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Epitaxial TiO 2 and Nb-doped TiO 2 thin films have been grown on (110) TiO 2 rutile substrates by molecular beam epitaxy using elemental Ti and Nb sources along with an electron cyclotron resonance oxygen plasma source. Film composition was measured by X-ray photoelectron spectroscopy. Reflection high-energy electron diffraction and low-energy electron diffraction patterns reveal excellent long-range crystallographic order and a rutile structure for both TiO 2 and Nb-doped TiO 2 films. The high degree of similarity in Ti and Nb core-level X-ray photoelectron diffraction angular distributions establishes that Nb is substitutionally incorporated in the rutile lattice. Analysis of the Nb 3d 5/2 core-level binding energy suggests an Nb 4+ oxidation state.