Transmission electron films

Transmission electron microscopy (TEM) can resolve features down to about 1 nm and allows the use of electron diffraction to characterize the structure. Since electrons must pass through the sample however, the technique is limited to thin films. One cryoelectron microscopic study of fatty-acid Langmuir films on vitrified water [13] showed faceted crystals. The application of TEM to Langmuir-Blodgett films is discussed in Chapter XV. 

Blodgett films direct imaging by scanning tunneling microscopy and high-resolution transmission electron... 

Figure C2.17.1. Transmission electron micrograph of a Ti02 (anatase) nanocrystal. The mottled and unstmctured background is an amorjihous carbon support film. The nanocrystal is centred in die middle of die image. This microscopy allows for die direct imaging of die crystal stmcture, as well as the overall nanocrystal shape. This titania nanocrystal was syndiesized using die nonhydrolytic niediod outlined in [79].

Figure 6 High-resolution transmission electron microscopy image of an epitaxial thin film of Y Ba2Cu307 j, grown on LaAI03, shown in cross section. (Courtesy of T. E. MKchell, Los Alamos National Laboratory)...

Historically, EELS is one of the oldest spectroscopic techniques based ancillary to the transmission electron microscope. In the early 1940s the principle of atomic level excitation for light element detection capability was demonstrated by using EELS to measure C, N, and O. Unfortunately, at that time the instruments were limited by detection capabilities (film) and extremely poor vacuum levels, which caused severe contamination of the specimens. Twenty-five years later the experimental technique was revived with the advent of modern instrumentation. The basis for quantification and its development as an analytical tool followed in the mid 1970s. Recent reviews can be found in the works by Joy, Maher and Silcox " Colliex and the excellent books by Raether and Egerton. ... 

Alternatives to XRD include transmission electron microscopy (TEM) and diffraction, Low-Energy and Reflection High-Energy Electron Diffraction (LEED and RHEED), extended X-ray Absorption Fine Structure (EXAFS), and neutron diffraction. LEED and RHEED are limited to surfaces and do not probe the bulk of thin films. The elemental sensitivity in neutron diffraction is quite different from XRD, but neutron sources are much weaker than X-ray sources. Neutrons are, however, sensitive to magnetic moments. If adequately large specimens are available, neutron diffraction is a good alternative for low-Z materials and for materials where the magnetic structure is of interest. 

As an indication of the changes in deformation modes that can be produced in ionomers by increase of ion content, consider poly(styrene-co-sodium methacrylate). In ionomers of low ion content, the only observed deformation mode in strained thin films cast from tetra hydrofuran (THF), a nonpolar solvent, is localized crazing. But for ion contents near to or above the critical value of about 6 mol%, both crazing and shear deformation bands have been observed. This is demonstrated in the transmission electron microscope (TEM) scan of Fig. 3 for an ionomer of 8.2 mol% ion content. Somewhat similar deformation patterns have also been observed in a Na-SPS ionomer having an ion content of 7.5 mol%. Clearly, in both of these ionomers, the presence of a... 

Dislocations are readily visible in thin-film transmission electron micrographs, as shown in Figs. 20.28 (top) and 20.33 (top). The slip step (Fig. 20.31c) produced by the passage of a single dislocation is not readily apparent. However, for a variety of reasons, a large number of dislocations often move on the same slip plane or on bands of closely adjacent slip planes this results in slip steps which are very easily seen in the light microscope, as shown by the slip lines in Fig. 20.33 (bottom). 

The microphase structure was clearly observed in transmission electron micrographs of the film of amphiphilic copolymers cast from aqueous solutions [29, 31]. An important finding was that no microphase structure was observed for the film cast from organic solutions. This difference indicates that a microphase structure is formed in aqueous solution, but not in organic solution. Different hydrophobic groups showed considerably different morphological features i.e. whether microphase separation leads to a secondary or higher structure depends on the type of hydrophobic units in the copolymers [31],... 

Usually, the molecular strands are coiled in the glassy polymer. They become stretched when a crack arrives and starts to build up the deformation zone. Presumably, strain softened polymer molecules from the bulk material are drawn into the deformation zone. This microscopic surface drawing mechanism may be considered to be analogous to that observed in lateral craze growth or in necking of thermoplastics. Chan, Donald and Kramer [87] observed by transmission electron microscopy how polymer chains were drawn into the fibrils at the craze-matrix-interface in PS films [92]. One explanation, the hypothesis of devitrification by Gent and Thomas [89] was set forth as early as 1972. 

ABA type poly(hydroxyethyl methacrylate) (HEMA) and PDMS copolymers were synthesized by the coupling reactions of preformed a,co-isocyanate terminated PDMS oligomers and amine-terminated HEMA macromonomers312). Polymerization reactions were conducted in DMF solution at 0 °C. Products were purified by precipitation in diethyl ether to remove unreacted PDMS oligomers. After dissolving in DMF/toluene mixture, copolymers were reprecipitated in methanol/water mixture to remove unreacted HEMA oligomers. Microphase separated structures were observed under transmission electron microscope, using osmium tetroxide stained thin copolymer films. 

In 1997, a Chinese research group [78] used the colloidal solution of 70-nm-sized carboxylated latex particles as a subphase and spread mixtures of cationic and other surfactants at the air-solution interface. If the pH was sufficiently low (1.5-3.0), the electrostatic interaction between the polar headgroups of the monolayer and the surface groups of the latex particles was strong enough to attract the latex to the surface. A fairly densely packed array of particles could be obtained if a 2 1 mixture of octadecylamine and stearic acid was spread at the interface. The particle films could be transferred onto solid substrates using the LB technique. The structure was studied using transmission electron microscopy. 

Khmenkov M, Nepijko S, Kuhlenbeck H, Baiimer M, Schldgl R, Ereund H-J. 1997. The structure of Pt-aggregates on a supported thin aluminum oxide film in comparison with unsupported alumina a transmission electron microscopy study. Surf Sci 391 27-36. 

It has been found that various material properties are thickness-dependent. Raman experiments show a dependence on the type of substrate (glass, c-Si, stainless steel, ITO on glass) and on the thickness (up to 1 /nm) of the films [392,393]. Recent transmission electron microscopy (TEM) results also show this [394]. This is in contrast to other results, where these effects are negligible for thicknesses larger than 10 nm [395, 396], as is also confirmed by ellipsometry [397] and IR absorption [398] studies. 

The hybridization of carbon atoms is the major structural parameter controlling DLC film properties. Electron energy loss spectroscopy (EELS) has been extensively used to probe this structural feature [5. 6]. In a transmission electron microscope, a monoenergetic electron beam is impinged in a very thin sample, being the transmitted electrons analyzed in energy. Figure 27 shows a typical... 

The use of lightly crosslinked polymers did result in hydrophilic surfaces (contact angle 50°, c-PI, 0.2 M PhTD). However, the surfaces displayed severe cracking after 5 days. Although qualitatively they appeared to remain hydrophilic, reliable contact angle measurements on these surfaces were impossible. Also, the use of a styrene-butadiene-styrene triblock copolymer thermoplastic elastomer did not show improved permanence of the hydrophilicity over other polydienes treated with PhTD. The block copolymer film was cast from toluene, and transmission electron microscopy showed that the continuous phase was the polybutadiene portion of the copolymer. Both polystyrene and polybutadiene domains are present at the surface. This would probably limit the maximum hydrophilicity obtainable since the RTD reagents are not expected to modify the polystyrene domains. 

The question arises of the extent to which, in polycrystalline films reactant gas has access to the substrate. It is clear that in high-temperature films the total absence of intercrystal gaps means that such access of gas is completely absent. In the case of films deposited at 0°C, one may estimate from the measured roughness factor and from transmission electron microscopic evidence that, of the total substrate area, more than 90% is in direct contact with metal in any case, the substrate at the base of a gap is almost certainly covered with a thin layer of metal. Thus, even in this case the gas cannot have more than trivial access to the substrate. 

Figure 7 (a, b, d, and e) shows transmission electron micrographs from Pd-Ag films of comparable weight, prepared and annealed at 400°C, and used once to catalyze the oxidation of ethylene at 240°C (40). The structure of this series of alloy films varied consistently with composition. Silver-rich films (e.g., Fig. 7a, 13% Pd) showed extensive coalescence of the crystallites, while at the other end of the composition range (e.g., Fig. 7e,...

High Resolution Transmission Electron Microscopy (HRTEM, Philips CM20, 200 kV) was applied to get structural and nanotextural information on the fibers, by imaging the profile of the aromatic carbon layers in the 002-lattice fringe mode. A carbon fiber coated with pyrolytic carbon was incorporated in epoxy resin and a transverse section obtained by ultramicrotomy was deposited on a holey carbon film. An in-house made image analysis procedure was used to get quantitative data on the composite. 

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