Noncentrosymmetric properties

A specific set of experiments which must be mentioned, being directly associated with the main topic of this paper, is the work of Bergman, et. al. (22) dealing with the second-order nonlinear optical properties of polyvinylidene fluoride (PVF2). Nonvanishing the second-order nonlinear electric dipole susceptibility, is expected in PVF2 since it exhibits other properties requiring noncentrosymmetric microscopic structure. These properties appear... 

It has been known that alternating LB films consisting of two different amphiphiles have noncentrosymmetric structures, and therefore, are expected to provide piezoelectric, pyroelectric and nonlinear optical properties. Therefore, we prepared alternating LB films consisting of 5-(p-dodecyloxyphenyl)pyrazine-2-carboxylic acid (DOPC)... 

Second-order nonlinear optical properties of noncentrosymmetric LB films composed of pyrazine derivatives... 

Ferroelectrics. Among the 32 crystal classes, 11 possess a centre of symmetry and are centrosymmetric and therefore do not possess polar properties. Of the 21 noncentrosymmetric classes, 20 of them exhibit electric polarity when subjected to a stress and are called piezoelectric one of the noncentrosymmetric classes (cubic 432) has other symmetry elements which combine to exclude piezoelectric character. Piezoelectric crystals obey a linear relationship P,- = gijFj between polarization P and force F, where is the piezoelectric coefficient. An inverse piezoelectric effect leads to mechanical deformation or strain under the influence of an electric field. Ten of the 20 piezoelectric classes possess a unique polar axis. In nonconducting crystals, a change in polarization can be observed by a change in temperature, and they are referred to as pyroelectric crystals. If the polarity of a pyroelectric crystal can be reversed by the application on an electric field, we call such a crystal a ferroelectric. A knowledge of the crystal class is therefore sufficient to establish the piezoelectric or the pyroelectric nature of a solid, but reversible polarization is a necessary condition for ferroelectricity. While all ferroelectric materials are also piezoelectric, the converse is not true for example, quartz is piezoelectric, but not ferroelectric. 

In view of the potential technological importance of noncentrosymmetric organic crystals, several approaches have been evolved to artificially achieve noncentrosym-metry, which include electric field poling of polymers, self-assembly of molecular layers, Langmuir-Blodgett assembly of films and host-guest interaction in noncentrosymmetric hosts (Marder et al, 1994). Prediction and/or control of the three-dimensional structure of crystals, given only the information of molecular properties, however, remains difficult at present. 

The use of salt formation to expand the number of crystals which contain a single molecular type was first applied by Meredith (26), and more recently by Marder et. al. (22). In the latter work, ionic interactions are used to offset dipolar interactions among achiral molecules, which enhances the probability that the resulting crystal will be noncentrosymmetric. In our case, of course, noncentrosymmetry is ensured by the chirality of the molecules involved. It is important to note that, within the picture we have presented, neither the assurance of noncentrosymmetry, nor the enhanced hyperpolarizability of the chiral molecule guarantees that the nonlinearity of any particular chiral organic salt crystal will be large. These properties simply ensure that each crystal so formed has an equal opportunity to express the molecular hyperpolarizability in an optimized way. 

In order to bridge the gap between an SHG-active material and one optimized for use in an optoelectronic device, many compounds have been synthesized, characterized, modified and then ultimately rejected during the past decade (i-3). This is not surprising, since the ideal material must fulfil a plethora of stringent requirements (4-7). The most critical condition for an SHG-active material is that it must form noncentrosymmetric structures however, thermal stability, in volatility, transparency, lack of colour, mechanical strength and crystal habit are also crucial properties for materials to be incorporated into practical devices. 

A centrosymmetric stress cannot produce a noncentrosymmetric polarization in a centrosymmetric crystal. Electric dipoles cannot form in crystals with an inversion center. Hence, only the twenty noncentrosymmetric point groups are associated with piezoelectricity (the noncentrosymmetric cubic class 432 has a combination of other symmetry elements which preclude piezoelectricity). The piezoelectric strain coefficients, dj for these point groups are given in Table 8.7, where, as expected, crystal symmetry dictates the number of independent coefficients. For example, triclinic crystals require the full set of 18 coefficients to describe their piezoelectric properties, but mono-chnic crystals require only 8 or 10, depending on the point group. 

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