Synchrotron X-ray Photoelectron Spectroscopy Study of Electronic Changes at the ZnO Surface Following Aryldiazonium Ion Grafting: A Metal-to-Insulator Transition

ZnO is a member of a small class of semiconductors that includes In2O3, SnO2, CdO, and InN, whose surfaces are highly unusual because their electronic bands bend downward to form a quantized potential well in which a two-dimensional electron gas is confined. At the O-polar ZnO(0001) surface, this effect arises from the adsorption of H adatoms which produces a hydroxyl-terminated surface. In this work, we investigate the effect of covalently anchored organic layers on the band bending at ZnO(0001) surfaces. We use aryldiazonium salt electrochemistry to deposit 4–5 nm thick layers of 4-nitrophenyl (NP) and 4-(trifluoromethyl)phenyl (TFMP) groups. Synchrotron X-ray photoelectron spectroscopy (XPS) showed that both NP and TFMP modifications permanently removed the downward band bending at the ZnO surface. This behavior can be explained by the direct covalent bonding of the aryl groups to the surface, also revealed by XPS analysis, and the electron-withdrawing character of both modifiers. Surprisingly, the i...