Layer-Dependent Quasiparticle Electronic Structure of the P3HT:PCBM Interface from a First-Principles Substrate Screening GW Approach

A prototypical organic photovoltaic material is a heterojunction composed of the blend of regioregular poly­(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM). Microscopic understanding of the energy conversion mechanism in this system involves the relationship between the electronic structure and the atomistic geometry of P3HT:PCBM interfaces. In this work, the effect of the number of P3HT layers on the electronic structure of the P3HT:PCBM interface is studied by means of first-principles GW. We apply the substrate screening approach to accelerate such calculations and to better understand the many-body dielectric screening at the interface. The quasiparticle band gap of the entire interface is found to decrease as the number of P3HT layers increases. The gaps of the individual components of the interface are found to be smaller than those of their isolated counterparts, with strong dependence on the number of P3HT layers. Importantly, when comparing the P3HT:PCBM system, where a single interface is present, and the P3HT:PCBM:P3HT system, where an interface is formed on either side of PCBM, we find that the two systems exhibit very different quasiparticle energy level alignments. We discuss the possible implications of our findings in related experiments. The observed trends in the layer-dependent quasiparticle electronic structures of P3HT:PCBM interfaces provide computational insight into energy conversion pathways in these materials.