Noninvasive Embedding of Single Co Atoms in Ge(111)2x1 Surfaces

TL;DR

This study combines STM and DFT to show that individual Co atoms can be noninvasively embedded in Ge(111)2x1 surfaces, revealing their atomic position, electronic structure, and surface perturbations.

Contribution

It provides the first detailed atomic-scale understanding of Co atom embedding and electronic configuration in Ge surfaces using combined experimental and theoretical methods.

Findings

Co atoms are embedded in Ge surface within Ge rings.

Embedded Co atoms form four covalent bonds with Ge.

STM images match DFT calculations across voltages.

Abstract

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.