Influence of the Auxiliary Acceptor on the Absorption Response and Photovoltaic Performance of Dye‐Sensitized Solar Cells

Three new dyes with a 2‐(1,1‐dicyanomethylene)rhodanine (IDR‐ I , ‐ II , ‐ III ) electron acceptor as anchor were synthesized and applied to dye‐sensitized solar cells. We varied the bridging molecule to fine tune the electronic and optical properties of the dyes. It was demonstrated that incorporation of auxiliary acceptors effectively increased the molar extinction coefficient and extended the absorption spectra to the near‐infrared (NIR) region. Introduction of 2,1,3‐benzothiadiazole (BTD) improved the performance by nearly 50 %. The best performance of the dye‐sensitized solar cells (DSSCs) based on IDR‐ II reached 8.53 % (short‐circuit current density (J_sc)=16.73 mA cm^?2, open‐circuit voltage (V_oc)=0.71 V, fill factor (FF)=71.26 %) at AM 1.5 simulated sunlight. However, substitution of BTD with a group that featured the more strongly electron‐withdrawing thiadiazolo[3,4‐c]pyridine (PT) had a negative effect on the photovoltaic performance, in which IDR‐ III ‐based DSSCs showed the lowest efficiency of 4.02 %. We speculate that the stronger auxiliary acceptor acts as an electron trap, which might result in fast combination or hamper the electron transfer from donor to acceptor. This inference was confirmed by electrical impedance analysis and theoretical computations. Theoretical analysis indicates that the LUMO of IDR‐ III is mainly localized at the central acceptor group owing to its strong electron‐withdrawing character, which might in turn trap the electron or hamper the electron transfer from donor to acceptor, thereby finally decreasing the efficiency of electron injection into a TiO₂ semiconductor. This result inspired us to select moderated auxiliary acceptors to improve the performance in our further study.