Asymmetric Substitution of End‐Groups Triggers 16.34% Efficiency for All‐Small‐Molecule Organic Solar Cells

Asymmetric substitution of end-groups is first applied in molecular donors. Three commonly used end-groups of 2-ethylhexyl cyanoacetate (CA), 2-ethylhexyl rhodanine (Reh), and 1H-indene-1,3(2H)-dione (ID) are combined to construct a series of symmetric and asymmetric donors. Correspondingly, the asymmetric donors SM-CA-Reh and SM-CA-ID show largely increased dipole moments (2.14 and 3.39 D, respectively) and enhanced aggregation propensity, as compared to those of symmetric donors of SM-CA, SM-Reh, and SM-ID. Using N3 as acceptor, interestingly, SM-CA-Reh integrates the photovoltaic characteristics of high fill factor (FF) for SM-CA and high short-circuit current density for SM-Reh, and delivers a record power conversion efficiency (PCE) of 16.34% with a high FF of 77.5%, which is much higher than 15.41% for SM-CA and 14.76% for SM-Reh. However, SM-CA-ID and SM-ID give the lower PCE of 8.20% and 2.76%. Characterization results suggest that the π-π interaction mainly dictates the packing morphology of blend films instead of dipole effect or crystallinity. Mono-substitution of Reh facilitates the molecular demixing appropriately but keeps the characteristic of the fine bicontinuous network of SM-CA:N3. SM-CA-Reh:N3 shows more efficient exciton extraction, higher hole transport, and better miscibility. These results well explain the merits integration and improved photovoltaic performance.