Quaternary Organic Solar Cells Enhanced by Cocrystalline Squaraines with Power Conversion Efficiencies >10%

The incorporation of multiple donors into the bulk‐heterojunction layer of organic polymer solar cells (PSCs) has been demonstrated as a practical and elegant strategy to improve photovoltaics performance. However, it is challenging to successfully design and blend multiple donors, while minimizing unfavorable interactions (e.g., morphological traps, recombination centers, etc.). Here, a new Förster resonance energy transfer‐based design is shown utilizing the synergistic nature of three light active donors (two small molecules and a high‐performance donor–acceptor polymer) with a fullerene acceptor to create highly efficient quaternary PSCs with power conversion efficiencies (PCEs) of up to 10.7%. Within this quaternary architecture, it is revealed that the addition of small molecules in low concentrations broadens the absorption bandwidth, induces cocrystalline molecular conformations, and promotes rapid (picosecond) energy transfer processes. These results provide guidance for the design of multiple‐donor systems using simple processing techniques to realize single‐junction PSC designs with unprecedented PCEs.