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 12.23. Scheme of selective absorption of Au nanoparticles on amphiphilic surfaces of azo LCBC lms with well-ordered microphase separation. D is the diameter of irradiated area. Source: Reproduced with modi cations from Watanabe et al., 2007.
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Figure 12.24. Potential representation of the preparation of SiO2 nanorod arrays with mesochannels normal to the substrate, combining the sol gel process with azo LCBC lm lithography.
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12.5. APPLICATIONS
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mesoporous silica materials have potential applications as innovative materials for waveguides, lasers, and biomacromolecular separation systems. The PEO-based azo LCBC lms with well-ordered microphase separation show excellent reproducibility and mass production through molecular or supramolecular self-assembly. Both parallel and perpendicular patterns of nanostructures with high regularity can be precisely manipulated, which guarantees the nanotemplate-based nanofabrication processes and results in diverse self-assembled nanostructures, leading to industrial use in plastics engineering.
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12.5.4. Volume Storage
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In recent years, advanced recording media with fast data transfer and high density have been developed. Optical holography provides unique opportunities for the next-generation storage technique, as shown in Fig. 12.25. The basis of the storage process is a photoinduced refractive index change in materials bearing chromophores. Desirable organic materials for holographic storage should exhibit high DE, fast response, high resolution, stable and reversible storage, low energy consumption during the recording and reading processes, as well as easy mass production. Azo-containing LC or amorphous polymers, photorefractive polymers, polymer-dispersed LC, and LC or glassy oligomers have been extensively investigated. But none of them meets all the aforementioned requirements. To increase storage density, Bragg-type gratings are often required. Generally, thick lms (W100 mm) with low absorption and no scattering of visible light are ideal for volume holograms. But this cannot be applied directly in Bragg gratings, since it is dif cult for visible light to pass through azo-containing thick lms (e.g., 100 mm) because of the large molar extinction coef cient of azo chromophores (B104 L mol 1 cm 1). One of the approaches related to solve this problem is to use the cooperative effect (Minabe et al., 2004). Ikeda and coworkers reported the formation of holographic gratings in a thick lm by modulation of the refractive index (Dnu), which was induced by the orientation of azo moieties and mesogens such as cyanobiphenyl or tolane moieties (e.g., Ishiguro et al., 2007). The random copolymers showed a maximum DE (Zmax) of 97% in the Bragg regime. Although
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Figure 12.25. Schematic illustrations of recording and reading processes in holographic storage.
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CHAPTER 12: AZO BLOCK COPOLYMERS IN THE SOLID STATE
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55 holograms with angular multiplicity were successfully recorded (Saishoji et al., 2007), the scattering could not be completely avoided. Recently, particular interest has been paid to the microphase separation of azo BC lms, because the azo chromophores can be constrained in one microphase-separated domain on the nanoscale by the microphase separation, thus eliminating the scattering of visible light, while maintaining the photoinduced change in refractive index (Yu et al., 2007). Schmidt and coworkers rst used this concept for holographic data storage in PS-based azo diblock random copolymers (Hackel et al., 2005). In the minority phase containing the mesogenic segments, the azo and benzoylbiphenyl mesogenic side groups were in a statistical distribution. Thus, it was possible to decrease the overall optical density, which plays an important role in the grating recording, while increasing the local refractive index difference between illuminated and unirradiated volume elements and improving the stability of the orientation. Furthermore, they prepared blends of the azo BCs and PS homopolymers and were able to obtain thick transparent lms (1.1 mm) (Hackel et al., 2007). On the basis of these lms, they performed angular multiplexing of 80 holograms at the same spatial position, which showed a long-term stability at room temperature.
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12.5.5. Other Applications
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Other than the optoelectronics and nanotechnology, the azo BCs have been widely explored in other elds. Zhao and coworkers combined optical and mechanical properties by designing thermoplastic elastomers using azo ABA-type BCs, with which they were able to prepare freestanding lms by simple casting (Cui et al., 2004). Recently, azo BCs with a low content of azo were used as surface-modifying agents of polymer substrates to allow dynamic control over surface properties, such as water wettability (Yoshida, 2005). Other applications of ABA-type LC triblock copolymers with lamellar structures are envisaged in the creation of arti cial muscle (Li et al., 2004); azo BCs with well-de ned structures can be utilized as photomobile materials (e.g., Yu et al., 2003; Ikeda et al., 2007), which is under way in Ikeda laboratory in Tokyo Institute of Technology.
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