Electronic structure investigation of Ti3AlC2, Ti3SiC2, and Ti3GeC2 by soft-X-ray emission spectroscopy

TL;DR

This study uses soft-X-ray emission spectroscopy and ab initio calculations to analyze the electronic structures of Ti3AlC2, Ti3SiC2, and Ti3GeC2, revealing bonding differences and their impact on material properties.

Contribution

It provides a detailed comparison of experimental and theoretical electronic structures of these nanolaminate materials, highlighting how elemental substitution affects bonding.

Findings

Weak Ti-Al covalent bond in Ti3AlC2

Disappearance of Al-related spectral shoulder with Si or Ge substitution

Strengthening of Ti-C bonds due to structural relaxation and charge transfer

Abstract

The electronic structures of epitaxially grown films of Ti3AlC2, Ti3SiC2 and Ti3GeC2 have been investigated by bulk-sensitive soft X-ray emission spectroscopy. The measured high-resolution Ti L, C K, Al L, Si L and Ge M emission spectra are compared with ab initio density-functional theory including core-to-valence dipole matrix elements. A qualitative agreement between experiment and theory is obtained. A weak covalent Ti-Al bond is manifested by a pronounced shoulder in the Ti L-emission of Ti3AlC2. As Al is replaced with Si or Ge, the shoulder disappears. For the buried Al and Si-layers, strongly hybridized spectral shapes are detected in Ti3AlC2 and Ti3SiC2, respectively. As a result of relaxation of the crystal structure and the increased charge-transfer from Ti to C, the Ti-C bonding is strengthened. The differences between the electronic structures are discussed in relation to the bonding in the nanolaminates and the corresponding change of materials properties.