Polymer physics and structure/property relationships of thermally stable polyarylene ethers for second order nonlinear optics.

摘要

Over the past decade, researchers have been actively involved in developing nonlinear optical polymers for device applications. One major obstacle with the current polymers is that the chromophores doped or covalently bonded to the backbones disorient following electric field poling and thus the nonlinear optical signal decreases with time. The optical stability must thus be optimized before useful devices made from these materials will be feasible. Although several synthetic approaches have been employed to optimize polymer structures and glass transition temperatures in order to maximize stability, the studies of the polymer physics of these high temperature stable polymers are still limited. It is critical to understand the polymer physics governing the relaxation behavior of these nonlinear optical polymers so that one can better predict the long-term thermal and temporal stability and changes in properties throughout the anticipated service life when utilizing them for device applications.;The goal of this research is to investigate the structure/property relationships that influence the relaxation behavior of a class of thermally stable polymers called polyarylene ethers (synthesized by Dr. Duane B. Priddy, Jr., Mr. Greg D. Lyle, and Dr. James E. McGrath at Virginia Polytechnic Institute and State University). Specific issues such as the effects of polymer backbone structures, dopant/polymer interactions, chromophore functionalization, and chromophore concentration on the dopant orientational dynamics and intermolecular cooperativity in these polymer systems were studied. Attempts to correlate the molecular level parameters including the molecular weight and polydispersities to the observed physical properties were made. The effect of physical aging during poling on the chromophore orientational dynamics was also examined. Second harmonic generation, a second order nonlinear optical effect, and dielectric relaxation are the two techniques employed for these studies. By examining the second order nonlinear optical properties of the doped or functionalized polymeric material as a function of time and temperature, and the dielectric relaxation phenomena as a function of frequency and temperature, information concerning the local mobility and relaxation phenomena of the polymer microenvironment surrounding the chromophores can be obtained. This information is important for better tailoring the polymers for second order nonlinear optical applications.