Invisible Surface Oxygen Vacancies in a Thin MgO Film: Impacts on the Chemical Activity and Secondary Electron...

Today, Fs defects in MgO as isolated surface neutral oxygen vacancies are in the focus of surface science, catalysis research, and emission coating of microchannel plates. With the 10^-4 atom % content at 750 K and under p_O = 10^-9 Torr, estimated by us from the known equilibrium T-x and p-T-x diagrams of MgO, Fs defects remain invisible or difficult-to-detect objects. The MgO(100) → MgO(100) + Fs + ¹/₂O₂ phase transition was studied in MgO films deposited by the metal-organic chemical vapor deposition (MOCVD) procedure from the mixed-ligand Mg precursor on Si substrates at 725 K in the O₂ flow where the nonstoichiometric phase (MgO/Fs) is formed in the gas medium containing simultaneous H₂, CO, H₂O, CO, and O₂ species in unbalanced concentrations. Realization of the above transition was proven theoretically and experimentally through kinetic-thermodynamic analysis of the nonequilibrium system with revealing thermodynamic motive forces, i.e., the positive enthalpy and entropy, as well as through a new combination of diagnostic methods including the original differential dissolution method, due to which separate determination of the point and morphological defects was achieved. It was found that Fs defects occur when oxygen in the immediate vicinity to the substrate surface is replaced practically completely by the oxidized products of the precursor and the resulting oxygen pressure becomes enough for this process. The 90 mass % of the as-deposited MgO-film-involved (MgO/Fs) phase; its chemical activity is demonstrated through dissolution in hot water, while the electron donor activity is through 9 at 750 eV secondary electron yield. A good understanding of gas-phase reactions between the precursors and oxygen provides the fundamental basis of the MOCVD process to deposit MgO films that are dense, free from carbon, and of homogeneous texture. This makes the MOCVD process suitable also for use as coatings of microchannel plates.