Temperature-dependent evolution of Ti 3d spectral features at surface of BaxTi8O16+δ

We have studied temperature-driven effects on photoemission spectra of hollandite-type ${\mathrm{Ba}}_{x}{\mathrm{Ti}}_{8}{\mathrm{O}}_{16+\ensuremath{\delta}}$ 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 ${\mathrm{Ba}}_{x}{\mathrm{Ti}}_{8}{\mathrm{O}}_{16+\ensuremath{\delta}}$.