Oxygen Lability on Thin Oxide Films on Mo(110)

• Published in: The journal of physical chemistry. B 2000-04, Vol.104 (14), p.3212-3218
• Main Authors: Nart, F. C, Kelling, S, Friend, C. M
• Format: Article
• Language: English
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp993479u

The formation and lability of doubly bound, terminal oxygen in thin-film oxides thermally grown on Mo(110) is studied using reflection−absorption infrared spectroscopy (RAIRS) and scanning tunneling microscopy (STM) and the implications for studies of oxidation reactions on these films is discussed. Isotopic labeling studies show that there is facile exchange of terminal oxygen with oxygen in high coordination sites mediated by defects, even for temperatures on the order of 100 K. The nature and heterogeneity of the MoO moieties depends strongly on the temperature used for oxidation. There are two different MoO species on an oxide prepared at high temperature, 1200 K, signified by vibrational peaks in the range of 995−999 and 1017−1026 cm-1, attributed to MoO moieties on terraces and at steps, respectively. Oxidation at lower temperature, 800 K, yields a more homogeneous film based on selective population of the peak in the range of 995−999 cm-1. The presence of the higher frequency peak is associated with formation of multiple steps bunched together on the surface, based on STM studies. The formation of these step bunches is reversible and is related to the amount of oxygen on the surface. Heating so as to diffuse oxygen into the bulk of the sample leads to the disappearance of the vibrations characteristic of terminal oxygen. Oxygen diffusion is proposed to occur preferentially at step edges based on STM results. The rate of depletion of the terminal oxygen is a diffusive process and has an activation barrier of ∼0.26 eV. The low barrier is attributed in part to the presence of defects, e.g., steps and oxygen vacancies. Interestingly, a peroxide-like species can also be formed on the oxide by dosing oxygen at low temperature (100 K). This species is signified by a band at 900 cm-1 which shifts to 853 cm-1 upon 18O labeling. The adsorbed O2 dissociates in the range of 200−300 K, forming a terminal site species with a ν(MoO) at 986 cm-1.