Charge Generation Dynamics in Organic Photovoltaic Blends under One-Sun-Equivalent Illumination Detected by Highly Sensitive Terahertz Spectroscopy

Organic photovoltaic (OPV) devices attain high performance with nonfullerene acceptors by utilizing the synergistic dual channels of charge generation that originate from excitations in both the donor and acceptor materials. However, the specific intermediate states that facilitate both channels are subject to debate. To address this issue, we employ time-resolved terahertz spectroscopy with improved sensitivity (ΔE/E < 10^-6), enabling direct probing of charge generation dynamics in a prototypical PM6:Y6 bulk heterojunction system under one-sun-equivalent excitation density. Charge generation arising from donor excitations is characterized with a rise time of ∼9 ps, while that from acceptor excitations shows a rise time of ∼18 ps. Temperature-dependent measurements further reveal notably distinct activation energies for these two charge generation pathways. Additionally, the two channels of charge generation can be substantially manipulated by altering the ratio of bulk to interfaces. These findings strongly suggest the presence of two distinct intermediate states: interfacial and intramoiety excitations. These states are crucial in mediating the transfer of electrons and holes, driving charge generation within OPV devices.