Pt3Zr(0001): A substrate for growing well-ordered ultrathin zirconia films by oxidation

We have studied the surface of pure and oxidized Pt3Zr(0001) by scanning tunneling microscopy (STM), Auger electron microscopy, and density functional theory (DFT). The well-annealed alloy surface shows perfect long-range chemical order. Occasional domain boundaries are probably caused by nonstoichiometry. Pt3Zr exhibits ABAC stacking along [ 0001]; only the A-terminated surfaces are seen by STM, in agreement with DFT results showing a lower surface energy for the A termination. DFT further predicts a stronger inward relaxation of the surface Zr than for Pt, in spite of the larger atomic size of Zr. A closed ZrO2 film is obtained by oxidation in 10(-7) mbar O-2 at 400 degrees C and post-annealing at approximate to 800 degrees C. The oxide consists of an O-Zr-O trilayer, equivalent to a (111) trilayer of the fluorite structure of cubic ZrO2, but contracted laterally. The oxide forms a (root 19 x root 19) R23 degrees superstructure. The first monolayer of the substrate consists of Pt and contracts, similar to the metastable reconstruction of pure Pt(111). DFT calculations show that the oxide trilayer binds rather weakly to the substrate. In spite of the O-terminated oxide, bonding to the substrate mainly occurs via the Zr atoms in the oxide, which strongly buckle down toward the Pt substrate atoms if near a Pt position. According to DFT, the oxide has a band gap; STM indicates that the conduction band minimum lies approximate to 2.3 eV above E-F