David Beljonne

Disordered or even seemingly amorphous, donor–acceptor type, conjugated copolymers with high charge-carrier mobility have emerged as a new class of functional materials, where transport along the conjugated backbone is key. Here, we report on non-adiabatic molecular dynamics simulations of charge-carrier transport along chains of poly (indacenodithiophene-co-benzothiadiazole), within a model Hamiltonian parameterized against first-principles calculations. We predict thermally activated charge transport associated with a slightly twisted ground-state conformation, on par with experimental results. Our results also demonstrate that the energy mismatch between the hole on the donor vs the acceptor units of the copolymer drives localization of the charge carriers and limits the intra-chain charge-carrier mobility. We predict that room-temperature mobility values in excess of 10 cm2 V−1 s−1 can be achieved through proper chemical tuning of the component monomer units.