A major challenge to increasing bandwidth in optical telecommunications is to encode electronic signals onto a lightwave carrier by modulating the light up to very fast rates. Polymer electro-optic materials have the necessary properties to function in photonic devices beyond the 40-GHz bandwidth currently available. An appropriate choice of polymers is shown to effectively eliminate the factors contributing to an optical modulator's decay in the high-frequency response. The resulting device modulates light with a bandwidth of 150 to 200 GHz and produces detectable modulation signal at 1.6 THz. These rates are faster than anticipated bandwidth requirements for the foreseeable future.

Three new azo-benzene-based push-pull chromophores with dendritic architecture were synthesized as active materials for electro-optic applications. These chromophores were synthesized in six or seven synthetic steps with an overall yield of around 80% per step and high purity. UV-vis spectroscopy showed significant influence of the transient dipole moment on the observed r(33) values. The chromophores were stable to photochemical oxidation in ambient light and air. The electrical poling conditions were optimized for each chromophore as the T(g) of the composite material varied significantly. The highest EO coefficient achieved was 22-25 pm/V at 1550 nm wavelength. STEM analysis of the blends enabled the correlation of the activity of these large chromophores with the blend morphology. An amorphous polycarbonate host effectively disperses the chromophores in 2-20 nm aggregates in the active materials. However, macrophase separation into 200-500 nm aggregates was observed in a methacrylate host matrix.

Recently, individual single-walled carbon nanotubes (SWNTs) functionalized with azo-benzene chromophores were shown to form a new class of hybrid nanomaterials for optoelectronics applications. Here we use a number of experimental and computational techniques to understand the binding, orientation, and nature of coupling between chromophores and the nanotubes, all of which are relevant to future optimization of these hybrid materials. We find that the binding energy between chromophores and nanotubes depends strongly on the type of tether that is used to bind the chromophores to the nanotubes. The pyrene tethers form a much stronger attachment to nanotubes compared to anthracene or benzene rings, resulting in more than 80% retention of bound chromophores post-processing. Density functional theory (DFT) calculations show that the binding energy of the chromophores to the nanotubes is maximized for chromophores parallel to the nanotube sidewall, even with the use of tethers; optical second harmonic generation measurements show that there is nonetheless a partial radial orientation of the chromophores on the nanotubes. We find weak electronic coupling between the chromophores and the SWNTs, consistent with noncovalent binding. This weak coupling is still sufficient to quench the chromophore fluorescence through a combination of static and dynamic processes. Photoluminescence measurements show a lack of significant energy transfer from the chromophores to isolated semiconducting nanotubes.

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