Structure of the Charge-Transfer State in PM6/Y6 and PM6/Y6:YT Composites Studied by Electron Spin Echo Technique

Nowadays, Y-shaped non-fullerene acceptors become increasingly important in organic photovoltaics (OPV). Their use in binary and ternary bulk heterojunction composites continuously pushes up the efficiency of OPV devices. However, the mechanism of OPV performance enhancement by the third component of a ternary composite is rarely understood. In the present work, pulse EPR technique was used to reveal the similarities and the differences of photoinduced charge separation process in binary PM6/Y6 and ternary PM6/Y6:Y-T composites, where PM6 is polymer donor, Y6 and Y-T are different non-fullerene acceptors. Out-of-phase electron spin echo signal was detected for both composites, which is the signature of the charge-transfer state (CT state) formed at the donor/acceptor interface upon exciton splitting. Nearly identical distribution of the distances between the electron and the hole constituting the CT state was obtained for these composites from the analysis of this signal. In both cases the average electron-hole distance was 3.5 nm. It implies that OPV efficiency increase with Y-T addition is not caused by the increased probability of CT state dissociation followed by free charge generation for PM6/Y6:Y-T composite.