The rate of photoinduced electron
transfer (PET) (κ<sub>PET</sub>), quantum yield of PET (QY<sub>PET</sub>), and charge extraction yield (EQE) are determined for
a series of donor–acceptor (DA) organic photovoltaic systems,
comprising low-band-gap polymer donors and the phenyl-C<sub>61</sub>-butyric acid methyl ester (PCBM) acceptor. The energetic alignment
of these polymer donors relative to PCBM provides driving forces for
PET (Δ<i>G</i><sub>PET</sub>) in the range of 0.18–0.57
eV. Femtosecond transient absorption (TA) spectroscopy was used to
assess the PET kinetics and QY<sub>PET</sub>, while time-resolved
charge extraction (TRCE) measurements were employed to assess EQE.
Near unity QY<sub>PET</sub> was observed in DA blend films with a
Δ<i>G</i><sub>PET</sub> of 0.57 and 0.30 eV, whereas
no resolvable PET was observed with a Δ<i>G</i><sub>PET</sub> of 0.18 eV. For the DA blends that exhibit PET, both κ<sub>PET</sub> and QY<sub>PET</sub> appear independent of Δ<i>G</i><sub>PET</sub>, with an average κ<sub>PET</sub> of
420 fs for the 70% PCBM blends. An increase in nanosecond charge separation
yield (TA) and EQE (TRCE) between DA systems was observed, which appears
not to be due to the PET process but rather the subsequent recombination
processes. DA systems should be designed to minimize Δ<i>G</i><sub>PET</sub>, minimizing associated losses in device
open-circuit potential; however, picosecond bimolecular recombination
severely limits achievable charge extraction yields in these DA systems