QM/MM calculations combined with the dimer approach on the static disorder at organic‐organic interfaces of thin‐film organic solar cells composed of small molecules

Abstract

AbstractA QM/MM approach using ωB97X‐D combined with AMOEBA calculations was used to analyze the energetic disorder in the vicinity of interfaces in amorphous organic heterostructures. Distributions of ground‐, excited‐, and cationic‐state energies as well as of ionization potentials and excitation energies, all being relevant quantities for the transport properties of thin films, were calculated. As already found for bulk amorphous organic semiconductors, local densities of states at molecular interfaces possess Gaussian‐shaped profiles with a significant amount of disorder. Assuming a disorder‐limited activation of exciton and charge transport, a decrease in the amount of disorder could improve the transport properties. Relating calculated disorders to molecular parameters revealed that in line with the Bässler model, especially the molecular polarity, its change upon electronic excitation, and the molecular polarizability are relevant quantities leading to energetically largely disordered films. Moreover, because of the different mechanisms of exciton and polaron delocalization, a given morphology with disordered charge‐transport levels gives not necessarily rise to disordered exciton‐transport levels and vice versa.