The bulk and surface electronic structure of In 2 O 3 has proved controversial, prompting the current combined experimental and theoretical investigation. The band gap of single-crystalline In 2 O 3 is determined as 2.93Ϯ 0.15 and 3.02Ϯ 0.15 eV for the cubic bixbyite and rhombohedral polymorphs, respectively. The valence-band density of states is investigated from x-ray photoemission spectroscopy measurements and density-functional theory calculations. These show excellent agreement, supporting the absence of any significant indirect nature of the In 2 O 3 band gap. Clear experimental evidence for an s-d coupling between In 4d and O 2s derived states is also observed. Electron accumulation, recently reported at the ͑001͒ surface of bixbyite material, is also shown to be present at the bixbyite ͑111͒ surface and the ͑0001͒ surface of rhombohedral In 2 O 3 .

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Graphene growth by low-pressure chemical vapor deposition on low cost copper foils shows great promise for large scale applications. It is known that the local crystallography of the foil influences the graphene growth rate. Here we find an epitaxial relationship between graphene and copper foil. Interfacial restructuring between graphene and copper drives the formation of (n10) facets on what is otherwise a mostly Cu(100) surface, and the facets in turn influence the graphene orientations from the onset of growth. Angle resolved photoemission shows that the electronic structure of the graphene is decoupled from the copper indicating a weak interaction between them. Despite this, two preferred orientations of graphene are found, ±8° from the Cu[010] direction, creating a non-uniform distribution of graphene grain boundary misorientation angles. Comparison with the model system of graphene growth on single crystal Cu(110) indicates that this orientational alignment is due to mismatch epitaxy. Despite the differences in symmetry the orientation of the graphene is defined by that of the copper. We expect these observations to not only have importance for controlling and understanding the growth process for graphene on copper, but also to have wider implications for the growth of two-dimensional materials on low cost metal substrates.