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A combination of Scanning Tunneling Microscopy/Spectroscopy and DensityFunctional Theory (DFT+U) is used to characterize excess electrons in TiO$_2$rutile and anatase, two prototypical materials with identical chemicalcomposition but different crystal lattices. In rutile, excess electrons canlocalize at any lattice Ti atom, forming a small polaron, which can easily hopto neighboring sites. In contrast, electrons in anatase prefer a free-carrierstate, and can only be trapped near oxygen vacancies or form shallow donorstates bound to Nb dopants. The present study conclusively explains thedifferences between the two polymorphs and indicates that even small structuralvariations in the crystal lattice can lead to a very different behavior.

A direct view at excess electrons in TiO$_2$ rutile and anatase