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Equation (3.1.50) can be developed further. Consider once again cell (3.1.40), together with Eq. (3.1.49). We shall assume that hydrogen gas is under standard pressure;t in addition, metallic silver, solid silver chloride and gaseous hydrogen at standard pressure are selected as standards, that is

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Figure 12.11. AFM images of PEO nanocylinders in bulk lms of azo LCBCs (3.1 mm 12.4 mm). In the left panel, the PEO nanocylinders are aligned parallel to the rubbing direction, whereas the PEO nanocylinders are oriented perpendicular to the substrate in the right panel. Source: Reproduced with modi cations from Yu et al., 2006b. See color insert.

MH+(W) = ju I+(w) + RT In a H + (w),

In fact, parallel processes for patterning densely packed nanostructures are required in diverse areas of nanotechnology (Kim et al., 2003). The regular nanostructures self-assembled in bulk lms of PEO-based azo LCBCs provide the opportunity to prepare such parallel stripe pattern by SMCM. To achieve this,

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Mcr(w) = fiMw) + RT and flH (w)flci-(w)

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a commercialized rubbing technique was chosen to homogeneously align azo mesogens in bulk LCBC lms. The periodic ordering of oriented azo mesogens might be transferred to microphase-segregated PEO nanocylinders by SMCM. Generally, LC molecules can be controlled to align along the rubbing direction on surfaces of rubbed polyimide lms because of the lower energy level along the rubbing-induced grooves (Berreman, 1972). Recently, this mechanical rubbing method has been extensively investigated with low molecular-weight compounds, LC polymers, and cross-linked LC gels (Ikeda, 2003b; Demus et al., 1998). It has been shown to have a strong in uence on the bulk lms of azo LCBCs in Fig. 12.12. After rubbing and annealing treatments, perfect alignment of PEO nanocylinders, coinciding with the azo LC orientation, was clearly observed by AFM, as shown in Fig. 12.12. Overall, an area of 500 nm 500 nm, B21 PEO nanocylinders with a diameter of 10 nm were regularly oriented along the rubbing direction. This defect-free periodic nanocylinder array in the azo LCBC lms can be acquired over arbitrarily large areas on the surface of rubbed polyimide lms (Fig. 12.11). Similar to other methods of controlling microphase-segregated domains in amorphous BC lms, such as electric eld (Morkved et al., 1996),

ci-(w),

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Figure 12.12. Fabrication of a parallel nanocylinder array in bulk lms of a PEObased azo LCBC by the mechanical rubbing technique. All the PEO nanocylinders are oriented along the rubbing direction. Source: Reproduced with modi cations from Yu et al., 2006b.

f C ( w ) + f*Mw)

Figure 12.13. FESEM and AFM images of cross-sections of a 3-D array of parallel PEO nanocylinders on the surface of rubbed polyimide lms in azo LCBC lms. Source: Reproduced with modi cations from Yu et al., 2006b.

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0 ,HCI(W),

FE = - ^ ( w ) ~ A*ci-(w) - 2RT ln a tHCi(w)

crystallization (Rosa et al., 2003), controlled interfacial interaction (Huang et al., 1998), chemically or topologically patterned substrates (Cheng et al., 2004), this rubbing technique exerted a forceful action on 3-D array of nanostructures, and appeared in the cross-sectional images (AFM and FESEM in Fig. 12.13). Most interestingly, the sample showed a regular surface relief of B3 nm with a periodicity of 24 nm, possibly due to the con ned crystallization of the PEO blocks embedded in the ordered LC phases (Reiter et al., 1999). Obviously, both the nanocylinder dimension and the surface periodicity can be easily adjusted by the volume fraction of PEO or azo blocks in the LCBCs. The macroscopic 3-D nanocylinder array in a long-range order with arbitrarily controlled direction in plane was successfully achieved by the SMCM, opening a novel pathway of controlling the nanoscopic domains over large areas (Yu et al., 2006b). The industrialized rubbing technique to regulate macroscopic nanoarray in azo LCBC lms has the advantages of simplicity, convenience, and low cost over other approaches (e.g., Morkved et al., 1996), which creates opportunities for manufacturing nanoscopic device components (Fasolka and Mayes, 2001). In the processes of nanocylinder alignment, the rubbing acts on the microphase domains by the bridge of the

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2iKH (3.1.53)

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