Temperature-dependent evolution of Ti 3d spectral features at surface of BaxTi8 O16+δ

We have studied temperature-driven effects on photoemission spectra of hollandite-type BaxTi8O16+δ across its metal-insulator transition (MIT) at 220 K by using surface-sensitive photon energies from 27 to 70 eV. The surface Ti 3d spectral weight was suppressed and shifted towards higher binding energy from the bulk if the surface was obtained by cleavage above the MIT temperature. The Ti 3d spectral weight was recovered once the sample was cooled across the MIT, indicating a transfer of Ti 3d electrons from the bulk to the surface across the MIT. The recovered Ti 3d spectral shape is consistent with the bulk-sensitive result and indicates strong localization character of the Ti 3d electron even in the metallic phase. Resonant photoemission spectroscopy with absorption from the Ti 3p core level exhibits resonances of the O 2p-Ti 3d and O 2p-Ti 4s,p hybridized states. The result suggests that the O 2p-Ti 4s,p hybridization plays a role in the interplay between the bulk and the surface in BaxTi8O16+δ.