Chemistry of thin film formation and stability during praseodymium oxide deposition on Si(111) under oxygen-deficient conditions

The growth of thin praseodymium oxide films on silicon (111) using small deposition rates under oxygen-deficient conditions was investigated in the range from submonolayer up to six monolayers coverage by transmission electron microscopy (TEM) and photoemission spectroscopy (PES). A detailed analysis of the silicon 2p and oxygen 1 s core level and valence band spectra reveals chemical reactions between deposited species, substrate, and the growing film. Silicate, silicide and oxide species are coexisting over the entire range of coverages investigated. Cross sectional TEM shows silicide inclusions extending from the surface several nanometers into the substrate and affecting the substrate band bending at the interface. The reactivity of the praseodymia overlayer leads to reactions in the as-deposited film even at room temperature and render it unstable. The article aims at providing a coherent picture of the chemistry proceeding during interface formation and film growth at low rates of deposition (0.06 nm/min). The results will be discussed in comparison to studies using higher rates, emphasizing the possibility of growth rate dependent reactions between substrate and deposited material and, consequently, distinctly different film compositions and structures for different rates of deposition.