Surfaces atomic processes

A number of methods that provide information about the structure of a solid surface, its composition, and the oxidation states present have come into use. The recent explosion of activity in scanning probe microscopy has resulted in investigation of a wide variety of surface structures under a range of conditions. In addition, spectroscopic interrogation of the solid-high-vacuum interface elucidates structure and other atomic processes. 

Xps is based on the photoelectric effect when an incident x-ray causes ejection of an electron from a surface atom. Figure 7 shows a schematic of the process for a hypothetical surface atom. In this process, an incident x-ray photon of energy hv impinges on the surface atom causing ejection of an electron, usually from a core electron energy level. This primary photoelectron is detected in xps. 

The lines of primary interest ia an xps spectmm ate those reflecting photoelectrons from cote electron energy levels of the surface atoms. These ate labeled ia Figure 8 for the Ag 3, 3p, and 3t7 electrons. The sensitivity of xps toward certain elements, and hence the surface sensitivity attainable for these elements, is dependent upon intrinsic properties of the photoelectron lines observed. The parameter governing the relative iatensities of these cote level peaks is the photoionization cross-section, (. This parameter describes the relative efficiency of the photoionization process for each cote electron as a function of element atomic number. Obviously, the photoionization efficiency is not the same for electrons from the same cote level of all elements. This difference results ia variable surface sensitivity for elements even though the same cote level electrons may be monitored. 

Numerous schemes can be devised to classify deposition processes. The scheme used herein is based on the dimensions of the depositing species, ie, atoms and molecules, softened particles, Hquid droplets, bulk quantities, or the use of a surface-modification process (1,2). Coating methods are as foHow (2) ... 

In the sputtering process, each surface atomic layer is removed consecutively. If there is no diffusion in the target, the composition of the vapor flux leaving the surface is the same as the composition of the bulk of the material being sputtered, even though the composition of the surface may be different from the bulk. This allows the sputter deposition of alloy compositions, which can not be thermally vaporized as the alloy because of the greatly differing vapor pressures of the alloy constituents. 

Figure 1 Schematic of DC glow-discharge atomization and ionization processes. The sample is the cathode for a DC discharge in 1 Torr Ar. Ions accelerated across the cathode dark space onto the sample sputter surface atoms into the plasma (a). Atoms are ionized in collisions with metastable plasma atoms and with energetic plasma electrons. Atoms sputtered from the sample (cathode) diffuse through the plasma (b). Atoms ionized in the region of the cell exit aperture and passing through are taken into the mass spectrometer for analysis. The largest fraction condenses on the discharge cell (anode) wall.

When a gas comes in contact with a solid surface, under suitable conditions of temperature and pressure, the concentration of the gas (the adsorbate) is always found to be greater near the surface (the adsorbent) than in the bulk of the gas phase. This process is known as adsorption. In all solids, the surface atoms are influenced by unbalanced attractive forces normal to the surface plane adsorption of gas molecules at the interface partially restores the balance of forces. Adsorption is spontaneous and is accompanied by a decrease in the free energy of the system. In the gas phase the adsorbate has three degrees of freedom in the adsorbed phase it has only two. This decrease in entropy means that the adsorption process is always exothermic. Adsorption may be either physical or chemical in nature. In the former, the process is dominated by molecular interaction forces, e.g., van der Waals and dispersion forces. The formation of the physically adsorbed layer is analogous to the condensation of a vapor into a liquid in fret, the heat of adsorption for this process is similar to that of liquefoction. 

The technique of INS is probably the least used of those described here, because of experimental difficulties, but it is also one of the physically most interesting. Ions of He" of a chosen low energy in the range 5-10 eV approach a metal surface and within an interaction distance of a fraction of a nanometer form ion-atom pairs with the nearest surface atoms. The excited quasi molecule so formed can de-excite by Auger neutralization. If unfilled levels in the ion fall outside the range of filled levels of the solid, as for He", an Auger process can occur in which an electron from the va-... 

M. Menon and R. E. AUen, New technique for molecular-dynamics computer simulations Hellmann- Feynman theorem and subspace Hamiltonian approach , Phys. Rev. B33 7099 (1986) Simulations of atomic processes at semiconductor surfaces General method and chemisorption on GaAs(llO) , ibid B38 6196 (1988). 

Two basic versions of the process plasma-based ion plating and vacuum-based ion plating. The coating material is vaporized in a manner similar to evaporation. Typically, the plasma is obtained by biasing the substrate to a high negative potential (5 kV) at low pressure. The constant ion bombardment of the substrate sputters off some of the surface atoms which results in improved adhesion and reduced impurities. Surface coverage of discontinuities is also improved. 

The present study revealed effects of various rutile/anatase ratios in titania on the reduction behaviors of titania-supported cobalt catalysts. It was found that the presence of rutile phase in titania could facilitate the reduction process of the orbalt catalyst. As a matter of fact, the number of reduced cobalt metal surface atoms, which is related to the overall activity during CO hydrogenation increased. 

The present research showed a dependence of various ratios of rutile anatase in titania as a catalyst support for Co/Ti02 on characteristics, especially the reduction behaviors of this catalyst. The study revealed that the presence of 19% rutile phase in titania for CoATi02 (C0/RI9) exhibited the highest number of reduced Co metal surface atoms which is related the number of active sites present. It appeared that the increase in the number of active sites was due to two reasons i) the presence of ratile phase in titania can fadlitrate the reduction process of cobalt oxide species into reduced cobalt metal, and ii) the presence of rutile phase resulted in a larger number of reduced cobalt metal surface atoms. No phase transformation of the supports further occurred during calcination of catalyst samples. However, if the ratios of rutile anatase were over 19%, the number of active sites dramatically decreased. 

The number of surface collisions at p=l bar and T = 300 K is thus rcoii-surf = 1-08 X 10 m s for hydrogen and 2.88 x 10 m s for nitrogen. Since there are typically 1.5 x 10 surface atoms per m, a surface atom will on average be hit a billion times per second under ambient conditions. This, however, does not necessarily mean that the gas molecule reacts, particularly if the reaction is an activated process. 

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