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23 September 2005 In-situ synthesis and alignment by poling of a zwitterionic NLO chromophore in a polymeric guest-host system
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The conversion of the complex salt of TCNQ and triethylamine; TEA(TCNQ)2 into the zwitterionic NLO chromophore DEMI can be achieved in a polymeric guest host system. Synthesis of the chromophore in a thin polymer film can be monitored by observation of the SHG in an in-situ poling experiment. We discuss the characterization of the conversion process, which could potentially lead to the "writing" of very small areas of nonlinearly active material into otherwise inactive polymer films. We have found that the transformation from organic salt to NLO (Non linear Optical) chromophore occurs at approximately 160°C, the transformation is accompanied by a dramatic change in colour from green to blue and by an accompanying decrease in conductivity. The resultant blue spectrum is identical to that obtained by doping DEMI into PMMA. All characteristic TCNQ- peaks in the UV/Vis absorption spectrum are completely diminished, and the reaction appears to be almost 100% efficient. In-situ corona poling experiments, while heating a thin film of TEA(TCNQ)2 in PMMA above its glass transition temperature reveal no SHG from an input wavelength of 1.9 microns until the conversion temperature is achieved. At this point when DEMI has been "synthesised" in the sample the SHG can be observed and its relative intensity measured relative to that of a quartz plate. We also discuss the attempted synthesis in situ of a related zwitterionic NLO chromophore Me-P3CNQ.
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Marek Szablewski and Graham H. Cross "In-situ synthesis and alignment by poling of a zwitterionic NLO chromophore in a polymeric guest-host system", Proc. SPIE 5949, Nonlinear Optics Applications, 594902 (23 September 2005);

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