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Upon heating, some order will be lost, with full isotropy restored after heating past Tg A short spacer between the chromophore and the polymer backbone slows the growth of birefringence yet promotes stability, owing to hindered motion Surprisingly, main-chain azos can achieve high levels of birefringence, indicating relatively high polymer mobility (Wu et al, 2001b; Xu et al, 2000; Lee et al, 1998) As might be expected, (nanosecond) pulsed experiments lead to thermal effects, which enhance chromophore motion and thereby induced greater birefringence at the same net dose compared with continuous-wave (cw) experiments (Cimrova et al, 2002; Hildebrandt et al, 1998) At very high pulsed uence, the thermal effects were too great and erased the induced birefringence The easily inscribed and erased birefringence has a number of unique applications Most readily, it can be used to create wave plates (Shi et al.





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, 1991a) and polarization lters, which can be used to separate right-handed from left-handed circularly polarized light (Natansohn and Rochon, 1999) The strong refractive index contrast, if patterned into a line, can serve as a channel waveguide (Watanabe et al, 1996; Shi et al, 1991b) This offers the unique possibility of optical devices that can be patterned, erased, and reused In principle, these photonic circuits could be altered during device operation, enabling optical routing of optical signals (ie, optical computing) The switching of orientational order can thus be used as an all-optical switch (Shishido et al, 1997) By illuminating an azo sample with a spatially varying light pattern, birefringence gratings can also be formed (Eichler et al, 2001; Nikolova et al, 1996; Couture and Lessard, 1988).

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These are phase gratings, as opposed to amplitude gratings, and diffract light on the basis of spatial variation of the refractive index This is the essence of holography: two interfering coherent beams generate a spatially varying light pattern, which is encoded into the material Under illumination of the material with one of the beams, the diffraction reproduces the other encoded beam In the case of liquid crystal samples, light induces a spatial pattern of nematic and isotropic zones (which have different refractive indices) These holographic phase grating can be rapidly formed, erased, and switched (Yamamoto et al, 2001)..

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1.2.3.2. Nonlinear Optics. The requirement for NLO response in any material is an asymmetric (strictly, anharmonic) response of the electronic system. Pseudo-stilbenes, which have push pull substituents, have a strongly asymmetric electron distribution, which makes them ideal NLO molecules (see, for instance, Fig. 1.10). For a bulk NLO response, one requires an overall noncentrosymmetric material. This requirement is achieved in many inorganic crystals. In organic systems, the broken symmetry is typically obtained by applying an electric eld at a temperature suf cient to allow for the molecular dipoles to align with the eld. This process is called electric eld poling and is accomplished using interdigitated or at electrodes or a sharp charged needle (or grid) held above a grounded sample (called corona poling). The NLO response is typically quanti ed using secondharmonic generation (SHG; the emission of light at double the frequency of the incident beam), the electrooptic effect (change of refractive index on application of an electric eld), or wave-mixing experiments (where various frequencies of light can be synthesized or enhanced). These also constitute the main applications of NLO materials: they can be used to synthesize new frequencies of light, to electrically switch a beam, or to allow two beams of light to interact and couple (which can form the basis of an all-optical switch) (Eaton, 1991).

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