12: AZO BLOCK COPOLYMERS IN THE SOLID STATE in Java

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CHAPTER 12: AZO BLOCK COPOLYMERS IN THE SOLID STATE
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Figure 12.14. Photoinduced alignment of PEO nanocylinders in azo LCBC lms as a result of SMCM. Source: Reproduced with modi cations from Yu et al., 2006a. See color insert.
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In nondoped lms of PEO-based azo LCBCs with well-de ned structures, macroscopic parallel patterning of PEO nanocylinders can be obtained easily in an arbitrary area by simple and convenient photocontrol. Furthermore, the noncontact method might provide the opportunity to control nanostructures even on curved surfaces. On the basis of the principle of SMCM, the orientation of microphase-separated nanocylinders dispersed in azo LC matrix should agree with the alignment direction of azo mesogens. The azo molecules can be 3-D
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12.4. CONTROL OF MICROPHASE SEPARATION
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Figure 12.15. Illustration of possible photomanipulated 3-D alignments of azo moieties and nanocylinders in azo LCBC lms by SMCM.
manipulated by unpolarized light, as shown in Fig. 12.15 (Wu et al., 1999). Both in-plane and out-of-pane alignment of nanocylinders coinciding with azo orientation might be precisely photocontrolled by SMCM, which is expected to provide complicated nanotemplates for top down-type nanofabrications such as lithography and beam processing.
12.4.4. Electric Field
Recently, Kamata et al. (2004) developed an electrochemical method to control alignment of PEO nanocylinders normal to the substrate in PEO-based azo LCBC lms. As shown in Fig. 12.16, the azo BC lms were prepared by spin coating from a toluene solution on an indium tin oxide (ITO) glass substrate kept at 501C for 2 days. Using the ITO glass as a working electrode, a sandwich-type cell was assembled with a Te on spacer and an injected KBr aqueous solution as electrolyte. Under the function of an electrolytic potential in the potentiostatic mode using Hokuto HZ-3000 with Pt counter electrode and Ag/AgCl reference electrode, all the PEO nanocylinders were oriented parallel to the electrolytic eld as the lowest energy alignment (Morkved et al., 1996). Since the hydrophilic PEO nanocylinders are ion conductive, they can be manipulated normal to the substrate by ion diffusion locally induced in the vicinity of the electrode (Kamata et al., 2004). The control process was carried out at 501C. All the PEO nanocylinders were aligned along the electrolytic eld, in spite of the non-microphase-separated state,
CHAPTER 12: AZO BLOCK COPOLYMERS IN THE SOLID STATE
Figure 12.16. Electrochemical control of assembly of nanocylinders in PEO-based azo LCBC lms. All the PEO nanocylinders were aligned along the electrolytic eld, in spite of a nonmicrophase-separated state, parallel or random alignment of PEO nanocylinders.
parallel or random alignment of PEO nanocylinders. This control using electrochemical potentials is a good candidate for the fabrication of nanocomposites. For a supramolecular system with hydrogen-bonding non-azo LCBCs, an AC electric eld was used to rapidly align the nanostructures at temperatures below the order disorder transition but above Tg (Chao et al., 2004). The low molecularweight mesogens play an important role in controlling microphase separation. The fast orientation switching of the nanostructures was attributed to the dissociation of hydrogen bonds, which might be used to control nanostructures in azo supramolecular BC systems.
12.4.5. Magnetic Field
Similar to the electric eld, the magnetic eld can be used to manipulate the microphase separation in azo LCBCs by SMCM. The noncontact orientation
12.4. CONTROL OF MICROPHASE SEPARATION
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Figure 12.17. Magnetically induced alignment of microphase-separated nanostructures in PS-based azo LCBCs. All the PS nanocylinders were oriented along the magnetic eld, which shows no effect on the lamellar morphologies. Source: Reproduced with modi cations from Tomikawa et al., 2005.
method provides a higher degree of freedom for sample shapes than the mechanical orientation method, and no danger is present, such as the dielectric breakdown that can be encountered in the electrical orientation approach. Moreover, the uniform orientation of LC polymers can be obtained over the whole region of a sample, regardless of the macroscopic shape of the sample and the strength of the magnetic eld (Tomikawa et al., 2005). As shown in Fig. 12.17, hexagonally packed PS nanocylinders dispersed in an azo mesogenic matrix were aligned along the magnetic eld upon annealing for a longer time (W2 h) in the nematic LC phase. Strangely, the magnetic eld shows no function on the lamellar nanostructures in lms, possibly because ordered lamellar microdomains with a long correlation length are only rearranged very little (Osuji et al., 2004). Therefore, although the LC was magnetically aligned in nanoscale layers, it showed no in uence on the inverse continuous phase (Hamley et al., 2004).