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The rate of the oxidation reaction (i.e. the amount of substance oxidized per unit surface area per unit time) is given by the relationship (cf. Eq. 5.2.3) Va = kaCRed and the rate of the reduction reaction by the relationship vc = kccOx (5.2.7) (5.2.6)

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The authors mentioned two differences in behavior in contrast to azobenzenecontaining polymers, namely, bleaching during SRG inscription (azodyes, in particular Congo Red, were photochemically not so stable as azobenzene-containing polymers) and recording ef ciency independence on polarization con guration of the writing beams. The authors mention here well-known (Brown, 1971) property of azobenzene derivatives with OH or NH2 group in ortho-position. The photochemistry of such derivatives is dominated by phototautomerization through proton transfer, leading to bleaching. Very thin LbL lms of (Direct Red 80)/PDADMAC consisting of 20 layers exhibited only 5-nm deep SRG and that required 3-h exposure (Kaneko et al., 2002; Shinbo et al., 2002). Generally one cannot expect much higher modulation depth in the lms of 15-nm thickness. Otherwise, when thick lms consisting of 600 layers of Brilliant Yellow alternated with either PDAMAC or PAH were used (Zucolotto et al., 2003), higher amplitude of 120 nm has been achieved after 1-h exposure. It may be adverted here for comparison to the formation of the ionic complex using the same azodye (Brilliant Yellow), discussed later in more detail, where SRGs with DE of 15% have been inscribed at the comparable conditions (Stumpe et al.,

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The oxidized and reduced forms can be dissolved in the electrolyte but can also be present as a solid phase (metal, insoluble compound) In the latter case, the concentration of these electroactive substances is constant and is set by convention equal to unity The reduced form can also be dissolved in the form of an amalgam in mercury representing the electrode material The rate of the electrode process similar to other chemical reactions depends on the rate constant characterizing the proportionality of the rate to the concentrations of the reacting substances As the charge transfer reaction is a heterogeneous process, these constants for first-order processes are mostly expressed in units of centimetres per second Similarly as for chemical reactions, the rate constants of the electrode reactions can be written in terms of the Arrhenius equation (528) (52.

2006a) In contrast to the results with Congo Red (He et al, 2000), strong dependence on the polarization con guration of the writing beams was observed for the layers with Brilliant Yellow (Zucolotto et al, 2003) It evidences different mechanisms of SRG formation Also, according to the authors (Zucolotto et al, 2003), bleaching is less important in the case of Brilliant Yellow in comparison with Congo Red, as already discussed The results with azobenzene-containing polyelectrolyte-based LbL structures were even less encouraging Strong ionic bonds between the layers were presumed to be responsible for working against the light-driven mass transport process, which is initiated at the sample surface (Lee et al, 2000) Using postdeposition owing to azo coupling, it was possible to obtain LbL layers of PAA-AN (Fig 28), where rather shallow SRG with pick-to-valley height of 25 nm could be written.

9) where Pa and Pc are the pre-exponential factors which are independent of the electrode potential, and A/ a and AHC are the activation enthalpies of the oxidation (anodic) and reduction (cathodic) electrode reactions, respectively The wavy line indicates that these quantities depend on the electric potential difference between the electrode and the solution, A0 = 0(m) 0(1) Since, according to Eq (3169), this quantity is identical, except for a constant, with the electrode potential, A$ = E constant, the activation + enthalpy depends on the electrode potential As demonstrated in a number of experiments, the rate of the electrode reaction is approximately an exponential function of the electrode potential; the rate of the cathodic (reduction) electrode reaction increases towards negative electrode potential values, while the rate of the anodic (oxidation) electrode reaction increases with increasing (positive) electrode potential.

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