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substrate (Mensinger et al., 1992) in a smectic polymer lm. The thicknessdependent orientational change of the nanocylinders observed here seems to be closely related to these phenomena. Then the two types of holographic irradiation [(p-:p-) and (s-:s-)] are performed. When the thickness after the migration is adjusted as to be above and below 70 nm in the thick and thin regions, respectively, the out-of-plane control is achieved, namely, the cylinders align normal or parallel to the substrate plane depending on the relief thickness. The difference in the holographic irradiation mode of (p-:p-) and (s-:s-) leads to contrasting in-plane orientations of the laid cylinders in the thin regions. The (p-:p-) and (s-:s-) mode interferences provide cylinders oriented parallel and orthogonal to the relief undulations, respectively (scheme shown in Fig. 8.21). Thus, both out-of-plane and in-plane orientations of MPS structure are controlled by the simple interference irradiation of laser beam. It is stressed here that a single irradiation leads to the formation of three different hierarchy levels, namely, the molecular orientation (subnanometer level), MPS structure (several 10 nm), and SRG (micrometers).
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This chapter summarizes several topics that are currently progressing in the research areas of photoresponsive monolayers and LC ultrathin polymer lms. The surface photoalignment method using command surface is now extending to a branch of organic inorganic nanohybrid systems. Thus, surfacemediated processes provide new opportunities to exert micropatterning of simple components to various composite systems. Such approaches would be of particular use in fabrication of optical devices. Surface-grafted LC photoresponsive polymer lm can be a new target of LC lm research. The orientation of the Az mesogenic group strongly in uences the photoresponse behavior and sensitivity. Since the planar-arranged Az mesogens should be more sensitive to LPL, fabrications of highly sensitive photorecording media may be realized. Furthermore, smart photoresponse functions such as photoswitchable anisotropic friction properties may be anticipated. In the LC molecular and polymer assembly systems, the light trigger is effectively converted into the molecular motions to induce orientation and migration in cooperative manners. Motions are basically driven by thermal selfassembly processes of the soft materials. Suggestive examples can be seen in the mass migration systems. In the LC PT type, the relief formation is most likely to be the consequence of the microscopic deformation of the lm occurring at the LC isotropic interface formed within the lm. This situation is in marked contrast to the migration mechanism in the conventional amorphous materials. As shown here, the detachment of Az chromophore (bleaching the color) will be a promising strategy to expand optical applications of the photogenerated relief structure. With respect to the alignment control, the marked research advance in the block copolymer systems is to be emphasized. Here, the photoalignment is not
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limited at the molecular level but ampli ed to regulate the MPS structure of the larger feature size. Understanding the interplay between different size hierarchies with retention of dynamic features should be a signi cant issue to create future soft materials. The nanopatterned surface of block copolymer lms can be applied as a template surface to fabricate various functional materials, including biological macromolecules (Kumar and Harn, 2005), conjugated polymers (Goren and Lennox, 2001), inorganic materials (Kim et al., 2004; Spatz et al., 1998), and metals (Fahmi and Stamm, 2005). When such patterns are tuned by light, more complicated and hierarchical structures that will be more suited for device fabrication would be realized. The topics dealt with in this chapter are mostly limited to 2-D systems, but the ultimate goal would be to create sophisticated dynamic 3-D systems similar to the biological ones. It is anticipated that studies on the motions of photoresponsive lms in the assembled states can give proper clues to such future directions.
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