The effects of thermal annealing on the bulk transport properties of poly(3-hexylthiophene) (P3HT) were studied by analyzing room temperature current-voltage characteristics of polymer thin films sandwiched between indium tin oxide/poly[ethylene dioxythiophene]:poly[styrene sulfonate] (ITO/PEDOT:PSS) and aluminum electrodes, before and after a thermal annealing step. It was observed that annealing takes place in two steps: (1) Dedoping of the polymer of impurities such as oxygen, remnant solvent, water, leading to a decrease in the conductivity of the film, and (2) thermally induced motion of the polymer chains leading to closer packing, thus, stronger inter-chain interaction and, consequently, increase in conductivity. It was also observed that the ITO/PEDOT:PSS/P3HT hole injection barrier increases on annealing the ITO/PEDOT:PSS/P3HT/Al thin film devices. The implications of impurity dedoping and closer packing on the output characteristics of bulk heterojunction polymer-fullerene thin film solar cells are discussed.
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