Triggered integer charge transfer: energy-level alignment at an organic-2D material interface

Weakly interacting systems such as organic molecules on monolayers of hexagonal boron nitride (h-BN) offer the possibility of single integer charge transfer leading to the formation of organic ions. Such open-shell systems exhibit unique optical and electronic properties which differ from their neutral counterparts. In this study, we used a joint experimental and theoretical approach to investigate the charge transfer of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) molecules on h-BN/Ni(111) by using differential reflectance spectroscopy (DRS), scanning tunneling spectroscopy (STS), and photoelectron orbital tomography (POT) measurements in combination with density functional theory (DFT) calculations. Our results show that the PTCDA monolayer consists of highly ordered organic radical anions and neutral molecules. In addition, the occurrence of the integer charge transfer is discussed based on the energy-level alignment. Since the integer charge transfer is not limited to PTCDA, we propose that the h-BN covered Ni(111) surface is a promising substrate for studying the optical and electronic properties of highly ordered organic anions.