Structure, stoichiometry and spectroscopy of oxide superconductors

In the new oxide superconductors, structure and oxygen stoichiometry play the most crucial role. Thus, all the high-temperature oxide superconductors are orthorhombic perovskites with low-dimensional features. Oxygen stoichiometry in YBa2Cu3O7-δ has an important bearing on the structure as well as superconductivity. This is equally true in the La3-xBa3+xCu 6O14+δ system of which only the 123 oxide (x = 1) with the orthorhombic structure shows high Tc. Orthorhombicity though not essential, is generally found ; it is necessary for the formation of twins. The nature of oxygen and copper in the cuprates has been examined by electron spectroscopy. Copper in these cuprates is only in 1 + and 2 + states. It seems likely that oxygen holes are responsible for superconductivity of the cuprates as well as Ba(Bi, Pb)O3. High Tc superconductivity is also found in oxides of the Bi-(Ca, Sr)-Cu-O and related oxides possessing Cu-O sheets.

Evidence for correlation effects in Sr2RuO4 from resonant and x-ray photoemission spectroscopy

We study the electronic structure of Sr2RuO4, a noncuprate layered superconductor (T-c=0.93 K), using electron spectroscopy. X-ray photoemission spectroscopy shows that the single particle occupied density of states (DOS) is in fair agreement with the calculated DOS. However, resonant photoemission spectroscopy across the Ru 4p-4d threshold establishes the existence of a correlation satellite to the Ru 4d band. The results indicate substantial charge-transfer character at the Fermi level, with on-site correlations U-dd comparable in magnitude to the Ru-O hopping integral, like the cuprates.

Between photocatalysis and photosynthesis: Synchrotron spectroscopy methods on molecules and materials for solar hydrogen generation

Energy research is to a large extent materials research, encompassing the physics and chemistry of materials, including their synthesis, processing toward components and design toward architectures, allowing for their functionality as energy devices, extending toward their operation parameters and environment, including also their degradation, limited life, ultimate failure and potential recycling. In all these stages, X-ray and electron spectroscopy are helpful methods for analysis, characterization and diagnostics for the engineer and for the researcher working in basic science.This paper gives a short overview of experiments with X-ray and electron spectroscopy for solar energy and water splitting materials and addresses also the issue of solar fuel, a relatively new topic in energy research. The featured systems are iron oxide and tungsten oxide as photoanodes, and hydrogenases as molecular systems. We present surface and subsurface studies with ambient pressure XPS and hard X-ray XPS, resonant photoemission, light induced effects in resonant photoemission experiments and a photo-electrochemical in situ/operando NEXAFS experiment in a liquid cell, and nuclear resonant vibrational spectroscopy (NRVS). (C) 2012 Elsevier B.V. All rights reserved.

Probing complex heterostructures using hard X-ray photoelectron spectroscopy (HAXPES)

X-ray Photoelectron Spectroscopy (XPS) plays a central role in the investigation of electronic properties as well as compositional analysis of almost every conceivable material. However, a very short inelastic mean free path (IMFP) and the limited photon flux in standard laboratory conditions render this technique very much surface sensitive. Thus, the electronic structure buried below several layers of a heterogeneous sample is not accessible with usual photoemission techniques. An obvious way to overcome this limitation is to use a considerably higher energy photon source, as this increases the IMFP of the photo-ejected electron, thereby making the technique more depth and bulk sensitive. Due to this obvious advantage, Hard X-ray Photo Electron Spectroscopy (HAXPES) is rapidly becoming an extremely powerful tool for chemical, elemental, compositional and electronic characterization of bulk systems, more so with reference to systems characterized by the presence of buried interfaces and other types of chemical heterogeneity. The relevance of such an investigative tool becomes evident when we specifically note the ever-increasing importance of heterostructures and interfaces in the context of a wide range of device applications, spanning electronic, magnetic, optical and energy applications. The interest in this nondestructive, element specific HAXPES technique has grown rapidly in the past few years; we discuss critically its extensive use in the study of depth resolved electronic properties of nanocrystals, multilayer superlattices and buried interfaces, revealing their internal structures. We specifically present a comparative discussion, with examples, on two most commonly used methods to determine internal structures of heterostructured systems using XPS. (C) 2015 Elsevier B.V. All rights reserved.

DOMINANCE OF SHORT-RANGE-ORDER EFFECTS IN LOW-ENERGY ELECTRON-DIFFRACTION INTENSITY SPECTRA

Using low-energy electron-diffraction (LEED) formalism, we demonstrate theoretically that LEED I-V spectra are characterized mainly by short-range order. We also show experimentally that diffuse LEED (DLEED) I-V spectra can be accurately measured from a disordered system using a video-LEED system even at very low coverage. These spectra demonstrate that experimental DLEED I-V spectra from disordered systems may be used to determine local structures. As an example, it is shown that experimental DLEED I-V spectra from K/Co {1010BAR} at potassium coverages of 0.07, 0.1, and 0.13 monolayer closely resemble calculated and experimental LEED I-V spectra for a well-ordered Co{1010BAR}-c(2X2)-K superstructure, leading to the conclusion that at low coverages, potassium atoms are located in the fourfold-hollow sites and that there is no large bond-length change with coverage.

X-ray photoelectron spectroscopy study on sintered Pb1-xLaxTiO3 ferroelectric ceramics

The Pb1-xLaxTiO3 sintered ferroelectric ceramics with x equal to 0, 0.10, 0.15, 0.20, and 0.30 were studied by X-ray photoelectron spectroscopy (XPS). The binding energy of the Ti 2p lines is consistent with only one chemical state, Ti4+. on the other hand, in the case of Pb 4f and 0 Is XPS spectra, apart from the main peaks attributed to the lattice ions, minor peaks related to the surface states were also observed. The presence of Pb-0 state on the surface of all samples was due to the reduction of lead ions caused by the preferential removal of the oxygen ions after sputtering. The non observation of Ti3+ ions confirms that the mechanism of charge compensation that should occurs owing to the substitution of Ph2+ by La3+ is due to the preferential formation of Pb site vacancies, and not to a reduction from Ti4+ to Ti3+ states. Within the limits of the present experiment, there is no evidence of the existence of non-equivalent Pb, Ti, and La sites as the Pb1-xLaxTiO3 ceramic changes from a normal to a relaxor ferroelectric state. (c) 2006 Elsevier B.V. All rights reserved.

Low-energy electron collisions with glycine

We report cross sections for elastic electron scattering by gas phase glycine (neutral form), obtained with the Schwinger multichannel method. The present results are the first obtained with a new implementation that combines parallelization with OpenMP directives and pseudopotentials. The position of the well known pi* shape resonance ranged from 2.3 eV to 2.8 eV depending on the polarization model and conformer. For the most stable isomer, the present result (2.4 eV) is in fair agreement with electron transmission spectroscopy assignments (1.93 +/- 0.05 eV) and available calculations. Our results also point out a shape resonance around 9.5 eV in the A' symmetry that would be weakly coupled to vibrations of the hydroxyl group. Since electron attachment to a broad and lower lying sigma* orbital located on the OH bond has been suggested the underlying mechanism leading to dissociative electron attachment at low energies, we sought for a shape resonance around similar to 4 eV. Though we obtained cross sections with the target molecule at the equilibrium geometry and with stretched OH bond lengths, least-squares fits to the calculated eigenphase sums did not point out signatures of this anion state (though, in principle, it could be hidden in the large background). The low energy (similar to 1 eV) integral cross section strongly scales as the bond length is stretched, and this could indicate a virtual state pole, since dipole supported bound states are not expected at the geometries addressed here. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.3687345]

On the production of N-2(+) ions at the N 1s edge of the nitrogen molecule

The N+2 ion yield of the N2 molecule has been measured at the N 1s → Rydberg excitations. It displays Fano-type line shapes due to interference between direct outer-valence photoionization and participator decay of the core-excited Rydberg states. The N+2 ion yield is compared with the total intensity of the outer-valence photoelectron lines obtained recently with electron spectroscopy (Kivimäki et al 2012 Phys. Rev. A 86 012516). The increasing difference between the two curves at the higher core-to-Rydberg excitations is most likely due to soft x-ray emission processes that are followed by autoionization. The results also suggest that resonant Auger decay from the core–valence doubly excited states contributes to the N+2 ion yield at the photon energies that are located on both sides of the N 1s ionization limit.

Non-metallic cold-cathode electron emission from composite metal-insulator microstructures

A detailed investigation has been undertaken into a field-induced electron emission (FIEE) mechanism that occurs at microscopically localised `sites' on uncoated, dielectric-coated and composite-coated metallic cathodes. An optical imaging technique has been used to observe and characterize the spatial and temporal behaviour of the populations of emission sites on these cathodes under various experimental conditions, e.g. pulsed-fields, gas environment etc. This study has shown that, for applied fields of 20MVm^-1, thin dielectric (750AA) and composite metal-insulator (MI) overlayers result in a dramatic increase in the total number of emission sites (typically 30cm^-2), and hence emission current. The emission process has been further investigated by a complementary electron spectroscopy technique which has revealed that the localised emission sites on these cathodes display field-dependent spectral shifts and half-widths, i.e. indicative of a `non-metallic' emission mechanism. Details are also given of a comprehensive investigation into the effects of the residual gas environment on the FIEE process from uncoated Cu-cathodes. This latter study has revealed that the well-known Gas Conditioning process can be performed with a wide range of gas species (e.g. O_2, N_2 etc), and furthermore, the degree of conditioning is influenced by both a `Voltage' and `Temperature' effect. These experimental findings have been shown to be particularly important to the technology of high-voltage vacuum-insulation and cold-cathode electron sources. The FIEE mechanism has been interpreted in terms of a hot-electron process that is associated with `electroformed' conducting channels in MI, MIM and MIMI surface microstructures.

A comparative study of different porous amorphous silica minerals supported TiO2 catalysts

Three porous amorphous silica minerals, including diatomite, opal and porous precipitated SiO2wereadopted to prepare supported TiO2catalysts by hydrolysis–deposition method. The prepared compoundmaterials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fouriertransform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM) and X-ray photo-electron spectroscopy (XPS). Through morphology and physical chemistry properties of the resultingTiO2/amorphous SiO2catalysts, it was proposed that the nature of silica supports could affect the particlesize and the crystal form of TiO2and then further influence the photocatalytic property of TiO2/amorphousSiO2catalysts. The catalytic properties of these porous amorphous silica supported photocatalysts(TiO2/SiO2) were investigated by UV-assisted degradation of Rhodamine B (RhB). Compared with pureTiO2(P25) and the other two TiO2/amorphous SiO2catalysts, TiO2/diatomite photocatalyst exhibits bet-ter catalytic performance at different calcined temperatures, the decoloration rate of which can be upto over 85% even at a relatively low calcined temperature. The TiO2/diatomite photocatalyst possessesmixed-phase TiO2with relatively smaller particles size, which might be responsible for higher photo-catalytic activity. Moreover, the stable and much inerter porous microstructure of diatomite could beanother key factor in improving its activity.

YBa2Cu3O7/NdGaO3/YBa 2Cu3O7 trilayers by modified off-axis sputtering

High-quality epitaxial YBa2Cu3O7-δ (YBCO) thin films were achieved by a modified off-axis sputtering technique with high deposition rates (3.3 nm/min). The film quality and the deposition rate depended crucially on the target-to-substrate separation. Epitaxial YBCO/NdGaO3(NGO)/YBCO trilayers were successfully grown onto SrTiO3, Y-ZrO2, and LaAlO3 substrates by dc and rf sputtering. The epitaxial relations were found to be [001] YBCO//[001]NGO, [100]YBCO, or [010] YBCO//[110]NGO and [001]YBCO//[110] NGO, [100]YBCO, or [010]YBCO//[001] NGO, where the latter orientation relationship was dominating. Subsequent top YBCO layers grew c axis oriented independently of the two epitaxial orientations of the NGO. The orientation relationships between YBCO and NGO were the same. Auger electron depth profiles and transmission electron microscopy indicated that the interdiffusion at the interface between the YBCO and NGO layers was not strong even at 740°C. The superconducting transition temperatures of the top and bottom YBCO layers were about the same as that of YBCO single layers, i.e., 87-90 K. Scanning electron microscopy of the surface morphologies of the YBCO and the NGO showed that a smaller substrate-target distance resulted in smoother films.

XPES studies of oxides of second- and third-row transition metals including rare earths

X-ray photoelectron spectroscopy has been employed to investigate oxides of second- and third-row transition metals, including those of rare earths. Systematics in the spin—orbit splittings and binding energies of core levels of the metals are described. In most of the cases studied, the dependence of the spin—orbit splittings on the atomic number Z is given by the relation ΔE = a(Z - Z0)4, where a is the quantum defect parameter and Z0 is the effective screening. Core-level binding energies are found to increase with the oxidation state of the metal. Most of the core-level binding energies are related to the atomic number Z by the expression E = x(Z - Z0)2, giving rise to linear plots of ln E versus ln Z. Specific features of individual oxides, with respect to satellites, multiplet structure, configuration mixing, and other properties are also discussed. The spectra of PrO2, Pr6O11, TbO2 and Tb4O7 are reported for the first time.