L-shell ionization of atoms and their subsequent decay by radiative and non-radiative transitions

The study of the ionization of atoms resulting in vacancies in their inner shells and the subsequent decay of the atomic-vacancy states by x-ray and Auger transitions continue to be an active area of interest. A rapid survey of the theoretical efforts to calculate the transition probabilities involvingL-subshells in the high-Z atoms is presented. A complete review of theL ₁-subshell yields for single-vacancy atomic states obtained by various experimental techniques is included. The production of multiple vacancies in theL shell and the role of the spectator vacancies in the decay process is discussed. A detailed case study of determining experimentally the number of multiple vacancies produced, and the x-ray fluorescence yields during ionization by heavy-ion bombardment is presented. It is established that the effect of spectator vacancies is to increase the x-ray fluorescence yields substantially.     

Large atomic disorder in nanostructured LaNi5 alloys: A La L3-edge extended X-ray absorption fine structure study

Local structure of the nanostructured LaNi₅ alloys, prepared by ball-milling, has been studied using La L₃-edge extended X-ray absorption fine structure spectroscopy. The near-neighbor distances tend to decrease with the ball-milling, and the mean square relative displacements (MSRD) show substantial increase suggesting an increased atomic disorder. High temperature annealing helps in partial recovery of atomic order in the ball-milled samples for milling times upto 20 h, however, the long-time ball-milled samples seems to gain only a local random order. The results suggest that reduced unit-cell volume together with large atomic-disorder might be causing a higher energy-barrier for the hydride-phase formation in the long time ball-milled LaNi₅ powders.     

Clustering and polymerization of Li15C60

The structural and electronic properties of lithium intercalated fullerides (of which Li₁₅C₆₀ is the most representative) are still puzzling and unclear. Above 520 K, x-ray/neutron diffraction shows an fcc phase in which the 15 Li atoms clusterize in the octahedral interstices. However, at lower temperatures, a change in the crystalline symmetry and also in the electronic properties takes place as observed from ¹³C, ⁷Li/⁶Li NMR and x-ray diffraction measurements. X-ray diffraction data suggest the presence of two different stable structures: a tetragonal monomeric and an orthorhombic polymerised phase. Detailed ¹³C magic angle spinning NMR experiments in the latter phase indicate sp ³ bondings among the carbon atoms, whereas the relative (sp ²/sp ³) intensities, together with x-ray data, suggest the C₆₀ polymerization to be a [2+2] cycloaddition. Multiple quantum NMR experiments on ⁷Li confirm the presence of lithium clusters, as observed by x-ray diffraction in the high temperature phase, also at lower temperatures. However, the inferred cluster size is significantly smaller than that suggested by the stoichiometry. The distortion in the low-T structure of L₁₅C₆₀ is supposed to induce the migration of Li atoms from octahedral to tetrahedral voids, thus accounting for the lower number of Li atoms in the clusters. Further evidence of this scenario is obtained also from preliminary measurements of line shapes and T ₁ relaxation times, which exhibit a multiexponential recovery with very different constants that are hardly compatible with a single family of Li atom sites.     

Electron energy loss spectra near structural defects in TiN and TiC

In this study, we use first principles multiple scattering calculations on atomic clusters to show how the carbon and nitrogen K-edge fine structures are modified in the vicinity of structural defects in TiN and TiC. Changes in the electron energy loss spectra are due to changes in the atomic structure of the first atomic shells around the absorbing atom. Two different kinds of defects, which both modify the structure of these atomic shells, are investigated here. In a first part, we describe a method which correctly takes into account the statistical spatial distribution of nitrogen vacancies in a TiN cluster. We study the influence of vacancy concentration on the shape of the nitrogen K-edge spectra and we find that vacancies mainly affect the height of the second peak of the spectra. This peak decreases when the number of vacancies in the second nitrogen shell increases. In a second part, we study the carbon K-edge spectrum modification near stacking faults in TiC. Two different stacking faults are studied. These two-dimensional defects are responsible for changes in the position of the carbon as well as titanium atoms of the atomic shells centered on the absorbing carbon atom. The shape of the spectra is strongly modified near the stacking faults and several peaks are affected by these modifications. We show that these fine structure modifications only concern the very first carbon atomic layers near the two-dimensional defects.     

Carbon‐Dot‐Decorated Nanodiamonds

The synthesis of a new class of fluorescent carbon nanomaterials, carbon‐dot‐decorated nanodiamonds (CDD‐ND), is reported. These CDD‐NDs are produced by specific acid treatment of detonation soot, forming tiny rounded sp² carbon species (carbon dots), 1–2 atomic layers thick and 1–2 nm in size, covalently attached to the surface of the detonation diamond nanoparticles. A combination of nanodiamonds bonded with a graphitic phase as a starting material and the application of graphite intercalated acids for oxidation of the graphitic carbon is necessary for the successful production of CDD‐ND. The CDD‐ND photoluminescence (PL) is stable, 20 times more intense than the intrinsic PL of well‐purified NDs and can be tailored by changing the oxidation process parameters. Carbon‐dot‐decorated DNDs are shown to be excellent probes for bioimaging applications and inexpensive additives for PL nanocomposites.     

M?ssbauer and XRD study of the Fe65Si35 alloy obtained by mechanical alloying

A study was made on the alloy Fe₆₅Si₃₅ using x-ray diffraction and M?ssbauer spectrometry. The alloy was obtained by mechanical alloying in a high energy planetary mill, with milling times of 15, 30, 50, 75 and 100?h. The results show that in the alloys two structural phases are present, a Fe-Si BCC disordered phase and ferromagnetic, and a Fe-Si SC phase, whose nature is paramagnetic and which decreases with milling time. In the temporal evolution of the milling two stages are differentiated: one between 15 and 75?h of milling, in which silicon atoms diffuse into the bcc matrix of iron and its effect is to reduce the hyperfine magnetic field; the other, after 75?h of milling, where the alloy is consolidated, the effect of the milling is only to increase the disorder of the system, increasing the magnetic order.     

掺杂剂对重掺n型直拉硅片的氧化诱生层错生长的影响

对比研究了电阻率几乎相同的重掺锑和重掺磷直拉硅片的氧化诱生层错(OSF)的生长, 以揭示掺杂剂对重掺n型直拉硅片的OSF生长的影响. 研究表明: 在相同的热氧化条件下, 重掺锑直拉硅片的OSF的长度大于重掺磷硅片的. 基于密度泛函理论的第一性原理计算结果表明: 与磷原子相比, 锑原子是更有效的空位俘获中心, 从而抑制空位与自间隙硅原子的复合. 因此, 在经历相同的热氧化时, 氧化产生的自间隙硅原子与空位复合后所剩余的数量在重掺锑硅片中的更多, 从而导致OSF更长.     

Temperature-dependent interfacial stiffness of the disorder layer in a thin Cu3Au alloy film

Epitaxial silicon carbide thin films grown on a silicon substrate were examined by short wavelength ( 0.71 A from a molybdenum anode) x-ray diffraction to study their atomic distortion and internal layer roughness. Up to 5 order Bragg peaks along (100) were measured and crystallographic structure factors were obtained. Electron density distributions along the surface normal were reconstructed via Fourier transform. In comparing to the ideal situation, it was found that, due to the lattice mismatch, the silicon atoms are no longer fixed on the same atomic plane, thus the corresponding electron distribution maxima were broadened. Also, the maxima for carbon atoms are flattened, indicating the randomized locations.     

Study of the electronic structure and properties of 13C-isotope-based composites

The morphology and electronic structure of ¹³C-isotope-based graphite composites were studied by transmission electron microscopy (TEM), x-ray diffraction, and x-ray fluorescence spectroscopy. High-resolution TEM images showed that composites contain several forms of carbon particles. According to an x-ray diffraction analysis, the size of graphene stacks of graphite particles is 20 and 40 Å. The CK _α x-ray fluorescence spectra of the initial ¹³C isotope powder and composites based on it detected an increase in the density of high-energy occupied states in comparison with the graphite spectrum. Ab initio quantum chemical calculation of the structure of C₁₅₀ graphene showed that the increase in the density of states stems from the electrons of dangling bonds of boundary carbon atoms of particles ～20 Å in size. Electrical properties of ¹³C-isotope-based samples were studied by analyzing the temperature dependence of the conductivity. It was assumed that the change in the logarithmic dependence of the conductivity observed at liquid-helium temperatures to the linear dependence as the temperature increases is caused by carrier transfers between the disordered graphene layers forming a nanocomposite.     

The presence of a (1 × 1) oxygen overlayer on ZnO(0001) surfaces and at Schottky interfaces

The atomic surface and interface structures of uncoated and metal-coated epi-polished ZnO(0001) Zn-polar wafers were investigated via surface x-ray diffraction. All uncoated samples showed the presence of a fully occupied (1 × 1) overlayer of oxygen atoms located at the on-top position above the terminating Zn atom, a structure predicted to be unstable by several density functional theory calculations. The same oxygen overlayer was clearly seen at the interface of ZnO with both elemental and oxidized metal Schottky contact layers. No significant atomic relaxations were observed at surfaces and interfaces processed under typical device fabrication conditions.     

Elastic scattering of a photon by an atom with an open shell

In the nonrelativistic approximation, the absolute values and the forms of the differential cross sections of the anomalous elastic scattering of a linearly polarized x-ray photon by manganese and copper atoms in the energy region of the ionization threshold of the 1s shell are calculated for the wave functions of one-electron states. We take into account the multiparticle effects of relaxation of atomic shells in the field of core vacancies, multiplet splitting, the configuration interaction, and Auger and radiative decays of vacancies, as well as the processes of double excitation/ionization of the ground state of the atom. The calculation results are in good agreement with the synchrotron experiment.     

Effect of oxygen vacancies on adhesion at the Nb/Al2O3 and Ni/ZrO2 interfaces

The atomic and electronic structures of the Nb/Al₂O₃(0001) and Ni/ZrO₂(001) interfaces are calculated using density-functional theory. The formation energy of oxygen vacancies is estimated in bulk materials and in surface layers and interfaces for different uppermost atomic layers of oxide surfaces. The work of separation of metal films from oxide surfaces is determined. The effect of oxygen vacancies on the bonding of transition metals to atoms of a substrate determining adhesion at the metal-oxide interfaces is discussed. It is shown that the Nb(Ni)-O interaction at the interfaces weakens in the presence of surface oxygen vacancies.     

Preparation and structure of carbon encapsulated copper nanoparticles

Carbon-encapsulated copper nanoparticles were synthesized by a modified arc plasma method using methane as carbon source. The particles were characterized in detail by transmission electron microscope, high-resolution transmission electron microscopy, selected-area electron diffraction, X-ray diffraction, thermogravimetric and differential scanning calorimetry. The encapsulated copper nanoparticles were about 30 nm in diameter with 3–5 nm graphitic carbon shells. The outside graphitic carbon layers effectively prevented unwanted oxidation of the copper inside. The effect of the ratio of He/CH₄ on the morphologies and the formation of the carbon shell were investigated.     

LiF中空位形成能的第一性原理计算

采用平面波展开和基于密度泛函理论框架下的第一性原理赝势法,计算了102GPa下LiF化合物中Li空位和F空位的形成能及空间周围的原子弛豫,讨论了空位形成时电荷密度的重新分布,相应的电子态密度以及能带结构等性质.结果表明:LiF晶体中F空位的形成能比大于Li空位的形成能;F空位对LiF晶体的电子结构等性质的影响要比Li空位的大.     

LiF中空位形成能的第一性原理计算

采用平面波展开和基于密度泛函理论框架下的第一性原理赝势法,计算了102GPa下LiF化合物中Li空位和F空位的形成能及空间周围的原子弛豫,讨论了空位形成时电荷密度的重新分布,相应的电子态密度以及能带结构等性质.结果表明:LiF晶体中F空位的形成能比大于Li空位的形成能;F空位对LiF晶体的电子结构等性质的影响要比Li空位的大.     

一维Fibonacci系列的X射线衍射峰轮廓的计算

用简单原子层的Fibonacci系列模型,根据振幅-相位关系,计算了其X射线衍射图谱,衍射峰位置在k=2π((m+nτ)/(1+2τ))d^-1,d为平均面间距。衍射峰角宽度β与原子层总厚度D仍满足Scherrer公式:β=0.88λ/Dcosθ。并用振幅-相位图解释了弱衍射峰的强度随原子层数增大时产生起伏的现象。 关键词：     

Structure of a CH3S monolayer on Au(111) solved by the interplay between molecular dynamics calculations and diffraction measurements

We have investigated the controversy surrounding the (sqrt[3] x sqrt[3]) R30 degrees structure of self-assembled monolayers of methylthiolate on Au(111) by first principles molecular dynamics simulations, energy and angle resolved photoelectron diffraction, and grazing incidence x-ray diffraction. Our simulations find a dynamic equilibrium between bridge site adsorption and a novel structure where 2 CH3S radicals are bound to an Au adatom that has been lifted from the gold substrate. As a result, the interface is characterized by a large atomic roughness with both adatoms and vacancies. This result is confirmed by extensive photoelectron and grazing incidence x-ray diffraction measurements.     

Analysis of ball-milled Mo powder using X-ray diffraction

X-ray diffraction measurements and analysis were carried out on ball-milled Mo powder. During the ball milling of Mo powder, several stages of deformation could be identified. After short durations of ball milling, still undeformed starting powder was present and the volume fraction of this was determined. The initial aggregates of deformed powder particles exhibited a deformation texture. On prolonged ball milling, the particle size decreased, the deformation texture disappeared and internal strains built up. By simulation and matching of the corresponding line profiles using a Monte Carlo type of line-profile simulation based on a simple three-dimensional model of the distribution of straight dislocations, an estimate of the dislocation density in the ball-milled particles was obtained.     

Hydrogenation of single-walled carbon nanotubes

Towards the development of a useful mechanism for hydrogen storage, we have studied the hydrogenation of single-walled carbon nanotubes with atomic hydrogen using core-level photoelectron spectroscopy and x-ray absorption spectroscopy. We find that atomic hydrogen creates C-H bonds with the carbon atoms in the nanotube walls, and such C-H bonds can be completely broken by heating to 600 degrees C. We demonstrate approximately 65 +/- 15 at % hydrogenation of carbon atoms in the single-walled carbon nanotubes, which is equivalent to 5.1 +/- 1.2 wt % hydrogen capacity. We also show that the hydrogenation is a reversible process.     

Growth of Si nanostructures on Ag(0 0 1)

The first stages of the growth of silicon on Ag(0 0 1) at moderate temperatures start by the formation of a p(3 × 3) superstructure, which continuously evolves with increasing coverage toward a more complex superstructure. In this paper, the atomic arrangement of the p(3 × 3) and of the “complex” superstructure has been investigated using scanning tunnelling microscopy, surface X-ray diffraction and low energy electron diffraction. The atomic model retained for the p(3 × 3) reconstruction consists in four silicon atoms (tetramers) adsorbed near hollow and bridge sites of the top most Ag(0 0 1) surface layer. For higher coverages, i.e., when the “complex” superstructure starts to develop, the silicon overlayer forms periodic stripes, most probably bi-layers, with a graphitic like structure.