We report on a combined scanning tunneling microscopy (STM) and density
functional theory (DFT) based investigation of Co atoms on Ge(111)2x1 surfaces.
When deposited on cold surfaces, individual Co atoms have a limited diffusivity
on the atomically flat areas and apparently reside on top of the upper
pi-bonded chain rows exclusively. Voltage-dependent STM imaging reveals a
highly anisotropic electronic perturbation of the Ge surface surrounding these
Co atoms and pronounced one-dimensional confinement along the pi-bonded chains.
DFT calculations reveal that the individual Co atoms are in fact embedded in
the Ge surface, where they occupy a quasi-stationary position within the big
7-member Ge ring in between the 3rd and 4th atomic Ge layer. The energy needed
for the Co atoms to overcome the potential barrier for penetration in the Ge
surface is provided by the kinetic energy resulting from the deposition
process. DFT calculations further demonstrate that the embedded Co atoms form
four covalent Co-Ge bonds, resulting in a Co4+ valence state and a 3d5
electronic configuration. Calculated STM images are in perfect agreement with
the experimental atomic resolution STM images for the broad range of applied
tunneling voltages.Comment: 19 pages, 15 figures, 3 table
