Enhanced Self-Stimulated Dissociation in Non-fullerene Layer-by-Layer Organic Solar Cells through Superimposed and Oriented Dipolar Polarization

Abstract

A non-fullerene layer-by-layer (LBL) structure can establish effective donor/acceptor (D/A) interfaces and lead to remarkable photovoltaic efficiencies based on facile solution processing properties, as compared with non-fullerene bulk heterojunction devices. However, the operating mechanisms have been remaining as an unaddressed issue to understand the role of D/A interfaces toward developing photovoltaic processes in non-fullerene LBL where the high electrically polarizable non-fullerene molecules exist. Here, we address the operating mechanisms of photovoltaic actions by in situ monitoring the dynamic D/A interfaces upon selectively exciting the non-fullerene acceptor layer to address the effects of optically induced superimposed and oriented dipoles on electron–hole pair self-stimulated dissociation in non-fullerene LBL organic solar cells [ITO/PEDOT:PSS/PM6/Y6/PDIN/Al]. Essentially, the self-stimulated dissociation at the D/A interfaces can be monitored by magneto-photocurrent while separately exciting the donor and acceptor components with two different laser beams. We observed an interesting phenomenon that optically exciting the non-fullerene Y6 acceptor component leads to easier electron–hole dissociation at D/A interfaces and consequently an increase on electron–hole pair self-stimulated dissociation to generate photocurrent in non-fullerene LBL solar cells. This phenomenon presents a hypothesis that optically exciting the compactly stacked non-fullerene Y6 molecules induces superimposed and oriented electrical dipoles within A–D–A–D–A structures to increase the self-stimulated dissociation at D/A interfaces toward developing the photovoltaic actions in non-fullerene LBL solar cells. This hypothesis is supported by our photoinduced capacitance result: photoexcitation increases bulk polarization in the dipolar polarization zone in non-fullerene LBL solar cells. Furthermore, optically generated dipoles are verified by photoinduced magneto-capacitance, solely generated by photoinduced polarization rather than photogenerated carriers, in non-fullerene LBL PM6/Y6. Clearly, the optically generating superimposed and oriented electrical dipoles become a critical parameter to operate the photovoltaic actions at D/A interfaces in non-fullerene LBL solar cells.