MEH-PPV photophysics: insights from the influence of a nearby 2D quencher

The effect of 2D quenching on single chain photophysics was investigated by spin coating 13 nm thick films of polystyrene lightly doped with MEH-PPV onto CVD grown graphene and observing the changes in several photoluminescent (PL) observables. With 99% of the PL quenched, we found a 60% drop in the PL lifetime, along with a significant blue-shift of the PL emission due to the preferential quenching of emission at longer wavelengths. During photo-bleaching, the blue spectral shift observed for isolated polymers was eliminated in the presence of the quencher up until 70% of the polymer was photo-bleached. Results were interpreted using a static disorder induced conjugation length distribution model. The quencher, by opening up a new non-radiative decay channel, ensures that excitons do not have sufficient time to migrate to nearby lower energy chromophores. The reduction of energy transfer into the lowest-energy chromophores thus reduces their rate of photo-bleaching. Finally, the difference between the quenched and non-quenched spectra allows the rate of energy transfer along the polymer backbone to be estimated at ∼2 ns^-1.