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The morphology of organic semiconductors is critical to their function in optoelectronic devices and is particularly crucial in the donor-acceptor mixture that comprises the bulk heterojunction of organic solar cells. Here, energy landscapes can play integral roles in charge photogeneration, and recently have been shown to drive the accumulation of charge carriers away from the interface, resulting in the buildup of large nanoscale electric fields, much like a capacitor. In this work we combine morphological and spectroscopic data to outline the requirements for this interdomain charge accumulation, finding that this effect is driven by a three-phase morphology that creates an energetic cascade for charge carriers. By adjusting annealing conditions, we show that domain purity, but not size, is critical for an electro-absorption feature to grow-in. This demonstrates that the energy landscape around the interface shapes the movement of charges and that pure domains are required for charge carrier buildup that results in reduced recombination and large interdomain nanoscale electric fields.

Organic photovoltaic (OPV) efficiencies continue to rise, raising their prospects for solar energy conversion. However, researchers have long considered how to suppress the loss of free carriers by recombination—poor diffusion and significant Coulombic attraction can cause electrons and holes to encounter each other at interfaces close to where they were photogenerated. Using femtosecond transient spectroscopies, we report the nanosecond grow-in of a large transient Stark effect, caused by nanoscale electric fields of ∼487 kV/cm between photogenerated free carriers in the device active layer. We find that particular morphologies of the active layer lead to an energetic cascade for charge carriers, suppressing pathways to recombination, which is ∼2000 times less than predicted by Langevin theory. This in turn leads to the buildup of electric charge in donor and acceptor domains—away from the interface—resistant to bimolecular recombination. Interestingly, this signal is only experimentally obvious in thick films due to the different scaling of electroabsorption and photoinduced absorption signals in transient absorption spectroscopy. Rather than inhibiting device performance, we show that devices up to 600 nm thick maintain efficiencies of >8% because domains can afford much higher carrier densities. These observations suggest that with particular nanoscale morphologies the bulk heterojunction can go beyond its established role in charge photogeneration and can act as a capacitor, where adjacent free charges are held away from the interface and can be protected from bimolecular recombination.