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The influence of molecular architecture on light-induced SRG formation was investigated. Polymers with different degree of branching were synthesized by ATRP and functionalized with azobenzene chromophores. The polymers differ only in their architecture - linear, 4-, 6-, or 12-arms stars. The photo-induced dichroism as well as the efficiency of SRG formation was similar for all polymers of this series. New consideration for the origin of the driving force was used to explain this behavior. The comparable SRG inscription rate in differently branched polymers can be rationalized by assuming that azobenzene acts as an internal molecular motor and can cause a non-turbulent motion on a scale smaller than that on which normal entanglement restriction forces act.
The influence of the azobenzene concentration on the photo-induced surface relief grating (SRG) formation in polymer films was investigated. Two series of polymers with 4-alkoxy-4'-cyanoazobenzene side groups were synthesized. In series A, the degree of substitution was varied, while in series B, azobenzene and biphenyl groups were introduced in varying composition, but the concentration of non-reacted HEMA-groups was kept constant. Photo-induction of the dichroism and the SRG was studied as function of the azobenzene concentration. An optimum was found for the SRG formation (76%), while the highest dichroism was induced at the lowest azobenzene concentration of 20%. The restriction of rotational and translational molecular motions observed at higher azobenzene concentration was explained by pi-pi stacking of the azobenzene moieties and interaction of unreacted HEMA groups