Host matrix dependent fluorescence intensity modulation by an electric field in single conjugated polymer chains

An electric field oscillating at a frequency similar to 1 Hz is found to induce strong modulation of the fluorescence intensity of single poly[2-methoxy,5-(2'-ethyl-hexyloxy)-p-phenylene vinylene] (MEH-PPV) molecules (M-W similar to 10(6)) embedded in a poly(methyl methacrylate) (PMMA) matrix. The MEH-PPV polymer chains are carefully isolated from the electrodes to avoid effects of injection. In a polystyrene matrix, fluorescence intensity modulations are on average much less pronounced. The difference in average modulation depth can be explained in terms of lower field-induced exciton dissociation rates in the MEH-PPV/polystyrene system compared to MEH-PPV/PMMA because of a lack of suitable acceptor sites. The observed electric field dependence of single-molecule fluorescence strongly suggests that energy transfer from singlet or even triplet excitons to long-living on-chain hole polarons contributes to the observed modulations. The observed large qualitative differences between the responses of different molecules probably reflect differences in chain topology and strongly anisotropic distributions of acceptor sites, while the hysteretic response of some molecules indicates conformational switching.