Fluorous Fullerene Acceptors in Vacuum‐Deposited Photovoltaic Cells

The first successful example of vacuum‐deposited organic photovoltaic (OPV) cells based on a fullerene derivative and a small‐molecule donor is reported. A series of thermally robust fluorous fullerene acceptors with experimental gas‐phase electron affinities ranging from 2.8 to 3.3 eV are paired with a new dicyanovinyl thiophene‐based molecular donor to enable direct comparison of their performance in planar and bulk heterojunction architectures in the cells fabricated by vacuum deposition. Unprecedented insights into the role of the acceptor intrinsic molecular and electronic structures are obtained, which are not obscured by solvent and additive effects as in the typical solution‐processed fullerene‐based OPV cells.