Compositional analysis surface layers

Chemical composition analysis complementing the microstructural information obtained from EM is known as analytical EM (AEM). Important compositional variations or non-stoichiometry in a material which is seemingly phase pure or stoichiometric by the criterion of bulk diffraction techniques and compositions of surface layers can be revealed using AEM. For quantitative microanalysis a ratio method for thin crystals (Cliff and Lorimer 1975) is used, given by the equation ... 

As is widely known, bulk species which have chromophores that absorb in the UV-Vis can be analyzed quantitatively and qualitatively by this spectroscopy. The study of electrodes or species adsorbed as thin layers by UV-Vis is more difficult, due to sensitivity problems and the availability of the appropriate chromophores [50], Another use of this type of analysis is electroreflectance [51,52], Adsorption of species on reflective electrode surfaces changes their reflectivity. Thus, this method can indicate electroadsorption processes very sensitively, in situ, although it does not provide specific information on the structure and composition of surface layers. 

A depth profile is a record of the variation of a property (such as composition) as a function of depth. Some of the techniques in this volume have essentially no intrinsic depth profiling capabilities the signal is representative of the material integrated over a fixed probing depth. Most, however, can vary the depth probed by varying the condition of analysis, or by removing the surface, layer by layer, while collecting data. 

In Total Reflection X-Ray Fluorescence Analysis (TXRF), the sutface of a solid specimen is exposed to an X-ray beam in grazing geometry. The angle of incidence is kept below the critical angle for total reflection, which is determined by the electron density in the specimen surface layer, and is on the order of mrad. With total reflection, only a few nm of the surface layer are penetrated by the X rays, and the surface is excited to emit characteristic X-ray fluorescence radiation. The energy spectrum recorded by the detector contains quantitative information about the elemental composition and, especially, the trace impurity content of the surface, e.g., semiconductor wafers. TXRF requires a specular surface of the specimen with regard to the primary X-ray light. 

The electrochemical behavior of single-crystal (100) lead telluride, PbTe, has been studied in acetate buffer pH 4.9 or HCIO4 (pH 1.1) and KOH (pH 12.9) solutions by potentiodynamic techniques with an RRDE setup and compared to the properties of pure Pb and Te [203]. Preferential oxidation, reduction, growth, and dissolution processes were investigated. The composition of surface products was examined by XPS analysis. It was concluded that the use of electrochemical processes on PbTe for forming well-passivating or insulating surface layers is rather limited. 

Another very important technique for fundamental consideration of multicomponent systems is low energy ion scattering (LEIS) [Taglauer and Heiland, 1980 Brongersma et al., 2007]. This is a unique tool in surface analysis, since it provides the ability to define the atomic composition of the topmost surface layer under UHV conditions. The signal does not interfere with the subsurface atomic layers, and therefore the results of LEIS analysis represent exclusively the response from the outer surface. In LEIS, a surface is used as a target that scatters a noble gas ion beam (He, Ne, ... 

Significant depletion of In, enrichment in iodine and simultaneous reduction of selenium to Se° was observed by XPS for n-CuInSe2 photoelectrode surfaces in an I2—1 —Cu+—HI electrolyte [129]. Over a distance of 100 A the composition of the surface layer gradually changes to that of the substrate. With the help of UPS analysis the surface film, assumed to be CuISe3, was characterized as p-type semiconductor [130],... 

Here we would like to emphasize that treatment with XeFj fluorinates the polymer surfaces, with the depth and degree of fluorination depending upon the reaction conditions. We never observed the formation of a perfluorinated surface layer after treatment with XeF,. Results of XPS analysis of XeFj-treated polyethylene film —(—CHj—CHj—) — showed that the maximum degree of fluorination corresponded to the composition —(—CF2—CH2—) —. After that, visible destruction of the polymer surface, i.e., cleavage of C—C bonds in the polymer macromolecule, would start. These results differ from those of the fluorination of polymer powders it was reported by Lagow and Margrave in the early 1970s that polymer powders were fully converted into perfluorinated polymers under the action of a F /N mixture. ... 

Composite interfaces exist in a variety of forms of differing materials. A convenient way to characterize composite interfaces embedded within the bulk material is to analyze the surfaces of the composite constituents before they are combined together, or the surfaces created by fracture. Surface layers represent only a small portion of the total volume of bulk material. The structure and composition of the local surface often differ from the bulk material, yet they can provide critical information in predicting the overall properties and performance. The basic unknown parameters in physico-chemical surface analysis are the chemical composition, depth, purity and the distribution of specific constituents and their atomic/microscopic structures, which constitute the interfaces. Many factors such as process variables, contaminants, surface treatments and exposure to environmental conditions must be considered in the analysis. 

Electron Microprobe Measurements. Compositional information regarding transpoirt 6T nickel and vanadium in the catalysts uppermost 10,000A surface layers was obtained from electron microprobe analysis of the samples. Scanning electron micrographs and x-ray spectra were obtained with a JEOL 733 scanning electron... 

Figure 5.28. In situ wet-ETEM of real-time catalytic hydrogenation of nitrile liquids over novel Co-Ru/Ti02 nanocatalysts, (a) Fresh catalyst with Co-Ru clusters (arrowed at C). The support is marked, e.g., at u. (b) Catalyst immersed in adiponitrile liquid and H2 gas in flowing conditions growth of hexamethylene diamine (HMD) layers (at the catalyst surface S in profile, arrowed) at 81 °C, confirmed by composition analysis and mass spectrometry, (c) ED pattern of HMD in (b) in liquid environments. Further growth is observed at 100 °C. The studies show that wet-ETEM can be used to design a catalytic process (after Gai 2002). (d) Scaled up reactivity data for novel Co-Ru/Ti02 nanocatalysts confirming wet-ETEM studies of high hydrogenation activity of the nanocatalyst (2). Plots 1 and 3 are the data for Raney-Ni complexes and Ru/alumina catalysts, respectively.

In most surface sensitive spectroscopies, the depth resolution is still much larger than one atomic layer. Thus even under the best conditions a true atomic layer depth resolution cannot be achieved in the compositional analysis. 

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