The charge-transport characteristics of phase-separated blend films of poly(3-hexylthiophene) (P3HT; electron donor) and poly[2, 7-(9, 9-didodecylfluorene)-alt-5, 5-(4′, 7′-bis(2-thienyl)-2′, 1′, 3′-benzothiadiazole)] (PF12TBT; electron acceptor) were visualized by conductive atomic force microscopy (C-AFM). The C-AFM hole-current images clearly showed two phases: an electrically conductive region assigned to the P3HT-rich donor domain and a nonconductive region assigned to the PF12TBT-rich acceptor domain. The hole current in the conductive region was small compared with that of a neat P3HT film with similar thickness, indicating that the P3HT-rich domain contained a large fraction of PF12TBT as a minor component. Thermal annealing initially increased the hole current throughout the P3HT-rich domain because of reorganization of the P3HT chains from their as-cast configurations. Further annealing increased the hole current mainly in the middle of the P3HT-rich domain, but it decreased the hole current in the boundary areas close to the PF12TBT-rich domain owing to the presence of an intermixed region with a gradient of the P3HT/PF12TBT composition ratio. After annealing at temperatures above the glass-transition point of PF12TBT, the widths of the intermixed regions decreased to ∼30 nm as phase separation proceeded with decomposition of the intermixed region. Such variations in the intermixed region, which were electrically resolved by the C-AFM, accounted for the temperature dependence of the photovoltaic properties of P3HT/PF12TBT blend solar cells.
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