Ultrahigh vacuums

Ultrahigh vacuum techniques have become common, especially in connection with surface spectroscopic and diffraction studies, but also in adsorption on very clean surfaces. The techniques have become rather specialized and the reader is referred to Ref. 8 and citations therein. 

For example, energy transfer in molecule-surface collisions is best studied in nom-eactive systems, such as the scattering and trapping of rare-gas atoms or simple molecules at metal surfaces. We follow a similar approach below, discussing the dynamics of the different elementary processes separately. The surface must also be simplified compared to technologically relevant systems. To develop a detailed understanding, we must know exactly what the surface looks like and of what it is composed. This requires the use of surface science tools (section B 1.19-26) to prepare very well-characterized, atomically clean and ordered substrates on which reactions can be studied under ultrahigh vacuum conditions. The most accurate and specific experiments also employ molecular beam teclmiques, discussed in section B2.3. 

Essential to modem surface science teclmiques is the attaimnent and maintenance of ultrahigh vacuum... 

Campbell R A and Goodman D W 1992 A new design for a multitechnique ultrahigh vacuum surface analysis chamber with high-pressure capabilities Rev. Sc/. Instrum. 63 172... 

Because of the generality of the symmetry principle that underlies the nonlinear optical spectroscopy of surfaces and interfaces, the approach has found application to a remarkably wide range of material systems. These include not only the conventional case of solid surfaces in ultrahigh vacuum, but also gas/solid, liquid/solid, gas/liquid and liquid/liquid interfaces. The infonnation attainable from the measurements ranges from adsorbate coverage and orientation to interface vibrational and electronic spectroscopy to surface dynamics on the femtosecond time scale. 

Carpick R W, Agrait N, Ogletree D F and Salmeron M 1996 Measurement of interfacial shear (friction) with an ultrahigh vacuum atomic force microscope J. Vac. Sc/. Technol. B 14 1289... 

Jarvis S P, Yamamoto S-l, Yamada H, Tokumoto H and Pethica J B 1997 Tip-surface interactions studied using a force controlled atomic force microscope in ultrahigh vacuum Appl. Phys. Lett. 70 2238... 

Bammerlin M, Luthi R, Meyer E, Baratoff A, Lu J, Guggisberg M, Gerber Ch, Howald L and Gutherodt H-J 1997 True atomic resolution on the surface of an insulator via ultrahigh vacuum dynamic force microscopy Probe Microsc. 1 3... 

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. 

Several striking examples demonstrating the atomically precise control exercised by the STM have been reported. A "quantum corral" of Fe atoms has been fabricated by placing 48 atoms in a circle on a flat Cu(lll) surface at 4K (Fig. 4) (94). Both STM (under ultrahigh vacuum) and atomic force microscopy (AFM, under ambient conditions) have been employed to fabricate nanoscale magnetic mounds of Fe, Co, Ni, and CoCr on metal and insulator substrates (95). The AFM has also been used to deposit organic material, such as octadecanethiol onto the surface of mica (96). New appHcations of this type of nanofabrication ate being reported at an ever-faster rate (97—99). 

Instmmentation for tern is somewhat similar to that for sem however, because of the need to keep the sample surface as clean as possible throughout the analysis to avoid imaging surface contamination as opposed to the sample surface itself, ultrahigh vacuum conditions (ca 10 -10 Pa) are needed in the sample area of the microscope. Electron sources in tern are similar to those used in sem, although primary electron beam energies needed for effective tern are higher, typically on the order of ca 100 keV. 

Hot-Cathode Ionization Gauges. For pressures below approximately lO " Pa, it is not possible, except under carehiUy controlled conditions, to detect the minute forces that result from the coUision of gas molecules with a soHd wall. The operation of the ion gauge is based on ionisa tion of gas molecules as a result of coUisions with electrons. These ions are then subsequendy collected by an ion collector. Ionisa tion gauges, used almost exclusively for pressure measurement in high, very high, ultrahigh, and extreme ultrahigh vacuums, measure molecular density or particle dux, not pressure itself. 

Separate all noncondensables before feeding to WEE or SPE unit (even a small amount of noncondensables overloads vacuum system, especially at ultrahigh vacuum ranges) most low molecular weight compounds do not condense at cooling water temperatures under high vacuum. 

CVD reactions are most often produced at ambient pressure in a freely flowing system. The gas flow, mixing, and stratification in the reactor chamber can be important to the deposition process. CVD can also be performed at low pressures (LPCVD) and in ultrahigh vacuum (UHVCVD) where the gas flow is molecular. The gas flow in a CVD reactor is very sensitive to reactor design, fixturing, substrate geometry, and the number of substrates in the reactor, ie, reactor loading. Flow uniformity is a particulady important deposition parameter in VPE and MOCVD. 

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.

Ultrasound frequencies can be introduced into the walls of the vacuum system. If a source of ultrasound is placed on the wall of an ultrahigh vacuum system, a large hydrogen peak is observed. Related phenomena, presumably from frictional effects, are observed if the side of a vacuum system is tapped with a hammer a desorption peak can be seen. Mechanical scraping of one part on another also produces desorption. 

The catalysts with the simplest compositions are pure metals, and the metals that have the simplest and most uniform surface stmctures are single crystals. Researchers have done many experiments with metal single crystals in ultrahigh vacuum chambers so that unimpeded beams of particles and radiation can be used to probe them. These surface science experiments have led to fundamental understanding of the stmctures of simple adsorbed species, such as CO, H, and small hydrocarbons, and the mechanisms of their reactions (42) they indicate that catalytic activity is often sensitive to small changes in surface stmcture. For example, paraffin hydrogenolysis reactions take place rapidly on steps and kinks of platinum surfaces but only very slowly on flat planes however, hydrogenation of olefins takes place at approximately the same rate on each kind of surface site. 

The typical industrial catalyst has both microscopic and macroscopic regions with different compositions and stmctures the surfaces of industrial catalysts are much more complex than those of the single crystals of metal investigated in ultrahigh vacuum experiments. Because surfaces of industrial catalysts are very difficult to characterize precisely and catalytic properties are sensitive to small stmctural details, it is usually not possible to identify the specific combinations of atoms on a surface, called catalytic sites or active sites, that are responsible for catalysis. Experiments with catalyst poisons, substances that bond strongly with catalyst surfaces and deactivate them, have shown that the catalytic sites are usually a small fraction of the catalyst surface. Most models of catalytic sites rest on rather shaky foundations. 

CO oxidation catalysis is understood in depth because potential surface contaminants such as carbon or sulfur are burned off under reaction conditions and because the rate of CO oxidation is almost independent of pressure over a wide range. Thus ultrahigh vacuum surface science experiments could be done in conjunction with measurements of reaction kinetics (71). The results show that at very low surface coverages, both reactants are adsorbed randomly on the surface CO is adsorbed intact and O2 is dissociated and adsorbed atomically. When the coverage by CO is more than 1/3 of a monolayer, chemisorption of oxygen is blocked. When CO is adsorbed at somewhat less than a monolayer, oxygen is adsorbed, and the two are present in separate domains. The reaction that forms CO2 on the surface then takes place at the domain boundaries. 

Fig. 4. Schematic of an ultrahigh vacuum molecular beam epitaxy (MBE) growth chamber, showing the source ovens from which the Group 111—V elements are evaporated the shutters corresponding to the required elements, such as that ia front of Source 1, which control the composition of the grown layer an electron gun which produces a beam for reflection high energy electron diffraction (rheed) and monitors the crystal stmcture of the growing layer and the substrate holder which rotates to provide more uniformity ia the deposited film. After Ref. 14, see text.

Table-top (ambient), 2.27—12 inch bolt-on flange (ultrahigh vacuum)... 

Contactless, nondestructive monitoring of band gaps in semiconductors Wide range of temperatures and ambients (air, ultrahigh vacuum) in-situ monitoring of semiconductor growth... 

Single-crystal samples of conductors best other solid samples are suitable, including polycrystalline metals, polymeric materials, semiconductors, and insulators, ultrahigh vacuum compatible typically > 5 mm diameter, 1-3 mm thick... 

Sample requirements Ultrahigh vacuum compadbility practical size -1 cm in diameter... 

Since then, STM has been established as an insttument fot foteftont research in surface physics. Atomic resolution work in ultrahigh vacuum includes studies of metals, semimetals and semiconductors. In particular, ultrahigh-vacuum STM has been used to elucidate the reconstructions that Si, as well as other semiconducting and metallic surfaces undergo when a submonolayer to a few monolayers of metals are adsorbed on the otherwise pristine surface. ... 

STM tips will last for a day or so in ultrahigh vacuum. Most ultrahigh-vacuum STM systems provide storj e for several tips so the chamber does not have to be vented just to change tips. In air, tips will oxidize more rapidly, but changing tips is a simple process. 

Unlike traditional surface science techniques (e.g., XPS, AES, and SIMS), EXAFS experiments do not routinely require ultrahigh vacuum equipment or electron- and ion-beam sources. Ultrahigh vacuum treatments and particle bombardment may alter the properties of the material under investigation. This is particularly important for accurate valence state determinations of transition metal elements that are susceptible to electron- and ion-beam reactions. Nevertheless, it is always more convenient to conduct experiments in one s own laboratory than at a Synchrotron radiation focility, which is therefore a significant drawback to the EXAFS technique. These focilities seldom provide timely access to beam lines for experimentation of a proprietary nature, and the logistical problems can be overwhelming. 

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