The photoinduced 3D orientational structures in films of a liquid crystalline polyester, containing azobenzene side groups, are studied both experimentally and theoretically. By using the null ellipsometry and the UV/Vis absorption spectroscopy, the preferential in-plane alignment of the azobenzene fragments and in-plane reorientation under irradiation with linearly polarized UV light are established. The uniaxial and biaxial orientational order of the azobenzene chromophores are detected. The biaxiality is observed in the intermediate stages of irradiation, whereas the uniaxial structure is maintained in the photosaturated state of the photo-orientation process. The components of the order parameter tensor of the azobenzene fragments are estimated for the initial state and after different doses of irradiation. The proposed theory takes into account biaxiality of the induced structures. Numerical analysis of the master equations for the order parameter tensor is found to yield the results that are in good agreement with the experimental dependencies of the order parameter components on the illumination time

We apply experimental technique based on the combination of methods dealing with principal refractive indices and absorption coefficients to study the photoinduced 3D orientational order in the films of liquid crystalline (LC) azopolymers. The technique is used to identify 3D orientational configurations of trans azobenzene chromophores and to characterize the degree of ordering in terms of order parameters. We study two types of LC azopolymers which form structures with preferred in-plane and out-of-plane alignment of azochromophores, correspondingly. Using irradiation with the polarized light of two different wavelengths we find that the kinetics of photoinduced anisotropy can be dominated by either photo-reorientation (angular redistribution of trans chromophores) or photoselection (angular selective trans-cis isomerization) mechanisms depending on the wavelength. At early stages of irradiation the films of both azopolymers are biaxial. This biaxiality disappears on reaching a state of photo-saturation. In the regime of photoselection the photo-saturated state of the film is optically isotropic. But, in the case of the photo-reorientation mechanism, anisotropy of this state is uniaxial with the optical axis dependent on the preferential alignment of azochromophores. We formulate the phenomenological model describing the kinetics of photoinduced anisotropy in terms of the isomer concentrations and the order parameter tensor. We present the numerical results for absorption coefficients that are found to be in good agreement with the experimental data. The model is also used to interpret the effect of changing the mechanism with the wavelength of the pumping light.

We applied ellipsometry to study the distribution of azobenzene fragments in the films of two types of comblike polymers with azobenzene moieties in the side chains before and after ultraviolet (UV) light irradiation. The polymer with an alkyl chain at the end of the azobenzene fragment forms structures with preferred homeotropic alignment of the fragments. Irradiation of this polymer with nonpolarized UV light at normal incidence induces a homeotropic alignment of azobenzene fragments. Oblique irradiation induces tilted structures. Polarized UV light irradiation at normal beam incidence induces biaxial structures with a fanlike distribution of azobenzene fragments and preferably out-of-plane alignment. The polymer with polar nitro group at the end of the azobenzene moiety shows preferential in-plane orientation. The degenerate in-plane alignment is retained for normal irradiation with nonpolarized UV light. Excitation with polarized light provides highly ordered in-plane alignment of the azobenzene fragments perpendicular to the UV light polarization. Re-orientation of the fragments under a second UV exposure with orthogonal polarization involves out-of-plane rotation of the fragments.

The combination of transmission null ellipsometry (TNE) and attenuated total reflection (ATR) methods supported by absorption measurements is shown to be an effective tool to study spontaneous and photoinduced 3D order in azopolymers. We investigated a series of azobenzene containing side-chain polyesters differing by the length of the main-chain spacer (CH2) m (m = 2, 8, 9, 10, 12, 13, 14, 16) and the tail substitutes (NO2, OCH3, and OC4H9) in azochromophore. The 3D order was induced by monochromatic polarized light of several wavelengths strictly distinguished by absorption efficiency of azochromophores. The orientational order under irradiation and after irradiation is studied. A big variety of 3D orientations (biaxial, uniaxial, and isotropic) is realized. The uniaxial and isotropic configurations correspond to the initial state and the saturation state of irradiation, while biaxiality is an attribute of the transient orientations. It is shown that both initial and photoinduced 3D orders are strongly determined by molecular structure of azopolymers. If we exclude the case of ultrathin polymer films (d < 200 nm), the observed regularities can be summarized as follow. The homologues with NO2 tail group and m > 8 demonstrate strong preference for in-plane alignment, which is random in the initial state and uniaxially ordered in the saturated state of irradiation. The change of the tail substitute in the succession NO2 → OCH3 → OC4H9 leads to transition from the in-plane to the out-of-plane alignment of azochromophores (nonirradiated films), increase of the tendency of isotropic ordering (excitation within ππ* absorption band), and transition from the positive (prolate) to the negative (oblate) in-plane uniaxial order (excitation within nπ* absorption band). The observed regularities are explained by competition of photoorientation determined by symmetry of light and intrinsic self-organization determined by the structure of polymer molecules.