Electro-optical materials

Electro-optic materials can be made using liquid crystal polymer combinations. In these applications, termed polymer-stabilized liquid crystals [83,86], the hquid crystal is not removed after polymerization of the monomer and the resulting polymer network stabilizes the liquid crystal orientation. 

This review will highlight the interrelationships between basic photopolymer science and practical applications of this technology. Each application of photopolymer technology can be described in terms of three primary descriptors the mode of exposure, the mechanism of the photopolymer reaction employed and the visualization method used. Using this foundation, the widely diverse applications of photopolymer technology to electronic materials, printing materials, optical and electro-optical materials, the fabrication of devices and polymeric materials, adhesives and coating materials will be discussed. 

More complex geometries have been developed [40] and the influence of the geometrical structure has been examined. Although straight-through microchannel emulsification has been developed [39,41], the production rates are still low compared to those obtained with standard emulsification methods. However, the very high monodispersity makes this emulsification process very suitable for some specific fechnological applicafions such as polymeric microsphere synfhesis [42,43], microencapsulation [44], sol-gel chemistry, and electro-optical materials. 

Helix is the most common higher-order structure of synthetic polymers such as peptides, polymethacrylates, polychloral, polyisocyanides, polyisocyanates, and polysilanes. Polyacetylenes bearing appropriate substituents also form a helix. Substituted helical polyacetylenes are promising candidates for enantioselective permeable materials, polarization-sensitive electro-optical materials, asymmetric electrodes, and hence their synthesis is currently under intensive research. This section overviews the synthesis and properties of helical polyacetylenes recently reported. 

Since the first synthesis of mesoporous materials MCM-41 at Mobile Coporation,1 most work carried out in this area has focused on the preparation, characterization and applications of silica-based compounds. Recently, the synthesis of metal oxide-based mesostructured materials has attracted research attention due to their catalytic, electric, magnetic and optical properties.2 5 Although metal sulfides have found widespread applications as semiconductors, electro-optical materials and catalysts, to just name a few, only a few attempts have been reported on the synthesis of metal sulfide-based mesostructured materials. Thus far, mesostructured tin sulfides have proven to be most synthetically accessible in aqueous solution at ambient temperatures.6-7 Physical property studies showed that such materials may have potential to be used as semiconducting liquid crystals in electro-optical displays and chemical sensing applications. In addition, mesostructured thiogermanates8-10 and zinc sulfide with textured mesoporosity after surfactant removal11 have been prepared under hydrothermal conditions. 

Table n. Potential Advantages of Polymer Electro-optic Materials... 

Precious Metals Products Services Zinc Smelting Mining Thin-Film Products Battery Materials Recycling Electro-Optic Materials Emissions Control Catalysts... 

Marc Van Sande, CTO/Exec. VP-Advanced Materials Hugo Morel, Exec. VP-Precious Metals Services Pascal Reymondet, Exec. VP-Precious Metals Products Michel Cauwe, Sr. VP-Electro-Optic Materials Karel Vinck, Chmn. 

L. R., Dalton, etal., From molecules to opto-chips organic electro-optic materials, J. Mater. Chem. 9, 1905-1920 (1999). 

In anisotropic materials, the electronic bonds may have different polarizabilities for different directions (you may think of different, orientation-dependent spring constants for the electronic harmonic oscillator). Remembering that only the E-vector of the light interacts with the electrons, we may use polarized light to test the polarizability of the material in different directions, lno is one of the most important electro-optic materials and we use it as an example. The common notations are shown in Figure 4.7. If the E-vector is in plane with the surface of the crystal, the wave is called a te wave. In this example, the te wave would experience the ordinary index na of LiNbOs (nG 2.20). If we rotate the polarization by 90°, the E-ve ctor will be vertical to the surface and the wave is called tm. In lno, it will experience the extraordinary index ne 2.29. Therefore these two differently polarized waves will propagate with different phase velocities v c/n. In the example of Figure 4.7, the te mode is faster than the tm mode. 

In this review, the focus is on electro-optic materials. Such materials are members of the more general class of second-order nonlinear optical materials, which also includes materials used for second harmonic generation (frequency doubling). The term second-order derives from the fact that the magnitude of these effects is defined by the second term of the power series expansion of optical polarization as a function of applied electric fields. The power series expansion of polarization with electric field can be expressed either in terms of molecular polarization (p Eq. 1) or macroscopic polarization (P Eq. 2)... 

Third, achieving the largest possible order parameter will be important for optimizing electro-optic activity. Moreover, this order parameter must be stable over the operational lifetime of a device utilizing the electro-optic material. 

The reader is also referred to other literature for a more comprehensive introduction to various aspects of optical nonlinearity and for more in-depth reviews of certain topics than can be covered in this review [2,3,5,24-87]. It is also suggested that the reader use these cited reviews to access literature not cited here. The literature on the topic of organic electro-optic materials now stands at many thousands of papers. It is unrealistic to attempt to even cite this entire body of literature here let alone discuss in depth all of the salient features of research into organic electro-optic materials. It is hoped that a readable overview of poled polymer electro-optic materials is provided in the following sections and that insight is provided both into the technological potential and problems associated with these materials. 

Assessing thermal and photochemical stability is important. Thermal stability can be readily measured by measuring properties such as second harmonic generation as a function of heating at a constant rate (e.g., 4-10 °C/min) [121]. The temperature at which second-order optical nonlinearity is first observed to decrease is taken as defining the thermal stability of the material [2,3,5,63,63]. It is important to understand that the loss of second-order nonlinear optical activity measured in such experiments is not due to chemical decomposition of the electro-optic material but rather is due to relaxation of poling-induced acentric... 

Fig. 6. Measurement of photostability of two polymeric electro-optic materials as carried out by researchers at IPITEK (TACAN) Corporation. The data represented by the solid line correspond to the LRD-3 DEC material of Dalton and co-workers [138] while the data represented by open circles correspond to a diaminonitrostilbene chromophore/poly(methyl methacrylate) guest/host material produced by IBM Almaden Laboratories. The dramatic improvement observed for the DEC material can be associated with increased lattice hardness from the chromophore coupling to adjacent polymer chains...

As is evident from a consideration of Figs. 7-9, each of these chromophores has exhibited electro-optic activity exceeding that of lithium niobate while at the same time exhibiting auxiliary properties of chemical stability (Td >300 °C) and solubility that permits preparation of device quality materials [183,210-212]. These materials also illustrate another major direction in the preparation of electro-optic materials namely, the development of bridging segments that lead to improved chemical stability, improved solubility in spin-casting solvents, improved compatibility with polymer host materials, and which inhibit unwanted intermolecular electrostatic interactions (we shall discuss such interactions... 

Kaino and co-workers [255] have investigated the effect of polymer polydis-persity on electro-optic materials properties. No dependence on polydispersity was observed for guest host materials but for Disperse Red chromophores covalently attached to monodisperse polystyrene weaker absorption tails were observed. This result suggests that chromophore-chromophore interactions are modified by the polymer host. 

Fig. 21. Dynamic thermal stability [121] of a variety of polymeric electro-optic materials. All materials involve the Disperse Red chromophore. Trace 1 PMMA composite material trace 2 chromophore covalently attached by one end to a soft (PMMA-like) matrix [138] trace 3 DEC chromophore with both ends attached to a soft polymer matrix [138] trace 4 Disperse Red chromophore covalently attached at one end to a polyimide polymer matrix [121] trace 5 DEC-type chromophore with both ends attached to a sol-gel type matrix [139]...

As already noted, resistive loss in metal electrode structures and in transition from millimeter wave waveguides to the electrode structure is the greatest problem in achieving 100 GHz and higher electro-optic modulation. Fetterman and co-workers [301] have shown by pulse techniques that the 3-dB bandwidth of polymeric electro-optic materials is typically in the order of 360 GHz for 1 cm of material. Stripline electrode structures have been used to achieve operation to somewhat above 100 GHz. Fetterman and co-workers [282] have recently described a novel finline transition between a millimeter waveguide and such elec-... 

Optical propagation loss for polymeric electro-optic materials is typically in the order of 1 dB/cm when care is taken to avoid scattering losses associated with processing and poling-induced damage [2, 3, 5, 63, 64, 257]. Lower loss values can be obtained by isotopic replacement of protons with deuterium and with halogens [211, 304, 305]. With effort, electro-optic material losses can be reduced to approximately 0.2 dB/cm for the telecommunication wavelengths of 1.3 and 1.55 microns. 

TACAN has prepared a summary table of the performance of polymeric electro-optic materials and comparison with inorganic materials (Table 5). Note that, although this compilation by TACAN is only a year old, the future performance of polymeric electro-optic materials has already been realized. 

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