Bonding mechanism in the nitrides Ti2 AlN and TiN: An experimental and theoretical investigation

Abstract

The electronic structure of nanolaminate Ti2 AlN and TiN thin films has been investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured Ti L2,3, 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 bondings 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 Ti2 AlN in comparison with 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 Ti2 AlN and TiN are discussed in relation to the intercalated Al layers of the former compound and the change of the materials properties in comparison with the isostructural carbides. © 2007 The American Physical Society.