Oxygen diffusion through thin Pt films on Si(100)

We have investigated the diffusion of oxygen through evaporated platinum films on Si(100) upon exposure to air using substrates covered with Pt films of spatially and continuously varying thickness (0–500 Å). Film compositions and morphologies before and after silicidation were characterized by modified crater edge profiling using scanning Auger microscopy, energy-dispersive X-ray microanalysis, scanning tunneling microscopy, and transmission electron microscopy. We find that oxygen diffuses through a Pt layer of up to 170 Å forming an oxide at the interface. In this thickness range, silicide formation during annealing is inhibited and is eventually stopped by the development of a continuous oxide layer. Since the platinum film consists of a continuous layer of nanometer-size crystallites, grain boundary diffusion of oxygen is the most probable way for oxygen incorporation. The diffusion constant is of the order of 10^–19 cm²/s with the precise value depending on the film morphology.     

Low energy electron spectroscopy of Pt (100) and Pt (100)/CO

Fine structure in the n_vi, _VIIVV spectrum of clean Pt (100) has been observed, and interpreted as “band like” in origin rather than quasi-atomic. Differences in the dependence of the Auger yield on primary beam energy are observed between the N_VI, _VIIVV and O_IIIVV peaks, and are associated with anomalies in the dependence of the inner shell ionization crossection of the 4f level. Low energy electron loss spectra on the clean surface have been investigated at primary energies in the range 71–774 eV and at angles of incidence of the beam 0–60°. The results are related to high energy loss and optical data, and assignments are given for inter-band and plasmon losses. With approximately $\text{3}\text{4}$ of a monolayer of CO on the surface there is a prominent additional loss at around 13.5 eV, which is interpreted as a one electron transition from a σ state below the d band to available states several electron volts above the Fermi level.     

High coverage states of oxygen adsorbed on Pt(100) and Pt(111) surfaces

Oxygen adsorption on the Pt(100) and Pt(111) surfaces was investigated using X-ray photo-emission and thermal desorption spectroscopies. Low pressure (ca. 10^?5 Pa) oxygen dosing at near ambient crystal temperature resulted in the formation of dissociated adsorbed species at saturation coverages of nominally 0.2–0.25 monolayer on both surfaces. The combination of higher pressure (ca. 10^?3 Pa) and higher surface temperature (570 K) dosing produced a three to five times higher saturation coverage than the low pressure dosing. The effect of dosing condition on the saturation coverage appears to reconcile apparent discrepancies for the Pt(100) surface in the literature. Characterization by XPS of the higher coverage state for oxygen showed that it is in the same chemical state as the oxygen adsorbed at very low coverage. Angle-resolved XPS has shown that in all cases the oxygen appears to reside on the surface with no significant penetration of oxygen into the bulk, as would be characteristic of oxidation. However, some penetration on the surface by oxygen, such as by a place-exchange type restructuring of the first two atomic layers, cannot be entirely ruled out.     

Field ion microscope observations of surface reconstructions on Pt(100) and Ir(100)

The reconstruction of the Pt(100) and Ir(100) plane has been studied by field ion microscopy. Small clusters of atoms produced by low-temperature field evaporation transform to new structures at temperatures above 270 K for Pt and 470 K for Ir. The atomic structure of reconstructed images is not resolved, but the shapes of the clusters suggest reconstructions consistent with current models based on low energy electron diffraction studies. Field evaporation of the reconstructed surfaces indicates that the restructuring extends to the second layer of atoms.     

Cyclic voltammograms for H on Pt(111) and Pt(100) from first principles

Cyclic voltammetry is a fundamental experimental method for characterizing electrochemical surfaces. Despite its wide use, a way to quantitatively and directly relate cyclic voltammetry to ab initio calculations has been lacking. We derive the cyclic voltammogram for H on Pt(111) and Pt(100), based solely on density functional theory calculations and standard molecular tables. By relating the gas phase adsorption energy to the electrochemical electrode potential, we provide a direct link between surface science and electrochemistry.     

Isomerization of n-butane on Pt (100): Monomolecular mechanism investigation

Density Functional Theory calculations have been performed on a skeletal isomerization of n-butane into isobutane in the absence and presence of hydrogen on a Pt (100) ultra thin film. A pathway implying monomolecular mechanism for the isomerization is assumed. A cyclic type mechanism is induced by the absence of hydrogen while a bond-shift mechanism is favored by its presence. Also, the presence of hydrogen facilitates isomerization by decreasing the energy barrier from 3.41 eV to 2.77 eV. The platinum thin film surface essentially acts as a hydrogen attractor. Afterwards the internal rearrangement of atoms of the activated hydrocarbons results in isomerization.     

The superstructures of the clean Pt(100) and Ir(100) surfaces

The clean and reconstructed surfaces of Pt(100) and Ir(100) were investigated by low energy electron diffraction (LEED). It is shown that two superstructures can be observed in the case of platinum. The structure Pt(100)-hex, which is commonly called Pt(100)-(5 × 20), transforms to Pt(100)-hex-R0.7° above 1100 K. It is shown that this stable phase differs from the first one by a slight rotation of the hexagonal surface layer by 0.7°. For Ir(100) only the well known (1 × 5) superstructure is observed without any rotation of the outer layer. The rotation angle of 0.7° for platinum and the stability of the unrelated structure for iridium can be interpreted by simple calculations of the coordination of surface atoms with those of the second layer. The method assumes that the surface layer is of ideal hexagonal structure in the case of platinum and nearly hexagonal in the case of iridium. The results are in good agreement with the experiment.     

Quantum diffusion of H on Pt(111): step effects

Using a linear optical diffraction technique, we have systematically investigated the defect effects on quantum surface diffusion of hydrogen on Pt(111) surfaces. The quantum tunneling effect was clearly observed for hydrogen diffusion at low temperatures as manifested by a leveling off of the diffusion coefficient on flat surfaces. The strong influence of surface defects on the quantum diffusion is in good agreement with the creation of an inhomogeneous surface with adsorption sites of different binding energies.     

Investigation of the peculiarities of Ge island growth on Si (100) under MBE conditions

The results of investigating the features of Ge-island formation on Si (100) under conditions of molecular-beam epitaxy is presented. Nanosized structures at heteroboundaries (islets and quantum dots) are attracting great interest due to new useful properties and broad prospects of their application.     

The formation of subsurface oxygen on Pt(100)

PhotoEmission Electron Microscopy (PEEM) enables imaging a surface via its work function. If a CO covered Pt(100) surface is exposed to oxygen patches are formed which appear dark in the PEEM image due to their high work function. As the surface is heated to temperatures above 650 K we observe the conversion of these dark islands into very bright ones with work functions much lower than even that of the clean surface. These findings are attributed to a change in the dipole moment of the adsorbed oxygen induced by their migration beneath the surface. A total work-function decrease of up to 1.2 eV has been evaluated independently using a Scanning Photoemission Microscope (SPM). The properties of this new kind of oxygen were also further investigated with thermal desorption spectroscopy and with Auger-electron spectroscopy.     

Adsorption of ethylene on the Pt(100) surface

Clean Pt(100) surfaces with bulk-like 1×1 structure, or the stable, reconstructed 5×20 structure and held at 200 or 330 K were exposed to ethylene. Ultraviolet photoemission spectroscopy identified the nature of the adsorbed species which depends on the structure and temperature of the clean surface and the amount adsorbed. It is ethylene on the 5 × 20 structure at 200 K, a vinyl radical on the same surface at 300 K up to half a monolayer, the remainder being added as acetylene; it is acetylene on the 1 × 1 surface at 330 K and a mixture of acetylene, vinyl and ethylene on the 1 × 1 surface at 200 K. Whatever the nature of the adsorbate, the surface coverage θ increased with exposure ? as $\text{(1 ? θ = C?}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>3</mtext>}}\text{)}$. By contrast, on a surface covered with any C₂ hydrocarbon acetylene adsorbs with Langmuir kinetics. The kinetics are explained in terms of the relationship between the attraction an approaching molecule experiences from the bare surface and its Van der Waals repulsion from preadsorbed molecules.