This article provides an overview on the recent development of solution processed organic, inorganic, and hybrid interfacial materials for bulk-heterojunction polymer solar cells. The introduction of proper interfacial materials to optimize the electronic and electrical properties between the interfaces of the light-harvesting active layer and the charge-collecting electrode has become an important criterion to improve the performance of polymer solar cells. The electronic processes at these interfaces play a critical role in determining the efficiency for photon-to-electricity conversion. An ideal interface requires the formation of Ohmic contact with minimum resistance and high charge selectivity to prevent charge carriers from reaching the opposite electrodes. For long-term stability of polymer solar cells, interfaces with matched surface energy are required to prevent interfacial dewetting and delamination. Several classes of interfacial materials including inorganic metal oxides, crosslinkable charge-transporting materials, conjugated polymer electrolytes, self-assembled functional molecules, and graphene-based materials are highlighted and the integration of these interfacial materials with new low bandgap polymers and fullerene derivatives as active materials in different device architectures is also discussed.
