In situ observation of wet oxidation kinetics on Si(100) via ambient pressure x-ray photoemission spectroscopy

e initial stages of wet thermal oxidation of Si (100) - (2??1) have been investigated by in situ ambient pressure x-ray photoemission spectroscopy, including chemical-state resolution via Si 2p core-level spectra. Real-time growth rates of silicon dioxide have been monitored at 100 mTorr of water vapor. This pressure is considerably higher than in any prior study using x-ray photoemission spectroscopy. Substrate temperatures have been varied between 250 and 500 ??C. Above a temperature of ???400 ??C, two distinct regimes, a rapid and a quasisaturated one, are identified, and growth rates show a strong temperature dependence which cannot be explained by the conventional Deal-Grove model.open7

Real-time observation of the dry oxidation of the Si(100) surface with ambient pressure x-ray photoelectron spectroscopy

We have applied ambient-pressure x-ray photoelectron spectroscopy with Si 2p chemical shifts to study the real-time dry oxidation of Si(100), using pressures in the range of 0.01-1 Torr and temperatures of 300-530 ??C, and examining the oxide thickness range from 0 to ???25 A. The oxidation rate is initially very high (with rates of up to ???225 Ah) and then, after a certain initial thickness of the oxide in the range of 6-22 A is formed, decreases to a slow state (with rates of ???1.5-4.0 Ah). Neither the rapid nor the slow regime is explained by the standard Deal-Grove model for Si oxidation.open171

A photoemission study of Pd ultrathin films on Pt (111)

The origin of surface core-level shift (SCLS) of Pd thin films on Pt(111) substrate is investigated. At sub-monolayer coverage of Pd thin films, the splitting of Pd 3d core level peaks indicate the contribution of both initial and final-state of photo-ionization processes while there is almost no change on valence band (VB) spectra. When the coverage of Pd reaches to single monolayer, the final-state relaxation effect on the Pd 3d vanishes and only the initial-state effect, a negative SCLS, is present. Also, the VB spectrum at Pd monolayer films shows a clear band narrowing, that is the origin of the negative SCLS at monolayer coverage. As the Pd coverage is increased to more than monolayer thickness, the Pd 3d peaks start to show the surface layer contribution from second and third layers, positive SCLS, and the VB spectrum shows even narrower band width, possibly due to the formation of surface states and strained effect of Pd adlayers on top of the first pseudomorphic layer

In-Situ observation of wet oxidation kinetics on Si (100) via ambient pressure x-ray photoemission spectroscopy

The initial stages of wet thermal oxidation of Si(100)-(2x1) have been investigated by in-situ ambient pressure x-ray photoemission spectroscopy (APXPS), including chemical-state resolution via Si 2p core-level spectra. Real-time growth rates of silicon dioxide have been monitored at 100 mTorr of water vapor. This pressure is considerably higher than in any prior study using XPS. Substrate temperatures have been varied between 250 and 500 C. Above a temperature of {approx} 400 C, two distinct regimes, a rapid and a quasi-saturated one, are identified and growth rates show a strong temperature dependence which cannot be explained by the conventional Deal-Grove model

Deactivation of Ru Catalysts under Catalytic CO Oxidation by Formation of Bulk Ru Oxide Probed with Ambient Pressure XPS

The surface science approach of using model catalysts in conjunction with the development of in situ spectroscopic tools, such as ambient pressure X-ray photoelectron spectroscopy (AP-XPS), offers a synergistic strategy for obtaining a substantially better understanding of deactivation phenomena. In this study, we investigated the nature of Ru oxides on a Ru polycrystalline film under oxidizing, reducing, and catalytic CO oxidation reaction conditions. Thus, bulk Ru oxide was easily formed on such Ru catalysts, the growth of which was dependent on reaction temperature. Once formed, such an oxide is irreversible and cannot be completely removed even under reducing conditions at elevated temperatures (200 °C). Our reaction studies showed substantial deactivation of the Ru film during catalytic CO oxidation, and its activity could be partially recovered after reduction pretreatment. Such continuous deactivation of a Ru film is correlated with irreversibly formed bulk Ru oxide, as shown by AP-XPS. Such in situ spectroscopic evidence of the transition of oxides to a catalytically inactive state can enable more effective design of catalysts with less deactivation.119181sciescopu

Biological Components and Bioelectronic Interfaces of Water Splitting Photoelectrodes for Solar Hydrogen Production

Artificial photosynthesis (AP) is inspired by photosynthesis in nature. In AP, solar hydrogen can be produced by water splitting in photoelectrochemical cells (PEC). The necessary photoelectrodes are inorganic semiconductors. Light-harvesting proteins and biocatalysts can be coupled with these photoelectrodes and thus form bioelectronic interfaces. We expand this concept toward PEC devices with vital bio-organic components and interfaces, and their integration into the built environment

Study of electro-chemical properties of metaloxide interfaces using a newly constructed ambient pressure X-ray photoelectron spectroscopy endstation

In this report, we briefly describe the general design principles and construction of a newly developed ambient pressure X-ray photoelectron spectroscopy system. This system provides an imaging mode with < 20 mu m spatial resolution in one dimension as well as an angle-resolved mode. The new imaging mode enables us to study structured surfaces under catalytically and environmentally relevant conditions. To illustrate this capability, in situ studies on a Au-SiO(2) heterojunction and Rh-TiO(2) metal-support system are presented. This new system can probe structured surfaces near ambient pressure as a function of temperature, pressure, electrical potential, local position, and time. It is a valuable in situ tool to detect material transformations at the micrometer scale.close1