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LC droplet configuration Multilayer film Normal LC Azo LC no no Polymer LC droplets Polymer Microstructure (a)
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Figure 11.29. (a) Schematic illustration of the re ection grating prepared with HPDLCs. The azobenzene compound dissolved in the LC droplets changes the LC order state upon UV and visible light irradiation. (b) Transmission spectra of an HPDLC-based re ection grating showing the optically switchable selective re ection in and without the absence of an electric eld. Source: Urbas et al., 2004b. Adapted with permission.
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The as-prepared grating has a high index modulation between polymer regions and the regions containing con ned LC droplets in which LC molecules are aligned; a re ection peak at B530 nm can be observed. In this state, exposure of the grating to UV light induces the nematic isotropic phase transition inside the
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droplets, and the reduced index modulation results in a decrease in diffraction ef ciency. Subsequent visible light exposure recovers the initial re ection ef ciency. However, the re ection of the as-prepared grating can be turned off by applying an electric eld that aligns LC molecules inside the droplets to change the index modulation. With the grating under a voltage, the re ection can be switched on using UV light and switched off using visible light.
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The reversible trans cis photoisomerization of azobenzene can be explored in designing materials for tunable diffraction gratings. On one hand, the photoisomerization can be used as the trigger for the structural rearrangement in the material leading to the periodic change in refraction index required for the diffraction grating. This is the case of ATEs used for mechanically tunable diffraction gratings and self-assembled LC gels containing an azobenzene gelator used for electrically switchable gratings. On the other hand, the photoisomerization-induced LC-to-isotropic phase transition can be utilized for optically controllable diffraction gratings based on both PDLC and PSLC. For mechanically controllable diffraction gratings, the advantage of thermoplastic elastomers is the easy lm preparation through solution casting or meltstate processing. To obtain a stable diffraction grating, a permanent structural rearrangement or reorganization in the lm needs to be induced by the photoisomerization. In the case of azo-SCLCP-grafted SBS, the authors study found that such structural rearrangement is more likely to occur in a lm under large strain, in which the optical plasticization of azobenzene polymer microdomains could facilitate the rearrangement of PS cylindrical microdomains acting as physical cross-links. In light of this, if azo-SCLCP constitutes the rigid cylindrical microdomains (like the triblock copolymer in Fig. 11.3), the photoisomerization, under strain, may give rise to a more important softening effect on the physical cross-links and thus trigger the structural rearrangement. It would be interesting to design ABA triblock copolymers, whose azo-SCLCP microdomains (A block) can undergo important optical plasticization upon illumination, and to investigate the resulting structural changes. One challenge here is to obtain ABA-type ATE that can exhibit large reversible deformation like that of SBS. Another future study of interest is to investigate in detail the reversible transition between Raman Nath (transmission) and Bragg (re ection) diffraction regimes. For instance, to prepare a grating with a period of 1 mm in a nonstretched lm of, say, 200-mm thickness, a grating with 6-mm period can be recorded on the lm stretched to 500% deformation with the thickness decreased to B82 nm. Therefore, under 500% strain, the grating should be in the thin lm regime (Raman Nath diffraction), whereas in the relaxed state, it should be in the thick lm regime (Bragg). The reversible transition between the two regimes can easily be investigated using ATE. Our preliminary observation found that the transition
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