Electric field poling, polar order

Three synthetic approaches to donor-acceptor-substituted conjugated molecules with enhanced orientability in electric fields, potentially applicable to the preparation of electro-optic polymers via electric field poling, are summarized. The three approaches are parallel attachment of chromophores to a common framework, embedding the chromophore in a zwitterion, and head-to-tail oligomerization of chromophores. The oligomerization method as well as the use of dyes as curing agents are briefly discussed in relation to the stability of electric field-induced polar order in polymer matrices. 

In the limit of the oriented gas model with a one-dimensional dipolar molecule and a two state model for the polarizability (30). the second order susceptibility X33(2) of a polymer film poled with field E is given by Equation 4 where N/V is the number density of dye molecules, the fs are the appropriate local field factors, i is the dipole moment, p is the molecular second order hyperpolarizability, and L3 is the third-order Langevin function describing the electric field induced polar order at poling temperature Tp - Tg. 

For dipolar chromophores that are the subject of this chapter, only one component of the molecular hyperpolarizability tensor, Pzzz, is important. Thus, the summation in Eq. (8) disappears. Electric field poling induces Cv cylindrical polar symmetry. Assuming Kleinman [12] symmetry, only two independent components of the macroscopic second-order nonlinear optical susceptibility tensor... 

The piezoelectric effect stems from hydrogen and fluorine atoms in the VDF, which are positioned perpendicularly to the polymer backbone. Fig. 5.7A shows a typical molecular structure of PVDF with different crystalline phases (Chang et al., 2012). The piezoelectric performance of PVDF is dependent on the nature of the crystalline phase (Crossley et al., 2014). Typically, PVDF has three crystalline phases, namely a, p, and y, and it is the a-phase that typically forms in most situations. While it is polar p-phase that shows the strongest piezoelectric behavior so this material needs to be electrically poled using an electric field with the order of 100 MV m or mechanically stretched. A higher P-phase crystalline can lead to a higher piezoelectric coefficient Note that the copolymer of P(VDF-TrFE) [(CH2-CF2) -(CHF-CF2)ml crystallizes more easily into the P-phase due to steric factors (Furukawa, 1989). So, the most applied material in piezoelectric generator is P(VDF-TrFE). 

Twieg and coworkers, reported preparation of poly(norbomene) copolymers functionalized with nonlinear optical chromophore side groups. Use was made of (ri -toluene)Ni(C6F5)2, catalyst in the polymerization of norbomene. The nickel complex used to polymerize the norbomene monomers is tolerant to many functional groups found in nonlinear optical chromophores. On the other hand, nitriles and amines other than trisubstituted amines strongly inhibit the reaction. A copolymer of hexylnorbomene and a norbomene-functionalized Disperse Red I chromophore was scaled up and studied in detail. Initial studies indicate that electric field poling is effective but that relaxation of polar order in the poly(norbomene) is faster than in a comparable methacrylate copolymer. The copolymer can be illustrated as follows ... 

However, organic polymers, being amorphous, do not show second-order NLO effects. In order to employ them in second-order NLO measurements a polar order is induced by an external means such as electric field poling process or the Langmuir-Blodgett (LB) technique. Poled polymers and the majority of the LB films possess Cocv symmetry. Therefore, the second-order optical susceptibility tensor for SHG has only three independent nonzero elements, namely, zS ZzM Under Klienman symmetry [9] conjecture... 

The early studies on electric field poling were performed mainly on the guest-host systems, for instance, DANS dissolved in thermotropic nematic liquid-crystalline polymers [12]. In this guest-host system polar order decays rapidly. The Xzz] value was about 1 pm/V. Therefore, the later investigations on guest-host systems were focused on both increasing the temporal stability as well as the x value. 

The statistically non-centrosymmetric polar order of the chromophore units reached during the poling procedure is thermodynamically stable only with the electric field on. Once cooled down at room temperature and switched off the field, that polar order becomes metastable and it will relax to the more stable centrosymmetric arrangement, which is not NLO active. So, an other fundamental issue is to reach an high time stability of the polar order. Industrial standards for device testing require stability of NLO performances for 10 years at 85°C, that are quite severe. 

It should be stated that an electric field of < 10 V/pm was applied to the cell in order to unwind the FLC helix of 3, and the observed NLO behavior is a combination of the electric field induced SHG (EFISH) and that due to the spontaneous polar order in the phase. While other FLCs give much lower SHG efficiency with the same applied fields, and achiral smectic LC phenylbenzoates in our hands give unobservable SHG under identical conditions, we cannot completely rule out at this time the possibility that a significant amount of the response from compound 3 is due to the electrical poling. Control experiments to test for this (e.g. by SHG from compound 5 and/or racemic 3) are in progress, as are further experiments aimed at obtaining the phase-matched SHG efficiency for 3. 

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