Surface artifacts

Single molecules (and not surface artifacts or specs of dust) are easier to see when the surface can be cleaned in ultra-high vacuum at low temperature, imaged to make sure no artifacts are present, and then volatile adsorbates are injected onto the cold surface without breaking vacuum. A nice tour de force was when at 4 K under ultra-high vacuum, Xe atoms were picked up by the STM tip and deposited onto a cold Ni substrate to "write" "IBM" on Ni [28]. It is not too clear exactly how far above the surface the atomically tip floats a good guess is 0.1 nm. 

The box-counting fractal dimension is calculated from the log-log plot of the number of occupied boxes, versus side length, /,. The slope of this line is used to determine the fractal dimension. Both very small and very large box sizes should be exempt from the calculation to reduce surface artifacts (Awad and Marangoni 2005). This method is most sensitive to the degree of fill as well as particle size and it can be expected that if there are void volumes it will have a characteristic low fractal dimension. 

A 40 X (NA = 0.75) air objective was used. This configuration resulted in some spherical aberration which effectively increases the effective confocal layer thickness. Therefore, in practice the confocal layer may have been 2-3 microns thick. The sample was imaged at a depth of about 15-20 microns, in order to get clear of surface artifacts. 

A few studies have found potential surfaces with a stable minimum at the transition point, with two very small barriers then going toward the reactants and products. This phenomenon is referred to as Lake Eyring Henry Eyring, one of the inventors of transition state theory, suggested that such a situation, analogous to a lake in a mountain cleft, could occur. In a study by Schlegel and coworkers, it was determined that this energy minimum can occur as an artifact of the MP2 wave function. This was found to be a mathematical quirk of the MP2 wave function, and to a lesser extent MP3, that does not correspond to reality. The same effect was not observed for MP4 or any other levels of theory. 

STM and SFM are free from many of the artifacts that afflict other kinds of profilometers. Optical profilometers can experience complicated phase shifts when materials with different optical properties are encountered. The SFM is sensitive to topography oidy, independent of the optical properties of the surface. (STM may be sensitive to the optical properties of the material inasmuch as optical properties are related to electronic structure.) The tips of traditional stylus profilometers exert forces that can damage the surfaces of soft materials, whereas the force on SFM tips is many orders of magnitude lower. SFM can image even the tracks left by other stylus profilometers. 

On the other hand, the sensitivity of STM to electronic structure can lead to undesired artifacts when the surface is composed of regions of varying conductivity. For example, an area of lower conductivity will be represented as a dip in the image. If the surface is not well known, separating topographic effects from electronic effects can be difficult. 

Other artifacts that have been mentioned arise from the sensitivity of STM to local electronic structure, and the sensitivity of SFM to the rigidity of the sample s surface. Regions of variable conductivity will be convolved with topographic features in STM, and soft surfaces can deform under the pressure of the SFM tip. The latter can be addressed by operating SFM in the attractive mode, at some sacrifice in the lateral resolution. A limitation of both techniques is their inability to distinguish among atomic species, except in a limited number of circumstances with STM microscopy. 

In addition to cleanliness (contamination effects), surface morpholt and the alteration of composition during specimen preparation can cause serious artifacts in microanalysis. In some older instruments, the microscope itself produces undesirable high-energy X rays that excite the entire specimen, making difficult the accurate quantitation of locally changing composition. Artifacts also are observed in the EDS X-ray spectrum itself (see the article on EDS). 

The major artifacts contributing to uncertainties in PDCE results stem from effects caused by bombardment of nonideal specimens, particularly thick specimens. The ideal thick specimen would be a homogeneous, smooth electrical conductor that does not change during bombardment. Except for rather simple, well-defined layered structures (e.g., surface oxide layers), specimens having compositional variations with depth yield spectra whose analyses can have large inaccuracies. 

Although SIMS is one of the most powerful surface analysis techniques, its application is complicated by a variety of artifacts. 

Apart from the application of XPS in catalysis, the study of corrosion mechanisms and corrosion products is a major area of application. Special attention must be devoted to artifacts arising from X-ray irradiation. For example, reduction of metal oxides (e. g. CuO -> CU2O) can occur, loosely bound water or hydrates can be desorbed in the spectrometer vacuum, and hydroxides can decompose. Thorough investigations are supported by other surface-analytical and/or microscopic techniques, e.g. AFM, which is becoming increasingly important. 

Other recent investigations involving AES, often with depth profiling, deal with the surface segregation of Ag in Al-4.2 % Ag [2.163], of Sn in Cu and formation of superficial Sn-Cu alloy [2.164], of Mg in Al-Mg alloy [2.165], and of Sb in Ee-4% Sb alloy [2.166]. Note the need to differentiate between, particularly, segregation, i. e. original sample properties, from the artifact of preferential sputtering. 

An example of interaction stiffness and force curves for a Si surface with a native oxide at 60% relative humidity (RH) is shown in Fig. 12 [104]. The stiffness and force data show an adhesive interaction between the tip and substrate. The hysteresis on retraction is due to a real change in contact area from surface oxide deformation and is not an experimental artifact. The adhesive force observed during retraction was consistent with capillary condensation and the surface energy measured from the adhesive force was close to that of water. 

Both space-filling and electron density models yield similar molecular volumes, and both show the obvious differences in overall size. Because the electron density surfaces provide no discernible boundaries between atoms (and employ no colors to highlight these boundaries), the surfaces may appear to be less informative than space-filling models in helping to decide to what extent a particular atom is exposed . This weakness raises an important point, however. Electrons are associated with a molecule as a whole and not with individual atoms. The space-filling representation of a molecule in terms of discernible atoms does not reflect reality, but rather is an artifact of the model. The electron density surface is more accurate in that it shows a single electron cloud for the entire molecule. 

The aspect of sample preparation and characterization is usually hidden in the smallprint of articles and many details are often not mentioned at all. It is, however, a very crucial point, especially with surface and interface investigations since there might be many unknown parameters with respect to surface contaminations, surface conformations, built-in stresses, lateral sample inhomogeneities, roughness, interfacial contact etc. This is in particular important when surfaces and interfaces are investigated on a molecular scale where those effects may be quite pronounced. Thus special care has to be taken to prepare well defined and artifact free specimens, which is of course not always simple to check. Many of these points are areas of... 

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