Electrodeposited structure

Fig. 15.7. Variation of electrodeposit structure with applied potential.

Substrate surface structure exerts a controlling influence upon monolayer electrodeposition, as can be seen by comparing deposition of Ag at I2-pretreated Pt(lll) and Pt(100), all else being equal [41,45] (Fig. 21). The UPD process at Pt(100)(v/2 x x/8)i 45°-I took place in two stages, rather than three, and the electrodeposit structures were related to the square mesh of the Pt(100) substrate in contrast to the hexagonal structures observed at Pt(lll). 

The epitaxy of nickel electrodeposits has been studied by electron microscopy using a new method for the preparation of sections [6.67, 6.68]. It was demonstrated that the electrodeposit structure results from competition between a simple epitaxial growth process maintaining substrate orientation and the formation of new randomly oriented nuclei which are rapidly submitted to the selection process, giving a fiber texture. TTiis competition depends on both the substrate orientation and the nucleation and growth processes leading to the final texture. 

FIGURE 26.23 Variation in metal electrodeposit structure as a function of the applied current density and limiting current density. Figure from [92] (copyright Elsevier 1994). 

LaVan DA, George PM, Danger R (2003) Simple, three-dimensional microfabiication of electrodeposited structures. Angew Chem 42 1262-1265... 

The development of scanning probe microscopies and x-ray reflectivity (see Chapter VIII) has allowed molecular-level characterization of the structure of the electrode surface after electrochemical reactions [145]. In particular, the important role of adsorbates in determining the state of an electrode surface is illustrated by scanning tunneling microscopic (STM) images of gold (III) surfaces in the presence and absence of chloride ions [153]. Electrodeposition of one metal on another can also be measured via x-ray diffraction [154]. 

Koinuma M and Uosaki K 1996 Atomic structure of bare p-GaAs(IOO) and electrodeposited Cu on p-GaAs (100) surfaces in H2SO4 solutions An AFM study J. Eiectroanai. Chem. 409 45-50... 

The surface consists of terraces of a height of 330 30 pm. Within error limits, this is the value that would be expected for Ge(lll) bilayers. Furthermore, we were able to observe that the electrodeposition gave rise to a less ordered surface structure with nanoclusters, transforming over a timescale of about 1 hour into a layered structure. With GeBr4 a transformation of clusters into such a layered surface was only partly seen with GeGl4 this transformation could not be observed. 

Electron diffraction investigations showed that epitaxy did indeed exist when one metal was electrodeposited on another, but that it persisted for only tens or hundreds of atomic layers beyond the interface. Thereafter the atomic structure (or lattice) of the deposit altered to one characteristic of the plating conditions. Epitaxy ceased before an electrodeposit is thick enough to see with an optic microscope, and at thicknesses well below those at which pseudomorphism is observed. 

Fig. 12.7 The disturbed structure of a scratch, with fragmented and distorted grains, is perpetuated by a strongly pseudomorphic electrodeposit...

Gold coatings on separable electric contacts and slip rings make use of the high hardness possible with electrodeposition to resist wear. Rhodium is another metal which can be exceptionally hard. Thick coatings have a cracked-sealed structure similar to that of chromium. 

Structure Although massive chromium has a body-centred cubic structure, electrodeposited chromium can exist as two primary modifications, i.e. a-(b.c.c.) and (c.p.h.). The precise conditions under which these forms of chromium can be deposited are not known with certainty. Muro" showed that at 40°C and 2-0-22 A/dm the deposit was essentially a-chromium but small amounts of 0- and 7- were present, while Koch and Hein observed... 

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. 

Fig. 3.8 XRD patterns (CuKc( source) showing a rich in selenium (x > 0.6) CdSej Tei-jt electrodeposited film, which adopts the hexagonal CdSe wurtzite structure by annealing at 520 °C (b). The as-deposited (from a typical acidic solution) film is rather amorphous (a). Segregation of a Te phase is observed in the solid. (Reprinted from Bouroushian et al. [137], Copyright 2009, with permission from Elsevier)...

The formation of colloidal sulfur occurring in the aqueous, either alkaline or acidic, solutions comprises a serious drawback for the deposits quality. Saloniemi et al. [206] attempted to circumvent this problem and to avoid also the use of a lead substrate needed in the case of anodic formation, by devising a cyclic electrochemical technique including alternate cathodic and anodic reactions. Their method was based on fast cycling of the substrate (TO/glass) potential in an alkaline (pH 8.5) solution of sodium sulfide, Pb(II), and EDTA, between two values with a symmetric triangle wave shape. At cathodic potentials, Pb(EDTA)2 reduced to Pb, and at anodic potentials Pb reoxidized and reacted with sulfide instead of EDTA or hydroxide ions. Films electrodeposited in the optimized potential region were stoichiometric and with a random polycrystalline RS structure. The authors noticed that cyclic deposition also occurs from an acidic solution, but the problem of colloidal sulfur formation remains. 

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