Tuning the Charge-Transport Parameters of Perylene Diimide Single Crystals via End and/or Core Functionalization: A Density Functional Theory Investigation

Perylene tetracarboxylic diimide (PTCDI) derivatives stand out as one of the most investigated families of air-stable n-type organic semiconductors for organic thin-film transistors. Here, we use density functional theory to illustrate how it is possible to control the charge-transport parameters of PTCDIs as a function of the type, number, and positions of the substituents. Specifically, two strategies of functionalization related to core and end substitutions are investigated. While end-substituted PTCDIs present the same functional molecular backbone, their molecular packing in the crystal significantly varies; as a consequence, this series of derivatives constitutes an ideal test bed to evaluate the models that describe charge-transport in organic semiconductors. Our results indicate that large bandwidths along with small effective masses can be obtained with the insertion of appropriate substituents on the nitrogens, in particular halogenated aromatic groups.