Bonding mechanism in the nitrides Ti2AlN and TiN: an experimental and theoretical investigation

TL;DR

This study combines experimental soft x-ray emission spectroscopy and ab initio calculations to analyze the bonding mechanisms in Ti2AlN and TiN thin films, revealing distinct bonding regions and hybridization effects.

Contribution

It provides a detailed experimental and theoretical analysis of the electronic structure and bonding in Ti2AlN and TiN, highlighting differences caused by intercalated Al layers.

Findings

Identified three types of bonding regions involving Ti, Al, and N.

Observed hybridization effects between Ti 3d and Al 3p states.

Compared electronic structures of Ti2AlN and TiN, relating differences to material properties.

Abstract

The electronic structure of nanolaminate Ti2AlN and TiN thin films has been investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured Ti L, N K, Al L1 and Al L2,3 emission spectra are compared with calculated spectra using ab initio density-functional theory including dipole transition matrix elements. Three different types of bond regions are identified; a relatively weak Ti 3d - Al 3p bonding between -1 and -2 eV below the Fermi level, and Ti 3d - N 2p and Ti 3d - N 2s bonding which are deeper in energy observed at -4.8 eV and -15 eV below the Fermi level, respectively. A strongly modified spectral shape of 3s states of Al L2,3 emission from Ti2AlN in comparison to pure Al metal is found, which reflects the Ti 3d - Al 3p hybridization observed in the Al L1 emission. The differences between the electronic and crystal structures of Ti2AlN and TiN are discussed in relation to the intercalated Al layers of the former compound and the change of the materials properties in comparison to the isostructural carbides.