In this work, a random terpolymer methodology combining two electron-rich units, asymmetric thienobenzodithiophene (TBD) and thieno[2,3-f]benzofuran segments, is systematically investigated. The synergetic effect is embodied on the molecular packing and nanophase when copolymerized with 1,3-bis(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione, producing an impressive power conversion efficiency (PCE) of 14.2% in IT-4F-based NF-PSCs, which outperformed the corresponding D-A copolymers. The balanced aggregation and better interpenetrating network of the TBD50:IT-4F blend film can lead to mixing region exciton splitting and suppress carrier recombination, along with high yields of long-lived carriers. Moreover, the broad applicability of terpolymer methodology is successfully validated in most electron-deficient systems. Especially, the TBD50/Y6-based device exhibits a high PCE of 15.0% with a small energy loss (0.52 eV) enabled by the low nonradiative energy loss (0.22 eV), which are among the best values reported for polymers without using benzodithiophene unit to date. These results demonstrate an outstanding terpolymer approach with backbone engineering to raise the hope of achieving even higher PCEs and to enrich organic photovoltaic materials reservoir.
Keywords: asymmetrical structure; microstructure; nonfullerene solar cell; nonradiative energy loss; power conversion efficiency; random terpolymer.