Ultrathin praseodymia films have been deposited on both Cl-passivated and nonpassivated Si(111) substrates by molecular beam epitaxy. Comparative studies on the crystallinity and stoichiometry are performed by x-ray photoelectron spectroscopy, x-ray standing waves, and x-ray reflectometry. On nonpassivated Si(111) an amorphous silicate film is formed. In contrast, praseodymia deposited on Cl-passivated Si(111) form a well-ordered crystalline film with cubic-Pr(2)O(3) (bixbyite) structure. The vertical lattice constant of the praseodymia film is increased by 1.4% compared to the bulk value. Furthermore, the formation of an extended amorphous silicate interface layers is suppressed and confined to only one monolayer. (C) 2010 American Institute of Physics. [doi:10.1063/1.3525175]