Growth underpotential deposition

The first electrodeposition of aluminum from an ionic liquid was reported in 1994 by Carlin etal. [157], Two years later, Zhao et al. [158] smdied the aluminum deposition processes on tungsten electrodes in trimethylphenylanunonium chlo-ride/aluminum chloride with mole ratio 1 2. It was shown that the deposition of aluminum was instantaneous as a result of three-dimensional nucleation with hemispherical diffusion-controlled growth, underpotential deposition of aluminum, corresponding to several monolayers. Liao et al. investigated the constant current electrodeposition of bulk aluminum on copper substrates was in 1-methyl-... 

Generally, the experimental results on electrodeposition of CdS in acidic solutions of thiosulfate have implied that CdS growth does not involve underpotential deposition of the less noble element (Cd), as would be required by the theoretical treatments of compound semiconductor electrodeposition. Hence, a fundamental difference exists between CdS and the other two cadmium chalcogenides, CdSe and CdTe, for which the UPD model has been fairly successful. Besides, in the present case, colloidal sulfur is generated in the bulk of solution, giving rise to homogeneous precipitation of CdS in the vessel, so that it is quite difficult to obtain a film with an ordered structure. The same is true for the common chemical bath CdS deposition methods. 

It appears that a way to efficient electrochemical growth of CdTe and other chalcogenides on silicon crystals is the utilization of light-assisted processes. Works in this direction will be discussed in a subsequent section regarding underpotential deposition studies. 

Underpotential deposition of heavy metals on H2 evolving electrodes is a well known problem [133], The existence of a direct correlation between H2 evolution activity and metal work function, makes UPD very likely on high work function electrodes like Pt or Ni. Cathode poisoning for H2 evolution is aggravated by UPD for two reasons. First, deposition potentials of UPD metals are shifted to more anodic values (by definition), and second, UPD favors a monolayer by monolayer growth causing a complete coverage of the cathode [100]. Thus H2 evolution may be poisoned by one monolayer of cadmium for example, the reversible bulk deposition potential of which is cathodic to the H2 evolution potential. 

A similar effect was observed in our work and in the work of others (5), where voltammetry curves changed after extended cycling, particularly if the cathodic sweep was reversed before the full Pb deposition coverage. The observed "cathodic memory effect" may be due to the proposed structural transformation phenomenon and subsequent step density growth, initially facilitated by a high step density on a UHV-prepared or chemically polished (6) Ag(lll) substrate. Post electrochemical LEED analysis on Ag(lll)-Pb(UPD) surfaces provided additional evidence of a step density increase during Pb underpotential deposition, which will be discussed later in this text. (See Figure 3.)... 

When underpotential deposition adsorption/desorption takes place randomly at any substrate site M, the following random adsorptioncontrolling treatment is to be employed, and when the process is controlled by a two-dimensional nucleation-growth mechanism, the process analysis should be carried out according to Section ni.l.(b). 

A kinetic study of Cu underpotential deposition was carried out to determine if it is best described by adsorption processes or by nucleation processes. The nucleation growth process is classified into two categories instantaneous nucleation growth and progressive nucleation growth. In the case of instantaneous nucleation growth, where nucleation site formation is so fast that no other following nucleation sites are created, the number of nucleation sites N(t) is expressed as... 

UPD Cd can also be used to obtain cadmium sulfide, an important semiconductor for electronics. Electrochemical epitaxial growth of organized CdS structures, involving underpotentially deposited Cd on Au(lll) was thus reported [161, 265]. 

With increasing amounts ofbenzoic acid (0 to 0.38 wt.%) we observe a decreasing peak current for the aluminum deposition (see Figure 8.7), the aluminum oxidation peak disappears and the underpotential deposition (UPD) of aluminum is also strongly diminished. These experiments lead to the conclusion that the additive molecules block the active growth sites and therefore the peak current of aluminum deposition increases with decreasing additive concentration. A further consequence... 

Atomic layer epitaxy (electrochemical) — Electrochemical atomic layer epitaxy (ECALE) is a self-limiting process for the formation of structurally well-ordered thin film materials. It was introduced by Stickney and coworkers [i] for the layer by layer growth of compound semiconductors (CdTe, etc.). Thin layers of compound semiconductors can be formed by alternating - underpotential deposition steps of the individual elements. The total number of steps determines the final thickness of the layer. Compared to flux-limited techniques... 

Aqueous deposition follows the same reactions as (a), More likely, however, a com-plexing agent, such as NH3, is used to reduce the reaction rate to improve film structure. This process can also be done electrolytically (with, e.g., CdS04 and Te02 as reactants) with underpotential deposition, the growth of one atomic layer at a time may be... 

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