Understanding Interfacial Electronic Structure and Charge Transfer: An Electrostatic Perspective.

Abstract

The challenge of understanding electronic structure and dynamics at organic semiconductor interfaces arises from the richness and importance of weak interactions in thin films of extended π-conjugated molecules. In this Perspective, I discuss a conceptually simple electrostatic approach toward a molecular-level description of the electronic structure and dynamics at a subset of such interfaces. Self-assembled monolayers of oriented dipolar molecules physisorbed on metal surfaces generate sizable collective electric fields, and electrostatics determines the key factors for energy level alignment and molecular electronic structure. A rigorous quantum mechanical treatment of such interfaces supports this conclusion and sheds light on the subtle interplay of the different interfacial interactions. The electrostatic model of the interface has the potential to offer also insights into the role of strong collective electric fields on interfacial charge-transfer dynamics.