Ultrafast Long-Range Charge Separation in Organic Semiconductor Photovoltaic Diodes

Early Separation In photovoltaic devices, electrons excited by the absorption of light must travel across a junction, while the positively charged “holes” they leave behind effectively migrate in the opposite direction. If the electrons and holes do not separate efficiently, they can recombine and fail to produce any appreciable current. Gélinas et al. (p. 512, published online 12 December; see the Perspective by Bredas) studied this separation process by ultrafast optical absorption spectroscopy in thiophene-derived donor-fullerene acceptor systems common in organic photovoltaics and report a rate significantly faster than simple charge diffusion would suggest. The results implicate a coherent charge delocalization process, likely to involve fullerene π-electron states. Ultrafast spectroscopy shows electrons and holes separating faster than simple diffusion would imply in organic photovoltaics. [Also see Perspective by Bredas] Understanding the charge-separation mechanism in organic photovoltaic cells (OPVs) could facilitate optimization of their overall efficiency. Here we report the time dependence of the separation of photogenerated electron hole pairs across the donor-acceptor heterojunction in OPV model systems. By tracking the modulation of the optical absorption due to the electric field generated between the charges, we measure ~200 millielectron volts of electrostatic energy arising from electron-hole separation within 40 femtoseconds of excitation, corresponding to a charge separation distance of at least 4 nanometers. At this separation, the residual Coulomb attraction between charges is at or below thermal energies, so that electron and hole separate freely. This early time behavior is consistent with charge separation through access to delocalized π-electron states in ordered regions of the fullerene acceptor material.