Photoinduced orientations of azobenzene chromophores in two distinct holographic diffraction gratings as studied by polarized Raman confocal microspectrometry

Abstract

Optically isotropic thin films (0.5 μm) of an amorphous side-chain copolymer containing 10% azobenzene moieties and 90% meso-azobenzene groups (K1-10 sample) were irradiated by two interfering orthogonal (±45°) or parallel (p + p) linearly polarized laser beams; permanent holographic diffraction gratings were thus inscribed. From atomic force microscopy (AFM) measurements, relatively weak amplitudes (about 50–60 nm) in the surface relief modulation (SRM) are detected but strong perturbations in the profiles and new substructures are evidenced at half-period positions. Using a confocal microspectrometric technique we have recorded various pre-resonance enhanced polarized Raman spectra from a large grating area and obtained spatially resolved Raman images of the intensity variations. This yields new insight into the photoinduced orientation effects, the angular distributions of the chromophore species, and finally the grating formation mechanisms. Different theoretical equations of the polarized Raman scattering intensities, taking account of the pump polarization directions and the high numerical aperture objective used, are derived. Then, an analysis of the experimental results allows us to extract values of the second 〈P₂〉 and fourth 〈P₄〉 coefficients in the chromophore orientation functions at several positions of the SRM, in particular at the top and bottom regions, and to calculate the corresponding normalized distribution functions ia information entropy theory. In both gratings, somewhat broader distributions are found in the bottom regions, regions of greater polymer removal. Thus, mass-transport phenomena have perturbed, to a weak extent in the (±45°) first case and to a larger extent in the (p + p) second case, the primary photoinduced orientations. So, two simultaneous and superimposed mechanisms appear to be responsible for the observed complex SRM in the highly birefringent K1-10 copolymer under study and significant second-order contributions are suggested. The grating surface profiles are thus reproduced by fitting the SRM amplitudes at the fundamental and doubled frequency and the corresponding phase constant parameters: a good agreement between the observed (AFM) and simulated profiles is obtained.