Out-of-Phase Electron Spin Echo Studies of Light-Induced Charge-Transfer States in P3HT/PCBM Composite

The light-induced charge-transfer (CT) state in the composite of the conductive polymer poly(3-hexylthiophene) (P3HT) and the fullerene derivative [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) has been studied by electron spin echo (ESE) spectroscopy. The out-of-phase ESE signal corresponding to the spin-correlated radical pair P3HT(+)/PCBM(-) has been observed in this composite material. The time-domain ESE shape for different delays between the laser flash and the microwave pulse sequence has been analyzed. In order to explain the evolution of the out-of-phase ESE signal as a function of the delay between the microwave pulses, a model of the CT state is proposed. The hole is assumed to be delocalized on the P3HT chain over several thiophene subunits, while the point-dipole approximation is used to describe the interaction with the electron on PCBM. The distribution of distances between the positive and negative charges in the CT state has been evaluated.