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Appl Phys Lett 79(15):2357 2359 Henneberg O, et al 2001b Formation and dynamics of polymer surface relief gratings Appl Surf Sci 182(3 4):272 279 Henneberg O, Geue T, Rochon P, Pietsch U 2003 X ray and VIS light scattering from light induced polymer gratings J Phys D Appl Phys 36(10A):A241 A244 Henneberg O, Geue T, Pietsch U, Saphiannikova M, Winter B 2004 Investigation of azobenzene side group orientation in polymer surface relief gratings by means of photoelectron spectroscopy Appl Phys Lett 84(9):1561 1563 Ho MS, Natansohn A, Rochon P 1995 Azo polymers for reversible optical storage 7 The effect of the size of the photochromic groups Macromolecules 28(18):6124 6127 Holme NCR, Nikolova L, Ramanujam PS, Hvilsted S 1997 An analysis of the anisotropic and topographic gratings in a side chain liquid crystalline azobenzene polyester Appl Phys Lett 70(12):1518 1520 Holme NCR, et al 1999.

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The photoexcited thionone, *Thi + is reduced by Fe 2 + to the unstable semithionine (Sem + ) which further disproportionates to Thi + and the doubly reduced form of thionine, leucothionine (Leu 2 + ): (5.10.9) (5.10.10) The anodic reaction (taking place in the illuminated cell compartment) is a two-electron process regenerating the initial form of Thi + : Leu 2+ -* Thi+ + 2e" + 3H + (5.10.11) *Thi Fe 2Sem +

Optically induced surface relief phenomena in azobenzene polymers Appl Phys Lett 74(4):519 521..

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(a) (b) Fig. 5.58 Scheme of a photogalvanic cell. The homogeneous photoredox process takes place in the vicinity of the optically transparent anode (a) or cathode (b) The two-electron oxidation of the dye is not very common; other dyes usually undergo one-electron redox reactions. The cathodic reaction (taking place in the non-illuminated cell compartment) regenerates the complementary redox system: Fe 3+ + e"- Fe 2 + (5.10.12) According to the reactions (5.10.9)-(5.10.12), we can classify this cell as a regenerative (AG = 0) photogalvanic cell based on reductive quenching (Fig. 5.58a). Good performance of the iron-thionine cell is conditioned by the generation of *Thi+ (and Leu2+) in close vicinity (below ca. 1 jum) of the anode; this can be achieved by using an optically transparent (e.g. SnO2) anode as a window (Fig. 5.58). The selectivity of the anode and cathode for the desired reactions (5.9.24) and (5.9.25) may be further increased by selecting the proper electrode materials or by chemical modification of the anode. A regenerative photogalvanic cell with oxidative quenching (Fig. 5.58b) is based, for example, on the Fe 3+ -Ru(bpy)| + system. In contrast to the iron-thionine cell, the homogeneous photoredox process takes place near the (optically transparent) cathode. The photoexcited *Ru(bpy)l+ ion reduces Fe3+ and the formed Ru(bpy)3+ and Fe 2+ are converted at the opposite electrodes to the initial state. More complicated photogalvanic cells may employ two light absorbing systems: one in the cathodic process and the other in the anodic process. An

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Hore DK, Natansohn AL, Rochon PL 2003 Anomalous cis isomer orientation in a liquid crystalline azo polymer on irradiation with linearly polarized light J Phys Chem B 107(10):2197 2204 Hubert C, Fiorini Debuisschert C, Maurin I, Nunzi JM, Raimond P 2002a Spontaneous patterning of hexagonal structures in an azo polymer using light controlled mass transport Adv Mater 14(10):729 Hubert C, et al 2002b Micro structuring of polymers using a light controlled molecular migration processes Appl Surf Sci 186(1 4):29 33 Ikawa T, et al 2000 Optical near eld induced change in viscoelasticity on an azobenzene containing polymer surface J Phys Chem B 104(39):9055 9058 Ikawa T, et al 2001 Azobenzene polymer surface deformation due to the gradient force of the optical near eld of monodispersed polystyrene spheres Phys Rev B 64(19) Ikeda T, Nakano M, Yu Y, Tsutsumi O, Kanazawa A 2003.

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