Electronic structure and chemical bonding in Ti4SiC3 investigated by soft x-ray emission spectroscopy and first-principles theory

摘要

Theelectronic structure in the new transition-metal carbide Ti4SiC3 has beeninvestigated by bulk-sensitive soft x-ray emission spectroscopy and compared tothe well-studied Ti3SiC2 and TiC systems. The measured high-resolution TiL, C K, and Si L x-ray emission spectra arediscussed with ab initio calculations based on density-functional theory includingcore-to-valence dipole matrix elements. The detailed investigations of the Ti-Cand Ti-Si chemical bonds provide increased understanding of the physicalproperties of these nanolaminates. A strongly modified spectral shape isdetected for the intercalated Si monolayers due to Si 3phybridization with the Ti 3d orbitals. As a result ofrelaxation of the crystal structure and the charge-transfer from Ti(and Si) to C, the strength of the Ti-C covalentbond is increased. The differences between the electronic and crystalstructures of Ti4SiC3 and Ti3SiC2 are discussed in relation tothe number of Si layers per Ti layer in thetwo systems and the corresponding change of materials properties.