UHV

Once a sample is properly oriented and polished, it is placed into a UHV chamber for the final preparation steps. Samples are processed in situ by a variety of methods in order to produce an atomically clean and flat surface. Ion bombardment and aimealing (IBA) is the most conunon method used. Other methods include cleaving and film growth. 

For some materials, the most notable being silicon, heating alone sufiBces to clean the surface. Commercial Si wafers are produced with a thin layer of silicon dioxide covering the surface. This native oxide is inert to reaction with the atmosphere, and therefore keeps the underlying Si material clean. The native oxide layer is desorbed, i.e. removed into the gas phase, by heating the wafer in UHV to a temperature above approximately 1100 °C. This procedure directly fonus a clean, well ordered Si surface. 

This interface is critically important in many applications, as well as in biological systems. For example, the movement of pollutants tln-ough the enviromnent involves a series of chemical reactions of aqueous groundwater solutions with mineral surfaces. Although the liquid-solid interface has been studied for many years, it is only recently that the tools have been developed for interrogating this interface at the atomic level. This interface is particularly complex, as the interactions of ions dissolved in solution with a surface are affected not only by the surface structure, but also by the solution chemistry and by the effects of the electrical double layer [31]. It has been found, for example, that some surface reconstructions present in UHV persist under solution, while others do not. 

Modem UHV chambers are constmcted from stainless steel. The principal seals are metal-on-metal, thus the use of greases is avoided. A combination of pumps is nomially used, including ion pumps, turbomolecular pumps, cryopumps and mechanical (roughing) pumps. The entire system is generally heatable to 500 K. This bakeout for a period of... 

MBE is accomplished under UHV conditions with pressures of the order of Torr. By using such low... 

Figure A3.10.12 Side view of die high-pressure eell showing die eomieedons to the UHV ehamber, the turbomoleeular pump and the gas handling system. The differentially pumped sliding seal is loeated between the high-pressure eell and the UHV ehamber [37],...

Single erystals are traditionally used in UHV studies beeause they provide an opportunity to well eharaeterize a surfaee. However, as diseussed above, single erystals are quite different from industrial eatalysts. Typieally, sueh eatalysts eonsist of supported partieles that ean have multiple erystal orientations exposed at the surfaee. Therefore, an obstaele in attempting surfaee seienee studies of eatalysis is the preparation of a surfaee in sueh a way that it mimies a real-world eatalyst. 

Figure A3.10.18 Surface concentration of nitrogen on different Fe single crystals following N2 exposure at elevated temperatures in UHV [48],...

Figure A3.10.25 Arrhenius plots of CO oxidation by O2 over Rli single crystals and supported Rli/Al203 at PCO = PO2 = 0.01 atm [43]. The dashed line in the figure is the predicted behaviour based on the rate constants for CO and O2 adsorption and desorption on Rli under UHV conditions.

Figure A3.14.il. Spiral waves imaged by photoelectron electron microscopy for the oxidation of CO by O2 on a Pt(l 10) single crystal under UHV conditions. (Reprinted with pennission from [35], The American Institute of Physics.)...

TPD is frequently used to detenuine (relative) surface coverages. The area below a TPD spectrum of a certain species is proportional to the total amount that desorbs. In this way one can detennine uptake curves that correlate gas exposure to surface coverage. If tire pumping rate of the UHV system is sufiBciently high, the mass spectrometer signal for a particular desorption product is linearly proportional to the desorption rate of the adsorbate [20, 21] ... 

Korzeniewski C 1997 Infrared spectroscopy in electrochemistry new methods and connections to UhV surface science Crit. Rev. Anai. Chem. 27 81... 

Ultra-high vacuum (UHV) surface science methods allow preparation and characterization of perfectly clean, well ordered surfaces of single crystalline materials. By preparing pairs of such surfaces it is possible to fonn interfaces under highly controlled conditions. Furthennore, thin films of adsorbed species can be produced and characterized using a wide variety of methods. Surface science methods have been coupled with UHV measurements of macroscopic friction forces. Such measurements have demonstrated that adsorbate film thicknesses of a few monolayers are sufficient to lubricate metal surfaces [12, 181. 

Haupt S, Collisi U, Speckmann H D and Strehblow H-H 1985 Specimen transfer from the electrolyte to the UHV in a closed system and some examinations of the double layer on Cu J. Electroanal. Chem. 194 179-90... 

In practical applications, gas-surface etching reactions are carried out in plasma reactors over the approximate pressure range 10 -1 Torr, and deposition reactions are carried out by molecular beam epitaxy (MBE) in ultrahigh vacuum (UHV below 10 Torr) or by chemical vapour deposition (CVD) in the approximate range 10 -10 Torr. These applied processes can be quite complex, and key individual reaction rate constants are needed as input for modelling and simulation studies—and ultimately for optimization—of the overall processes. 

MetallorganicMBE (MOMBE). tire solid source Knudsen cells in conventional MBE are replaced witli gaseous beams of organometallic precursors, directed toward a heated substrate in UHV. Compared to MOCVD, MOMBE eliminates gas phase reactions tliat may complicate tire deposition surface reactions, and provides lower growtli temperatures. 

It is difficult to observe tliese surface processes directly in CVD and MOCVD apparatus because tliey operate at pressures incompatible witli most teclmiques for surface analysis. Consequently, most fundamental studies have selected one or more of tliese steps for examination by molecular beam scattering, or in simplified model reactors from which samples can be transferred into UHV surface spectrometers witliout air exposure. Reference [4] describes many such studies. Additional tliemes and examples, illustrating botli progress achieved and remaining questions, are presented in section C2.18.4. 

Xps ndAes Instrumentation. The instmmentation required to perform xps and aes analyses is generally sophisticated and expensive (19). The need for UHV conditions in order to retain surface cleanliness for a tractable period of time was mentioned above. Beyond this requirement (and the hardware that accompanies it), the most important components of an electron spectrometer system are the source, the electron energy analyzer, and the electron detector. These will be discussed in turn below. 

It has been suggested that gold does not have a stable surface oxide (227), and therefore, its surface can be cleaned simply by removing the physically and chemically adsorbed contaminants. However, more recently it has been shown that oxidation of gold by uv and ozone at 25°C gives a 1.7 0.4 — nm thick AU2O2 layer (228), stable to extended exposure to ultra high vacuum (UHV) and water and ethanol rinses. 

Fig. 2. Behavior of electron-field emission at room temperature from Spindt-type arrays of 5000 tips per mm, beginning and ending with ultrahigh vacuum (UHV), eg, ultracontrol (UC) (a) water (b) hydrogen and (c) oxygen, where the dashed line indicates noise. To convert Pa to torr, divide by 133.3.

Central Board of Irrigation atid Power. India, Earthing system parameters for HV, EHV and UHV sub-stations. Technical Report No. 49, Sept. (1985). 

EHV - above 245 kV. UHV - 1150kV (ultra high voltage used in the USA). 

The data above were collected in UHV environment to achieve the most pristine surface. Spectroscopy in air is usually more difficult to interpret due to contamination with oxides and other species, as is the case with all surface-sensitive spectroscopies. 

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