Electrical Performance of Organic Solar Cells with Additive‐Assisted Vertical Phase Separation in the Photoactive Layer

Understanding the vertical phase separation of donor and acceptor compounds in organic photovoltaics is requisite for the control of charge transport behavior and the achievement of efficient charge collection. Here, the vertically phase‐separated morphologies of poly(3‐hexylthiophene):[6,6]phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) blend films are examined with transmission electron microtomography, dynamic secondary ion mass spectroscopy, and X‐ray photoelectron spectroscopy. The 3D morphologies of the processed films are analyzed and how the solvent additive causes vertical segregation is determined. The photocurrent–voltage characteristics of the vertically segregated blend films are strongly dependent on the 3D morphological organization of the donor and acceptor compounds in the photoactive layer. This dependence is correlated with asymmetric carrier transport at the buried interface and the air surface in the vertically segregated blend films.