Nonlinear optical behavior

Third-order NLO behavior generally involves three photons, resulting in effects similar to those obtained for second-order NLO behavior. Third-order NLO behavior does not require the presence of asymmetric structures. 

Polymers that have been already been found to offer NLO behavior include polydiacetylenes and a number of polymers with liquid crystal side chains. Polymers are also employed as carriers of materials that themselves are NLO materials. Applications include communication devices, routing components, and optical switches. 

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The semiconducting properties of the compounds of the SbSI type (see Table XXVIII) were predicted by Mooser and Pearson in 1958 228). They were first confirmed for SbSI, for which photoconductivity was found in 1960 243). The breakthrough was the observation of fer-roelectricity in this material 117) and other SbSI type compounds 244 see Table XXIX), in addition to phase transitions 184), nonlinear optical behavior 156), piezoelectric behavior 44), and electromechanical 183) and other properties. These photoconductors exhibit abnormally large temperature-coefficients for their band gaps they are strongly piezoelectric. Some are ferroelectric (see Table XXIX). They have anomalous electrooptic and optomechanical properties, namely, elongation or contraction under illumination. As already mentioned, these fields cannot be treated in any detail in this review for those interested in ferroelectricity, review articles 224, 352) are mentioned. The heat capacity of SbSI has been measured from - 180 to -l- 40°C and, from these data, the excess entropy of the ferro-paraelectric transition... 

These spectroscopic studies have advanced our knowledge of the structure-property relations, which are extremely important for understanding the nonlinear optical behavior of these dyes, and specifically for their 2PA properties discussed below. 

Related to this are materials whose response to applied light varies according to the intensity of the applied light. This kind of behavior is referred to as nonlinear behavior. In general, polymers with whole-chain delocalization or large-area delocalization where electrons are optically excited may exhibit such nonlinear optical behavior. 

Another chemical approach to improve our microscopic understanding of optical nonlinearities is a study of nonlinear optical behavior of sequentially built and systematically derivatized structures. Most past work for third-order nonlinearities have focused on conjugated polymers. This ad hoc approach is not helpful in identifying functionalities necessary to enhance optical nonlinearities. A systematic study and correlation of Y values of systematically varied structure is an important approach for material development. 

Evaluation of the Second-Order Nonlinear Optical Behavior... 

Synthetic strategy has been developed that permits the efficient preparation of organometallic polymers which have structural characteristics necessary for nonlinear optical behavior. Complex t 5-C5H4CH20H - i 5-C5H4CH=C(CN)C02Et Fe (4) was prepared and homopolymerized through a thermally induced transesterification-polycondensation reaction. 

Finally, in Section IV dithiolene complexes with interesting optical properties, such as strong near-IR (NIR) absorption, nonlinear optical behavior, and the use of some dithiolene complexes for optical data storage will be reviewed. In Section V, attempts toward coupling conducting, and magnetic or optical properties will be discussed briefly. 

Semiconductor nanoparticles have been extensively studied in recent years owing to their strongly size-dependent optical properties. Among these nanomaterials, CdS and PbS are particularly attractive due to their nonlinear optical behavior and unusual fluorescence or photoluminescence properties [ 136,137]. A number of studies have been published recently regarding the preparation of CdS, PbS and ZnS nanoparticles in inverse microemulsion systems [138-143]. In these works, NP-5/NP-9 was the most commonly used surfactant and petroleum ether the most commonly used oil. The aqueous phase for each inverse microemulsion consisted of cadmium nitrate (0.1 M) and ammonia sulfide (0.1 M) respectively. CdS was recovered from the mixture of double microemulsions [141]. Electron microscopy revealed that the spherical particles were aroimd 10-20 nm in diameter, as seen in Fig. 14. 

Solid phosphates show a huge variety of crystal structures, and it is not practical to classify them in terms of structural types as is done with simple oxides, halides, etc. However, some general classes of metal phosphate structures will be considered three-dimensional frameworks of linked phosphate tetrahedra and tetrahedrally or octahedrally coordinated cations, layered phosphates, and phosphate glasses. In all of these materials the size and topology of pores within the structure are of importance, as these determine the ability of ions and molecules to move within the structure, giving rise to useful ion exchange, ionic condnction, or catalytic properties. Ion exchange can also be nsed to modify the properties of the host network, for example, the nonlinear optical behavior of potassium titanyl phosphate (KTP) derivatives. 

Coe, B.J., Harris, J.A., Brunschwig, B.S., Garin, J., Orduna, J., Coles, S.J., Hursthouse, M.B. Contrasting linear and quadratic nonlinear optical behavior of dipolar pyridinium chromophores... 

The linear and nonlinear optical behaviors of poly-(1,6-heptadiyne)s containing NLO chromophores was summarized in Table 22. It was found that n of the copolymers gave higher values than that of poly-76 not bearing any chromophore while the values of Amax were similar to each other. This result clearly shows the effects of incorporation of chromophore into the polymer backbone. The values of electrooptic coefficients, r33, for poled film samples of poly-77 to poly-81 by using a simple reflection technique reported by Teng et al. was measured. Table 22 shows the measured electrooptic coefficients of polymer films at... 

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