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of low-molecular-weight azobenzene compound (He et al., 2000), where the contribution of dye bleaching has been suggested. Also, in the sol gel materials, in which some cross-linking of polymer takes place, the ef ciency of polarization recording was minimal (Darracq et al., 1998). The result of holographic irradiation is a modulation of lm thickness that replicates the interference pattern created by the laser beams. This enables the hologram to be encoded as a relief pattern. A weak probe 633-nm laser has been typically used to diffract from this phase hologram. The DE of nth diffracted order may be calculated as Zn In =SIn , where In are the intensities of the nth-order diffracted beams. In the literature, typically the DE of the rst diffraction order has been characterized. Note that it is correct until the recorded gratings are not very deep (that is often the case) and the grating pro le remains sinusoidal. Deep relief gratings have many diffraction orders in Raman Nath regime of diffraction, and their pro les deviate often from sinusoidal form. In this case, the characterization of grating by the total DEs proved to be an advantage. Total DE is determined as the sum of DEs of all nonzero orders, Ztot Z 1 Z 2 . The best-reported example of recording kinetics in ionic complexes is shown in Fig. 2.14 (Kulikovska et al., 2007). The grating was recorded in the material (Methyl Red)/PDADMAC with moderate irradiation intensities of 250 mW/cm2. After 20 min of irradiation, 98% of the probe light was diffracted by the recorded grating. Maximum diffraction of 45% in rst diffraction order was reached after 17 min, whereas maximum of 35% of light diffracted into second diffraction
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0th Order
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0 0 10 20 30 Time (min) 40 50 60
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Figure 2.14. Kinetics of the diffraction ef ciencies of the 0th, 1st, and 2nd diffraction orders upon holographic irradiation in (Methyl Red)/PDADMAC lm (Fig. 2.7). Source: Kulikovska et al., 2007. Reprinted with permission from American Chemical Society.
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Figure 2.15. AFM image of surface relief grating inscribed in (Methyl Red)/ PDADMAC lm (Fig. 2.7). Source: Kulikovska et al., 2007. Reprinted with permission from American Chemical Society.
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orders after 35 min of irradiation. The diffraction behavior reveals a very deep grating. An atomic force microscopy (AFM) image of the corresponding grating with a peak-to-valley height of ca. 1.65 mm and a period of 2.3 mm is presented in Fig. 2.15. One may estimate the recording rate to be as high as 10%/min for this grating. Very high modulation depths of relief gratings achieved in these materials are the highest values among the azobenzene-containing materials reported so far. In other respects, the inscription of SRG in ionic complex materials was comparable to the azobenzene-functionalized polymers. The gratings could be erased, if were irradiated with spatially homogeneous unpolarized UV light, and then recorded again into the same lm. Also, the successive recording was demonstrated as a proof of the process reversibility. In this way, two-dimensional (2-D) cross-gratings consisting of up to 13 linear gratings have been successively inscribed into the lm. Figure 2.16 displays an example of the 2-D grating adopted from Kulikovska et al. (2008b). Remarkably, because the induced SRGs are thermally very stable, only heating the samples above 1501C can erase them. The thermal stability of the light-induced surface structures in the ionic complex materials is worthy to discuss here in comparison to the stability of gratings in the azobenzene-functionalized polymers. It is well established now that SRGs in polymers are stable below the glass transition temperature of the polymers and can be erased if heated above Tg. It has been noted that the higher the glass transition temperature, the lower is the SRG formation ef ciency. Only shallow, though thermally stable, gratings could be induced in polymers with high Tg of about 1501C (Che et al., 2002; Lee et al., 1998) and in polymer with rigid backbone, for which no Tg was found (Sukwattanasinitt et al., 1998). Very effective SRGs, stable up to Tg of 1471C, were inscribed in azobenzene-based amorphous molecular material with a spirobi uorene core (Chun et al., 2003). The high ef ciency was attributed to the high concentration of azobenzene groups per molecule and the good mobility of
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