Bulk and surface sensitive x-ray spectroscopic techniques are applied in tandem to show that the valence band edge for In2O3 is found significantly closer to the bottom of the conduction band than expected on the basis of the widely quoted bulk band gap of 3.75 eV. First-principles theory shows that the upper valence bands of In2O3 exhibit a small dispersion and the conduction band minimum is positioned at Gamma. However, direct optical transitions give a minimal dipole intensity until 0.8 eV below the valence band maximum. The results set an upper limit on the fundamental band gap of 2.9 eV.

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 .

High-resolution x-ray photoemission spectroscopy, infrared reflectivity and Hall effect measurements, combined with surface space-charge calculations, are used to show that electron accumulation occurs at the surface of undoped single-crystalline In2O3. From a combination of measurements performed on undoped and heavily Sn-doped samples, the charge neutrality level is shown to lie approximately 0.4 eV above the conduction band minimum in In2O3, explaining the electron accumulation at the surface of undoped material, the propensity for n-type conductivity, and the ease of n-type doping in In2O3, and hence its use as a transparent conducting oxide material.

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Thin films of In2O3 have been grown on Y-stabilized ZrO2(100) by oxygen plasma assisted molecular beam epitaxy with a substrate temperature of 650°C. Ordered epitaxial growth was confirmed by high resolution transmission electron microscopy. The position of the valence band onset in the x-ray photoemission spectra of the epitaxial films is found to be inconsistent with the widely quoted value of 3.75eV for the fundamental bandgap of In2O3 and suggests a revised value of 2.67eV.