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Kim M J, Seo E M, Vak D, Kim D Y 2003 Photodynamic properties of azobenzene molecular lms with triphenylamines Chem Mater 15(21):4021 4027 Kumar GS, DePra P, Zhang K, Neckers DC 1984 Chelating copolymers containing photosensitive functionalities 2 Macromolecules 17(12):2463 2467 Kumar J, et al 1998 Gradient force: the mechanism for surface relief grating formation in azobenzene functionalized polymers Appl Phys Lett 72(17):2096 2098 Labarthet FL, Buffeteau T, Sourisseau C 1998 Analyses of the diffraction ef ciencies, birefringence, and surface relief gratings on azobenzene containing polymer lms J Phys Chem B 102(15):2654 2662 Labarthet FL, Rochon P, Natansohn A 1999 Polarization analysis of diffracted orders from a birefringence grating recorded on azobenzene containing polymer Appl Phys Lett 75(10):1377 1379 Labarthet FL, et al 2000 Photoinduced orientations of azobenzene chromophores in two distinct holographic diffraction gratings as studied by polarized Raman confocal microspectrometry Phys Chem Chem Phys 2(22):5154 5167.

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respectively. SHE is the energy level of the standard hydrogen electrode referred to e0 (see Section 3.1.5). The energy levels of several redox couples as well as the positions of the band edges of typical semiconductors in equilibrium with aqueous electrolyte (pH 7) are compared in Fig. 5.59. The electrochemical potential of an electron in a solid defines the Fermi energy (cf. Eq. 3.1.9). The Fermi energy of a semiconductor electrode (eF) and the electrolyte energy level (VREDOX) are generally different before contact of both phases (Fig. 5.60a). After immersing the semiconductor electrode into the electrolyte, an equilibrium is attained:

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Labarthet FL, Buffeteau T, Sourisseau C 2001 Time dependent analysis of the formation of a half period surface relief grating on amorphous azopolymer lms J Appl Phys 90(7):3149 3158 Labarthet FL, Bruneel JL, Buffeteau T, Sourisseau C 2004 Chromophore orientations upon irradiation in gratings inscribed on azo dye polymer lms: a combined AFM and confocal Raman microscopic study J Phys Chem B 108(22):6949 6960 Lagugne Labarthet F, Buffeteau T, Sourisseau C 2002 Optical erasures and unusual surface reliefs of holographic gratings inscribed on thin lms of an azobenzene functionalized polymer Phys Chem Chem Phys 4(16):4020 4029 Lagugne Labarthet F, Bruneel JL, Rodriguez V, Sourisseau C 2004 Chromophore orientations in surface relief gratings with second order nonlinearity as studied by confocal polarized Raman microspectrometry J Phys Chem B 108(4):1267 1278 Lee S H, et al 2000 Azo polymer multilayer lms by electrostatic self assembly and layer by layer post azo functionalization.

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Macromolecules 33(17):6534 6540 Lee TS, et al 1998 Photoinduced surface relief gratings in high Tg main chain azoaromatic polymer lms J Polym Sci, Part A: Polym Chem 36(2):283 289 Le n P, Fiorini C, Nunzi JM 1998a Anisotropy of the photo induced translation diffusion of azobenzene dyes in polymer matrices Pure Appl Opt 7(1):71 82 Le n P, Fiorini C, Nunzi JM 1998b Anisotropy of the photoinduced translation diffusion of azo dyes Opt Mater 9(1 4):323 328 Leopold A, et al 2000 Thermally induced surface relief gratings in azobenzene polymers J Chem Phys 113(2):833 837 Li XT, Natansohn A, Rochon P 1999 Photoinduced liquid crystal alignment based on a surface relief grating in an assembled cell Appl Phys Lett 74(25):3791 3793 Matsumoto M, et al 1998 Reversible light induced morphological change in Langmuir Blodgett lms J Am Chem Soc 120(7):1479 1484.

The equilibration proceeds by electron transfer between the semiconductor and the electrolyte. The solution levels are almost intact ( R E D O X REDOX)> since the number of transferred electrons is negligible relative to the number of the redox system molecules (cox and cred). On the other hand, the energy levels of the semiconductor phase may shift considerably. The region close to the interface is depleted of majority charge carriers and the energy bands are bent upwards or downwards as depicted in Fig. 5.60b. The equilibrium potential between the bulk of the semiconductor and the bulk of the electrolyte (Galvani potential, Af$) is expressed by Eq. (4.5.6). e(eV) 0

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Mechau N, Neher D, Borger V, Menzel H, Urayama K 2002 Optically driven diffusion and mechanical softening in azobenzene polymer layers Appl Phys Lett 81(25): 4715 4717..

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Mechau N, Saphiannikova M, Neher D 2005 Dielectric and mechanical properties of azobenzene polymer layers under visible and ultraviolet irradiation Macromolecules 38(9):3894 3902 Mechau N, Saphiannikova M, Neher D 2006 Molecular tracer diffusion in thin azobenzene polymer layers Appl Phys Lett 89(25):251902 3 Mitus AC, Pawlik G, Miniewicz A, Kajzar F 2004 Kinetics of diffraction gratings in a polymer matrix containing azobenzene chromophores: experiment and Monte Carlo simulations Mol Cryst Liq Cryst 416:113 126 Moniruzzaman M, Sabey CJ, Fernando GF 2004 Synthesis of azobenzene based polymers and the in situ characterization of their photoviscosity effects Macromolecules 37(7):2572 2577 Nagata T, Matsui T, Ozaki M, Yoshino K, Kajzar F 2001 Novel optical properties of conducting polymer photochromic polymer systems Synth Met 119(1 3):607 608 Nakano H, Takahashi T, Kadota T, Shirota Y 2002 Formation of a surface relief grating using a novel azobenzene based photochromic amorphous molecular material.

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