TAB L E 1 2 .2 . All the Movements in Grating Formation and Enhancement in Java

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TAB L E 1 2 .2 . All the Movements in Grating Formation and Enhancement
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Process Molecular scale Annealing effect
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12.5. APPLICATIONS
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CH3 O CH3 CH2 C CH3CH2 O C C block CH3 C O118 O CH3 R1 = R2 = CH2(CH2)4CH2O CH2(CH2)4CH2O N=N
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CH3 O CH3 CH3 CH2 C CH3CH2 O C C block CH2 C ran 8 118 CH3 C O C O O O CH3 R1
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C O O R2
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Figure 12.20. Enhancement of surface index modulation of azo BCs by cooperative effect. A is aligned, and R is random. Source: Reproduced from Yu et al., 2008a.
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over a large area on soft or hard substrates (PET sheets, Si wafers, and quartz plates) via the selective Ag+ doping of the hydrophilic PEO domains in a microphase-separated azo LCBC lm and an associated vacuum ultraviolet UV (VUV) treatment to eliminate the LCBC templates to reduce simultaneously the Ag+. Obviously, the periodicity of the highly dense Ag nanoparticles was precisely controlled by the nanotemplates of the azo LCBC lms. The simple and facile fabrication of a metal nanoparticle array can be used as a novel type of BC photolithography to overcome the size limitations of conventional top down lithography, with the goal of macroscopically fabricating hierarchical nanopatterns with controlled ordering for potential applications ranging from photonics and plasmonics to metal wiring in molecular electronics (Suzuki et al., 2007). The self-assembly from azo LCBC lm templates also provides a good method to modify the nanoscale shape of various kinds of functional materials, such as electric conducting RuO2, magnetic Fe, or organic conducting polymers (Suzuki et al., 2007).
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CHAPTER 12: AZO BLOCK COPOLYMERS IN THE SOLID STATE
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PEO domain
Azo domain Ag+ loading
AgNO3 solution
Substrate Microphase-separated nanotemplate d D Substrate Ag nanoparticles VUV reduction VUV etching
Substrate Rinsing d D
Substrate
Figure 12.21. Fabrication of periodic array of Ag nanoparticles on either exible or rigid substrates. The gray closed circles represent the photoreduced metallic Ag nanoparticles with regular particle size and periodicity. Source: Reproduced with modi cations from Li et al., 2007b.
Figure 12.10 presents a PEO-based azo LCBC lm, which exhibits wellordered hydrophilic PEO nanocylinders with hexagonal packing embedded in an azo LC matrix. The anisotropic PEO nanocylinders can be used as ion-conductive channels since PEO has been widely used as a solid electrolyte (Fig. 12.22). By incorporating LiCF3SO3 into the PEO nanocylinders, a supramolecular complexed structure and anisotropic ion transportation were achieved on the basis of the azo LCBC nanotemplate (Li et al., 2007a). Highly ordered ion-conducting PEO nanocylinder arrays with perpendicular orientation were formed by coordination between the lithium cations and the ether oxygens of the PEO blocks. At low- and medium salt concentration, selective complexation of Li+ with the PEO phase leads to the formation of an ordered array of ion-conducting PEO nanocylinders, which are perpendicular to the substrate surface, and on the right-hand side of Fig. 12.22, there is a 3-D illustration of the corresponding phase-segregated structure, in which anisotropic ion transport is observed. At high salt concentration, the lithium salt is dissolved in both PEO and azo domains. This decreases LC ordering and disturbs microphase separation. An array of tilted and distorted nanocylinders is formed with poor regularity. Consequently, the anisotropic value of ion conductivity is reduced (Breiner, 2007). On the surface of PEO-based azo LCBC lms, each hydrophilic PEO domain appears as a circular hollow surrounded by the hydrophobic azo matrix. These amphiphilic properties enable the selective absorption of Au nanoparticles with hydrophilic or hydrophobic surface modi cations. Of course, the surface properties of the gold nanoparticles are a critical factor in this nanofabrication (Watanabe et al., 2007). To extend site coverage further and favor high selectivity,
12.5. APPLICATIONS
O CH3(OCH2CH2)114O O Br
Azo LCBC
Azo block Ion insulating
CH2CH2CH2CH3
CH2(CH2)9CH2C
PEO Ion conducting Li+
CF3SO3
PEO cylinder Azo matrix
Low Medium concentration
Substrate High concentration
Lithium salt
Selective doping
Substrate
Figure 12.22. Schematic illustration of anisotropic ionic conduction in nanochannels with nanotemplates of azo LCBC lms. The complexes PEO+LiCF3SO3 were prepared at low-, medium-, and high salt concentration. Source: Reproduced from Li et al., 2007a.
the gold nanoparticles should be modi ed by additional functional ligands, which provide electrostatic and hydrogen bond interactions. As shown in Fig. 12.23, sitespeci c recognition of gold nanoparticles was obtained in the nanocylinder domains of PEO blocks or the azo continuous domains. The on-site coverage and selective effects of the surface properties, the concentration of gold nanoparticles, the dipping time, and the composition of the dispersion medium were investigated by a simple dip coating method. Then the ordering of the gold nanoparticles from the template was transferred to the substrate by the inexpensive VUV approach, which was effective in removing the templates without destroying the regularity of the assembled nanoparticles. Such facile transfer is characteristic of soft (organic) templates compared with hard (inorganic) templates. The sol gel process can also be incorporated with azo BC lm lithography. A hexagonally ordered SiO2 nanorod array with mesochannels aligned along the longitudinal axes was obtained for the rst time, as shown in Fig. 12.24 (Chen et al., 2008). The mesochannels inside the SiO2 nanorods were aligned perpendicularly to the substrate and had a diameter of B2 nm. The aspect ratio of the SiO2 nanorods was controlled by the immersion time and the lm thickness. A height of several hundreds of nanometers can be achieved. This hierarchically ordered