The unique properties of organic semiconductors make them versatile base
materials for many applications ranging from light emitting diodes to
transistors. The low spin-orbit coupling typical for carbon-based materials and
the resulting long spin lifetimes give rise to a large influence of the
electron spin on charge transport which can be exploited in spintronic devices
or to improve solar cell efficiencies. Magnetic resonance techniques are
particularly helpful to elucidate the microscopic structure of paramagnetic
states in semiconductors as well as the transport processes they are involved
in. However, in organic devices the nature of the dominant spin-dependent
processes is still subject to considerable debate. Using multi-frequency pulsed
electrically detected magnetic resonance (pEDMR), we show that the
spin-dependent response of P3HT/PCBM solar cells at low temperatures is
governed by bipolar polaron pair recombination involving the positive and
negative polarons in P3HT and PCBM, respectively, thus excluding a unipolar
bipolaron formation as the main contribution to the spin-dependent charge
transfer in this temperature regime. Moreover the polaron-polaron coupling
strength and the recombination times of polaron pairs with parallel and
antiparallel spins are determined. Our results demonstrate that the pEDMR pulse
sequences recently developed for inorganic semiconductor devices can very
successfully be transferred to the study of spin and charge transport in
organic semiconductors, in particular when the different polarons can be
distinguished spectrally
