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The crystal structure and chemical bonding of magnetron-sputtering deposited nickel carbide Ni₁-xCx (0.05 ⩽ x⩽0.62) thin films have been investigated by high-resolution x-ray diffraction, transmission electron microscopy, x-ray photoelectron spectroscopy, Raman spectroscopy, and soft x-ray absorption spectroscopy. By using x-ray as well as electron diffraction, we found carbon-containing hcp-Ni (hcp-NiCy phase), instead of the expected rhombohedral-Ni₃C. At low carbon content (4.9 at%), the thin film consists of hcp-NiCy nanocrystallites mixed with a smaller amount of fcc-NiCx. The average grain size is about 10-20 nm. With the increase of carbon content to 16.3 at%, the film contains single-phase hcp-NiCy nanocrystallites with expanded lattice parameters. With a further increase of carbon content to 38 at%, and 62 at%, the films transform to x-ray amorphous materials with hcp-NiCy and fcc-NiCx nanodomain structures in an amorphous carbon-rich matrix. Raman spectra of carbon indicate dominant sp(2) hybridization, consistent with photoelectron spectra that show a decreasing amount of C-Ni phase with increasing carbon content. The Ni 3d-C 2p hybridization in the hexagonal structure gives rise to the salient double-peak structure in Ni 2p soft x-ray absorption spectra at 16.3 at% that changes with carbon content. We also show that the resistivity is not only governed by the amount of carbon, but increases by more than a factor of two when the samples transform from crystalline to amorphous.

The electronic structure of nanocrystalline ͑nc-͒ TiC/amorphous C nanocomposites has been investigated by soft x-ray absorption and emission spectroscopy. The measured spectra at the Ti 2p and C 1s thresholds of the nanocomposites are compared to those of Ti metal and amorphous C. The corresponding intensities of the electronic states for the valence and conduction bands in the nanocomposites are shown to strongly depend on the TiC carbide grain size. An increased charge transfer between the Ti 3d-e g states and the C 2p states has been identified as the grain size decreases, causing an increased ionicity of the TiC nanocrystallites. It is suggested that the charge transfer occurs at the interface between the nanocrystalline-TiC and the amorphous-C matrix and represents an interface bonding which may be essential for the understanding of the properties of nc-TiC/amorphous C and similar nanocomposites.

This is a critical review of MAX-phase carbides and nitrides from an electronic-structure and chemical bonding perspective. This large group of nanolaminated materials is of great scientific and technological interest and exhibit a combination of metallic and ceramic features. These properties are related to the special crystal structure and bonding characteristics with alternating strong M-C bonds in high-density MC slabs, and relatively weak M-A bonds between the slabs. Here, we review the trend and relationship between the chemical bonding, conductivity, elastic and magnetic properties of the MAX phases in comparison to the parent binary MX compounds with the underlying electronic structure probed by polarized X-ray spectroscopy. Spectroscopic studies constitute important tests of the results of state-of-the-art electronic structure density functional theory that is extensively discussed and are generally consistent. By replacing the elements on the M, A, or X-sites in the crystal structure, the corresponding changes in the conductivity, elasticity, magnetism and other materials properties makes it possible to tailor the characteristics of this class of materials by controlling the strengths of their chemical bonds.

The electronic structure of CoO is studied by resonant inelastic soft x-ray scattering spectroscopy using photon energies across the Co 2p absorption edges. The different energy-loss structures in the Raman scattering spectra are identified as due to d-d and charge-transfer excitations. For excitation energies close to the L 3 resonance, the spectral features are dominated by quartet-quartet and quartet-doublet transitions of the 3d 7 configuration. At excitation energies corresponding to the satellites in the Co 2p x-ray-absorption spectrum of CoO, the emission features are instead dominated by charge-transfer transitions to the 3d 8 L Ϫ1 final state. The spectra are interpreted and discussed with the support of simulations within the single-impurity Anderson model with full multiplet effects which are found to yield consistent spectral functions to the experimental data.

We investigate the amorphous structure, chemical bonding, and electrical properties of magnetron sputtered Fe(1-xCx) (0.21 ⩽ x ⩽ 0.72) thin films. X-ray, electron diffraction and transmission electron microscopy show that the Fe(1-xCx) films are amorphous nanocomposites, consisting of a two-phase domain structure with Fe-rich carbidic FeC(y), and a carbon-rich matrix. Pair distribution function analysis indicates a close-range order similar to those of crystalline Fe(3)C carbides in all films with additional graphene-like structures at high carbon content (71.8 at% C). From x-ray photoelectron spectroscopy measurements, we find that the amorphous carbidic phase has a composition of 15-25 at% carbon that slightly increases with total carbon content. X-ray absorption spectra exhibit an increasing number of unoccupied 3d states and a decreasing number of C 2p states as a function of carbon content. These changes signify a systematic redistribution in orbital occupation due to charge-transfer effects at the domain-size-dependent carbide/matrix interfaces. The four-point probe resistivity of the Fe(1-xCx) films increases exponentially with carbon content from ∼200 μΩ cm (x = 0.21) to ∼1200 μΩ cm (x = 0.72), and is found to depend on the total carbon content rather than the composition of the carbide. Our findings open new possibilities for modifying the resistivity of amorphous thin film coatings based on transition metal carbides through the control of amorphous domain structures.

The electronic structure of the nanolaminated transition metal carbide Ti 2 AlC has been investigated by bulk-sensitive soft x-ray emission spectroscopy. The measured Ti L, C K, and Al L emission spectra are compared with calculated spectra using ab initio density-functional theory including dipole matrix elements. The detailed investigation of the electronic structure and chemical bonding provides increased understanding of the physical properties of this type of nanolaminates. Three different types of bond regions are identified: The relatively weak Ti 3d -Al 3p bond 1 eV below the Fermi level and the Ti 3d -C 2p and Ti 3d -C 2s bonds which are stronger and deeper in energy are observed around 2.5 and 10 eV below the Fermi level, respectively. A strongly modified spectral shape of the 3s final states in comparison to pure Al is detected for the intercalated Al monolayers indirectly reflecting the Ti 3d -Al 3p hybridization. The differences between the electronic and crystal structures of Ti 2 AlC, Ti 3 AlC 2 , and TiC are discussed in relation to the number of Al layers per Ti layer in the two former systems and the corresponding change of the unusual materials properties.

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