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to the grating direction could be attributed to photoaggregation of the azo dye molecules or buckling of the elastomeric surface. Indeed all of these otherwise contradictory results can be reconciled by considering a more general photomechanical explanation, where both photoexpansion (for materials below a crossover mobility temperature; i.e., amorphous) and photocontraction (for materials above a mobility threshold; i.e., liquid crystal samples) both occur (Yager and Barrett, 2006b). Further investigations into reconciling this model with the polarization dependence of inscription are in order, where presumably photoorientation will play a key role.
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The single-step, rapid, and reversible all-optical surface patterning effect discovered in a wide variety of azobenzene systems has, of course, been suggested as the basis for numerous applications. Azobenzene is versatile, amenable to incorporation in a wide variety of materials. The mass patterning is reversible, which is often advantageous. However, one may use a system where cross-linking enables permanent xation of the surface patterns (Zettsu et al., 2001). Many proposed applications are optical and t well with azobenzene s already extensive list of optical capabilities. The gratings have been demonstrated as optical polarizers (Tripathy et al., 2000), angular or wavelength lters (Stockermans and Rochon, 1999; Rochon et al., 1997), and couplers for optical devices (Paterson et al., 1996). They have also been suggested as photonic band gap materials (Nagata et al., 2001), and have been used to create lasers where emission wavelength is tunable via grating pitch (Rocha et al., 2001; Dumarcher et al., 2000). The process has, of course, been suggested as an optical data storage mechanism (Egami et al., 2000). The high speed and single-step holographic recording has been suggested to enable instant holography (Ramanujam et al., 1999), with obvious applications for industry or end consumers. Since the hologram is topographical, it can easily be used as a master to create replicas via molding. The surface patterning also allows multiple holograms to be superimposed, if desired. A novel suggestion is to use the patterning for rapid prototyping of optical elements (Neumann et al., 1999). Optical elements could be generated or modi ed quickly and during device operation. They could thereafter be replaced with permanent components, if required. The physical structure of the surface relief can be exploited to organize other systems. For instance, it can act as a command layer, aligning liquid crystals (Kaneko et al., 2002; Parfenov et al., 2001, 2000; Kim et al., 2000; Li et al., 1999). The grating can be formed after the LC cell has been assembled and can be erased and rewritten. Colloids can also be arranged into the grooves of an SRG, thereby templating higher order structures (Yi et al., 2002a, 2001). These lines of colloids can then be sintered to form wires (Yi et al., 2002b). The surface topography inscription process is clearly amenable to a variety of optical-lithography patterning schemes. These possibilities will hopefully be more thoroughly investigated. An advantage of holographic patterning is that there is guaranteed
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registry between features over macroscopic distances. This is especially attractive as technologies move toward wiring nanometer-sized components. One example in this direction involved evaporating metal onto an SRG, and then annealing. This formed a large number of very long (several millimeter) but extremely thin (200 nm) parallel metal wires (Noel et al., 1996). Of interest for next-generation patterning techniques is the fact that the azo surface modi cation is amenable to near- eld patterning, which enables high resolution nanopatterning by circumventing the usual diffraction limit of far- eld optical systems. Proof of principle was demonstrated by irradiating through polystyrene spheres assembled on the surface of an azo lm. This results in a polarization-dependent surface topography pattern (Watanabe et al., 2000) and a corresponding surface density pattern (Ikawa et al., 2000). Using this technique, resolution on the order of 20 nm was achieved (Hasegawa et al., 2001). This process appears to be enhanced by the presence of gold nanoislands (Hasegawa et al., 2002). It was also shown that volume is not strictly conserved in these surface deformations (Keum et al., 2003). In addition to being useful as a subdiffraction limit patterning technique, it should be noted that this is also a useful technique for imaging the near eld of various optical interactions (Fukuda et al., 2001). The (as of yet not fully explained) fact that subdiffraction limit double-frequency SRGs can be inscribed via far- eld illumination (Lagugne-Labarthet et al., 2004; Labarthet et al., 2001, 2000; Naydenova et al., 1998a) further suggests the azopolymers as versatile high resolution patterning materials.
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