Built-In Potentials Induced by Molecular Order in Amorphous Organic Thin Films.

Many molecules used to fabricate organic semiconductor devices carry an intrinsic dipole moment. Anisotropic orientation of such molecules in amorphous organic thin films during the deposition process can lead to the spontaneous buildup of an electrostatic potential perpendicular to the film. This so-called giant surface potential (GSP) effect can be exploited in organic electronics applications and was extensively studied in experiment. However, presently, an understanding of the molecular mechanism driving the orientation is lacking. Here, we model the physical vapor deposition process of seven small organic molecules employed in organic light-emitting diode applications with atomistic simulations. We are able to reproduce experimental results for a wide range of strength of the GSP effect. We find that the electrostatic interaction between the dipole moments of the molecules limits the GSP strength and identify short-range van der Waals interactions between the molecule and the surface during deposition as the driving force behind the anisotropic orientation. We furthermore show how the GSP effect influences the energy levels responsible for charge transport, which is important for the design of organic semiconductors and devices.