Nonlinear optical chromophore-cross-linked

Photochemical cross-linking has, to the present, been only marginally successful because of interference with the absorption of the nonlinear optical chromophore with the absorption of light by the photochemically active moiety [12]. 

Polymers and supermolecules modified using electron push-pull chro-mophores are also of particular interest for nonlinear optics (NLO) [10-15]. NLO material has attracted much interest over the past 20 years and has been widely applied in various field (telecommunications, optical data storage, information processing, microfabrication, etc.). Chemists have developed ways to introduce NLO chromophores into many type of polymers, such as Hnear polymers, cross-linked polymers, and branched polymers, and have demonstrated their performance in NLO appHcations. 

The hb-PAEs of hb-P13 and hb-P15 contain NLO-active azo-functionalities, which are soluble, film-forming, and morphologically stable (Tg > 180 °C). Their poled films exhibited high SHG coefficients ( 33 up to 177pm/V), thanks to the chromophore-separation and site-isolation effects of the hyperbranched structures of the polymers in the three-dimensional space (Table 5) [28]. The optical nonlinearities of the poled films of the polymers are thermally stable with no drop in d33 observable when heated to 152 °C (Fig. 8), due to the facile cross-linking of the multiple acetylenic triple bonds in the hb-PAEs at moderate temperatures (e.g., 88 °C). 

The nonlinear absorption of Ptn acetylide chromophores has also continued to retain the interest of many researchers. Malmstrom and coworkers have recently investigated Pt-acetylide chromophores blended with solid-state polymer matrices [94], An example of such a complex is 4.7. They found that the photoluminescence properties of the blends agreed well with that of dilute THF solutions containing the Pt-acetylides. Optical power limiting experiments showed that the clamping levels for dyes nonbonded to the polymer host were about half that for dyes in the highly cross-linked solids at similar concentrations. 

This chapter concentrates on the design of efficient dipolar NLO chromophores and the different approaches for their incorporation in non-centrosymmetric materials, including guest-host polymer systems, chromophore-functionalized polymers (side-chain and main-chain), cross-linked chromophore-macromolecule matrices, dendrimers, and intrinsically acentric self-assembled chromophoric superlattices. The different architectures will be compared together with the requirements (e.g., large EO coefficient, low optical absorption, high stability, and processability) for their incorporation into practical EO devices. First, a brief introduction to nonlinear optics is presented. 

Fig. 5. Second harmonic generation is shown as a function of temperature for heating at a rate of 10°C per minute for two samples. The uncross-linked sample (chromophore is attached covalently by one end to a PMMA backbone) starts to lose second-order optical nonlinearity (acentric chromophore order) before 100°C. The cross-linked sample corresponds to both ends of the chromophore being covalently coupled to the pol3maer lattice. For this sample, thermally stable second-order optical nonlinearity is observed imtil nearly 170°C.

Because of the versatility of the polyurethane system it is possible to introduce comonomers which can affect the physical properties of the derived polymers. For example, photo cross-linkable polyurethanes are formulated using 2,5-dimethoxy-2,4 -diisocyanato stilbene as a monomer (76). Comonomers, having an azoaromatic chromophore, are used in optical bleaching applications (77), or in the formation of photorefractive polymers (78). The latter random poljnners have second-order nonlinear optical (NLO) properties. Linear poljnners are also obtained from HDI/PTMG and diacetylenic diols. These polymers can be cross-linked through the acetylenic linkages producing a network polymer with properties similar to poly(diacetylenes) (79). 

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