Ensemble and single molecules fluorescence studies of polymers

The effects of chain conformation on the photo-oxidation and green emission of poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO) are investigated at both single molecule and ensemble levels. Single molecule studies reveal the conformation of PFO chains to be more globular when cast from THF than from toluene. Intensity transients of single molecules show that the elongated molecules cast from toluene have more fluctuations due to a fewer number of emitting centers on the polymer. Photochemical degradation leads to intensity fluctuations for the elongated molecules, while the globular chains show monotonic decays. Emission spectra of the single molecules show that photochemical oxidation leads to reduction in the emission of the molecule with no change in the emission spectra. No green emission is detected for single molecules indicating that formation of emissive ketone defects occurs rarely. Ensemble studies show that molecule cast from THF develop some green emission upon photodegredation while those cast from toluene don't. The increase in green in the globular molecules suggests that interchain contacts are necessary for the photochemical formation of emissive ketone defects in the PFO. All emission spectra of the aggregated and nonaggregated PFO during photooxidation are also analyzed by using a modified FranckCondon progression model with an additional independent Gaussian component and fitting results from single PFO spectrum. While emission spectrum of single PFO molecule shows a good fitting result to the model, the other two bulk PFO films display needs to introduce an additional term for better fit. This additional independent Gaussian component implies that green emission comes from non-Franck-Condon process. Rotational dynamics of poly(methyl acrylate) is investigated by single molecule spectroscopy. Polarized fluorescence transients from single rhodamine 6G dye embedded in polymer matrix above glass transition are analyzed and the correlation function of reduced linear dichroism is fit by a stretched exponential function. The fitting results suggest that non-exponential decay of correlation function. However, more rigorous study is needed because of the intrinsic statistical error of limited experimental data and the effect of high numerical objective.