Growth and characterization of Ca—Mo mixed oxide films on Mo(001)

Calcium-molybdate ultrathin films were prepared on a Mo(001) crystal and characterized by means of scanning tunneling microscopy (STM), electron diffraction, photoelectron spectroscopy, and density functional theory (DFT). The films were grown via reactive Ca deposition, followed by a vacuum annealing step to trigger Mo diffusion from the support into the Ca—O ad-layer. A series of crystalline oxide configurations was revealed that evolves from a (3 × 3) to a (4 × 4) and (6 × 6) superstructure with increasing annealing temperature and finally decays to a binary MoO_x phase. The stoichiometry of the initial (3 × 3) phase was estimated to CaMo₃O₆, yet with decreasing Ca concentration at higher temperature. In the search for a suitable structure model for DFT calculations, we have started with a bulk CaMo₅O₈ configuration that was iteratively modified to match the experimental data. The optimized structure is made of regular sequences of flat-lying and upright standing Mo octahedrons, being separated from each other by Ca²⁺ ion rows. With decreasing Ca content, the central Mo units grow in size, which explains the observed transition from (3 × 3) to (6 × 6) superstructures upon annealing. The proposed structure model rationalizes the periodicity and corrugation of the regular oxide surface as well as the characteristic domain patterns in the film. Its electronic properties, as deduced from STM conductance spectroscopy, can be correlated with an increasing metallicity of the ad-layer upon annealing. Our work presents a facile pathway to produce high-quality ternary oxide films via interdiffusion of atoms from a suitable metal support into a binary oxide layer.