The origin of the almost unique combination of optical transparency and the ability to bipolar dope tin monoxide is explained using a combination of soft and hard Xray photoemission spectroscopy, O K-edge X-ray emission and absorption spectroscopy, and density functional theory calculations incorporating van der Waals corrections. We reveal that the origin of the high hole mobility, bipolar ability, and transparency is a result of (i) significant Sn 5s character at the valence band maximum (due to O 2p−Sn 5s antibonding character associated with the lone pair distortion), (ii) the combination of a small indirect band gap of ∼0.7 eV (Γ−M) and a much larger direct band gap of 2.6−2.7 eV, and (iii) the location of both band edges with respect to the vacuum level. This work supports Sn 2+ -based oxides as a paradigm for nextgeneration transparent semiconducting oxides.
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