Origin of the Ba core-level binding-energy difference between tetragonal and orthorhombic YBa2Cu3O7−δ

Abstract

Sintered bulk samples of the orthorhombic, superconducting, phase of ${\mathrm{YBa}}_2$ ${\mathrm{Cu}}_3$ ${\mathrm{O}}_{7\mathrm{-}\mathrm{\delta }}$ exhibit a ≃1.5 eV Ba core-level decrease compared to the tetragonal, nonsuperconducting phase. This is also observed for thin-film material in the two phases. Using ab initio cluster calculations, we show that shifts of this magnitude are explainable by isotropic contraction of the Ba-O bond length in the 0.01- to 0.02-Å range, values compatible with the known lattice-parameter changes between the phases. Finally, even in situ cleaved good-quality single crystals of the orthorhombic phase show a chemically shifted Ba component for some regions of the surface, which may be due to Ba-O bond-length contractions at the surface-vacuum interface.