In order to understand exciton migration and fluorescence intensity fluctuation mechanisms in conjugated polymer single molecules, we studied fluorescence decay dynamics at "on" and "off" fluorescence intensity levels with 20 ps time resolution using MEH-PPV [poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene] dispersed in PMMA. Two types of intensity fluctuations were distinguished for single chains of conjugated polymers. Abrupt intensity fluctuations (blinking) were found to be always accompanied by corresponding changes in fluorescence lifetime. On the contrary, during "smooth" intensity fluctuations no lifetime change was observed. Time-resolved data in combination with data on fluorescence emission and excitation anisotropy lead to a picture where a single polymer molecule is seen as consisting of several energy transfer domains. Exciton migration is efficient within a domain and not efficient between domains. Each domain can have several emitting low-energy sites over which the exciton continuously migrates until it decays. Emission of individual domains is often highly polarized. Fluorescence from a domain can be strongly quenched by Forster energy transfer to a quencher (hole polaron) if the domain overlaps with the quenching sphere.
Single chains of the conjugated polymer MEH-PPV (poly(2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene)) were studied with wide-field fluorescence microscopy (dispersion in inert polymer matrices) and with fluorescence correlation spectroscopy (chloroform solution). The fluorescence yield of individual molecules in matrices was found to be 1-2 orders of magnitude lower than that in solution and it decreased substantially with increasing chain length. It suggests that isolation of MEH-PPV molecules in polymer matrices creates favorable conditions for photogeneration of nonemissive primary excited states.
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