Dynamical experimental studies on the diffraction efficiencies and the formation of birefringence grating and surface relief grating on doped and/or covalently bonded azobenzene derivatives containing polymer films were carried out using laser beams with different polarizations. From polarization analyses of the first-order ((1) diffracted beams, the contributions to the diffraction efficiency are separated into an anisotropic (or birefringence) part and a surface relief part. During the growth of the gratings the dynamical responses of both contributions appear to be quite distinct, and estimates of the time variations of the anisotropic phase shift, ∆ , due to the induced birefringence and of the surface relief height, 2∆d, due to the polymer mass transport are obtained. Calculations and simulations of the theoretical expressions allow us to confirm the experimental findings and to reproduce all the observed polarized first-order diffraction curves with good agreement, even when the surface relief is important in the covalently bonded azobenzene polymer films. In these functionalized systems we thus conclude that very efficient permanent surface relief gratings are formed using right-circular and left-circular interfering laser beams.

ABSTRACT:In situ dynamical study of the photoinduced orientation of the DR1 azobenzene derivative in a doped PMMA matrix and in p(DR1A-co-MMA) copolymers was carried out using real-time visible and infrared spectroscopies. The different mechanisms occurring during the photoisomerization cycles were highlighted by following the time dependence of the normalized average absorbance (T 0), the normalized linear dichroism (T2) and the order parameter (P2) during the orientation (laser on) and the relaxation (laser off) periods. The thermal cis-trans back-relaxation and the angular redistribution were followed separately from the T0 and T2 relaxation curves, respectively. The orientation and relaxation curves were fitted by the Kohlrausch-Williams-Watts (KWW) function in order to compare the rate constant and the distribution width for various samples. On one hand, the chromophore-matrix interactions were investigated in doped systems by changing the tacticity of the PMMA matrix. On the other hand, the chromophore-chromophore interactions in functionalized polymers were studied by changing the concentration of azobenzene units in copolymer systems.

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