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We study the surface and bulk electronic structure of the room-temperature ferromagnet Co:TiO2 anatase films using soft and hard x-ray photoemission spectroscopy with probe sensitivities of ~1 nm and ~10 nm, respectively. We obtain direct evidence of metallic Ti$^{3+}$ states in the bulk, which get suppressed to give a surface semiconductor, thus indicating a surface-bulk dichotomy. X-ray absorption and high-sensitivity resonant photoemission spectroscopy reveal Ti$^{3+}$ electrons at the Fermi level (E$_F$) and high-spin Co$^{2+}$ electrons occurring away from E$_F$. The results show the importance 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 the Co 3d-O 2p-Ti 3d exchange interaction pathway of the occupied orbitals.
361 - Y. Ishida , T. Baba , R. Eguchi 2009
Soft-x-ray photoemission and absorption spectroscopies are employed to investigate the electronic structures of Sr_{1-x}Rh_{2}O_{4}. Similarly to the layered cobaltates such as Na_{1-x}CoO_{2}, a valence-band satellite feature (VBS) occurs at higher binding energy to the O 2p band. We find that the VBS resonates at the O 1s edge. Additionally, core absorption shows clear x dependence in the O 1s edge rather than in the Rh 3p edge. These results indicate that the holes in the initial state mainly have O 2p character presumably due to d-p rehybridizations affected by Sr^{2+} vacancy potentials. The resultant inhomogenous charge texture may have impact on the TE transport properties at low x.
We report the three-dimensional (3-D) momentum-resolved soft x-ray photoemission spectroscopy of the Fermi liquid LaNiO$_3$. The out-of-plane and in-plane cuts of the 3-D electron- and hole-Fermi surfaces (FSs) are observed by energy- and angle- depe ndent photoemission measurements. The energy bands forming the electron FS suggest an $omega^2$ dependence of the imaginary part of the self-energy and a `correlation kink at an energy scale of 0.25 eV. In contrast, the bands which form nesting character hole FSs do not show kinks and match local density approximation calculations. The results indicate a momentum-dependent mass renormalization, leading to electron-hole asymmetry in strongly correlated LaNiO$_3$.
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