Bulk deposition

The weld was riddled with mildly undercut, gaping pits. Attack was confined to fused and heat-affected zones, with a pronounced lateral or circumferential propagation (as in Fig. 6.10). The resulting perforation at the external surface was quite small. Pits were filled with deposits, friable oxides, and other corrosion products. Black plugs embedded in material filling the gaping pit contained high concentrations of iron sulfide. Bulk deposits contained about 90% iron oxide. Carbonaceous material was not detected. 

Zinc and tin The electrodeposition of Zn [52] has been investigated in acidic chloroaluminate liquids on gold, platinum, tungsten, and glassy carbon. On glassy carbon only three-dimensional bulk deposition was observed, due to the metal s underpotential deposition behavior. At higher overvoltages, codeposition with A1... 

Germanium In situ STM studies on Ge electrodeposition on gold from an ionic liquid have quite recently been started at our institute [59, 60]. In these studies we used dry [BMIM][PF<3] as a solvent and dissolved Gel4 at estimated concentrations of 0.1-1 mmol 1 the substrate being Au(lll). This ionic liquid has, in its dry state, an electrochemical window of a little more than 4 V on gold, and the bulk deposition of Ge started several hundreds of mV positive from the solvent decomposition. Furthermore, distinct underpotential phenomena were observed. Some insight into the nanoscale processes at the electrode surface is given in Section 6.2.2.3. 

These results are quite interesting. The initial stages of Al deposition result in nanosized deposits. Indeed, from the STM studies we recently succeeded in making bulk deposits of nanosized Al with special bath compositions and special electrochemical techniques [10]. Moreover, the preliminary results on tip-induced nanostructuring show that nanosized modifications of electrodes by less noble elements are possible in ionic liquids, thus opening access to new structures that cannot be made in aqueous media. 

Copper electrodeposition on Au(111) Copper is an interesting metal and has been widely investigated in electrodeposition studies from aqueous solutions. There are numerous publications in the literature on this topic. Furthermore, technical processes to produce Cu interconnects on microchips have been established in aqueous solutions. In general, the quality of the deposits is strongly influenced by the bath composition. On the nanometer scale, one finds different superstmctures in the underpotential deposition regime if different counter-ions are used in the solutions. A co-adsorption between the metal atoms and the anions has been reported. In the underpotential regime, before the bulk deposition begins, one Cu mono-layer forms on Au(lll) [66]. 

Numerous works have been implemented on tellurium electrochemistry and its adsorption at metal surfaces. The morphological structures of electrodeposited Te layers at various stages of deposition (first UPD, second UPD, and bulk deposition) are now well known [88-93]. As discussed in the previous paragraphs, Stickney and co-workers have carried out detailed characterizations of the first Te monolayer on Au single-crystal surfaces in order to establish the method of electrochemical atomic layer epitaxy of CdTe. 

Let us add here that the fabrication of polycrystalline semiconductive films with enhanced photoresponse and increased resistance to electrochemical corrosion has been attempted by introducing semiconductor particles of colloidal dimensions to bulk deposited films, following the well-developed practice of producing composite metal and alloy deposits with improved thermal, mechanical, or anti-corrosion properties. Eor instance, it has been reported that colloidal cadmium sulfide [105] or mercuric sulfide [106] inclusions significanfly improve photoactivity and corrosion resistance of electrodeposited cadmium selenide. 

While the above XPS results give the impression, that the electrochemical interface and the metal vacuum interface behave similarly, fundamental differences become evident when work function changes during metal deposition are considered. During metal deposition at the metal vacuum interface the work function of the sample surface usually shifts from that of the bare substrate to that of the bulk deposit. In the case of Cu deposition onto Pt(l 11) a work function reduction from 5.5 eV to 4.3 eV is observed during deposition of one monolayer of copper [96], Although a reduction of work function with UPD metal coverage is also observed at the electrochemical interface, the absolute values are totally different. For Ag deposition on Pt (see Fig. 31)... 

Fig. 32. Valence band spectra (UPS) of a polycrystalline Pt electrode emersed at a different potential where underpotential deposition of Cu (0.3V, 0.1 V) and bulk deposition (—0.2 V) of Cu occurs. Clean Pt and Cu surfaces are shown for comparison.

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. 

Figure 2.J5 shows an image collected at —0.1 V in the perchlorate solution after the bulk deposition of several monolayers of Cu. 1 he Cu-Cu distance...

Ideally, CdTe could be formed using reductive UPD of Te and Cd. If, however, acidic HTeOj solutions are used, reductive Te UPD requires a potential of near 0.0 V (Figure 9B) in order to avoid bulk deposition. Cd UPD is optimal between —0.4 and —0.6 V. Cd atomic layers, however, will strip during the Te deposition step. On the other hand, Te can be deposited at —0.5 V, where the Cd remains stable, but some bulk Te is formed along with the Te(UPD) ... 

Deposition of more than a ML/cycle is alarming, however, even for only the first few cycles, as it suggests bulk deposition non layer-by-layer or 3D growth. That high growth rates were observed initially is understandable, in that the potentials had to be chosen for essentially bulk growth conditions for Cd and Te, in order that at steady state, reasonable amounts of deposit would form. 

Alternatively, it might be that the underpotentials needed to form atomic layers of the elements were decreasing, shifting closer to the formal potentials for deposition of the bulk elements. This scenario may be a factor, but it is frequently observed that the steady state potentials are more negative then the formal potentials for the elements, where bulk deposits of the elements would be expected to form. 

Of course, deposition times can be decreased by using a larger driving force, but that runs the risk of bulk deposition. It is easy to envision a cycle where overpotentials are used, and the deposition is simply stopped after a monolayer of charge has passed. Such a cycle would not involve surface limited reactions and 3D growth would be expected. 

The voltammograms in Figure 9 also indicate that it is possible to electrodeposit Ag-Al alloys in a potential range positive of the potential where the bulk deposition of aluminum is normally observed, i.e., 0 V versus A1(III)/A1. The Ag-Al alloy composition, represented as the fraction of Al in the alloy, 1 — x, was estimated from the voltammograms in Figure 9 by using the following expression... 

The energetic aspects of underpotential deposition can be investigated by a slow (i.e., a few millivolts per second) potential scan starting at a potential so high that no adsorption takes place. As the potential is lowered, one or more current peaks axe observed, which are caused by the adsorption of the metal ions (see Fig. 4.9). According to the usual convention, the adsorption current is negative (i.e., cathodic). Different peaks may correspond to different adsorption sites, or to different structures of the adsorbate layer. If the potential is scanned further past the equilibrium potential [Pg.46]

The difference between the potential of the current peak for the desorption and the bulk deposition potential is known as the underpotential shift simple systems the value of Gibbs energies of adsorption and deposition shift both according to the Nernst equation. Deviations from this behavior may indicate coadsorption of other ions. 

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