Microscopy AFM, STM

Tanaka and co-workers observed two stages in the deposition of polymer by non-contact AFM in vacuum [192], Initially, rapid diffusion of molecules allows association and organization before laying down on the surface. Bulk solvent dries, but solvent trapped between the polymer and the surface takes much longer. This allows adsorbed aggregates to reorient for favorable correspondence with the substrate lattice. 

---

The most popular of the scanning probe tecimiques are STM and atomic force microscopy (AFM). STM and AFM provide images of the outemiost layer of a surface with atomic resolution. STM measures the spatial distribution of the surface electronic density by monitoring the tiumelling of electrons either from the sample to the tip or from the tip to the sample. This provides a map of the density of filled or empty electronic states, respectively. The variations in surface electron density are generally correlated with the atomic positions. 

Scanning probe microscopy AFM, STM (arene-rich dendrimers)... 

The ability to control the position of a fine tip in order to scan surfaces with subatomic resolution has brought scanning probe microscopies to the forefront in surface imaging techniques. We discuss the two primary techniques, scanning tunneling microscopy (STM) and atomic force microscopy (AFM) the interested reader is referred to comprehensive reviews [9, 17, 18]. 

We confine ourselves here to scanning probe microscopies (see Section VIII-2B) scanning tunneling microscopy (STM) and atomic force microscopy (AFM), in which successive profiles of a surface (see Fig. VIII-1) are combined to provide a contour map of a surface. It is conventional to display a map in terms of dark to light areas, in order of increasing height above the surface ordinary contour maps would be confusing to the eye. 

Several striking examples demonstrating the atomically precise control exercised by the STM have been reported. A "quantum corral" of Fe atoms has been fabricated by placing 48 atoms in a circle on a flat Cu(lll) surface at 4K (Fig. 4) (94). Both STM (under ultrahigh vacuum) and atomic force microscopy (AFM, under ambient conditions) have been employed to fabricate nanoscale magnetic mounds of Fe, Co, Ni, and CoCr on metal and insulator substrates (95). The AFM has also been used to deposit organic material, such as octadecanethiol onto the surface of mica (96). New appHcations of this type of nanofabrication ate being reported at an ever-faster rate (97—99). 

The very new techniques of scanning tunnelling microscopy (STM) and atomic force microscopy (AFM) have yet to establish themselves in the field of corrosion science. These techniques are capable of revealing surface structure to atomic resolution, and are totally undamaging to the surface. They can be used in principle in any environment in situ, even under polarization within an electrolyte. Their application to date has been chiefly to clean metal surfaces and surfaces carrying single monolayers of adsorbed material, rendering examination of the adsorption of inhibitors possible. They will indubitably find use in passive film analysis. 

Film-forming chemical reactions and the chemical composition of the film formed on lithium in nonaqueous aprotic liquid electrolytes are reviewed by Dominey [7], SEI formation on carbon and graphite anodes in liquid electrolytes has been reviewed by Dahn et al. [8], In addition to the evolution of new systems, new techniques have recently been adapted to the study of the electrode surface and the chemical and physical properties of the SEI. The most important of these are X-ray photoelectron spectroscopy (XPS), SEM, X-ray diffraction (XRD), Raman spectroscopy, scanning tunneling microscopy (STM), energy-dispersive X-ray spectroscopy (EDS), FTIR, NMR, EPR, calorimetry, DSC, TGA, use of quartz-crystal microbalance (QCMB) and atomic force microscopy (AFM). 

Valette-Hamelin approach,67 and other similar methods 24,63,74,218,225 (2) mass transfer under diffusion control with an assumption of homogeneous current distribution73 226 (3) adsorption of radioactive organic compounds or of H, O, or metal monolayers73,142,227 231 (4) voltammetry232,233 and (5) microscopy [optical, electron, scanning tunneling microscopy (STM), and atomic force microscopy (AFM)]234"236 as well as a number of ex situ methods.237 246... 

Scanning tunneling microscopy (STM) Atomic force microscopy (AFM) 234-236... 

Table 2.7 lists techniques used to characterise carbon-blacks. Analysis of CB in rubber vulcanisates requires recovery of CB by digestion of the matrix followed by filtration, or by nonoxidative pyrolysis. Dispersion of CB within rubber products is usually assessed by the Cabot dispersion test, or by means of TEM. Kruse [46] has reviewed rubber microscopy, including the determination of the microstructure of CB in rubber compounds and vulcanisates and their qualitative and quantitative determination. Analysis of free CB features measurements of (i) particulate and aggregate size (SEM, TEM, XRD, AFM, STM) (ii) total surface area according to the BET method (ISO 4652), iodine adsorption (ISO 1304) or cetyltrimethylammonium bromide (CTAB) adsorption (ASTM D 3765) and (iii) external surface area, according to the dibutylphthalate (DBP) test (ASTM D 2414). TGA is an excellent technique for the quantification of CB in rubbers. However, it is very limited in being able to distinguish the different types of... 

The objective of this book is to highlight the important strides being made toward a molecular understanding of the processes that occur at surfaces through the unique information provided by the proximal scanning probe family of techniques this principally involves scanning tunneling microscopy (STM) but some atomic force microscopy (AFM) experiments are also included. 

The success of STM has resulted in the development of a whole variety of related scanning probe microscopes, the most important of which is atomic force microscopy, AFM, also known as scanning force microscopy. AFM was first reported in 1986 by Binnig, Quate and Gerber. 

Atomic force microscopy (AFM) is a variant of STM and was introduced in 1986 by Binnig et al. (11). AFM belongs to a family of near-field microscopies and is capable of imaging a wide variety of specimens surface down to an atomic scale. The technique employs a probe (pyramidal tip) mounted at the end of a sensitive but rigid cantilever (see Fig. 2). The probe is drawn across the specimen under very light mechanical loading (1). Measurements of the probe s interaction with the sample s surface are accomplished with a laser beam reflected from the cantilever. 

Figure 7.12 Images at atomic resolution of graphite obtained with scanning tunneling (left) and atomic force microscopy (middle). The graphite lattice contains two types of sites A-sites with a carbon atom neighbor in the second layer and B-sites without a neighbor in the next layer. STM detects the B-sites, whereas the A-sites show up better in AFM. (STM image courtesy of TopoMetrix AFM image courtesy of M.W.G.M. Verhoeven, Eindhoven).

---