过程。同时，又采用了俄歇电子能谱(AES)和X射线光电子谱(XPS)对照分析了铀的初始氧化过程。     

Direct atomic scale analysis of the distribution of Cu valence states in Cu/γ-Al2O3 catalysts

In this paper, the microstructure of a 1 wt.% Cu/γ-Al₂O₃ catalyst that was reduced in a 4% hydrogen/argon atmosphere at temperatures of 523, 773 and 1073 K, is studied by Z-contrast imaging and electron energy-loss spectroscopy (EELS) in a scanning transmission electron microscope (STEM). Results show that the copper species are well dispersed when the catalyst is reduced below 523 K. At 773 K, separated Cu(I) and Cu(0) species are found existing as ring-like and bulk-like particles. This appears to indicate that the copper has not been reduced to its metallic form due to the interaction between the copper oxide and the support. Large spherical particles having core-shell structures with Cu(I) in the shells and Cu(0) in the cores are generated when the catalyst is reduced at 1073 K. The formation of partially oxidized copper species upon reduction at 1073 K is attributed to the metallic copper interaction with the alumina support. This study also demonstrates that high-spatial resolution Z-contrast imaging and EELS performed simultaneously can provide unique information on the morphology and chemistry of metal species in supported metal catalysts.     

Quantitative analysis of complex carbo-nitride precipitates in steels

Two new types of extraction replicas for precipitate analysis in steels have been developed. These replicas, based on alumina, allow accurate quantification of the carbon to nitrogen ratios in carbo-nitride precipitates using parallel electron energy loss spectroscopy in the TEM. Experiments on microalloyed steels show the importance of the nitrogen content in promoting precipitation even at low temperatures.     

OptaDOS: A tool for obtaining density of states,core-level and optical spectra from electronic structure codes

We present OptaDOS, a program for calculating core-electron and low-loss electron energy loss spectra (EELS) and optical spectra along with total-, projected- and joint-density of electronic states (DOS) from single-particle eigenenergies and dipole transition coefficients. Energy-loss spectroscopy is an important tool for probing bonding within a material. Interpreting these spectra can be aided by first principles calculations. The spectra are generated from the eigenenergies through integration over the Brillouin zone. An important feature of this code is that this integration is performed using a choice of adaptive or linear extrapolation broadening methods which we show produces higher accuracy spectra than standard fixed-width Gaussian broadening. OptaDOS  may be straightforwardly interfaced to any electronic structure code. OptaDOS  is freely available under the GNU General Public licence from http://www.optados.org.     

New approach in depositing thick, layered cubic boron nitride coatings by oxygen addition—structural and compositional analysis

Cubic boron nitride (c-BN) can be produced by PVD and PA-CVD techniques by intensive ion bombardment leading to highly stressed films limiting its use in industrial applications. Various attempts have been undertaken to reduce the compressive stress of c-BN thin films. A significant reduction in compressive stress and a substantially improved adhesion was achieved by a new coating concept consisting of a two-step adhesion-promoting base layer, a compositional-graded nucleation layer obtained by a stepwise decrease of the oxygen content in the Ar/N₂/O₂ atmosphere and a low-stressed c-BN:O top layer with controlled oxygen addition. The four-layer c-BN:O film with a thickness of 3 μm was deposited by unbalanced radio frequency magnetron sputtering of a hot-pressed hexagonal boron nitride target on silicon substrates. The adhesion layer was deposited in a mixed Ar/O₂ atmosphere of 0.26 Pa with a stepwise increased nitrogen gas flow and a subsequent increase of the ion energy by increasing the substrate bias from 0 to − 250 V. The c-BN nucleation was gradually initiated by decreasing the O₂ gas flow. The present study was focused on the investigation of the morphology, the microstructure on the nanoscale, and the bonding structure using scanning electron microscopy (SEM), Fourier-Transmission infra-red spectroscopy (FTIR), high-resolution transmission electron microscopy (HRTEM) and electron energy loss spectroscopy (EELS) employing analytical scanning transmission electron microscopy (ASTEM). The HRTEM images revealed a four-layer coating consisting of a gradual nucleation of t-BN, on which a gradual nucleation of c-BN was achieved by decreasing the oxygen gas flow.     

Thickness measurements with electron energy loss spectroscopy

Measurements of thickness using electron energy loss spectroscopy (EELS) are revised. Absolute thickness values can be quickly and accurately determined with the Kramers-Kronig sum method. The EELS data analysis is even much easier with the log-ratio method, however, absolute calibration of this method requires knowledge of the mean free path of inelastic electron scattering lambda. The latter has been measured here in a wide range of solids and a scaling law lambda approximately rho(-0.3) versus mass density rho has been revealed. EELS measurements critically depend on the excitation and collection angles. This dependence has been studied experimentally and theoretically and an efficient model has been formulated.     

On the estimation variance for the specific Euler–Poincaré characteristic of random networks

The factors that determine the local magnetic properties of FeCo/SiO₂ nanocomposite powders and films have been analysed by electron energy‐loss spectroscopy (EELS) and transmission electron microscopy (TEM). Attention has been given to the chemical composition, the local electronic structure and the atomic arrangement. The results show that the nanoparticles from sol‐gel prepared powders are generally Fe‐rich, whereas they are Co‐rich in sol‐gel prepared films. In addition, a subnanometre oxide layer at the surface of the FeCo nanoparticles has been clearly observed in the powder sample. It is found that the magnetic moment should be partly governed by alloying effects. Numerical values of the near‐surface magnetic moment have been obtained using the ab‐initio layer‐KKR method. These values should be helpful in understanding the layer‐by‐layer changes of the white line ratio close to the surface of the nanoparticles.     

NaxCoO2·yH2O体系的高分辨电子能量损失谱和电子结构研究

本文通过高分辨电子能量损失谱(EELS)的实验分析与密度泛函计算相结合的方法,研究了NaxCoO2·yH2O系统的电子结构特性和电子关联效应.实验结果表明,金属性Na0.3CoO2材料和电荷有序绝缘体Na0.5CoO2的O-K吸收边存在明显的结构差别,在Na0.5CoO2的EELS中第一个峰发生明显分裂,密度泛函计算证实这种分裂现象和电子关联效应直接相关.通过理论模拟谱线与实验谱线的比较确定了其电子关联强度为U=3.0 eV.在Na0.3CoO2·yH2O(y=0,0.6,1.3)超导体系中,实验发现其能损谱的低能部分随着水含量的增加发生系统的变化,损失峰向低能量方向逐步移动.电子结构计算表明水分子的插入可以引起费米面附近能态原子轨道杂化情况的改变,从而导致EELS的变化.