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transport the material by light, certain stiffness is necessary to prevent any relaxation of the induced relief structure. The compromise between these opposite effects has to be found for effective grating formation. Thermal treatment is only one of the possible ways to shift this equilibrium. As expected, the gratings recorded in ionic materials are thermally very stable. After heating the sample to 1001C, they remained stable with ZnormE90%, where Znorm=Zheated/Zrecorded. Heating to 1501C erased the grating to ZnormE75%, but even after heating the sample to 2001C, ZnormE40% retained. The grating could not be written again onto the thermally treated lm that may be explained by further sol gel condensation, which increases the rigidity of the matrix. Thus the latter approach combines a very high ef ciency of SRG formation with a high stability of the induced surface structures provided by the simultaneously formed polymer network. Another example of the additional functionalization of the supramolecular material presents the H-bonded system, where the azobenzene moieties can be detached from the polymer chains and even removed from the lm (Zettsu et al., 2008). The removal of the strongly colored azobenzene derivative is of particular advantage for the applications such as liquid crystal alignment layer. Chemical structure of the H-bonded complex is shown in Fig. 2.4c. The complex exhibited a single glass transition at 91C and complicated subsequent mesophase at temperatures up to 1091C. In the temperature region of liquid crystalline phase, a smectic phase was formed. Spin-coated lms of typical thickness, 50 nm, were prepared. Very characteristic for the material was that the E Z photoisomerization caused the phase transition from the liquid crystalline phase to isotropic melt in the lm. It has been veri ed that the photoisomerization and the associating phase transition did not break the hydrogen bonding. When the formation of intermolecular H-bonds was insuf cient, the ef ciency of SRG formation reduced drastically. Most effectively the SRGs were inscribed in the smectic mesophase. Remarkably, the relief height of 110 nm was obtained, starting from an originally 50-nm thick lm. Another characteristic feature of the SRG formation in this material is its polarization independence. The authors classi ed the mechanism of mass transfer in the H-bonded material as phototriggered surface relief formation rather than a photoinduced one, similar to the functionalized polymer reported earlier (Zettsu et al., 2007). This phototriggered process has been observed only for azobenzene polymers exhibiting a liquid crystal phase at the ambient temperature, independently of the polymer architectures (Zettsu and Seki, 2004). The selective extraction of azobenzene units from the lm was performed after the chemical post xation of the SRG structure. The strategy of this process is indicated in Fig. 2.19. The extraction of azobenzene derivative was followed by a drastic reduction in the height of SRG from 250 to 50 nm, approximately corresponding to the loss of mass. The authors reported that their attempts to recover the volume contraction by adapting hydrogen accepting guest molecules were not successful. Anyway, the extraction of azobenzene from the SRG has demonstrated the additional functionality granted by the supramolecular character of the material.
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: Azobenzene molecule with H-bond acceptor group : Host-soft polymer with H-bond donor group : Cross-linking bond
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Figure 2.19. Schematic illustration of the SRG formation in an H-bonded supramolecular liquid crystalline polymer lm and the strategy for the selective detachment of azobenzene unit. Source: Zettsu et al., 2008. Reproduced with permission from Wiley-VCH.
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In this chapter, the authors have reviewed the very recent results on photoinduction of anisotropy and SRGs in azobenzene-based supramolecular materials. They have tried to discuss these results starting from and in the framework of other materials well known for these phenomena, like low-weight molecular compounds
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