Rational design of D–A1–D–A2 conjugated polymers with superior spectral coverage

Abstract

The spectral coverage of a light-harvesting polymer largely determines the maximum achievable photocurrent in organic photovoltaics, and therefore constitutes a crucial parameter for improving their performance. The D–A₁–D–A₂ copolymer motif is a new and promising design strategy for extending the absorption range by incorporating two acceptor units with complementary photoresponses. The fundamental factors that promote an extended absorption are here determined for three prototype D–A₁–D–A₂ systems through a combination of experimental and computational methods. Systematic quantum chemical calculations are then used to reveal the intrinsic optical properties of ten further D–A₁–D–A₂ polymer candidates. These investigated polymers are all predicted to exhibit intense primary absorption peaks at 615–954 nm, corresponding to charge-transfer (CT) transitions to the stronger acceptor, as well as secondary absorption features at 444–647 nm that originate from CT transitions to the weaker acceptors. Realization of D–A₁–D–A₂ polymers with superior spectral coverage is thereby found to depend critically on the spatial and energetic separation between the two distinct acceptor LUMOs. Two promising D–A₁–D–A₂ copolymer candidates were finally selected for further theoretical and experimental study, and demonstrate superior light-harvesting properties in terms of significantly extended spectral coverage. This demonstrates great potential for enhanced light-harvesting in D–A₁–D–A₂ polymers via multiple absorption features compared to traditional D–A polymers.