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Effects of side-chain modification on poling efficiency of highly polarizable nonlinear optical chromophores in electro-optical polymers

Monte Carlo simulations suggest that the functionalization of bulky side groups on highly efficient nonlinear optical chromophores will improve the poling efficiency of the electro-optic polymers by reducing the intermolecular electrostatic interactions from these large dipole moments (μ) chromophores. However, very little information has been provided from theoretical simulation to describe the optimal functionality of the bulky side group needed on individual chromophore in order to be compatible with its environment, e.g. neighboring chromophores and polymer matrix. To further understand the influence of side-chain modification of chromophore on both chromophore-chromophore and chromophore-polymer matrix interactions, we have synthesized a series of highly polarizable nonlinear optical chromophores with various side-chain modifications in terms of shape, rigidity and functionality. Linear E-O coefficients (r33) of these functionalized chromophores in amorphous poly(carbonate) were evaluated using the contact poling technique. Several important chromophore and polymer parameters, such as, steric hindrance and free volume were used to explain the overall results from chromophore-chromophore and chromophore-polymer matrix interactions on E-O property.