Step edges

Figure Al.7.2. Large-scale (5000 Atimes 5000 A) scanning tiimielling microscope image of a stepped Si (111)-(7 X 7) surface showing flat terraces separated by step edges (courtesy of Alison Baski).

Although all real surfaces have steps, they are not usually labelled as vicinal unless they are purposely misoriented in order to create a regular array of steps. Vicinal surfaces have unique properties, which make them useful for many types of experiments. For example, steps are often more chemically reactive than terraces, so that vicinal surfaces provide a means for investigating reactions at step edges. Also, it is possible to grow nanowires by deposition of a metal onto a surface of another metal in such a way that the deposited metal diflfiises to and attaches at the step edges [3]. 

Figure Al.7.5(a) shows a larger scale schematic of the Si(lOO) surface if it were to be biilk-tenninated, while figure Al.7.5(b) shows the arrangement after the dimers have been fonned. The dashed boxes outline the two-dimensional surface unit cells. The reconstructed Si(lOO) surface has a unit cell that is two times larger than the bulk unit cell in one direction and the same in the other. Thus, it has a (2 x 1) synnnetry and the surface is labelled as Si(100)-(2 x i). Note that in actuality, however, any real Si(lOO) surface is composed of a mixture of (2 X 1) and (1 x 2) domains. This is because the dimer direction rotates by 90° at each step edge.

The atoms on the outennost surface of a solid are not necessarily static, particularly as the surface temperature is raised. There has been much theoretical [12, 13] and experimental work (described below) undertaken to investigate surface self-diffiision. These studies have shown that surfaces actually have dynamic, changing stmetures. For example, atoms can diflfiise along a terrace to or from step edges. When atoms diflfiise across a surface, they may move by hopping from one surface site to the next, or by exchanging places with second layer atoms. 

It has also been shown that sufiBcient surface self-diflfiision can occur so that entire step edges move in a concerted maimer. Although it does not achieve atomic resolution, the low-energy electron microscopy (LEEM) technique allows for the observation of the movement of step edges in real time [H]. LEEM has also been usefiil for studies of epitaxial growth and surface modifications due to chemical reactions. 

Figure A3.10.3 STM images of the early stages of sulfur segregation on Ni(l 11). Sulfur atoms are seen to preferentially mieleate at step edges [8],...

Figure A3.10.10 STM image (55 x 55 mn ) of a Si(lOO) surface exposed to molecular bromine at 800 K. The dark areas are etch pits on the terraces, while the bright rows that run perpendicular to the terraces are Si dimer chains. The dimer chains consist of Si atoms released from terraces and step edges during etching [28],...

Figure A3.10.14 STM image of 0.25 ML Aii vapour-deposited onto Ti02(l 10). Atomie resolution of the substrate is visible as parallel rows. The Au elusters are seen to nueleate preferentially at step edges.

Since atomic bonds are broken at the step edge, a surface-step costs an energy J per atomic length. At very low temperatures, where the step... 

If the kinetics is fast enough and the diffusion of adatoms along the step edge or perimeter is rate limiting, then the width increases slowly as [66]... 

One can now immediately deduce the normal growth rate of a crystal due to the screw dislocation. Whenever a step edge passes by a fixed point on the crystal surface, this point gains the height of a lattice unit. The normal growth rate V of the crystal is then... 

For the explanation of macroscopic phenomena, the thickness of the phase boundary (interface) often plays no important role. As an example, we describe the movement of a phase boundary in two dimensions or the movement of a step edge on a crystal surface. We start with a Ginzburg-Landau equation [69]... 

Ayu is the chemical potential difference between the regions behind and before the step edge, S is the integration path along the step. The first integral must be transcribed such that it contains 6 S) as a product in... 

Figure 1.14 Energetics (kilojoules per mole) and structure of CO dissociating from Ru step-edge site [15].

The activation energy of such molecules depends strongly on the structure of the catalytically active center. The structures of reactant, transition state as well as product state at a step-edge site are shown for CO dissociation in Figure 1.14. 

Whereas the adsorption energies of the adsorbed molecules and fragment atoms only slightly change, the activation barriers at step sites are substantially reduced compared to those at the terrace. Different from activation of a-type bonds, activation of tt bonds at different sites proceeds through elementary reaction steps for which there is no relation between reaction energy and activation barrier. The activation barrier for the forward dissociation barrier as weU as for the reverse recombination barrier is reduced for step-edge sites. 

Interestingly, when the particle size of metal nanoparticles becomes less than 2 nm, terraces become so small that they carmot anymore support the presence of step-edge site metal atom configurations. This can be observed from Figure 1.15, which shows a cubo-octahedron just large enough to support a step-edge site. 

Class 111-type behavior is the consequence of this impossibihty to create step-edge-type sites on smaller particles. Larger particles wiU also support the step-edge sites. Details may vary. Surface step directions can have a different orientation and so does the coordinative unsaturation of the atoms that participate in the ensemble of atoms that form the reactive center. This wiU enhance the activation barrier compared to that on the smaller clusters. Recombination as well as dissociation reactions of tt molecular bonds will show Class 111-type behavior. 

Figure 1.15 Cubo-octahedron with step-edge sites [18].

When the selectivity of a reaction is controlled by differences in the way molecules are activated on different sites, the probability of the presence of different sites becomes important. An example again can be taken from the activation of CO. For methanation, activation of the CO bond is essential. This will proceed with low barriers at step-edge-type sites. If one is interested in the production of methanol, catalytic surfaces are preferred, which do not allow for easy CO dissociation. This will typically be the case for terrace sites. The selectivity of the reaction to produce methanol will then be given by an expression as in Eq. (1.29a) ... 

In this expression, Xi and Xi are the fractions of terrace versus step-edge sites, ri is net rate of conversion of adsorbed CO to methanol on a terrace site, and t2 is the rate of CO dissociation at a step-edge-type site. Increased CO pressure will also enhance the selectivity, because it will block dissociation of CO. 

The relevance of the same nonsurface metal atom sharing principle in transition states is nicely illustrated by the similar lowering of the transition state for NH activation by O in a step site as for the (100) surface, as illustrated in Figure 1.21 [19]. Similarly, OH formation by recombination of oxygen and hydrogen is substantially lower at a step edge than on the (111) terrace. 

The contact potential image (Ico) shows a striking contrast difference below and above point A. At low humidity there is a strong enhancement of Ac]) at the step edges i.e.. 

FIG. 32 Top Semilog plot of the time constant t for ionic motion as a function of RH for KF. Bottom Simultaneously measured contact potential. At a critical humidity A, there is a break or a change in slope in these two surface properties. Below A, water solvates preferentially cations at the step edges. Above A, the rates of dissolution (solvation) of anions and cations are similar and water uni-... 

H2 adsorption is weak on the anatase surfaces [8], No dissociative adsorption of H2 takes place over the smooth surfaces of Au at temperatures below 473 K [9,10]. On small Au particles, adsorption is possible at low temperature. Dissociative adsorption of H2 can be accelerated by the negatively charged molecular oxygen species at steps, edges, comers of Au particles [5]. 

Walter EC, Murray BJ, Favier F, Kaltenpoth G, Giunze M, Penner RM (2002) Noble and coinage metal nanowires by electrochemical step edge decoration. J Phys Chem B 106 11407-11411... 

Zach MP, Inazu K, Ng KH, Hemminger JC, Penner RM (2002) Synthesis of molybdenum nanowires with millimeter-scale lengths using electrochemical step edge decoration. Chem Mater 14 3206-3216. 

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