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We study the surface and bulk electronic structure of the room-temperatureferromagnet Co:TiO2 anatase films using soft and hard x-ray photoemissionspectroscopy with probe sensitivities of ~1 nm and ~10 nm, respectively. Weobtain direct evidence of metallic Ti$^{3+}$ states in the bulk, which getsuppressed to give a surface semiconductor, thus indicating a surface-bulkdichotomy. X-ray absorption and high-sensitivity resonant photoemissionspectroscopy reveal Ti$^{3+}$ electrons at the Fermi level (E$_F$) andhigh-spin Co$^{2+}$ electrons occurring away from E$_F$. The results show theimportance of the charge neutrality condition: Co$^{2+}$ + V$_{O}$$^{2-}$ +2Ti$^{4+}$ $\leftrightarrow$ Co$^{2+}$ + 2Ti$^{3+}$ (V$_O$ is oxygen vacancy),which gives rise to the elusive Ti 3d carriers mediating ferromagnetism via theCo 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.

Nanoscale Dichotomy of Ti 3d Carriers Mediating the Ferromagnetism in Co:TiO2 Anatase Thin Films