Design, synthesis and characterization of novel nonlinear optical chromophores for electro-optical applications

This dissertation involves the design, synthesis and characterization of second order nonlinear optical chromophores for electro-optic applications. The design concept, that poling efficiency and macroscopic nonlinearities can be improved by modifying a chromophore's shape, has been explored.; Chapter 1 gives an introduction into theoretical background of nonlinear optics and electro-optic phenomenon in organic molecules and poled polymers.; Chapter 2 involves the design and synthesis of GLD-2 and GLD-3 chromophores, both with bulky substituents on the ring-fused bridge. The optical studies and HRS measurement show that the two alkyl groups on the bridge blueshift the lambdamax in chloroform by 20 nm and decrease the beta values. DSC and TGA thermal analysis show Td of GLD-2 and GLD-3 over 240°C. The maximum achievable r33 of GLD-2/PMMA is 61 pm/V, compared to the 92.4 pm/V of GLD-1/PMMA. But GLD-2/APC shows r33 of 45.2pm/V, higher than GLD-1/APC due to the improved compatibility with APC. The optical loss of 13 wt% GLD-2/PMMA at 1.55mum is 1.4 dB compared to the 2.3 dB of 17 wt% GLD-1/PMMA. Optical loss studies prove that adding two bulky substituents on bridge help attenuate electrostatic interactions. GLD-3 show deteriorated solubility in common used organic solvents, probably due to the combination of two TBDMS and two lengthy alkyl groups.; Chapter 3 presents synthesis of thiophene-based chromophores with variously positioned TBDMS groups. The optical studies of these chromophores show one TBDMSO substitution on the thiophene bridge yields little influence on the lambda max in chloroform. FTCDS chromophore with two TBDMS groups, one on donor and one on thiophene bridge, shows to be the best structure with regards the thermal stability and achievable maximum EO coefficient value, 65.9 pm/V, at only 24 wt% loading density at 1.3 mum.; Chapter 4 deals with three novel bridges for NLO chromophores. Synthetic methodologies of the diketone precursor of rigidified dithienylbutadiene have been explored. One CF3 and two CF3 modified isothianaphthenes, two potential highly efficient conjugation bridges, have been synthesized successfully. Two CF3 modified isothianaphthene shows much improved thermal and chemical stabilities.