To elucidate mechanism of the efficient photo-carrier generation by the photoactive bulkheterojunction layers of the organic photovoltaic (OPV) devices, we have employed the time-resolved electron paramagnetic resonance method on solid blends composed of 6,6-C_(61)-butyric acid methyl ester (PCBM) and of poly(3-hexylthiophene-2,5-diyl) (P3HT) with different regioregularities. The photoinduced charge-separated (CS) states have been detected at the boundary regions between the P3HT and PCBM domains at T = 77 K. We have characterized molecular geometries, electronic couplings, and molecular motions of the long-range CS states. From the CS structure, it is indicated that the pentagonal or hexagonal aromatic rings of the buckyball in PCBM directly face the aromatic plane of the π-stacked P3HT surfaces. It has been concluded that the distant CS states are produced via fast hole-delocalization process from the contact charge-transfer (CT) states. Such hole dynamics is explained by a coupling of the hole to librations of chains in the conjugated polymer. It has been concluded that both the enthalpy stabilization and the enhancement of the entropy occur through the orbital delocalization by the electron—phonon coupling, overcoming the initial CT binding to generate the molecular photocurrent.
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