The Role of Entropy Gains in the Exciton Separation in Organic Solar Cells

Abstract In organic solar cells (OSCs), the lower dielectric constant of organic semiconductor material induces a strong Coulomb attraction between electron–hole pairs, which leads to a low exciton separation efficiency, especially the charge transfer (CT) state. The CT state formed at the electron‐donor (D) and electron‐acceptor (A) interface is regarded as an unfavorable property of organic photovoltaic devices. Since the OSC works in a nonzero temperature condition, the entropy effect would be one of the main reasons to overcome the Coulomb energy barrier and must be taken into account. In this review, the present understanding of the entropy‐driven charge separation is reviewed and how factors such as the dimensionality of the organic semiconductor, energy disorder effect, the morphology of the active layer, are described, as well as how the nonequilibrium effect affects the entropy contribution in compensating the Coulomb dissociation barrier for CT exciton separation and charge generation process. The investigation of the entropy effect on exciton dissociation mechanism from both theoretical and experimental aspects is focused on, which provides pathways for understanding the underlying mechanisms of exciton separation and further enhancing the efficiency of OSCs.