Surface effects in the valence band XPS spectrum of copper

Comparison of valence band XPS spectra of Cu samples with theoretical density of states shows a high intensity near the upper edge of the d-band. This is a feature common for most d-band metals. However, if the difference in the density of states of the first two atomic layers with respect to the bulk is taken into account, good agreement between theory and experiment is found.     

Invar-type new ferromagnetic amorphous Fe-B alloys

Measurements of magnetization, electrical resistivity, thermal expansion and differential thermal change were made on amorphous Fe_100-xB_x (9 ≦ X ≦ 21) alloys prepared by rapid quenching from the liquid state.With decreasing boron content in the alloys, the Curie temperature falls remarkably, while the magnetic moment increases sluggishly. The thermal expansion curves exhibit the invar characteristics below the Curie temperature due to a large positive spontaneous volume magnetostriction, and the reduced magnetization curves decrease much more rapidly with increasing temperature than those of other ferromagnetic amorphous alloys.     

NMR study of rapidly quenched crystalline and amorphous Fe-B alloys

Amorphous and microcrystalline Fe-B alloys (4–25 at % B) obtained by rapid quenching of the melt were studied using the pulsed nuclear magnetic resonance (NMR) of ¹¹B nuclei at 4.2 K. Alloy samples were prepared from both a natural isotope mixture and a mixture of the ⁵⁶Fe and ¹¹B isotopes. The NMR spectra were measured as a function of the boron content. The maximum hyperfine fields at the ¹¹B nuclei sites are 25–29 kOe and overlap the values of the hyperfine fields at the ¹¹B nuclei sites in the tetragonal and orthorhombic Fe₃B phases and also in the α-Fe phase containing boron as a substitutional impurity. The short-range order and local atomic structure of the amorphous Fe-B alloys were determined. The amorphous alloys are found to consist of microregions (clusters) with a short-range order similar to that in the tetragonal or orthorhombic Fe₃B phase or the α-Fe phase.     

Short-range order in amorphous ferromagnetic Fe-B alloys

Amorphous and quenched crystalline Fe-B alloys in the composition range of 4–25 at % B were prepared by melt spinning and investigated by ⁵⁷Fe Mössbauer spectroscopy at T = 87 K. The states of iron atoms in the α-Fe phases, including iron atoms having boron atoms in the nearest coordination sphere, and in the orthorhombic (o) and tetragonal (T) Fe₂B phases are detected in the microcrystalline alloys. The short-range order and the local atomic structure of the amorphous Fe-B alloys are determined. The amorphous alloys consist of microregions (clusters) with short-range order of the t- and o-Fe₂B and α-Fe types. The dependence of the content of various types of clusters on the alloy composition is quantitatively estimated.     

Local structure of amorphous and microcrystalline Fe-B alloys

Amorphous and microcrystalline Fe-B alloys in the composition range (4–25) at % B, fabricated by melt spinning, were investigated by pulse nuclear magnetic resonance (NMR) on ¹¹B nuclei at 4.2 K. Alloy samples were prepared both from a natural mixture of isotopes and an isotope mixture ⁵⁶Fe-¹¹B. The NMR spectra were measured at different boron contents. The local atomic structure of amorphous Fe-B alloys has been determined. The amorphous alloys consist of microregions (clusters) with short-range order of the tetragonal and orthorhombic Fe₃B-phase types, as well as of the α-Fe type.     

The XPS valence band of nickel metal

The XPS valence band spectrum of evaporated nickel is compared with a theoretical density of states curve and with a synthetic density of states curve obtained by adding two XPS valence band spectra of copper shifted by 0.3eV with respect to each other. Both calculated curves agree with the main features of the XPS valence band spectrum.     

The XPS valence band spectra of NbC

The x-ray photoemission valence band spectra of NbC have been measured and are compared with the x-ray emission spectra and with the results from band structure calculations. This comparison leads to a large enhancement of theC2 _p photoabsorption cross section (at=1,487 eV) compared to the value calculated for the free atom. The effect of the nonmetal vacancy in the valence band can be described very well with vacancy cluster calculations.     

First-principle study of the structural, electronic, and magnetic properties of amorphous Fe-B alloys

The structural, electronic, and magnetic properties of amorphous Fe_100−xB_x alloys (x=9, 17, 25, 27.3, 33.3, 36.3) are investigated using first-principles calculations. In these amorphous alloys, the short-range order is manifested as a series of Fe- or B-centered polyhedra such as tricapped trigonal prism, icosahedron, and bcc-like structural unit. The electron densities of states of the amorphous alloys resemble those of crystalline Fe borides, which further confirm the similarity of the local order in the amorphous and crystalline phases. All B atoms carry small negative moments of about −0.1μ_B, while small negative moments are also found on very few Fe sites for the Fe-rich compositions (x=9, 17). The average magnetic moment per Fe atom decreases nonlinearly with increasing B composition, which can be associated with the nonlinear relationship between mass density and composition.     

Investigation of valence band structures in Cu-Pd alloys

With the use of a HP 5950 A spectrometer X-ray photoelectron spectra (XPS) of valence band were obtained for Cu-Pd alloys and the density of electron states was calculated by the coherent potential method. It is found that d-resonance states of Pd are present in the alloys containing a high percentage of copper but there are no apparant d-resonance states of Cu in the alloys containing a high percentage of palladium.     

The pressure- and temperature dependence of the electrical resistivity of some amorphous Fe-B alloys

We report measurements of the electrical resistivity of the amorphous alloys Fe₄₀Ni₄₀P₁₄B₆ (Metglas 2826). Fe₃₂Ni₃₆Cr₁₄P₁₂B₆ (Metglas 2826A) Fe₈₀B₂₀ (Metglas 2605) and Fe₇₅B₂₅ as a function of pressure and temperature. The pressure is varied between 0 and 12 GPa, the temperature between 1.2 and 380 K. At low temperatures the pressure dependence yields additional information on the scattering mechanism.     

Itenerant magnetic properties of amorphous metallic systems: Numerical studies of the Fe-B alloys

A self-consistent method to compute local magnetic moments and spin polarized electron densities of states and to test the stability of the ferromagnetic vs. the paramagnetic state is developed within the framework of the itinerant electron theory. The tight-binding Hamiltonian, with Coulomb correlation among d electrons, is parametrized according to the Slater-Koster interpolation scheme. The method goes beyond the rigid band splitting approximation. We apply it to the Fe_1−xB_x amorphous system for 0 ⩽x⩽0.6 and obtain the magnetization for T=0 as a function of x in agreement with experimental data in the experimentally-accessible concentration region.     

High resolution core and valence band XPS spectra of non-conductor pyroxenes

High resolution core level and valence band (VB) X-ray photoelectron spectra (XPS) of the non-conductor pyroxene minerals, bronzite ((Mg_0.8,Fe_0.2)₂Si₂O₆) and diopside (Ca(Mg_0.8Fe_0.2)Si₂O₆) have been obtained with the Kratos magnetic confinement charge compensation which minimizes differential charge broadening. Observed Si 2p, O 1s, Mg 2p and Ca 2p total linewidths are all about 1.3 eV, very similar to those observed previously with the same instrument for SiO₂ and olivines ((Mg,Fe)₂SiO₄); and we consider that these widths are within 0.05 eV of the minimum room temperature linewidths for these samples with the experimental resolution of this instrument of 0.35 eV. These linewidths are all determined by vibrational broadening due to the M-O symmetric stretch in the ion states. The Si 2p binding energies (BE) are intermediate between the quartz and olivine Si 2p binding energies; but the O 1s spectra resolve the bridging oxygen (BO) and non-bridging oxygen (NBO) in the unit, with the NBO O 1s very close in BE to the O in olivine, and the BO very close to the BO in SiO_2. Indeed in both diopside and bronzite, it is possible to separate the three structurally inequivalent O atoms in the O 1s spectra: the BO at a BE of about 532.6 eV, a NBO peak from the MgOSi moiety (Mg in the M1 site) at about 531.3 eV, and a NBO peak at 531 eV from the CaOSi or the FeOSi moieties (Ca and Fe in the M2 site). The O 1s BE increases with the increase in the electronegativity Ca < Mg < Fe < Si. Moreover, the linewidths of these peaks increase when Fe and Mg are both present in either M1 (diopside) or M2 (bronzite) sites.The valence band spectra for the two pyroxenes are rather similar, and quite different from the VB spectra of quartz and olivines. The dispersion of the pyroxene VB spectra is intermediate between the VB spectra of quartz and olivines; the valence band spectrum of pyroxenes are more dispersed than in olivines by about 1.5 eV but less dispersed than quartz by about 1.5 eV. These VB spectra can be assigned using the previous olivine VB spectra and high quality pseudopotential density functional theoretical calculations in the generalized gradient (GGA) approximation. As for the olivine VB spectra, the Fe 3d t_2g and e_g orbitals in M1 and M2 sites of the pyroxene are located at the top of the pyroxene valence band, and the BE of the Fe 3d peaks from M1 are about 0.7 eV smaller than the Fe 3d peaks in M2. The theoretical XPS valence band spectra using the theoretical density of states and the Gelius intensity approximation are is in good semi-quantitative agreement with the experimental spectra. This intermediate dispersion of pyroxenes is due to the partial polymerization of the Si-O units in pyroxenes, and the intermediate charge on the Si atoms as indicated by the Si 2p BE.     

Surface effects on Sm valence in amorphous Sm alloys

We present the results of XPS and X-ray absorption measurements performed on the amorphous Sm Au and La Sm Au compounds. The XPS Sm 3d$\text{5}\text{2}$ core level spectra in these compounds reveal that at the surface (5 ? 7 Å) the samarium ions present both the Sm²⁺ (4f⁶) and Sm³⁺ (4f⁵) configurations. When the concentration in samarium decreases it is shown that the Sm²⁺ configuration is strongly enhanced at the surface whereas the X-ray absorption measurements indicate on the contrary that in the bulk only the Sm³⁺ configuration is present. Comparison is made with similar findings in pure crystalline Sm and various crystalline rare earth compounds.     

On the influence of oxygen on the valence band shape of carbon measured by XPS

XPS-spectra of the valence band of pyrolytic graphite with different amounts of contamination by oxygen have been investigated. The strong influence of oxygen on the XPS-spectra is discussed in terms of adsorbed as well as chemisorbed oxygen. A carbon valence band shape free from distortion by oxygen is presented.     

Mössbauer study of Fe-B alloys containing Nd additives

The influence of a few percent neodynium additives to Fe-B alloy on the hyperfine parameters was investigated. It was found that Nd decreases the hyperfine field of amorphous Fe-B alloys. The samples annealed at temperatures between 600°C and 700°C contain α-Fe and Fe₃B phases. The average hyperfine field of Fe₃B phase increases with increasing Nd content and decreases with increasing annealing temperature. The average isomer shift of Fe₃B phase decreases with increasing Nd content. The experimental data show that the change of hyperfine parameters of the Fe₃B phase in the studied alloys is due to Nd atom.     

Application of factor analysis to XPS valence band of superparamagnetic iron oxide nanoparticles

X-Ray photoelectron spectra of nano-sized superparamagnetic iron oxide nanoparticles were examined with the aim to discriminate the different degree of iron oxidation. Careful analysis of the valence band regions reveals the presence of both Fe₃O₄ and Fe₂O₃. The application of factor analysis enabled us to extract the relative molar concentrations of these oxides in the nanoparticles. This is of particular interest in improving the magnetic properties of iron oxide nanoparticles whose superparamagnetic character can be optimized to obtain better contrast in images from nuclear magnetic resonance. As a result, the factor analysis allows tuning the nanoparticle synthesis conditions in order to obtain the optimal magnetic properties for imaging. Results obtained by the XPS valence band analysis were compared to the transmission electron microscopy, X-ray diffraction and Raman measurements.     

Density-of-states in the valence band of some alloys on a gold base

The present work deals with the investigation of X-ray photoelectronic spectra of the alloys PtAu, CuAu, NiAu. It is shown that d-states of the components preserve their individualities in these alloys to a marked degree.     

A new interpretation of the valence band density of states of amorphous group IV-semiconductors

The disappearance of significant structures in the density of states of the lower (s-like) valence bands of amorphous Group IV-semiconductors is explained as a consequence of fluctuations in second nearest neighbour positions which lead to an additional pseudopotential coefficient V₍₂₀₀₎. Silicon is treated as an example. An explanation is proposed for the different behaviour of III-V compounds, where a doublet structure of the valence band density of states occurs also in the amorphous phases.     

<Superscript>57</Superscript>Fe NMR study of amorphous and rapidly quenched crystalline Fe-B alloys

Amorphous and crystalline Fe-B alloys (5–25 at % B) were studied using pulsed ⁵⁷Fe nuclear magneticr esonance at 4.2 K. The alloy samples were prepared from a mixture of the ⁵⁷Fe and ¹⁰B isotopes by rapid quenching from the melt. In the microcrystalline Fe-(5–12 at %) B alloys, the resonance frequencies were measured for local states of ⁵⁷Fe nuclei in the tetragonal and orthorhombic Fe₃B phases and also in α-Fe. The resonance frequencies characteristic of ⁵⁷Fe nuclei in α-Fe crystallites with substitutional impurity boron atoms in the nearest neighborhood were also revealed. In the resonance frequency distribution P(f) in the amorphous Fe-(18–25) at % B alloys, there are frequencies corresponding to local Fe atom states with short-range order of the tetragonal and orthorhombic Fe₃B phases. As the boron content decreases below 18 at %, the P(f) distributions are shifted to higher frequencies corresponding to ⁵⁷Fe NMR for atoms exhibiting a short-range order of the α-Fe type. The local magnetic structure of the amorphous Fe-B alloys is also considered.