The electro-optical properties of thin films of electron donor-acceptor blends of a fluorene copolymer (PF10TBT) and a fullerene derivative (PCBM) were studied. Transmission electron microscopy shows that in these films nanocrystalline PCBM clusters are formed at high PCBM content. For all concentrations, a charge transfer (CT) transition is observed with absorption spectroscopy, photoluminescence, and electroluminescence. The CT emission is used as a probe to investigate the dissociation of CT excited states at the donor-acceptor interface in photovoltaic devices, as a function of an applied external electric field and PCBM concentration. We find that the maximum of the CT emission shifts to lower energy and decreases in intensity with higher PCBM content. We explain the red shift of the emission and the lowering of the open-circuit voltage (V(OC)) of photovoltaic devices prepared from these blends with the higher relative permittivity of PCBM (epsilon(r) = 4.0) compared to that of the polymer (epsilon(r) = 3.4), stabilizing the energy (E(CT)) of CT states and of the free charge carriers in blends with higher PCBM concentration. We show that the CT state has a short decay time (tau = ca. 4 ns) that is reduced by the application of an external electric field or with increasing PCBM content. The field-induced quenching can be explained quantitatively with the Onsager-Braun model for the dissociation of the CT states when including a high electron mobility in nanocrystalline PCBM clusters. Furthermore, photoinduced absorption spectroscopy shows that increasing the PCBM concentration reduces the yield of neutral triplet excitons forming via electron-hole recombination, and increases the lifetime of radical cations. The presence of nanocrystalline domains with high local carrier mobility of at least one of the two components in an organic heterojunction may explain efficient dissociation of CT states into free charge carriers.

A power conversion efficiency of 4.2% (AM1.5, 1000W∕m2) is measured for an organic solar cell based on an active layer of an alternating copolymer, containing a fluorene and a benzothiadiazole unit with two neighboring thiophene rings, and a fullerene derivative. Using optical modeling, the absorption profile in the active layer of the solar cell is calculated and used to calculate the maximum short circuit current. The calculated currents are compared with measured currents from current-voltage measurements for various film thicknesses. From this the internal quantum efficiency is estimated to be 75% at the maximum for the best device.