Fine-tuning the electrostatic properties of an alkali-linked organic adlayer on a metal substrate

The performance of modern organic electronic devices is often determined by the electronic level alignment at a metal-organic interface. This property can be controlled by introducing an interfacial electrostatic dipole via the insertion of a stable interlayer between the metallic and the organic phases. Here, we use density functional theory to investigate the electrostatic properties of an assembled structure formed by alkali metals coadsorbed with 7,7,8,8-tetracyanoquinodimethane (TCNQ) molecules on a Ag(100) substrate. We find that the interfacial dipole buildup is regulated by the interplay of adsorption energetics, steric constraints and charge transfer effects, so that choosing chemical substitutions within TCNQ and different alkali metals provides a rich playground to control the systems' electrostatics and in particular fine-tune its work-function shift.