Understanding electron-withdrawing substituent effect on structural, electronic and charge transport properties of perylene bisimide derivatives

A series of n-type perylene bisimide (PBI) derivatives with electron-withdrawing substituents at both bay and imide nitrogen positions were investigated. The effects of these substituents on internal energy relaxation, molecular orbitals, air stability, electronic properties and charge transport behaviors were systematically discussed with density functional theory (DFT) which has been demonstrated reliable for organic semiconductor study. The investigated derivatives with electron-withdrawing substituents show favorable performances in terms of these properties. The LUMO levels are greatly stabilized by at least 0.3 eV and these derivatives show the strong absorption from 400 to 700 nm which match with the solar spectra very well. The charge transport mainly happens between molecules in the same organic molecular layer and electronic couplings between layer-to-layer molecules are very weak, thus the mobility along layer-to-layer direction is less efficient. The variation of molecular packings and intermolecular interactions produce the highly anisotropic mobilities. The derivative with two fluorine atoms at bay positions and -CH2C3F7 at imide group has broad and strong absorption in the UV-Visible region and the electron mobility could get to 0.514 cm(2) V (1) s (1) which is greatly encouraging for molecular and material design in organic solar-cell devices. These calculated results are in good agreement with the experimental data. However, not all the functionalization with halogen substituents would induce the increase of the electronic coupling and electron mobility. The derivatives with four halogen substituents at the bay positions could not show advantages in terms of electron mobility which is induced by the distorted conjugated structures. The theoretical understanding of these n-type organic semiconductors figures out the importance of tuning the molecular geometry to get high performance semiconductor materials. (C) 2011 Elsevier B.V. All rights reserved.