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Figure 9.1. Schematic illustration of the photoimmobilization of biomolecules (immunoglobulin) on the surface of an azopolymer. The surface of the azopolymer is deformed to the shape of the immunoglobulin after photoirradiation. Source: Narita, 2007.
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Figure 9.2. The chemical structures of the azopolymers described in this chapter.
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(Narita et al., 2007; Ikawa et al., 2006; Watanabe, 2004). First, the microobject (immunoglobulin in the case shown in Fig. 9.1) is set on the surface of the azopolymers, which is then photoirradiated from above. The surface of the azopolymer deforms in the presence of the immunoglobulin because the viscoelastic properties of azopolymer surfaces change during photoirradiation. The deformation occurs such that it enfolds the immunoglobulin, and so the contact area between the surfaces of the immunoglobulin and the azopolymer increases. This deformation mainly occurs through the photoplasticization of the azopolymer matrix owing to a trans cis trans isomerization cycle of the azobenzene moiety, as shown in Fig. 9.2. The surface of the azopolymer glaciates again and maintains the deformed shape after ceasing the irradiation, as shown in Fig. 9.1 (right-hand side). As a result, the immunoglobulin is effectively immobilized on the surface of the azopolymer without chemical modi cation. This novel method is useful for the immobilization of a variety of small particles such as charged proteins, negatively charged DNA, and hydrophobic polystyrene microspheres on azopolymer surfaces, and it has been shown that the immobilized biomolecules can maintain their higher order structure without damage to their functionality. This versatility in terms of immobilization is a signi cant advantage of this technique. The photoinduced immobilization technique is closely related to the formation process used for surface relief gratings (SRG) because both phenomena are based on mass transportation of the azopolymer surface. The relief structure on the azopolymer surface is induced by the interference of the two coherent beams that are used for the irradiation, with the same periodic structure as the interference light, as shown in Fig. 9.3. Intensive studies for SRG formation have been reported since it was rst developed in 1995 (Batalla et al., 1995; Kim et al., 1995). Various deformed structures that can be induced by photoirradiation
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Figure 9.3. Formation of SRG on an azopolymer, as generated by two-beam interference irradiation. The grating pitch, Lgr is determined by the wavelength and the incident angle of the irradiated light. The gure on the right exhibits a topographical image as measured by AFM.
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have been demonstrated in addition to SRG (Fukuda et al., 2001; Ye et al., 2001). The surface deformation mechanism needs to be understood by considering not only photochemical phenomena involving the azobenzene moiety and the mobility of the polymer matrix but also by interactions of the irradiation light with electric elds. Therefore, a large number of researchers are making continued efforts to clarify the complex deformation mechanism (Barada et al., 2006; Barret et al., 1996; Kumar et al., 1998; Pedersen et al., 1998).
The authors have recently switched the objectives of their research into SRG formation to now consider interactions between small objects and azopolymer surfaces, such as mass transportation and molecular reorientation, and have investigated photoinduced nanofabrication using a novel approach. They have discovered some interesting phenomena that are applicable to nanometer-scale fabrication by irradiating light onto microobjects set on azopolymer surfaces (Keum et al., 2003; Hasegawa et al., 2002b, 2001; Ikawa et al., 2001a,b, 2000; Watanabe et al., 2006, 2001, 2000). The resolution of recording or fabrication processes that is de ned by light is determined by how narrowly the irradiating light can be focused, and, because of to diffraction limits, in practice this equates to about half of the wavelength of the irradiating light. The use of the optical near eld can overcome diffraction limits to reach nanometer-scale dimensions, and this has been expected to become a powerful tool for attaining nanometer-scalemanufacturing capability (Knoll and Keilmann, 1999; Ohtsu, 1998; Betzig and Trautman, 1992). This section demonstrates nanoscale deformation phenomena that can be induced by the optical near eld when using microobjects set onto an azopolymer; these phenomena were investigated by the authors and triggered their work into photoinduced immobilization. Various sizes of microspheres (from tens of nanometers to several micrometers) made of various materials such as polystyrene or silica can be easily obtained, and it is possible to place these into an ordered arrangement because of the uniformity of their diameters. If a microsphere is irradiated with light, an optical near eld is induced around the microspheres, as shown in Fig. 9.4. The authors selected polystyrene microspheres for use as the near- eld light source and demonstrated a topographical nanostructure-patterning technique on the surface of an azopolymer. Nanostructured patterning was carried out as shown schematically in Fig. 9.5 using the azopolymer shown in Fig. 9.2, which has a glass transition temperature of 145 1C and a maximum absorption of 475 nm. A lm of azopolymer with a thickness of 0.5 mm was spin coated onto a glass substrate from a pyridine solution, and the surface of the lm before irradiation with light showed no regular structural periodicity. An aqueous solution containing polystyrene spheres was dropped onto the surface of the polymer lms, and then the spheres were allowed to arrange themselves into a hexagonal-packed monolayer by a selforganization process. After drying the samples, they were irradiated from the side