Films structure electron diffraction methods

Electron Diffraction and Electron Microscopy. A limited amount of information regarding graphite structure has been obtained by the use of electron beams. Grisdale (27) has measured the degree of orientation using electron diffraction methods on films of pyrolytic carbon deposited on a silica surface under a variety of conditions. Oxidation of the graphite causes an increase in the degree of orientation. 

The structure of crystals can be investigated by the electron-diffraction method as well as by the x-ray-diffraction method. The electron-diffraction method has been especially useful in studying the strueture of very thin films on the surface of a crystal. For example, it has been shown that when argon is adsorbed on a clean face of nickel crystal the argon atoms occupy only one-quarter of the positions formed by triangles of nickel atoms (in the octahedral face of the cubic closest-packed crystal Figure 2-7). The structure of very thin films of metal oxide that are formed on the surface of metals, and that protect them against further corrosion, has been studied by this method. 

This chapter contains articles on six techniques that provide structural information on surfaces, interfeces, and thin films. They use X rays (X-ray diffraction, XRD, and Extended X-ray Absorption Fine-Structure, EXAFS), electrons (Low-Energy Electron Diffraction, LEED, and Reflection High-Energy Electron Diffraction, RHEED), or X rays in and electrons out (Surfece Extended X-ray Absorption Fine Structure, SEXAFS, and X-ray Photoelectron Diffraction, XPD). In their usual form, XRD and EXAFS are bulk methods, since X rays probe many microns deep, whereas the other techniques are surfece sensitive. There are, however, ways to make XRD and EXAFS much more surfece sensitive. For EXAFS this converts the technique into SEXAFS, which can have submonolayer sensitivity. 

Figure 15. Crystal structure of a-Tl2Se solved in projeetion via direct methods using quantified intensities from the selected area electron diffraction pattern shown in (a) [film data]. The potential map (E-map) in (b) was used to eonstruet an initial structural model which was later improved by kinematical least-squares (LS) refinement (c). Note that the potential of the selenium atoms in (c) appear after LS-refinement somewhat stronger than the surrounding titanium atoms (see the structural model in figure lOd). The average effective thiekness of the investigated thiekness of the crystal is about 230 A [22].

No direct method exists by which monolayer film structures on water can be studied. Therefore, the LB method has been used to study molecular structures in past decades. The most useful method for investigating the detailed LB-deposited film structure is the well-known electron diffraction technique (or the scanning probe microscope [Birdi, 2002a]). The molecular arrangements of deposited mono-and multilayer films of fatty acids and their salts, using this technique, have been reported. The analyses showed that the molecules were almost perpendicular to the solid surface in the first monolayer. It was also reported that Ba-stearate molecules have a more precise normal alignment compared to stearic-acid monolayers. In some investigations, the thermal stability of these films has been found to be remarkably stable up to 90°C. 

Additional data about the structure of black films are obtained by X-ray diffraction method. The first steps [336,338] have been performed with vertical foam films in a frame in a horizontal scanning diffractometer. Black films from decyltrimethyl ammonium decyl sulphate and NaBr solutions have been studied. The film thickness was calculated using a model of the mean electron density projection on the film normal. However, there was no indication whether the films were CBF or NBF. Platikanov et al. [339,340] used a new device for investigation of a horizontal black films from aqueous NaDoS solution (see Section 2.2.6). They found essentially different X-ray diffraction traces for the three types of black films CBF, NBF and stratified black films. This indicates their different structure. Precise X-ray reflectivity measurements with CBF and NBF films from NaDoS and NaCl aqueous solutions [341-343] provided more details about their structure. The data obtained for the thicknesses of the respective layers which detail the film structure are given below... 

Matsui has found for an I.G. catalyst that the aluminum oxide at its surface is present in the form of ferrous aluminate which covers parts of the metal surface, consisting of a-iron. The same author prepared a small single crystal of iron coated by an oxide film and studied its structure by the transmission method of electron diffraction. The pattern shows, Fig. 14, that the (111) plane of magnetite is produced parallel to the (111) plane and also to the (110) plane of iron, suggesting that with the... 

There are several important methods for determining the structure of monolayers that can be employed only when the substrate is solid. For example, LB films can be studied by electron diffraction, a technique... 

Among the ex situ methods that can be employed in surface analysis, low-energy electron diffraction (LEED) and x-ray photoelectron spectroscopy (XPS) can give the crystal structure and the nature of the surface ad-layers after the electrochemical and adsorption experiments as explained in this chapter [31,32]. Among the in situ non-electrochemical techniques, the radiotracer method [33] gives information about the adsorbed quantities however, infrared spectroscopy in FTIR mode [34] allows the identity of the bonding of the adsorbed molecules, and finally ellipsometry [35] makes possible the study of extremely thin films. Recently, some optical methods such as reflectance, x-ray diffraction, and second harmonic generation (SHG) [36] have been added to this list. 

X-ray diffraction techniques are the only way of determining the crystal structure of natural and synthetic polymers, although the x-ray data itself obtained from a crystalline polymeric fiber or film is not sufficient to allow complete refinement of the structure. Conformational analysis and electron diffraction represent complementary methods which will facilitate the determination of the structure. The necessary requirements for the x-ray approach are crystallinity and orientation. X-ray data cannot be Obtained from an amorphous sample which means that a noncrystalline polymeric material must be treated in order to induce or improve crystallinity. Some polymers, such as cellulose andchitin, are crystalline and oriented in the native state.(1 )... 

Various sophisticated methods were applied to determine the crystal structure of passive films. A long discussion was devoted to the role of ex situ measurements that were carried out first. After removal from the electrolyte, crystallization, oxidation by air and oxide growth may take place. For example, it is well known that the amorphous passive films crystallize under irradiation with electrons [29]. Therefore, electron diffraction measurements yield crystalline AI2O3-, Ta20s-, or Fe203-films, which differ from the in situ structure. EXAFS measurements [30-32],... 

It was reported recently, that polymeric can also form quasicrystals. Hayashida et al. [50] demonstrated that certain blends of polyisoprene, polystyrene, and poly(2-vinylpyridine) form starshaped copolymers that assemble into quaskrystals. By probing the samples with transmission electron microscopy and X-ray diffraction methods, they conclude that the films are composed of periodic patterns of triangles and squares that exhibit 12-fold symmetry. These are signs of quasicrystalline ordering. Such ordering differ from conventional crystals lack of periodic structures yet are well-ordered, as indicated by the sharp diffraction patterns they generate. Quasi-crystals also differ from ordinary crystals in another fundamental way. They exhibit rotational symmetries (often five or tenfold). There are still some basic questions about their stracture. 

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