Modification of anatase TiO$_2$(001) surface electronic structure by Au impurity

TL;DR

This study uses density functional theory to explore how gold impurities modify the electronic structure of anatase TiO2(001), revealing impurity-induced metallization and changes in Fermi level positioning.

Contribution

It provides new insights into how Au impurities incorporate and alter the electronic properties of TiO2 surfaces and bulk, including impurity states and metallization effects.

Findings

Au can be encapsulated inside TiO2 slabs or adsorbed on the surface.

Au impurities introduce impurity states that cause metallization.

The position of Au affects the Fermi level and electronic structure.

Abstract

We have used density functional theory calculations based on the projector augmented wave method to investigate the electronic structure of Au-incorporated anatase TiO$_2$(001) surface. Due to the coordination with several level oxygens, Au atoms can be encapsulated inside TiO$_2$ slab. Au is adsorbed over the surface Ti--O bond, so called the bridge site on anatase TiO$_2$(001)--1$\times$1 surface. However, for 0.25 ML coverage, Au atoms energetically prefer to stay at 0.64 {\AA} above the midpoint of the two surface oxygens which is significantly closer to the surface layer. When implanted inside the slab for full coverage, Au forms parallel metallic wires inside TiO$_2$ lattice where interlayer distances increase due to local segregation. Au brings half-filled impurity states into the band gap leading to metallization, in addition to other filled surface and impurity bands within the gap. These Au-driven Fermi-level-pinning gap states are close to, or even in some cases inside, the conduction band of the host slab. On the other hand, if Au is substituted for the surface Ti atom, Fermi level falls lower in the gap closer to the valence band top.