Local structuring of diketopyrrolopyrrole (DPP)-based oligomers from molecular dynamics simulations

The microscopic structure of high mobility semiconducting polymers is known to be essential for their performance but it cannot be easily deduced from the available experimental data. A series of short oligomers of diketopyrrolopyrrole (DPP)-based materials that display high charge mobility are studied by molecular dynamics simulations to understand their local structuring at an atomic level. Different analyses are proposed to compare the ability of different oligomers to form large aggregates and their driving force. The simulations show that the tendency for this class of materials to form aggregates is driven by the interaction between DPP fragments, but this is modulated by the other conjugated fragments of the materials which affect the rigidity of the polymer and, ultimately, the size of the aggregates that are formed. The main structural features and the electronic structure of the oligomers are fairly similar above the glass transition temperature and at room temperature.