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cross-talk between encoded pages. Some azo chromophores exhibit biphotonic phenomena, which could be employed to enhance optical data storage. 1.2.6.4. Surface Mass Transport. In 1995, a surprising and unprecedented optical effect was discovered in polymer thin lms containing the azo chromophore Disperse Red 1 (DR1). The Natansohn Rochon (Rochon et al., 1995) research team and the Tripathy Kumar collaboration (Kim et al., 1995) simultaneously and independently discovered a large-scale surface mass transport when the lms were irradiated with a light interference pattern. In a typical experiment, two coherent laser beams, with a wavelength in the azo-absorption band, are intersected at the sample surface. The sample usually consists of a thin spin-cast lm (10 1000 nm) of an amorphous azo polymer on a transparent substrate. The sinusoidal light interference pattern at the sample surface leads to a sinusoidal surface patterning, that is, a surface relief grating (SRG). These gratings were found to be extremely large, up to hundreds of nanometers, as con rmed by atomic force microscopy (AFM). The SRGs diffract very ef ciently, and in retrospect, it is clear that many reports of large diffraction ef ciency before 1995, attributed to birefringence, were in fact due to surface gratings. The process occurs readily at room temperature (well below the Tg of the amorphous polymers used) with moderate irradiation (1 100 mW cm 2) over seconds to minutes. The phenomenon is a reversible mass transport, not irreversible material ablation, since a at lm with the original thickness is recovered upon heating above Tg. Critically, it requires the presence and isomerization of azobenzene chromophores. Other absorbing but nonisomerizing chromophores do not produce SRGs. Many other systems can exhibit optical surface patterning (Yamaki et al., 2000), but the amplitude of the modi cation is much smaller, does not involve mass transport, and usually requires additional processing steps. The all-optical patterning unique to azobenzenes has been studied intensively since its discovery, yet there remains controversy regarding the mechanism. The competing interpretations are evaluated in 4, where they are discussed at length. Many reviews of the remarkable body of experimental results are available (Natansohn and Rochon, 2002; Delaire and Nakatani, 2000; Yager and Barrett, 2001; Viswanathan et al., 1999).
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This work is dedicated to Professors Almeria Natansohn and Sukant Tripathy, teachers and pioneers in the eld of azo polymers, who were unable to see the completion of this book.
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Abraham G, Purushothaman E. 1998. Synthesis and photostimulated dilation changes of polymers with azobenzene cross links. Indian J Chem Technol 5(4):213 216.
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CHAPTER 1: AZOBENZENE POLYMERS FOR PHOTONIC APPLICATIONS
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Advincula R, Park M K, Baba A, Kaneko F. 2003. Photoalignment in ultrathin lms of a layer by layer deposited water soluble azobenzene dye. Langmuir, 19(3):654 665. Advincula RC. 2002. Polyelectrolyte layer by layer self assembled multilayers containing azobenzene dyes. In: Tripathy SK, Kumar J, Nalwa HS, editors. Handbook of Polyelectrolytes and Their Applications. Stevenson Ranch (CA): American Scienti c Publishers, p. 65 97. Advincula RC, Fells E, Park M K. 2001. Molecularly ordered low molecular weight azobenzene dyes and polycation alternate multilayer lms: aggregation, layer order, and photoalignment. Chem Mater 13(9):2870 2878. Agolini F, Gay FP. 1970. Synthesis and properties of azoaromatic polymers. Macromo lecules 3(3):349 351. Aida T, Jiang D L, Yashima E, Okamoto Y. 1998. A new approach to light harvesting with dendritic antenna. Thin Solid Films 331(1 2):254 258. Algers J, Sperr P, Egger W, Liszkay L, Kogel G, Baerdemaeker J, Maurer FHJ. 2004. Free volume determination of azobenzene PMMA copolymer by a pulsed low energy positron lifetime beam with in situ UV illumination. Macromolecules 37(21):8035 8042. Altomare A, et al. 2001. Synthesis and polymerization of amphiphilic methacrylates containing permanent dipole azobenzene chromophores. J Polym Sci, Part A 39(17):2957 2977. Altomare A, Ciardelli F, Tirelli N, Solaro R. 1997. 4 Vinylazobenzene: polymerizability and photochromic properties of its polymers. Macromolecules 30(5):1298 1303. Anderle K, Birenheide R, Eich M, Wendorff JH. 1989. Laser induced reorientation of the optical axis in liquid crystalline side chain polymers. Makromol Chem, Rapid Commun 10(9):477 483. Anderle K, Birenheide R, Werner MJA, Wendorff JH. 1991. Molecular addressing Studies on light induced reorientation in liquid crystalline side chain polymers. Liq Cryst 9(5):691 699. Angeli C, Cimiraglia R, Hofmann H J. 1996. On the competition between the inversion and rotation mechanisms in the cis trans thermal isomerization of diazene. Chem Phys Lett 259(3 4):276 282. Angiolini L, Caretti D, Carlini C, Salatelli E. 1995. Optically active polymers bearing side chain photochromic moieties: synthesis and chiroptical properties of methacrylic and acrylic homopolymers with pendant L lactic acid or L alanine residues connected to trans 4 aminoazobenzene. Macromol Chem Phys 196(9):2737 2750. Antipov AA, Sukhorukov GB, Mohwald H. 2003. In uence of the ionic strength on the polyelectrolyte multilayers permeability. Langmuir 19(6):2444 2448. Anzai J I, Osa T. 1994. Photosensitive arti cial membranes based on azobenzene and spirobenzopyran derivatives. Tetrahedron 50(14):4039 4070. Aoki K, Nakagawa M, Ichimura K. 2000. Self assembly of amphoteric azopyridine carboxylic acids: organized structures and macroscopic organized morphology in u enced by heat, pH change, and light. J Am Chem Soc 122(44):10997 11004. Arai K, Kawabata Y. 1995. Changes in the sol gel transformation behavior of azobenzene moiety containing methyl cellulose irradiated with UV light. Macromol Rapid Commun 16(12):875 880. Asakawa M, et al. 1999. Photoactive azobenzene containing supramolecular complexes and related interlocked molecular compounds. Chem Eur J 5(3):860 875.
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