Correlating the electron-donating core structure with morphology and performance of carbon-oxygen-bridged ladder-type non-fullerene acceptor based organic solar cells

The chemical structure of non-fullerene acceptors (NFAs) affects their light-harvesting capabilities, energy levels and molecular orders, all of which play a crucial role in determining the efficiency of organic solar cells (OSCs). In this work, we have systematically investigated a series of ladder-type NFAs having different carbon-oxygen-bridged electron-donating cores, and revealed the effects of core structures and film casting conditions on molecular ordering and performance of OSCs. We found that NFAs containing the thieno [3,2-b]thiophene centered, 6 or 8 fused rings (i.e. COi6DFIC, COi8DFIC) exhibit narrower optical band gaps than NFAs containing the benzene centered, 5 or 7 fused rings (i.e. COi5DFIC, COi7DFIC). NFAs containing less fused rings in the carbon-oxygen-bridged core (i.e. COi5DFIC and COi6DFIC) exhibit edge-on molecular orientation in the blends with face-on oriented PTB7-Th donor, and result in low device efficiency. Although NFAs containing more fused rings (i.e. COi7DFIC and COi8DFIC) possess a pronounced flat-on lamellar crystalline structure in the pure state, the crystallization can be reduced when blending with PTB7-Th and under hot-substrate casting, while the lamella in COi8DFIC can be effectively suppressed to form face-on H- and J-type aggregates, leading to enhanced efficiency.