Chlorination: An Effective Strategy for High‐Performance Organic Solar Cells

This work summarizes recent developments in polymer solar cells (PSCs) prepared by a chlorination strategy. The intrinsic property of chlorine atoms, the progress of chlorinated polymers and small molecules, and the synergistic effect of chlorination with other methods to elevate solar conversions are discussed. Halogenation of donor–acceptor (D–A) materials is an effective method to improve the performance of PSCs, which mainly affects the push–pull of electrons between donor and acceptor units due to their strong electron‐withdrawing capabilities. Although chlorine is less electronegative than fluorine, it can form very strong noncovalent interactions, such as Cl···S and Cl···π interactions, because its empty 3d orbits can help to accept the electron pairs or π electrons. This synergistic effect of electronegativity together with the empty 3d orbits of chlorine atoms leads to increased intramolecular and intermolecular interactions and a much stronger capability to down‐shift the molecular energy levels. This work is intended to support a better understanding of the chlorination strategy to modify the material properties, and thus improve the performance of solar devices. Eventually, it will provide the research community with a clearer pathway to choose proper substitution methods according to different situations for high and stable solar energy conversion.