Modulating the Mixing Gibbs Free Energy to Enhance Solid–Liquid Phase Separation for High‐Performance Organic Solar Cells

Abstract Organic solar cells (OSC) feature a hierarchical structure with the electron donor/acceptor layer sandwiched by anode and cathode, which raises the importance of controlling the molecular crystal orientation, domain size, and vertical distribution to facilitate the charge collection at electrodes. However, the similar conjugated backbone of donor/acceptor material and fast film‐formation kinetics have led to spinodal‐decomposition‐orientated phase separation that result in the film presenting an intimately mixed morphology and random molecular orientation. To solve the issue, the mixing Gibbs free energy‐triggered solid–liquid phase separation during the film formation process is enhanced by solidifying one component and solvating the other based on a liquid additive. Following the liquid evaporation process, a favorable vertical distribution is obtained. Meanwhile, the prolonged solvation process enlarges the domain size and assists the molecules to diffuse and orient properly, enabling better exciton/charge dynamics during the power conversion processes. As a result, the fabricated devices exhibit a fill factor over 80% and an efficiency of 18.72%, which is one of the top efficiencies for binary OSCs. Insights and a methodology is provided here to manipulate the organic donor/acceptor phase separation in terms of mixing Gibbs free energy.