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- Holographic Investigation of Azobenzene-Containing Low-Molecular-Weight Compounds (2011)
- In the present thesis, holographic volume and surface relief gratings in azobenzene-containing low-molecular-weight compounds are investigated to obtain a broader understanding of this new class of material. Azobenzene chromophores undergo light-induced trans-cis-trans isomerization cycles leading to a reorientation of the long axis of the chromophores. If linearly polarized light is incident on the sample, these isomerizations result in a reorientation of this axis perpendicular to the light polarization. A holographic light grating, which can be formed by the interference of two coherent laser beams, leads to the inscription of a refractive-index modulation in the material. The azobenzene-containing low-molecular-weight compounds studied in this thesis consist of different building blocks: the core unit, the azobenzene chromophores with substituents, and the spacer and the linkage group between chromophore and core unit. These components can be used in a modular-design principle to synthesize a large library of low-molecular-weight compounds. Surprisingly, some of the investigated low-molecular-weight compounds form also a liquid-crystalline phase besides the amorphous phase as evidenced by polarized microscopy. If these liquid-crystalline compounds are prepared as solid films, however, they are quenched to an amorphous state. Upon reorientation of the azobenzene chromophores by illumination with a holographic light grating, a phase transition from the amorphous to an ordered state can be induced. This phase change in the latent liquid-crystalline low-molecular-weight compounds is very interesting for applications. The latent liquid-crystalline low-molecular-weight compounds show a post-development of the refractive-index modulation after the writing process. The holographic gratings are even stable at temperatures higher than the glass transition temperature, which further proves the light-induced formation of an ordered domain. In contrast to their polymeric counterparts, molecular materials are expected to show a faster response to light because of the absence of polymer chain entanglements. Therefore, molecular glasses can be used as blending material for photo-addressable polymers to improve the photo-sensitivity of the blend as compared to the pure polymer. The influence of the core and the substituent was investigated in low-molecular-weight compounds which do not form liquid-crystalline phases. An azobenzene-containing diblock copolymer for holographic data storage consists of an inert majority block and a minority block containing the covalently bound photo-sensitive azobenzene chromophores. Blending a few weight percent of the optimized molecular glass to the diblock copolymer leads to an increase of sensitivity with increasing content of the molecular glass, mainly because the writing time to the maximum of the refractive-index modulation decreased. The increase of the sensitivity is much larger than the observed rise of the refractive-index modulation due to the higher concentration of azobenzene chromophores. It was demonstrated that the shorter writing times are not caused by thermal effects, the molecules of the molecular glass in the inert block, or by changes of the free volume or the morphology, but that they are due to the azobenzene chromophores of the molecular glass in the minority block. They reorient faster than the chromophores attached to the polymer backbone and, thereby create free volume. Additionally, they can assist the reorientation of the azobenzene chromophores bound to the polymer by cooperative effects, i.e. dipolar and steric interactions. Both effects result in shorter writing time and higher sensitivity of the system. In a blend containing two weight percent of the molecular glass, the inscribed gratings are still long-term stable and the sensitivity increases by a factor of 1.7 as compared to the pure diblock copolymer. Upon illumination of an azobenzene-containing material with a holographic light grating, besides the volume grating, also a surface relief grating can develop. Surface modulations with heights of up to 600 nm were achieved in molecular glasses. It was found that the build-up of the surface relief grating depends on the electrical susceptibility of the material at the optical frequency of the laser and the polarization of the laser beams. These experimental findings are in agreement with the gradient force model. According to this theory, the macroscopic material transport results from the forces on the polarized material in the electrical field gradient caused by the holographic light grating. For many applications it is important that the holographically produced surface relief gratings can be transferred to polymer surfaces. Replica molding can be used to easily copy the surface modulations to e.g. polycarbonate.