Electronic properties of donor:acceptor complexes in all-polymer solar cells based on density functional theory

Abstract

The electronic properties at the donor (D):acceptor (A) interface are a crucial factor in determining the efficiency of organic photovoltaic devices. Here, based on first-principles calculations, the electronic properties of ten configuration complexes composed of D polymer PDPPTPT and A polymer PNDI2OD-TVT were simulated. Results show that the bandgap values of the homo-/heterojunctions decrease with the increase of the number of molecular layers, and that of AAA is close to zero. This indicates that the homogeneous stacking is favorable for charge transport; furthermore, the bandgap of the complexes is affected by the molecular arrangement. Through the differential charge density and Bader charge analysis method, it was found that charge transfer will occur intermolecularly, which promotes the formation of a dipole moment at the D:A interface, and the dipole electric field then helps the dissociation of excitons in the active layer. The amount of charge transfer at the D:A interface in the DDA, DAA and DDAA configurations is about twice that in the DA configuration alone, demonstrating that homogeneous accumulation in complexes can enhance the interface dipole interaction. The comprehensive analysis suggests that homogeneous accumulation is conducive to charge transport, that heterogeneous stacking helps to promote exciton dissociation, and that there should be an optimal ratio. Furthermore, the dipole electric fields formed at the D:A interface exhibit the characteristics of local and non-uniform distribution.