LEED, single crystal analysis

LEED is the most powerfiil, most widely used, and most developed technique for the investigation of periodic surface structures. It is a standard tool in the surface analysis of single-crystal surfaces. It is used very commonly as a method to check surface order. The evolution of the technique is toward greater use to investigate surface disorder. Progress in atomic-structure determination is focused on improving calculations for complex molecular surface structures. 

Prior to the publication in 1980 of Clavilier s historic paper (1) reporting anomalous voltammetry of Pt(lll), there had been a number of studies of the voltammetry of single crystal Pt electrodes, with some using modern methods of surface analysis (e.g., LEED or RHEED) for characterization of the structure of the crystal prior to immersion in electrolyte (2-6). and all were in qualitative agreement with the seminal work (in 1965) on Pt single crystals by Will (7.). 

Other techniques such as low-energy electron diffraction (LEED) are also used for surface analysis, primarily for large single crystals. Single crystal metal surfaces have been used to study hydrocarbon catalysis on platinum (Anderson 1975). Techniques such as x-ray photoelectron spectroscopy (XPS) are also used for surface analysis but normally the reports describe mostly idealized single-crystal surfaces in high vacuum as opposed to using real-life (practical) catalyst systems under reaction environments. 

As with all surface analytical methods, surface preparation is critical to obtaining reproducible SHG from metallic surfaces and single crystals in particular. For surfaces prepared in UHV and then transferred to an electrochemical cell, sputtering and heating or annealing followed by Auger analysis of impurities should proceed inert transfer. Low energy electron diffraction (LEED) can also be used to check surface order. Metal electrode surfaces, particularly for the rotational anisotropy ex-... 

Determination of lateral periodicities in the self-assembled layer is an important goal in surface analysis. 2D surface crystal structures are best studied with low energy electrons, since their escape depth, contrary to X-rays, is basically limited to the top-most atomic layers. Consequently, LEED has become the most important method in surface monolayer crystallography. However, single-crystalline substrates are required. Via this technique, 2D supramolecular chiral lattice structures on single crystal surfaces had already been observed in 1978 [19]. 

It is also an effect which is very difficult to quantify. The most successful quantitative methods are MEIS and LEED 1(E) especially when the latter technique is coupled with LEIS. However, these techniques rely on single crystal measurements which may have limited relevance to measurements on bimetallic nanoparticles. Nonetheless, the ability to achieve layer by layer compositional analysis under the influence of an adsorbate means that MEIS data helps to explain why segregation is observed even at relatively low temperatures where bulk diffusion is extremely slow. Activation barriers for near-surface to surface diffusion must be significantly lower than bulk diffusion barriers. 

For surface structure studies, perhaps the most popular technique has been LEED (373). Elastically diffracted electrons from a monoenergetic beam directed to a single-crystal surface reveal structural properties of the surface that may differ from those of the bulk. Some applications of LEED to electrocatalyst characterization were cited in Section IV (106,148,386). Other, less specific, but valuable surface examination techniques, such as scanning electron microscopy (SEM) and X-ray microprobe analysis, have not been used in electrocatalytic studies. They could provide information on surface changes caused by reaction, some of which may lead to catalyst deactivation (256,257). Since these techniques use an electron beam, they can be coupled with previously discussed methods (e.g. AES or XPS) to obtain a qualitative mapping of the structure and composition of a catalytic surface. 

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