Nucleation monolayer formation

Obviously, the nucleation is a randon process which is amplified by subsequent deposition of many thousands of silver atoms before the surface is completely covered (if integrated over the time interval of monolayer formation the current in each pulse corresponds to an identical charge). Such an amplification of random processes is the only way they can be observed. This situation is quite analogous, for example, to radioactive decay where a single disintegration is followed, in a Geiger tube, by the flow of millions of electrons. ... 

Doudevski I, Hayes WA, Schwartz DK (1998) Submonolayer island nucleation and growth kinetics during self-assembled monolayer formation. Phys Rev Lett 81 4927-4930... 

Fig. 2.14 - Schematic diagrams of I-t transients obtained for various types of phase formation process, (a) monolayer formation with instantaneous nucleation (b) monolayer formation with progressive nucleation (c) three-dimensional nucleation and growth process (d) successive monolayer formation.

On the other hand, whenever AV exceeds the value of AVq the formation of a dense monolayer film appears to be the continuous process. It has been demonstrated that the observed crossover between those two regimes is due to the changes in the mechanism of the adsorbate nucleation, as determined by the calculation of the nucleated cluster size distribution functions. For... 

The dependence on film thickness is attributed to the dewetting nucleation, which occurs in the 2.5-4.5 nm thickness range via the formation of randomly distributed droplets rather than the formation of holes. When the initial film thickness exceeds 4.5 nm, dewetting is trigged via nucleation of holes instead of droplets, and for film thickness above 10 nm, dewetting develops slowly via hole nucleation at defects. The different dewetting processes observed for different initial film thicknesses can be explained in terms of the variation of disjoining pressure and the inability of the polymer to spread on its own monolayer. 

The authors [35] emphasize that their result regarding the first HgS monolayer, which involves reversible underpotential adsorption, suggests that nucleation cannot be considered as a universal mechanism for the formation of anodic films. Analogous conclusions have been inferred for cathodic HgSe films electrodeposited on mercury electrode by the reduction of selenous acid [37] the first monolayer appeared to be reversibly adsorbed, while formation of the following two layers was preceded by nucleation. 

After complete formation of each successive monolayer of atoms, the next layer should start to form. This requires two-dimensional nucleation by the union of several adatoms in a position 1. Like three-dimensional nucleation, two-dimensional nucleation requires some excess energy (i.e., elevated electrode polarization). Introducing the concept of excess linear energy p of the one-dimensional face (of length L) of the nucleus, we can derive an expression for the work of formation of such a nucleus (analogous to that used in Section 14.2.2). When the step of two-dimensional nucleation is rate determining, the polarization equation becomes, instead of (14.39),... 

Fig. 3.5 Representation of a scheme of an experiment (upper set of drawings) and the obtained experimental results presented as AFM images (middle part) and cross-sectional profiles (bottom) that provides evidence of silica nucleation and shell formation on biopolymer macromolecules. Scheme of experiment. This includes the following main steps. 1. Protection of the mica surface against silica precipitation. It was covered with a fatty (ara-chidic) acid monolayer transferred from a water substrate with the Langmuir-Blodgett technique. This made the mica surface hydrophobic because of the orientation of the acid molecules with their hydrocarbon chains pointing outwards. 2. Adsorption of carbohydrate macromolecules. Hydrophobically modified cationic hydroxyethylcellulose was adsorbed from an aqueous solution. Hydrocarbon chains of polysaccharide served as anchors to fix the biomacromolecules firmly onto the acid monolayer. 3. Surface treatment by silica precursor. The mica covered with an acid mono-...

Nucleation and growth processes of the metal lattice. Understanding of the nucleation and growth of surface nuclei, formation of monolayers and multilayers, and growth of coherent bulk deposit is based on knowledge of condensed-matter physics and physical chemistry of surfaces. 

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