Understanding the formation of surface relief gratings in azopolymers: A combined molecular dynamics and experimental...

The formation of surface relief gratings in thin azopolymeric films is investigated using atomistic molecular dynamics simulations and compared to experimental results for the specific case of poly-disperse-orange3-methyl-methacrylate. For this purpose, the film is illuminated with a light pattern of alternating bright and dark stripes in both cases. The simulations use a molecular mechanics switching potential to explicitly describe the photoisomerization dynamics between the E and Z isomers of the azo-units and take into account the orientation of the transition dipole moment with respect to the light polarization. Local heating and elevation of the illuminated regions with the subsequent movement of molecules into the neighboring dark regions are observed. This leads to the formation of valleys in the bright areas after re-cooling and is independent of the polarization direction. To verify these observations experimentally, the azopolymer film is illuminated with bright stripes of varying width using a spatial light modulator. Atomic force microscopy images confirm that the elevated areas correspond to the previously dark areas. In the experiment, the polarization of the incident light makes only a small difference since tiny grain-like structures form in the valleys only when the polarization is parallel to the stripes.