X-ray emission spectra and electronic structure of amorphous silicon

X-ray K and L emission bands of c-Si and a-Si are reported and compared with available XPS and UPS measurements. The experimental results for a-Si are found to be consistent and in excellent agreement. From comparison of the experimental results with available electron density-of-states calculations based on different structure models of the amorphous state, we conclude that only ST-12 structure and the Polk-Boudreaux model provide results that are compatible with experiment.Furthermore we have studied the high energy L satellite band of c-Si and a-Si.     

X-ray photoelectron spectroscopy of sodium phosphate glasses

X-ray photoelectron spectroscopy (XPS, ESCA) has been applied to sodium phosphate glasses with compositions between 15 and 50 mol% Na₂O and for the purpose of comparison also to crystalline compounds containing oxygen and phosphorus. From the measurements a discrimination between bridging and non-bridging oxygen atoms was possible. The method provides a quantitative technique for structural analysis of phosphate glasses.     

X-ray photoelectron spectroscopy (XPS) and magnetic susceptibility studies of vanadium phosphate glasses

Vanadium phosphate glasses with the nominal chemical composition [(V₂O₅)_x(P₂O₅)_1?x], where x = 0.30, 0.40, 0.50, and 0.60, have been prepared and investigated by X-ray photoelectron spectroscopy (XPS) and magnetization measurements. Asymmetries found in the O 1s, P 2p, and V 2p core level spectra indicate the presence of primarily P–O–P, P–O–V, and V–O–V structural bonds, a spin–orbit splitting of the P 2p core level, and more than one valence state of V ions being present. The magnetic susceptibility data for these glasses follow a Curie–Weiss behavior which also indicates the presence of some V ions existing in a magnetic state, i.e., a valence state other than that of the non-magnetic V⁵⁺. From qualitative comparisons of the abundance of the bridging oxygen or P–O–P sites as determined from the areas under the various O 1s peaks with the abundances of differing phosphate structural groups associated with the presence of different valence states of the vanadium ions, a glass structure model consisting of a mixture of vanadate phosphate phases is proposed for these glass samples. These include V₂O₅, VOPO₄, (VO)₂P₂O₇, VO(PO₃), and V(PO₃)₃ with the abundance of orthophosphate (PO₄)^3? units increasing with increasing vanadium content.     

X-ray diffraction study of the morphology and structure of pulse-anodized porous Si multilayers

Porous Si layers, obtained by pulsed electrochemical etching of n-Si(001) substrates (resistivity 0.01 Ω cm) in a 1: 1 mixture of hydrofluoric acid and ethanol, have been investigated by high-resolution X-ray diffraction and electron microscopy. The average structural parameters of the layers grown (thickness, strain, porosity, pore size) are determined. It is found that pulsed anodic oxidation leads to a decrease in the average strain of layers. It is established that, at frequencies up to 1 Hz, anodic oxidation makes obtaining porous silicon multilayers with layer thicknesses of 20–300 nm containing Si nanocrystallites possible. It is shown that X-ray diffuse scattering from pores yields information about their ordering and can be used to monitor the processes of electrochemical etching used to form porous layers.     

X-ray diffraction analysis of multilayer porous InP(001) structure

Multilayer structures composed of four porous bilayers have been studied by high-resolution X-ray diffraction using synchrotron radiation, and the photoluminescence of these structures has been investigated at 4 K. The porous structures were formed by anodic oxidation of InP(001) substrates in aqueous HCl solution. The structural parameters of the sublayers were varied by changing the electrochemical etching mode (potentiostatic/galvanostatic). The X-ray scattering intensity maps near the InP 004 reflection are obtained. A model for scattering from such systems is proposed based on the statistical dynamical diffraction theory. Theoretical scattering maps have been fitted to the experimental ones. It is shown that a mathematical analysis of the scattering intensity maps makes it possible to determine the structural parameters of sublayers. The reconstructed parameters (thickness, strain, and porosity of sublayers and the shape and arrangement of pores) are in satisfactory agreement with the scanning electron microscopy data.     

Short-range order evolution in S-rich Ge-S glasses by X-ray photoelectron spectroscopy

The structure of binary Ge_xS_100 − x chalcogenide glasses (10 < x < 30) is determined by high-resolution X-ray photoelectron spectroscopy (XPS). On the basis of compositional dependence of fitting parameters for Ge and S core level XPS spectra, the ratio between edge- and corner-shared tetrahedra is determined. It is shown that short-range order of these glasses includes fragments of high-temperature crystalline form of GeS₂. When subjected to X-irradiation, the structure of investigated glasses appears to become more homogeneous than that of the as-prepared samples.     

X-ray and synchrotron methods in studies of cultural heritage sites

X-ray and synchrotron methods that are most widely used in studies of cultural heritage objects (including archaeological sites)—X-ray diffraction analysis, X-ray spectroscopy, and visualization techniques— have been considered. The reported examples show high efficiency and informativeness of natural science studies when solving most diverse problems of archaeology, history, the study of art, museology, etc.     

X-ray absorption study of tantalum oxide films on silicon

The results of X-ray absorption measurements are used to demonstrate that non-crystalline Ta_0.29O_0.71 films, prepared by thermal oxidation of deposited Ta on Si single crystals, are glassy in the sense that the short range order and bond (chemical) ordering closely resemble those in β-Ta₂O₅.     

Photoelectron spectroscopic studies of anodic potentiostatic oxidation on various platinum surfaces

Using XPS method it is shown that the anodic charge transfer supported oxidation of platinum single crystal electrodes in aqueous 0.1 M HClO₄ solution is influenced by the atomic surface arrangements. The best electrode stability is received for the (111) surface with the largest atomic density in the case reported here.     

Synthesis by sol–gel process,characterization and catalytic activity of vanadia–silica mixed oxides

This paper describes a new route for the preparation of V₂O₅–SiO₂ mixed oxides with high vanadium content and high surface area by the sol–gel processing method. Dry samples were characterized by powder X-ray diffraction, electron paramagnetic resonance, Fourier-transform infrared, and energy dispersive X-ray spectrometry. Our results show that the incorporation of vanadium pentoxide into the silica matrix was obtained by intimate mixing of the two different inorganic polymers (Si–O and V–O based polymers), and the overall structure is held together by a Si–O–Si network interpenetrated with V–O–V polymeric chains. The catalytic activity of the V₂O₅–SiO₂ mixed oxides was evaluated in the oxidation of the cyclooctene and styrene in liquid phase.     

Alteration and corrosion phenomena in Roman submerged glass fragments

In the present paper the surface analytical techniques of XPS (X-ray photoelectron spectroscopy) and SIMS (secondary ions mass spectrometry) have allowed an understanding of the alteration and corrosion phenomena occurring in Roman glass fragments. The samples come from the seawater archaeological site of the Roman ship Iulia Felix, which sank near Grado (Gorizia, Italy) in the second century A.D. Through XPS the surface concentration of the main chemical elements and their depth profiles have been obtained. Attention has been focused on the oxidation states of the elements, oxygen/silicon ratio, peculiar presence of carbonate salts and concentration trends of some elements in the outer atomic layers. Depth trends of aluminium, calcium, magnesium and carbon were studied also through SIMS depth profiles. The whole set of XPS and SIMS data allows the segregation of particular chemical species and the evolution of the original glass to a multilayer system.     

New Temperature Control Apparatus for X-ray Experiments

A temperature control apparatus for X-ray experiments for organic compounds was newly designed. It is a gas furnace system equipped with a proportional integrated differential (PID) controller. In this study, a position sensitive proportional counter (PSPC) was used as a detector in order to make quick measurements. Using this apparatus, the long spacing of 1-octadecanol was measured by the small angle X-ray scattering (SAXS) method. The long spacings of 1-octadecanol in the high temperature phase and the low temperature stable one were 48.7 and 41.7 Å, respectively. The result obtained was consistent with that reported. It was confirmed that the apparatus designed here operated properly for the temperature control of organic compounds in X-ray experiments and was useful for the structural study on the phase transition of organic samples.     

Broadening of X-ray diffraction lines of crystals containing dislocation distributions

The first part of the paper deals with a brief review over the present stage of the (kinematical) theory of the broadening of X-ray diffraction lines of crystals containing dislocation distributions. In the second part experiments of X-ray line broadening of plastically deformed Cu and NaCl single crystals are reported by which the validity of the theoretical approaches are tested. It is shown that values of the dislocation density and the elastically stored energy derived from broadened X-ray diffraction lines agree well with corresponding data obtained by other experimental techniques.     

Bridging, non-bridging and free (O) oxygen in Na2O-SiO2 glasses: An X-ray Photoelectron Spectroscopic (XPS) and Nuclear Magnetic Resonance (NMR) study

High resolution Na 1s, O 1s and Si 2p core level XPS spectra of six Na₂O-SiO₂ glasses ranging in composition from 100 to 45 mol % SiO₂ have been collected using the Kratos Ultra Axis instrument with its unique charge compensation system. The O 1s spectra for the glasses are well resolved so that bridging oxygen (BO, Si-O-Si) and non-bridging oxygen (NBO, Na-O-Si) signals can be accurately fitted and quantified without resorting to constraints or assumptions. The same samples were analysed by ²⁹Si MAS NMR to obtain Q-species abundances from which BO and NBO proportions were calculated. Similar BO:NBO ratios were obtained by both methods over the entire compositional range studied. They are also consistent with most previous XPS and NMR results for glasses containing more than ~ 65 mol % SiO₂. Our XPS and NMR experimental results, however, differ somewhat from previously published XPS and NMR results for glasses containing less than about 65 mol % SiO₂.Na is mobile in the X-ray beam and mobility causes BO:NBO ratios to increase with time of exposure. Na mobility here has been circumvented to yield reliable BO:NBO ratios of the glasses. The ratios are lower than previously reported in XPS studies and are similar to ratios obtained from our ²⁹Si MAS NMR results on the same glasses. The XPS and ²⁹Si MAS NMR results also indicate the presence of a third oxygen species in sodic glasses. As has been proposed for CaSiO₃ glass and for sodic and potassic glasses containing La, we suggest that O²⁻ is present in sodic glasses at small concentrations. The O²⁻ content correlates with increased soda content and may be associated with, and instrumental in development of, three dimensional percolation channels in the glasses. The XPS O 1s line width of the BO peak is broader than the NBO peak, indicating more than one contribution to the BO peak. As observed in crystalline Na metasilicate and Na disilicate, BO of Na-silicate glasses may be of two types, one arising from BO bridging two Si atoms, and the second BO signal arising from BO bonded not only to two Si atoms but also to Na.     

X-ray photoelectron spectroscopy of erbium-activated-silica–hafnia waveguides

X-ray photoelectron spectroscopy (XPS) has been used in the study of sol gel-derived Er³⁺-activated xHfO₂–(100 − x)SiO₂ (x = 10, 20, 30, 40, 50 mol) planar waveguides. The analysis of Si 2p and O 1s core lines were related to the Hf/Si molar ratio to assess the role of hafnia in modifying the silica network. Increasing the HfO₂ content brings about a change of the Si 2p and O 1s binding energy respect to those from pure silica. This trend is explained with a formation of hafnium silicate in the matrix with successive phase separation between HfO₂ and SiO₂ rich phases. XPS results show that hafnia is well dispersed in the silica matrix for molar concentration below 30%. Formation of pure HfO₂ domains was detected at higher hafnia concentrations in agreement with previous spectroscopic analyses.     

X-ray Photoelectron Spectroscopic Studies of Sellinite and Eulytite BGO and BSO Crystals

Single crystals of Bi₁₂GeO₂₀, Bi₁₂SiO₂₀, Bi₄Ge₃O₁₂, and Bi₄Si₃O₁₂ are grown by Floating zone and Czochralski techniques. The X-ray photoelectron spectroscopic (XPS) studies have been carried out on BSO and BGO crystals. XPS is employed to characterise the surface quality and bulk nature of the crystals. The surface contamination on both types of crystals are identified. In addition to the contamination, some amount of Bi atoms are observed with Bi ions on sellinite. It is demonstrated that the eulytite crystals are chemically more robust to degradation than the sellinite crystals. The predominant covalent and ionic character of Bi₄Ge₃O₁₂ and Bi₄Si₃O₁₂ respectively is explained from their oxygen 1s core level spectra.     

X-ray photoelectron spectroscopy of silica in theory and experiment

Fourier deconvolved X-ray photoelectron spectroscopy (XPS) valence band spectra obtained from crystalline and amorphous silica, used in conjuction with the results of quantum chemical calculations of the SiO₄ tetrahedral unit and other spectrometric measurements (soft X-ray emission, UV absorption and reflectivity, photoconductivity, photoinjection and energy loss spectroscopy), suggest a reinterpretation of the electronic band structure of silica that is consistent with all the data. A unique method for pinning the Fermi level of insulators to that of a metal calibrant is described, resulting in the ability to obtain absolute binding energies of the electronic levels in wide bandgap insulators. Observe peaks in UV reflectivity and energy loss spectra of silica are all assigned to direct interband transitions, and no excitonic states need be involved to explain the data. Upper and lower limits for the bandgap of dry crystalline (α-quartz) and amorphous (Corning Code 7940 glass) silica are adjusted downward from the 8.9 eV bandgap proposed by DiStefano and Eastman [1] to 7.8–5.55 eV for α-quartz and 7.3–5.05 eV for fused silica, respectively. This in no way compromises the obvious insulating properties of silica in MOS devices, since the conductivity is governed by the high barrier height (～3.8 eV in the case of gold) for metal-insulator electron transfer. The lowered bandgap results from increased low-energy electron density in the valence band, which we ascribe to the 1t₁ molecular orbital predicted by various quantum formalisms, but heretofore not detected experimentally in bulk (thick) silica. Disappearances of this orbital and rearrangement of the non-binding 5t₂ and 1e orbitals in silicas rich in silanols (OH), as may be the case for thin-film silica on Si metals, would increase the bandgap to 8.3 eV, in better agreement with previous determinations.     

Interface and material characterization of thin Al2O3 layers deposited by ALD using TMA/H2O

Thin Al₂O₃ layers were grown by atomic layer deposition using trimethylaluminum (TMA) and water as precursors on 1.2 nm thermal SiO₂ and HF cleaned Si surfaces. The stoichiometry and the contamination (H, OH and C) of as-deposited and N₂ annealed thick Al₂O₃ layers were characterized by secondary ion mass spectrometry (SIMS), elastic recoil detection analysis (ERDA) and X-ray photoelectron spectroscopy (XPS). We show a perturbed region (≈5 nm thick) at the Al₂O₃/Si interface by XPS and Auger electron spectrometry (AES). Post-deposition annealings induced important interface oxidation, Si atoms injection and SiO₂/Al₂O₃ mixture whereas the initial interface was abrupt. Silicon oxidation before Al₂O₃ growth highly limits interfacial oxidation and improves interfacial quality. We proposed that OH groups may play a key role to explain silicon oxidation during post-deposition annealings in inert ambience with low oxygen contamination levels.     

Ru@Pt/CNTs纳米粒子的制备及催化乙醇氧化电化学活性的研究

通过乙醇还原方法制备了不同比例的碳纳米管负载钌铂核壳结构的纳米粒子(Ru@Pt/CNTs),并用作直接乙醇燃料电池的阳极催化剂。利用透射电镜(TEM)、X射线衍射(XRD)和X射线光电子能谱(XPS)等手段表征该催化剂的结构。结果表明Ru@Pt/CNTs纳米颗粒具有核壳结构(以钌为核),Ru@Pt/CNTs在乙醇电氧化反应(EOR)中表现出优良的电化学催化活性,其中,当铂∶钌摩尔比为0.75时,催化性能达到最优,电流密度值达到1 767.77 mA/mg Pt,是商业Pt/C的3.25倍。另外,耐久性的实验发现当铂∶钌摩尔比为1.00时, CV测试循环了250圈后衰减了19.7%。因此,具有核壳结构的Ru@Pt/CNTs纳米粒子对乙醇氧化反应有优良的催化活性。