Controlling the nature of the electronic states within organic layers holds the promise of truly molecular electronics. To achieve that we, here, develop a modular concept for a versatile tuning of electronic properties in organic monolayers and their interfaces. The suggested strategy relies on directly exploiting collective electrostatic effects, which emerge naturally in an ensemble of polar molecules. By means of quantum-mechanical modeling we show that in this way monolayer-based quantum-cascades and quantum-well structures can be realized, which allow a precise control of the local electronic structure and the localization of electronic states. Extending that concept, we furthermore discuss strategies for activating spin sensitivity in specific regions of an organic monolayer.
Keywords: collective electrostatics; density‐functional theory; interface design; monolayer quantum‐well; self‐assembled monolayer.