Photoalignment of Chromonic LC Silica Nanohybrid in Java

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8.2.3. Photoalignment of Chromonic LC Silica Nanohybrid
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Among vast varieties of lyotropic LCs, chromonic mesophases are the families of new research target starting only about two or three decades ago. The properties are different from those of ordinary lyotropic mesogens of surfactant type. The molecules constitute aromatic(s) in the center, and hydrophilic parts are scattered around the molecules rather than aliphatic structures. Therefore, they are rigid and planar disklike or planklike, rather than micelles of exible molecular assemblies of ordinary surfactants. The molecules aggregate in solution to form
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Figure 8.4. Patterned photoalignment of mesochannels using a photomask. Photomask (top) and the obtained silica lm (bottom). Reprinted with permission from the American Chemical Society.
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columns via the p p stacking, rather than rodlike micelles via the hydrophobic effect. The resultant columnar structure of the dye aggregate forms lyotropic mesophases. Recently, such chromonic mesophases have been attracting great attention because of their potential utilities for fabrication of optical elements. The photoalignment of azo dye aggregate by the command surface was rst demonstrated by Ichimura et al. (1995). Further investigations reveal that the photoaligning of the resulting dry lm is achieved in the lyotropic state (Fujiwara and Ichimura, 2002; Ichimura et al., 2002). The dried lms, via chromonic LC of an anionic bis-azo dye, C.I. Direct Blue 67 (B67), have been found to be aligned and patterned by the alignment layer that is preirradiated with LPL (Ruslim et al., 2004; Matsunaga et al., 2003, 2002). The fundamental phase diagrams and mesomorphic properties of B67 have been reported by Ruslim et al. (2003). These innovative ndings are reviewed by Lydon (2004).
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Nanohybridization of B67 with silica network was recently attempted by Hara et al. (2007). The chromonic LC of B67 was mixed with silica precursor of tetraethoxysilane (TEOS) together with an anionic surfactant (EmalC20) and 2-(2-aminoethoxyl)ethanol (AEE). Here AEE plays an important role in stabilizing the columnar structure of B67. This molecule works as the mediator of the interface between the anionic B67 aggregate and silica. Without AEE, the columnar structure is transformed to a lamella structure in the process of drying (Hara et al., 2007). The optical anisotropy of the nanohybrid lms obviously obeys the direction of the preirradiated LPL to the photocrosslinkable polymer liquid crystal (PPLC) lm, and the effect of ow orientation because the lifting from the sol solution is
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Direction of PPLC mesogen Substrate
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Figure 8.5. Photoalignment of chromonic LC/silica nanohybrid. Chemical structure of the component and a scheme of B67 columns on a photoaligned PPLC lm. See color insert.
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almost negligible. Polarized optical microscopy indicates the in-plane orientation of the dye aggregates over large areas. The spectroscopic data and in-plane XRD measurements indicate that the B67 molecules are stacked to form a column where the planar B67 molecules (light absorption transition moment) are stacked orthogonal to the column direction. The structure of the photoaligned B67 and columns are schematically indicated in Fig. 8.5. The molecular axis of B67 coincides with the direction of photooriented mesogens (parallel to LPL) of PPLC lm, and therefore, the columns are extended orthogonal to the LPL direction. The orientation of the chromonic columns of B67 aligned by the LPLirradiated PPLC lm exactly agrees with that of rodlike micelles formed by ordinary surfactant aggregates (Fukumoto et al., 2006). However, the dip coating procedure without LPL irradiation obviously brings about macroscopic alignment of the B67 columns along the lifting direction (Hara et al., 2007). The macroscopic alignment should stem from the ow orientation in this case. On the basis of these facts, micropatterning of the chromonics silica hybrid can be attained utilizing a combination of photo- and ow orientation. A patterned irradiation with LPL onto the PPLC lm is made through a photomask, and then the dip coating is achieved to prepare the chromonic silica hybrid lm. In this procedure, the directions of LPL and dipping are arranged to be consistent so that the orientation of the columns in the regions of irradiated and nonirradiated areas become orthogonal with each other.
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