Quantum and Nanoscale Modelling of Exciton Dynamics in Polymeric Systems

One of the factors that limit the efficiency of polymer-based optoelectronic devices, such as photovoltaic solar cells and light emitting diodes, is the exciton diffusion within the polymeric network. Due to the amorphous nature the of polymeric materials, the diffusion of excitons is limited by the energetic and spatial disorder in such systems, which is a consequence not only of the chemical structure of the polymer but also from its morphology at nanoscale. To get a deep understanding on how such effects influence exciton dynamics we performed a quantum molecular dynamics simulations to determine the energetic disorder within the polymer system, and Monte Carlo simulations to study exciton diffusion in three-dimensional (3D) polymer networks that present both spatial and energetic disorder at nanometre scale. Our results show clearly that exciton diffusion in poly(pphenylenevinylene) (PPV) occurs preferentially in the direction parallel to the electrodes surface for a polymer-based optoelectronic devices with the orientation of the conjugated strands similar to those obtained by the spin-coating technique and the decay of such excitons occurs preferentially in longer strands which allow us to get insight on exciton behaviour in polymeric systems that are not possible to be obtained directly from the experiments.