Abstract
Rational molecular design of π‐conjugated donor polymers is critical for developing high‐performance organic solar cells. Random copolymerization strategy is a facile method of synergistic fine‐tuning the light absorption, HOMO/LUMO energy levels, charge mobility, and solubility of donor (D)–acceptor (A) copolymers. Terpolymers PF8TBT which composed of three components, i.e., electron‐rich 9,9‐dioctylfluorene (F8), electron‐deficient benzothiadiazole (BT), and π‐bridge thiophene (T) moieties, are designed in such a way that only F8 unit possesses soluble side‐chains. This strategy enables a facile and precise control of the influences of side chains on solubility, energy levels, molecular packing, and fullerene (PCBM) intercalation of PF8TBT. The optimal terpolymer PF8TBT21 (F8:T:BT = 0.67:1:0.33 mol%) maximally balances the solubility and the PL quenching efficiency with PCBM while exhibiting notable π–π stacking. The resulting additive‐free inverted photovoltaic cell based on the PF8TBT21:PCBM blend shows a power conversion efficiency of 3.88% with an impressive open‐circuit voltage close to 1 V. image
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