Oscillatory Electrodeposition

According to the literature [21], all reported electrochemical oscillations can be classified into four classes depending on the roles of the true electrode potential (or Helmholtz-layer potential, E). Electrochemical oscillations in which E plays no essential role and remains essentially constant are known as strictly potentiostatic (Class I) oscillations, which can be regarded as chemical oscillations containing electrochemical reactions. Electrochemical oscillations in which E is involved as an essential variable but not as the autocatalytic variable are known as S-NDR (Class II) oscillations, which arise from an S-shaped negative differential resistance (S-NDR) in the current density (/) versus E curve. Oscillations in which E is the autocatalytic variable are knovm as N-NDR (Class III) oscillations, which have an N-shaped NDR. Oscillations in which the N-NDR is obscured by a current increase from another process are knovm as hidden N-NDR (HN-NDR Class IV) oscillations. It is known that N-NDR oscillations are purely current oscillations, whereas HN-NDR oscillations occur in both current and potential. The HN-NDR oscillations can be further divided into three or four subcategories, depending on how the NDR is hidden. 

Another example is dendritic crystal growth under diffusion-limited conditions accompanied by potential or current oscillations. Wang et al. reported that electrodeposition of Cu and Zn in ultra-thin electrolyte showed electrochemical oscillation, giving beautiful nanostmctured filaments of the deposits [27,28]. Saliba et al. found a potential oscillation in the electrodeposition of Au at a liquid/air interface, in which the Au electrodeposition proceeds specifically along the liquid/air interface, producing thin films with concentric-circle patterns at the interface [29, 30]. Although only two-dimensional ordered structures are formed in these examples because of the quasi-two-dimensional field for electrodeposition, very recently, we found that 

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Microspectroscopic Study of Self-Organization in Oscillatory Electrodeposition... 

Raman Microspectroscopy Study of Oscillatory Electrodeposition of Au at an Air/Liquid Interface... 

As has been shown above, oscillatory electrodeposition is interesting from the point of view of the production of micro- and nanostructured materials. However, in situ observation of the dynamic change of the deposits had been limited to the micrometer scale by use of an optical microscope. Inspections on the nanometer scale were achieved only by ex situ experiments. Thus, information vdth regard to dynamic nanostructural changes of deposits in the course of the oscillatory growth was insufHcient, although it is very important to understand how the macroscopic ordered structures are formed with their molecular- or nano-components in a self-organized manner. 

Surface-enhanced Raman scattering (SERS) is a candidates for resolving this issue. Since the SERS effect is observed only at metal surfaces with nanosized curvature, this technique can also be used to investigate nanoscale morphological structures of metal surfaces. It is thus worth investigating SERS under oscillatory electrodeposition conditions. The author of this chapter and coworkers recently reported that... 

We have reviewed studies of the self-organized formation of ordered nanostructures by oscillatory electrodeposition. Although the mechanism is totally different in different cases and the structures of the resultant deposits vary greatly, they agree in that a unit structure is formed with one cycle of the oscillation. Periodic ordered... 

Nakanishi, S., Fukami, K, Tada, T. and Nakato, Y. (2004) Metal latticeworks formed by self-organization in oscillatory electrodeposition. /. Am. Chem. Soc., 126, 9556-9557. 

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