Two-Dimensional Crystals as a Buffer Layer for High Work Function Applications: The Case of Monolayer MoO₃

We propose that the crystallinity of two-dimensional (2D) materials is a crucial factor for achieving highly effective work function (WF) modification. A crystalline 2D MoO₃ monolayer enhances substrate WF up to 6.4 eV for thicknesses as low as 0.7 nm. Such a high WF makes 2D MoO₃ a great candidate for tuning properties of anode materials and for the future design of organic electronic devices, where accurate evaluation of the WF is crucial. We provide a detailed investigation of WF of 2D α-MoO₃ directly grown on highly ordered pyrolytic graphite, by means of Kelvin probe force microscopy (KPFM) and ultraviolet photoemission spectroscopy (UPS). This study underlines the importance of a controlled environment and the resulting crystallinity to achieve high WF in MoO₃. UPS is proved to be suitable for determining higher WF attributed to 2D islands on a substrate with lower WF, yet only in particular cases of sufficient coverage. KPFM remains a method of choice for nanoscale investigations, especially when conducted under ultrahigh vacuum conditions. Our experimental results are supported by density functional theory calculations of electrostatic potential, which indicate that oxygen vacancies result in anisotropy of WF at the sides of the MoO₃ monolayer. These novel insights into the electronic properties of 2D-MoO₃ are promising for the design of electronic devices with high WF monolayer films, preserving the transparency and flexibility of the systems.