STM measurements

The most popular of the scanning probe tecimiques are STM and atomic force microscopy (AFM). STM and AFM provide images of the outemiost layer of a surface with atomic resolution. STM measures the spatial distribution of the surface electronic density by monitoring the tiumelling of electrons either from the sample to the tip or from the tip to the sample. This provides a map of the density of filled or empty electronic states, respectively. The variations in surface electron density are generally correlated with the atomic positions. 

STM measurements suggested for the bilayer fonned by Cu and coadsorbed Cl either a (5 x 5) long range order similar to that of the (111) plane of CuCl or a (4 x 4)-based stmcture [46, 77, 78], while the bilayer fonned with Cu... 

Because STM measures a quantum-mechanical tunneling current, the tip must be within a few A of a conducting surface. Therefore any surface oxide or other contaminant will complicate operation under ambient conditions. Nevertheless, a great deal of work has been done in air, liquid, or at low temperatures on inert surfaces. Studies of adsorbed molecules on these surfaces (for example, liquid crystals on highly oriented, pyrolytic graphite ) have shown that STM is capable of even atomic resolution on organic materials. 

Scanning tunneling spectroscopy (STS) can, in principle, probe the electronic density of states of a singlewall nanotube, or the outermost cylinder of a multi-wall tubule, or of a bundle of tubules. With this technique, it is further possible to carry out both STS and scanning tunneling microscopy (STM) measurements at the same location on the same tubule and, therefore, to measure the tubule diameter concurrently with the STS spectrum. No reports have yet been made of a determination of the chiral angle of a tubule with the STM technique. Several groups have, thus far, attempted STS studies of individual tubules. 

Several methods have been employed to study chemical reactions theoretically. Mean-field modeling using ordinary differential equations (ODE) is a widely used method [8]. Further extensions of the ODE framework to include diffusional terms are very useful and, e.g., have allowed one to describe spatio-temporal patterns in diffusion-reaction systems [9]. However, these methods are essentially limited because they always consider average environments of reactants and adsorption sites, ignoring stochastic fluctuations and correlations that naturally emerge in actual systems e.g., very recently by means of in situ STM measurements it has been demon-... 

Changing the substrate from gold to silver has been shown to strongly affect the structure of the first few layers of CdS grown by ECALE. STM measurements carried out on the first CdS layer on Ag(lll) revealed a much less compact structure than the one found on Au(lll). This disparity was tentatively attributed to the different structure of the first S layer on Ag(l 11), as obtained by oxidative UPD from sulfide ion solutions, due to a higher affinity of sulfur for silver than for gold. The Cd layers were attained on S by reductive UPD from cadmium ion solutions. Precursors for both elements were dissolved in pyrophosphate/NaOH at pH 12 [43 5],... 

We refrain here from giving an extensive overview of studies on the surface structure of vanadium oxide nanolayers, as this has already been done for up to year 2003 in our recent review [97]. Instead, we would like to focus on prototypical examples, selected from the V-oxide-Rh(l 1 1) phase diagram, which demonstrate the power of STM measurements, when combined with state-of-the-art DFT calculations, to resolve complex oxide nanostructures. Other examples will highlight the usefulness of combining STM and STS data on a local scale, as well as data from STM measurements, and sample area-averaging spectroscopic techniques, such as XPS and NEXAFS, to derive as complete a picture as possible of the investigated system. 

For in-situ STM measurements, the tip inevitably is immersed into the electrolyte. Hence, the tip acts as a fourth electrode with reactions occurring at the tip-electrolyte... 

Fig. 11 Correlation between electrochemical potentials and OMTS bands for more than ten compounds including polyacenes, phthalo-cyanines, and porphyrins. OMTS data were acquired both from tunnel junctions and STM measurements. The standard potential relative to the normal hydrogen electrode associated with the half reaction M(solution) + e-(vac) —> M-(solution) is the y axis. The three outliers are assigned to the ring oxidation of porphyrins. (Reprinted with permission from [26])...

The dynamics of upd reactions have also been examined by STM. The formation of the ordered copper/sulfate layer [354] and copper chloride layer [355] on Au(lll) was examined in a dilute solution of Cu where the reaction was under diffusion control so that growth proceeded on a time scale compatible with STM measurements [354]. In another study, the importance of step density on nucleation was examined and the voltammetric and chronoamperometric response for Cu upd on vicinal Au(lll) was shown to be a sensitive function of the crystal miscut, as... 

Fig. 15 (a) Schematic illustration of the potential-controlled STM measurement, (b) Cyclic voltammetry of the Cgo-modified substrate in a 0.1 M TBAPFs DMF solution, (c) Representative current-time curves upon potential sweep for the bare gold surface trans-2-C Q in a 0.1 M TB APFg DMF solution. (Reprinted with permission from [107])... 

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