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We report the existence of metallic two-dimensional electron gases (2DEGs) atthe (001) and (101) surfaces of bulk-insulating TiO2 anatase due to localchemical doping by oxygen vacancies in the near-surface region. Usingangle-resolved photoemission spectroscopy, we find that the electronicstructure at both surfaces is composed of two occupied subbands of d_xy orbitalcharacter. While the Fermi surface observed at the (001) termination isisotropic, the 2DEG at the (101) termination is anisotropic and shows a chargecarrier density three times larger than at the (001) surface. Moreover, wedemonstrate that intense UV synchrotron radiation can alter the electronicstructure and stoichiometry of the surface up to the complete disappearance ofthe 2DEG. These results open a route for the nano-engineering of confinedelectronic states, the control of their metallic or insulating nature, and thetailoring of their microscopic symmetry, using UV illumination at differentsurfaces of anatase.

Engineering two-dimensional electron gases at the (001) and (101) surfaces of TiO2 anatase using light