Electronic structure and chemical bonding in Ti4 Si C3 investigated by soft x-ray emission spectroscopy and first-principles theory

Abstract

The electronic structure in the new transition-metal carbide Ti4 Si C3 has been investigated by bulk-sensitive soft x-ray emission spectroscopy and compared to the well-studied Ti3 Si C2 and TiC systems. The measured high-resolution Ti L, C K, and Si L x-ray emission spectra are discussed with ab initio calculations based on density-functional theory including core-to-valence dipole matrix elements. The detailed investigations of the Ti-C and Ti-Si chemical bonds provide increased understanding of the physical properties of these nanolaminates. A strongly modified spectral shape is detected for the intercalated Si monolayers due to Si 3p hybridization with the Ti 3d orbitals. As a result of relaxation of the crystal structure and the charge-transfer from Ti (and Si) to C, the strength of the Ti-C covalent bond is increased. The differences between the electronic and crystal structures of Ti4 Si C3 and Ti3 Si C2 are discussed in relation to the number of Si layers per Ti layer in the two systems and the corresponding change of materials properties. © 2006 The American Physical Society.