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Using single-bonded and fused aromatic rings are two methods for extending the π-conjugation in the vertical direction of benzo [1,2-b:4,5-b'] dithiophene (BDT) unit. To investigate which method is more efficient in nonfullerene systems, two novel polymers based on alkylthionaphthyl and alkylthiobiphenyl substituted BDT named PBDTNS-FTAZ and PBDTBPS-FTAZ are designed and synthesized. Two polymers only exhibit small differences in structure, but huge differences in photovoltaic properties. They are studied by blended with 3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)indanone)-5,5,11,11-tetrakis(4-hexylphenyl)dithieno [2,3-d':2,3'-d']-s-indaceno [1,2-b:5,6-b'] dithiophene (ITIC). The device based on PBDTNS-FTAZ:ITIC showed the best power conversion efficiency (PCE) of 9.63% with the Voc of 0.87 V, a Jsc of 18.06 mA/cm 2 and a fill factor of 61.21%, while the PBDTBPS-FTAZ:ITIC only exhibit a maximum PCE of 7.79% with a Voc of 0.86 V, a Jsc of 16.24 mA/cm 2 and a relatively low fill factor of 55.92%. Therefore, extending π-conjugation with alkylthionaphthyl is more effective against constructing nonfullerene solar cells.

Comparing Benzodithiophene Unit with Alkylthionaphthyl and Alkylthiobiphenyl Side-Chains in Constructing High-Performance Nonfullerene Solar Cells