STM

The most important of these techniques is scanning tunnelling microscopy (STM), the invention of Binning and Rohrer45, for which they won the Nobel Prize in Physics in 1986, followed by atomic force microscopy (AFM)47, and which are described in this section, indicating their application to the study of electrode processes. 

Other local probe techniques to be discussed, of an electrochemical nature, which rely on much of the same instrumental technology, are scanning electrochemical microscopy (SECM) and scanning ion conductance microscopy (SICM). 

This local probe technique relies on a tunnelling current being passed between tip and substrate. For electron tunnelling to be possible the distance between tip and substrate must be less than about 2 nm, and the 

Much of the initial work was done in vacuum and with semiconductor and metal monocrystals. These experiments showed evidence of surface reconstruction, and the presence of substances that adsorb on these substrates. 

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As the reservoir pressure drops from the initial reservoir pressure towards the bubble point pressure (PJ, the oil expands slightly according to its compressibility. However, once the pressure of the oil drops below the bubble point, gas is liberated from the oil, and the remaining oil occupies a smaller volume. The gas dissolved in the oil is called the solution gas, and the ratio of the volume gas dissolved per volume of oil is called the solution gas oil ratio (Rg, measured in scf/stb of sm /stm ). Above the bubble point, Rg is constant and is known as the initial solution gas oil ratio (Rgj), but as the pressure falls below the bubble point and solution gas is liberated, Rg decreases. The volume of gas liberated is (Rg - Rg) scf/stb. 

As solution gas is liberated, the oil shrinks. A particularly important relationship exists between the volume of oil at a given pressure and temperature and the volume of the oil at stock tank conditions. This is the oil formation volume factor (B, measured in rb/stb or rm /stm ). 

The development of scanning probe microscopies and x-ray reflectivity (see Chapter VIII) has allowed molecular-level characterization of the structure of the electrode surface after electrochemical reactions [145]. In particular, the important role of adsorbates in determining the state of an electrode surface is illustrated by scanning tunneling microscopic (STM) images of gold (III) surfaces in the presence and absence of chloride ions [153]. Electrodeposition of one metal on another can also be measured via x-ray diffraction [154]. 

The ability to control the position of a fine tip in order to scan surfaces with subatomic resolution has brought scanning probe microscopies to the forefront in surface imaging techniques. We discuss the two primary techniques, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) the interested reader is referred to comprehensive reviews [9, 17, 18]. 

Fig. VIII-1. Schematic illustration of the scanning tunneling microscope (STM) and atomic force microscope (AFM). (From Ref. 9.)...

A novel modification of the STM supplements images with those due to the thermopower signal across the tip-sample temperature gradient [49]. Images of guanine on graphite illustrate the potential of this technique. 

Fig. VIII-2. Scanning tunneling microscopy images illustrating the capabilities of the technique (a) a 10-nm-square scan of a silicon(lll) crystal showing defects and terraces from Ref. 21 (b) the surface of an Ag-Au alloy electrode being electrochemically roughened at 0.2 V and 2 and 42 min after reaching 0.70 V (from Ref. 22) (c) an island of CO molecules on a platinum surface formed by sliding the molecules along the surface with the STM tip (from Ref. 41).

SECM Scanning electrochemical microscopy [40] An STM serves as microelectrode to reduce electroactive species Electrochemical reactions on surfaces... 

STM Scanning tunneling microscopy [9, 19, 31] Tunneling current from probe scans a conducting surface Surface structure... 

We have considered briefly the important macroscopic description of a solid adsorbent, namely, its speciflc surface area, its possible fractal nature, and if porous, its pore size distribution. In addition, it is important to know as much as possible about the microscopic structure of the surface, and contemporary surface spectroscopic and diffraction techniques, discussed in Chapter VIII, provide a good deal of such information (see also Refs. 55 and 56 for short general reviews, and the monograph by Somoijai [57]). Scanning tunneling microscopy (STM) and atomic force microscopy (AFT) are now widely used to obtain the structure of surfaces and of adsorbed layers on a molecular scale (see Chapter VIII, Section XVIII-2B, and Ref. 58). On a less informative and more statistical basis are site energy distributions (Section XVII-14) there is also the somewhat laige-scale type of structure due to surface imperfections and dislocations (Section VII-4D and Fig. XVIII-14). 

We confine ourselves here to scanning probe microscopies (see Section VIII-2B) scanning tunneling microscopy (STM) and atomic force microscopy (AFM), in which successive profiles of a surface (see Fig. VIII-1) are combined to provide a contour map of a surface. It is conventional to display a map in terms of dark to light areas, in order of increasing height above the surface ordinary contour maps would be confusing to the eye. 

Figure XVIII-2 shows how a surface reaction may be followed by STM, in this case the reaction on a Ni(llO) surface O(surface) + H2S(g) = H20(g) + S(surface). Figure XVIII-2a shows the oxygen atom covered surface before any reaction, and Fig. XVIII-2h, the surface after exposure to 3 of H2S during which Ni islands and troughs have formed on which sulfur chemisorbs. The technique is powerful in the wealth of detail provided on the other hand, there is so much detail that it is difficult to relate it to macroscopic observation (such as the kinetics of the reaction).

Fig. XVni-2. Successive STM images of (a) Ni(llO) with a chemisorbed layer of oxygen atoms and (b) after exposure to 3 1 of H2S. The area shown in 85 x 91 A. [From F. Besenbacher, P. T. Sprunger, L. Ruan, L. Olesen, I. Stensgaard, and E. Lcegsgaard, Tap. Catal., 1, 325 (1994).]...

Fig. XVin-3. AFM image of DNA strands on mica. Lower figure image obtained in the contact mode under water. The contrast shown covers height variations in the range of 0-2 nm. Upper figure observed profile along the line A-A of the lower figure. (From S. N. Magnov and M.-H. Whangbo, Surface Analysis with STM and AFM, VCH, New Yoric, 1996.)...

STM and AFM profiles distort the shape of a particle because the side of the tip rides up on the particle. This effect can be corrected for. Consider, say, a spherical gold particle on a smooth surface. The sphere may be truncated, that is, the center may be a distance q above the surface, where q < r, the radius of the sphere. Assume the tip to be a cone of cone angle a. The observed profile in the vertical plane containing the center of the sphere will be a rounded hump of base width 2d and height h. Calculate q and r for the case where a - 32° and d and h are 275 nm and 300 nm, respectively. Note Chapter XVI, Ref. 133a. Can you show how to obtain the relevent equation ... 

Figure Al.7.7. Atomic-resolution, empty-state STM image (100 A x 100 A) of the reconstmcted Si(l 11)-7 7 surface. The bright spots correspond to a top layer of adatoms, with 12 adatoms per unit cell (courtesy of Alison Baski).

More recently, studies employing STM have been able to address surface self-diffiision across a terrace [16, 17. 18 and 19], It is possible to image the same area on a surface as a fiinction of time, and watch the movement of individual atoms. These studies are limited only by the speed of the instrument. Note that the performance of STM instruments is constantly improving, and has now surpassed the 1 ps time resolution mark [20]. Not only has self-diflfiision of surface atoms been studied, but the diflfiision of vacancy defects on surfaces has also been observed with STM [18]. 

At a surface, not only can the atomic structure differ from the bulk, but electronic energy levels are present that do not exist in the bulk band structure. These are referred to as surface states . If the states are occupied, they can easily be measured with photoelectron spectroscopy (described in section A 1.7.5.1 and section Bl.25.2). If the states are unoccupied, a teclmique such as inverse photoemission or x-ray absorption is required [22, 23]. Also, note that STM has been used to measure surface states by monitoring the tunnelling current as a fiinction of the bias voltage [24] (see section BT20). This is sometimes called scamiing tuimelling spectroscopy (STS). 

Adsorbed atoms and molecules can also diflfiise across terraces from one adsorption site to another [33]. On a perfect terrace, adatom diflfiision could be considered as a random walk between adsorption sites, with a diflfiisivity that depends on the barrier height between neighbouring sites and the surface temperature [29]. The diflfiision of adsorbates has been studied with FIM [14], STM [34, 35] and laser-mduced themial desorption [36]. 

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