Dynamics of Additive Migration to Form Cathodic Interlayers in Organic Solar Cells

Migration of additives to organic/metal interfaces can be used to self-generate interlayers in organic electronic devices. To generalize this approach for various additives, metals, and organic electronic devices it is first necessary to study the dynamics of additive migration from the bulk to the top organic/metal interface. In this study, we focus on a known cathode interlayer material, polyethylene glycol (PEG), as additive in P3HT:PC₇₁BM blends and study its migration to the blend/Al interface during metal deposition and its effect on organic solar cell (OSC) performance. Using dynamic secondary ion mass spectroscopy (DSIMS) depth profiles and X-ray photoelectron spectroscopy surface analysis (XPS), we quantitatively correlate the initial concentration of PEG in the blend and sequence of thermal annealing/metal deposition processes with the organic/Al interfacial composition. We find that PEG is initially distributed within the film according to the kinetics of the spin coating process, i.e., the majority of PEG accumulates at the bottom substrate, while the minority resides in the film. During electrode evaporation, PEG molecules kinetically "trapped" near the film surface migrate to the organic/Al interface to reduce the interfacial energy. This diffusion-limited process is enhanced with the initial concentration of PEG in the solution and with thermal annealing after metal deposition. In contrast, annealing the film before metal deposition stalls PEG migration. This mechanism is supported by corresponding OSC devices showing that V_oc increases with PEG content at the interface, up to a saturation value associated with the formation of a continuous PEG interlayer. Presence of a continuous interlayer excludes the driving force for further migration of PEG to the interface. Revealing this mechanism provides practical insight for judicious selection of additives and processing conditions for interfacial engineering of spontaneously generated interlayers.