Studies on PtNi alloys: AES and photoemission determination of the surface composition and interaction with oxygen and hydrogen

Three PtNi alloys with 20, 40 and 70 at% Ni were studied by Auger and photoelectron spectroscopies. The clean surfaces were found to be enriched in platinum in an amount increasing with increasing platinum concentration in the bulk. On the contrary oxidation treatments resulted in a nickel surface segregation which was only slightly offset after reduction. Chemical shifts characteristic of oxidation were observed on XPS peaks of both platinum and nickel under experimental conditions where pure platinum could not be oxidized.     

Equilibrium surface segregation for Ni15%Cr(110)

The surface segregation of an atomically clean binary Ni15%Cr(110) was studied using AES, It was shown that Ni segregated preferentially to surface in vacuum at temperatures between 500 and 650°C, and heat of segregation was 2500 cal/mol. Based on theoretical models and the data commonly used to predict the segregating species, Cr rather than Ni would be expected to surface segregate. We have therefore used this system to demonstrate two important points; first the surface energy of solids rather than liquids must be used to properly predict surface segregation, the segregating species should be predicted based upon the surface energy per unit atom rather than on the basis of a unit area.     

Dynamical behaviour of PtRh(100) alloy surface during dissociative adsorption of NO and reaction of NO with H2

When a clean Pt-Rh(100) alloy surface was exposed to NO at T > 440 K, the LEED pattern changed sequentially as p(1 × 1) → c(2 × 2) → c(2 × 2) + p(3 × 1) → p(3 × 1), where the c(2 × 2) pattern appeared immediately after the exposure to NO. In contrast to this, the appearance time for the p(3 × 1) depends strongly on the initial Rh concentration on the surface adjusted by annealing. When the p(3 × 1) surface was exposed to H₂ by mixing H₂ into NO gas, the AES intensity of O(a) decreased and of N(a) increased markedly and the LEED pattern changed from p(3 × 1) to c(2 × 2). These results suggest that N(a) has equal affinity to Pt and Rh atoms so that the N(a) does not distinguish the Pt and Rh sites on the alloy surface. On the other hand, O(a) makes a stronger bond with Rh atoms so that Rh atom segregation onto the surface is induced. By reacting randomly distributed Rh atoms on the Pt-Rh(100) surface with oxygen, a surface compound in a p(3 × 1) arrangement is built on the surface.     

Electronic structures of CO adsorbed Pt-skin surface on Pt–Co and Pt–Ni alloys

By using angle resolved photoemission spectroscopy, we investigate the electronic structures of Pt-skin layer of Pt–Co and Pt–Ni alloys with CO molecules on the surface. Measured Fermi surface maps and band dispersions reflect the signatures of chemical bonding between Pt-skin layer and CO molecules. Furthermore, the degree of chemical bonding strength of CO molecules, estimated from the energy shift of the participating bands, is found to be reduced on both Pt bimetallic alloys. Our results show how the surface band structure of Pt bimetallic alloys is modified with molecular orbitals of CO molecules on the surface, revealing the important role of the electronic structure in the determination of chemical properties of bimetallic alloys.     

X-ray photoemission studies of PtSn and PtPb bimetallic systems

The Pt(5d) and Pt(4f) in PtSn and PtPb composites produced by sequential vapor deposition have been examined by X-ray photoelectron spectroscopy. At low concentrations of Pt, the Pt(5d) becomes a single, narrow resonance at about 4 eV below the Fermi level. Its density of states at the Fermi level is small. This leads to a large suppression of the Pt(4f) lineshape asymmetry. As the Pt concentration increases, d-d interactions split the Pt(5d) resonance and increase the 5d density of states at the Fermi level by pushing one of the split resonances to the Fermi level. Consequently, the Pt(4f) lineshape asymmetry increases. The evolution of the Pt(4f) and Pt(5d) in PtSn and PtPb are very similar but different from that of small Pt particles supported on carbon. The close similarity of the electronic properties of Pt in PtSn and PtPb suggests that the poisoning of Pt by Pb is not entirely due to electronic effects although there are indications of stronger interaction between Pt and Pb than between Pt and Sn atoms. The strong surface enrichment of Pb on PtPb points to the importance of the physical blockage of Pt atoms by surface Pb in determining the poisoning effect of Pb.     

Radiation acceptors in GeSi alloys

The Hall-effect, conductivity, isochronal and isothermal annealing of defects in n-type Gez.sbnd;Si alloys irradiated by electrons and

-quantum are investigated. Maximum content of minority component was equal to 1,5 at .% Si. It is shown that in Gez.sbnd;Si three types of radiation acceptors are being generated. The energetic parameters of defects, their dependence on the content of Si in Gez.sbnd;Si are calculated. The effect of radiation acceptors on the change of carriers concentration and mobility in Gez.sbnd;Si is investigated.     

Superconductivity of TiZrNi alloys containing quasicrystals

Superconductivity of rapidly quenched ribbons Ti₅₃Zr₂₇Ni₂₀ at 1.94 K and the beginning of the transition to the superconductivity in ribbons Ti₄₅Zr₃₈Ni₁₇ below 1.5 K were found. X-rays diffractometry measurements showed that the icosahedral quasicrystal phase is dominant in all samples.     

Magnetic properties of TiZr alloys

Magnetic susceptibility measurements of TiZr alloys are reported. Zirconium, by alloying, acts on the Néel temperature giving rise to a complicated magnetic phase diagram. The main mechanism in the T_N shift is the change of the Fermi level. The experimental dependence between T_N and X₀ is in good agreement with the theoretical dependence obtained on the Fedders-Martin model by taking into account the effect of nonmagnetic impurity on the Fermi level.     

Solute-atom segregation/structure relations at high-angle (002) twist boundaries in dilute Ni−Pt alloys

Monte Carlo simulations, utilizing embedded atom method (EAM) potentials, are employed to investigate in detail solute-atom segregation behavior at high-angle symmetrical (002) twist boundaries, at T=850 K, in Pt-3 at.% Ni and Ni-3 at.% Pt alloys. Solute enhancement in those alloys occurs on both sides of the phase diagram, although it is considerably higher on the Ni-rich side. The distributions of solute concentrations within the first and the second planes are very inhomogeneous, with the sites highly enhanced in solute being in the minority. The remaining sites exhibit little or no enhancement. The highest level of solute concentrations at individual sites continues to increase with the value of the rotations angle, , until saturation occurs at about the =5 misorientation. The large differences in concentrations between different types of sites suggest the possibility of an ordered grain-boundary phase. The correlation between the structure and solute species concentrations in most cases follows the trends observed for low-angle boundaries: Pt as a solute prefers the structural units of the perfect crystal type, while Ni as a solute tends to segregate at the filler units associated with the cores of the primary grain boundary dislocations. A strong correlation is observed between the position of a site in the first or second (002) plane and the plane of the interface. Rigid-body translations are detected for two boundaries on the Pt-rich side of the phase diagram. Roughening and possible structural multiplicity occur in the =5 boundary on the Ni-rich side. The same boundary on the Pt-rich side of the phase diagram exhibits a considerable amount of structural and chemical disorder.     

Suppression of electron correlations in the superconducting alloys of Rh17−xIrxS15

We have studied the effect of Iridium doping (Rh_17?xIr_xS₁₅) in the rhodium sites of the strongly correlated superconductor Rh₁₇S₁₅. Even at low levels of doping (x = 1 and 2) we see a drastic change in the superconducting properties as compared to those of the undoped system. We deduce that there is a reduction in the density of states at the Fermi level from reduced Pauli susceptibility and Sommerfeld coefficient in the doped samples. Moreover, the second magnetization peak in the isothermal magnetization scan (‘fishtail’) which was very prominent in the magnetization data of the undoped crystal is suppressed in the doped samples. The temperature dependence of resistivity of the doped crystals show a remarkably different behavior from that of the undoped crystal with the appearance of a minima at lower temperatures, the position of which is fairly constant at different fields. Our data supports the notion that Iridium, which is a bigger atom than rhodium expands the lattice thereby, reduces the electron correlations that existed due to the interaction between closer lying rhodium atoms in the undoped system.     

Ion mixing of near surface layers in AuCu,CuMo systems irradiated by HPIB

New results on mixing in single layered metal structures exposed to nanosecond high power ion beams (HPIB) are presented. Au/Cu and Cu/Mo structures have been investigated using RBS, SIMS, AES and transmission electron microscopy. It is shown that HPIB-induced mixing was initiated at the substrate-deposited-layer interface in contrast to laser melting which starts at the surface. Cu₃Au superstructure phase, CuAu metastable state and an amorphous structure have been revealed. Cu/Mo structures which cannot produce equilibrium alloys and compounds and strongly differ in their thermophysical properties, can be mixed in the gaseous and liquid phases by three HPIB pulses with 0.95 J/cm² energy density.     

Atomic fraction around defects associated with nanoparticles in AlCuMg alloys

A positron annihilation spectroscopy analysis method to obtain a quantitative determination of the chemical composition around defects inside nanoparticles is presented here. This methodology is applied to AlCuMg alloys to study the rapid hardening phenomena associated with solute-vacancy aggregation. Coincidence Doppler Broadening (CDB) and lifetime spectroscopy measurements of reference samples of pure elements with and without defects were analyzed to give quantitative information of the average chemical environment around vacancies, i.e. the atomic fraction of the first neighbors of these defects, in the alloys studied. The accuracy and reproducibility of the methodology is confirmed not only by good fits to the experimental data but, in most cases, by the consistency between the mean lifetime values predicted, using the CDB estimation, and the mean lifetime values independently measured. Discrepancies in the methodology are expected when there is poor CDB contrast between elements, i.e. having similar electronic structure (for example, Al and Mg). The criterion for establishing the statistical accuracy of the separation of elements in these special cases is discussed. The methodology can be applied not only to study homogeneous materials as metallic alloys, but also to study the depth profile in thin films.     

Infrared radiative recombination in Rh3+doped AgBr

Infrared photoluminescence was used to characterize the low-temperature radiative recombination processes in Rh³⁺doped silver bromide single crystals. A single structureless band was observed with a peak emission wavelength of 1.6 μm. The results of our experiments suggest that Rh³⁺ impurity sites are responsible for this emission. The lifetime of the emission was determined as a function of temperature; the 6.5 K lifetime is 1.6 ± 0.1 ms. A configuration coordinate model for the electronic states of transition-metal impurities in silver halides is used to describe the results.     

Surface demagnetizing field as a source of uniaxial surface anisotropy in GdCoMo thin amorphous films

Surface magnetic anisotropy energy was studied for (Gd_0.26Co_0.74)_0.96Mo_0.04 and (Gd_0.29Co_0.71)_0.96Mo_0.04 thin amorphous films by means of microwave spectroscopy at the X-band within the temperature range 4–295 K. Excitations of surface spin waves were observed in the spin wave resonance spectra. The experiment was performed in a rotating external magnetic field. The angular dependence of the resonance field for the uniform mode (spin wave vector k=0) and the surface mode made it possible to determine the surface uniaxial anisotropy constant K_s and its temperature dependence. An inhomogeneity of the saturation magnetization M_s within a close-to-surface layer of thickness d can generate the surface anisotropy energy with anisotropy constant K_s given by the formula: K_s=4πM^b_s (M^b_s−M^surf_s)d, where the indexes b and surf correspond to the bulk and surface values, respectively. The temperature dependence of K_s calculated by means of the formula agrees qualitatively with temperature dependence of K_s found in the experiment.     

Kinetic limitations to surface segregation during MBE growth of III–V compounds: Sn in GaAs

The incorporation of Sn as a dopant in GaAs has been studied in the temperature range of 500°–650° C, over a wide range of Ga and As fluxes, the latter being incident as either As₄ or As₂ molecules. The results are explained in terms of a surface segregation model in which the behaviour at high growth temperatures (above 600 °C) approaches thermal equilibrium, but growth at lower temperatures involves a kinetic limitation to the segregation process.     

Density and surface tension of diluted Sn–In alloys

The results from measuring the density and surface tension of Sn–In melts via the sessile drop method in a helium atmosphere and at a residual gas pressure of 0.01 Pa are presented. The density polytherms of all samples are linear with negative temperature coefficients. In the range of 550–750°C, the surface tension falls linearly as the temperature rises.     

Concentration dependence of thermodynamic,transport and surface properties in Ag–Cu liquid alloys

Thermodynamic, transport and surface properties of Ag–Cu liquid alloys have been investigated on the basis of a simple statistical model. The free energy of mixing, heat of mixing and entropy of mixing have been computed to understand the thermodynamic properties of Ag–Cu alloys in liquid state at 1,423 K. The concentration–concentration fluctuations in the long wavelength limit and the chemical short range order parameter have been determined to comprehend the microscopic and structural information of the alloy. The viscosity and surface tension of the alloy have been evaluated to analyze the transport and surface properties. The theoretical analysis reveals that the energy parameter is temperature dependent, and that Ag–Cu liquid alloy is a weakly interacting-phase separating system.