Metal atoms nucleation

Maitani MM, Allara DL, Ohlberg DAA, Li Z, Williams RS, Stewart DR (2010) High integrity metal/organic device interfaces via low temperature buffer layer assisted metal atom nucleation. Appl Phys Lett 96(17) 173109-173113... 

Removal of lattice oxygen from the surface of nickel oxide in vcumo at 250° or incorporation of gallium ions at the same temperature [Eq. (14)] causes the reduction of surface nickel ions into metal atoms. Nucleation of nickel crystallites leaves cationic vacancies in the surface layer of the oxide lattice. The existence of these metal crystallites was demonstrated by magnetic susceptibility measurements (33). Cationic vacancies should thus exist on the surface of all samples prepared in vacuo at 250°. However, since incorporation of lithium ions at 250° creates anionic vacancies, the probability of formation of vacancy pairs (anion and cation) increases and consequently, the number of free cationic vacancies should be low on the surface of lithiated nickel oxides. Carbon monoxide is liable to be adsorbed at room temperature on cationic vacancies and the differences in the chemisorption of this gas are related to the different number of isolated cationic vacancies on the surface of the different samples. 

Since the demonstration by Schumacher et al ) of the use of alkali metal vapor inclusion into a supersonic beam to produce clusters, there have been a number of attempts to generalize the approach. It has recently been recognized that instead of high temperature ovens, with their concommitant set of complex experimental problems, an intense pulsed laser beam focused on a target could be effectively used to produce metal atoms in the throat of a supersonic expansion valve. ) If these atoms are injected into a high pressure inert gas, such as helium, nucleation to produce clusters occurs. This development has as its most important result that clusters of virtually any material now can be produced and studied with relative ease. 

The nucleation behavior of transition metal particles is determined by the ratio between the thermal energy of the diffusing atoms and the interaction of the metal atoms at the various nucleation sites. To create very small particles or even single atoms, low temperatures and metal exposures have to be used. The metal was deposited as metal atoms impinging on the surface. The metal exposure is given as the thickness (in monolayer ML) of a hypothetical, uniform, close-packed metal layer. The interaction strength of the metals discussed here was found to rise in the series from Pd < Rh < Co ( Ir) < V [17,32]. Whereas Pd and Rh nucleate preferentially at line defects at 300 K and decorate the point defects at 90 K, point defects are the predominant nucleation center for Co and V at 300 K. At 60 K, Rh nucleates at surface sites between point defects [16,33]. 

The intensity of the dicarbonyl at 2116cm is considerably reduced as compared to the 90 K deposit, indicating that the amount of metal atoms trapped at point defects is reduced for growth at 60 K. The difference in the nucleation sites is also reflected by the lower thermal stability of the systems, which decompose between 80 and 150 K as compared to 200 to 250 K for the 90 K deposits. With isotope mixing experiments the peak at 2087 cm was assigned to a carbonyl with three or more CO ligands, while the peak at 1999 cm is associated to a monocarbonyl [32]. 

In summary, we have shown that metal carbonyls formed in situ by adsorption of CO under ultrahigh vacuum condition can serve as a very sensitive tool for monitoring the nucleation site as well as the environment of the metal atom. It was shown that low coordinated metal atoms, in particular... 

We have reviewed experiments on two classes of systems, namely small metal particles and atoms on oxide surfaces, and Ziegler-Natta model catalysts. We have shown that metal carbonyls prepared in situ by reaction of deposited metal atoms with CO from the gas phase are suitable probes for the environment of the adsorbed metal atoms and thus for the properties of the nucleation site. In addition, examples of the distinct chemical and physical properties of low coordinated metal atoms as compared to regular metal adsorption sites were demonstrated. For the Ziegler-Natta model catalysts it was demonstrated how combination of different surface science methods can help to gain insight into a variety of microscopic properties of surface sites involved in the polymerization reaction. 

As a rule, short nucleation times are the prerequisite for monodisperse particle formation. A recent mechanistic study showed that when Pt(acac)2 is reduced by alkylalu-minium, virtually all the Pt cluster nuclei appear at the same time and have the same size [86]. The nucleation process quickly consumes enough of the metal atoms formed initially to decrease their concentration below the critical threshold. No new metal cluster nuclei are created in the subsequent diffusion-controlled growth stage. 

In both cases, the Au nanoparticles behave as molecular crystals in respect that they can be dissolved, precipitated, and redispersed in solvents without change in properties. The first method is based on a reduction process carried out in an inverse micelle system. The second synthetic route involves vaporization of a metal under vacuum and co-deposition of the atoms with the vapors of a solvent on the walls of a reactor cooled to liquid nitrogen temperature (77 K). Nucleation and growth of the nanoparticles take place during the warm-up stage. This procedure is known as the solvated metal atom dispersion (SMAD) method. 

The calculation for the important case of two-dimensional nuclei growing only in the plane of the substrate will be based on the assumption that these are circular and that the electrode reaction occurs only at their edges, i.e. on the surface, 2nrhy where r is the nucleus radius and h is its height (i.e. the crystallographic diameter of the metal atom). The same procedure as that employed for a three-dimensional nucleus yields the following relationship for instantaneous nucleation ... 

After Faraday s seminal report on the preparation of transition metal clusters in the presence of stabilizing agents in 1857 [31], Turkevich [19-21] heralded the first reproducible protocol for the preparation of metal colloids and the mechanism proposed by him for the stepwise formation of nanoclusters based on nucleation, growth, and agglomeration [19] is still valid but for some refinement based on additional information available from modem analytical techniques and data from thermodynamic and kinetic experiments [32-41], Agglomeration of zero-valent nuclei in the seed or, alternatively, collisions of already formed nuclei with reduced metal atoms are now considered the most plausible mechanism for seed formation. Figure 3.1 illustrates the proposed mechanism [42],... 

Metal coordination is another important bonding opportunity with respect to self-assembly. This is important in many natural molecules such as hemoglobin and chlorophyll, where the metal atom acts both as the site of activity and as a centralizing agent with respect to shape and thus acts as a nucleating agent for self-assembly. 

You have now learned about how to use DFT calculations to compute the rates of individual activated processes. This information is extremely useful, but it is still not enough to fully describe many interesting physical problems. In many situations, a system will evolve over time via many individual hops between local minima. For example, creation of catalytic clusters of metal atoms on metal oxide surfaces involves the hopping of multiple individual metal atoms on a surface. These clusters often nucleate at defects on the oxide surface, a process that is the net outcome from both hopping of atoms on the defect-free areas of the surface and in the neighborhood of defects. A characteristic of this problem is that it is the long time behavior of atoms as they move on a complicated energy surface defined by many different local minima that is of interest. 

Reactive metals are of interest for two primary reasons (1) reaction with the uppermost part of the SAM which can drive uniform nucleation with no penetration and (2) for electropositive metals, injection of electrons into the SAM to create a favorable dipole at the metal/SAM interface for device operation. With respect to the first, as opposed to the results with non-reactive metal deposition, some reports of reactive metal deposition appear to show prevention of metal penetration with the avoidance of short-circuits across the M junction. In general, serious concerns remain that some of metal atoms react destructively with the SAM backbone to produce inorganic species, e.g., carbides and oxides in the case of aggressive metals such as titanium. 

METAL CLUSTER NUCLEATION AND GROWTH 2.1. Principles of Metal Atom Formation... 

Catalyst particle nucleation in the initial stages and their subsequent growth play an important role in catalytic mechanisms. In a model Pt/alumina catalyst, the general view is that the formation of particles is a stepwise process incorporating the following steps (Wynblatt and Gjostein 1975, Cottrell 1971) individual metal atoms (called monomers) transform to two-dimensional islands, which subsequently transform to three-dimensional clusters. These clusters eventually transform into finite-sized particles. 

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