New modified polyimide polymers with pendent side group nonlinear optical (NLO) azo chromophores and moderate to high glass transition temperatures (140 °C < Te < 190 °C) have been prepared. Corona poled films of these polymers possess large nonlinear optical susceptibilities of d3J = 23 pm/V and electrooptic (EO) coefficients of ri3 -6.5 pm/V at a wavelength of X = 1.3 gm. The structural properties (glass transition, molecular weight, chromophore density) and optical properties (refractive index, optical nonlinearity) of these polyimides can easily be varied to fulfill the requirements of potential electrooptic devices. Due to the relatively high glass transition temperatures of these polymers, long-term stability of the optical nonlinearity of typically one to hundreds of years at operating temperatures of 80-100 °C is predicted from accelerated time-temperature measurements. Using a development of a phenomenological theory of the glass transition, a normalized relaxation law is proposed with (Tg -T)/T as the relevant scaling parameter.
Novel amorphous nonlinear optical (NLO) polymers with modified polyimide backbones and functionalized azo chromophores have been synthesized for applications as electro-optic materials. The most attractive aspects of these polymers are the ease of modification of the NLO side-chain chromophores and the high thermal stability provided by glass transition temperatures in excess of 140 °C. The dispersion of the linear and nonlinear optical properties of these polymers has been determined. The time-temperature behaviour of the chromophore relaxation has been modeled to obtain estimates of the lifetimes of electro-optic devices using these polymers.
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