Subject scanning electrochemical microscopy

Combination with scanning electrochemical microscopy (SECM), the subject of Chapter 3.3, has also been explored and the tip-surface separation was found to influence the crystal impedance [53]. Viewed from the opposite perspective, the observation of stress effects on crystal resonant... 

It is not necessary to deal with these techniques in detail here, since there are several books and monographs on the subject. The fundamental theory and practice of electrochemical and spectroelectrochemical methods can be found in [1,2] and also in [3-5], where investigations of polymeric surface layers are emphasized. Excellent monographs on EQCM [6-9] and PBD [10] are also recommended for further studies. Infrared, Mdssbauer spectroscopy, ellipsometry, etc., are described in [I I], while electron spin resonance is discussed in [12], radiotracer in [13], scanning tunneling microscopy in [14], and scanning electrochemical microscopy in [15]. The fundamentals of electrochemical impedance spectroscopy are treated in [1,2,16] however, the different models elaborated for electrochemically active films and membranes can be found in various papers (see later), while the most important methods for analyzing impedance spectra, as reported before 1994, are well summarized in [3]. Nevertheless, the essential elements of these techniques are briefly discussed here, in order to help the reader to understand the experimental material presented in this book. 

The properties and applications of microelectrodes, as well as the broad field of electroanalysis, have been the subject of a number of reviews. Unwin reviewed the use of dynamic electrochemical methods to probe interfacial processes for a wide variety of techniques and applications including various flow-channel methods and scanning electrochemical microscopy (SEM), including issues relating to mass transport (1). Williams and Macpherson reviewed hydrodynamic modulation methods and their mass transport issues (2). Eklund et al. reviewed cyclic voltammetry, hydrodynamic voltammetry, and sono-voltammetry for assessment of electrode reaction kinetics and mechanisms with discussion of mass transport modelling issues (3). Here, we focus on applications ranging from measnrements in small volumes to electroanalysis in electrolyte free media that exploit the uniqne properties of microelectrodes. 

Under appropriate conditions, the faradaic current may be used to form images of the electrochemical reactivity of a surface. This is known as scanning electrochemical microscopy (SECM), where the transport and heterogeneous redox activity of species within the junction mediate the tip-substrate interaction. This subject has been thoroughly reviewed [43,44], and an excellent paper demonstrating the transition from STM to SECM is available [45]. The possible contribution of confined redox species to resonant tunneling has also been examined [19,46,47]. 

Cathodic disbonding has recently been the subject of many investigations. Different methods are used for this, most frequently electrochemical impedance spectroscopy (Mansfeld, 1989 UmeyamaandTakai, 1989), scanning acoustic microscopy (Kendig et al., 1989), ellipsometry (Ritter and Kruger, 1980 Ritter, 1984), and the method of labeled atoms (Parks and Leidheiser, 1986). 

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