  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.
