Langmuir-Blodgett films nonlinear materials

As this volume attests, a wide range of chemistry occurs at interfacial boundaries. Examples range from biological and medicinal interfacial problems, such as the chemistry of anesthesia, to solar energy conversion and electrode processes in batteries, to industrial-scale separations of metal ores across interfaces, to investigations into self-assembled monolayers and Langmuir-Blodgett films for nanoelectronics and nonlinear optical materials. These problems are based not only on structure and composition of the interface but also on kinetic processes that occur at interfaces. As such, there is considerable motivation to explore chemical dynamics at interfaces. 

The material system is a Langmuir-Blodgett film of the S enantiomer of a chiral polymer deposited on a glass substrate. The polymer is a poly(isocyanide)30 functionalized with a nonlinear optical chromophore (see Figure 9.14). In this particular system the optical nonlinearity and chirality are present on two different levels of the molecular structure. The chirality of the polymer is located in the helical backbone whereas the nonlinearity is present in the attached chromophores. Hence, this opens the possibility to optimize both properties independently. 

Ashwell, G.J. (1999) Langmuir-blodgett films Molecular engineering of noncentrosymmetric structures for second order nonlinear optical applications. Journal of Materials Chemistry, 9, 1991-2003. 

On a conceptual level, the ideal format for thin-film materials for nonlinear optics is the Langmuir-Blodgett film. Molecularly engineered chrom-ophores with large hyperpolarizabilities can, in principle, be incorporated at high concentration, with well-defined orientations into films having thicknesses defined by molecular resolution. Extremely large resonantly enhanced values of have been reported in LB films several layers thick (30, 3i) thus the considerable promise of this approach is established. 

A separate section is devoted to phthalocyanines and porphyrins as discotic liquid crystals. The nonlinear optical effects as well as photoconductivity and the possibility of the formation of Langmuir-Blodgett-films of phthalocyanines and derivatives is discussed at some length. Several practical applications of these unconventional materials are mentioned. 

One core chiral system that shows dramatic amplification of its chiral structure is the substituted helicenes of Katz and coworkers [83]. In essence, this research cuts the helix into a number of six-helicene subunits that self-assemble (Figure 10). Only when these subunits, which look like lock washers, are prepared in optically pure form the material associates into supramolecular helical columns [84]. The assemblies have been synthesized with different amounts of substitution around the exterior. Depending on the helicenes substitution, the material exhibits hexagonally ordered soft-crystalline [84] or liquid-crystalline phases [85]. The liquid-crystalline versions of these molecules switch when electric fields are applied to neat and solution-phase samples and have been characterized as a dielectric response [85-87]. Upon association, these materials have enormous changes in their CD intensities and optical rotations [74]. In addition, this supramolecular chirality also significantly enhances the second-order nonlinear optical behavior of these materials in Langmuir-Blodgett films [88]. 

A new approach to second-order nonlinear materials was reported by Verbiest et al. (56) in which chirality plays the key role. These authors investigated Langmuir-Blodgett films of chiral helicenes which lack features commonly associated with a high SHG response. The molecules adopt a helical structure on a solid support and this chiral supramolecular arrangement enhances the second-order NLO susceptibility by a factor of 30 when compared to the corresponding racemic mixture. An adequate description of the SHG response in a chiral system requires additional tensor elements. Experimental evidence was provided that those tensor elements which are only allowed in a chiral environment dominate the SHG response of the helicene system. 

A huge number of other applications exist, where the chemical and physical requirements are totally different. These applications include reflectors, temperature measurement with thermochromic materials, nonlinear optics, pol3mier materials, SAMs (self-assembled mono-layers) and LB (Langmuir-Blodgett) films, the use of Uquid crystals in template synthesis of porous materials, drug delivery, and many more. 

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