The authors investigate sputtering of a Ti₃SiC₂ compound target at temperatures ranging from RT (no applied external heating) to 970 °C as well as the influence of the sputtering power at 850 °C for the deposition of Ti₃SiC₂ films on Al₂O₃(0001) substrates. Elemental composition obtained from time-of-flight energy elastic recoil detection analysis shows an excess of carbon in all films, which is explained by differences in the angular distribution between C, Si, and Ti, where C scatters the least during sputtering. The oxygen content is 2.6 at. % in the film deposited at RT and decreases with increasing deposition temperature, showing that higher temperatures favor high purity films. Chemical bonding analysis by x-ray photoelectron spectroscopy shows C–Ti and Si–C bonding in the Ti₃SiC₂ films and Si–Si bonding in the Ti₃SiC₂ compound target. X-ray diffraction reveals that the phases Ti₃SiC₂, Ti₄SiC₃, and Ti₇Si₂C₅ can be deposited from a Ti₃SiC₂ compound target at substrate temperatures above 850 °C and with the growth of TiC and the Nowotny phase Ti₅Si₃C_x at lower temperatures. High-resolution scanning transmission electron microscopy shows epitaxial growth of Ti₃SiC₂, Ti₄SiC₃, and Ti₇Si₂C₅ on TiC at 970 °C. Four-point probe resistivity measurements give values in the range ∼120 to ∼450 μΩ cm and with the lowest values obtained for films containing Ti₃SiC₂, Ti₄SiC₃, and Ti₇Si₂C₅.

The electronic structure and chemical bonding of ß-Ta synthesized as a thin 001-oriented film (space group P 2₁m) is investigated by 4f core level and valence band X-ray photoelectron spectroscopy and compared to α-Ta bulk. For the b-phase, the 4f_7/2 peak is located at 21.91 eV and with the 4f_5/2 at 23.81 eV which is 0.16 eV higher compared to the corresponding 4f peaks of the a-Ta reference. We suggest that this chemical shift originates from higher resistivity and tensile strain in the ß-Ta film. Furthermore, the 5d-5s states at the bottom of the valence band are shifted by 0.75 eV towards higher binding energy in ß-Ta compared to α-Ta. This is a consequence of the lower number of nearest neighbors with four in ß-Ta compared to eight in the α-Ta phase. The difference in the electronic structures, spectral line shapes of the valence band and the energy positions of the Ta 4f, 5p core-levels of b-Ta versus a-Ta are discussed in relation to calculated states of ß-Ta and α-Ta. In particular, the lower number of states at the Fermi level of ß-Ta (0.557 states/eV/atom) versus α-Ta (1.032 states/eV/atom) that according to Mott’s law should decrease the conductivity in metals and affect the stability by charge redistribution in the valence band. This is experimentally supported from resistivity measurements of the film yielding a value of ~170 µW cm in comparison to α-Ta bulk with a reported value of ~13.1 µW cm.

With the examples of the C K-edge in graphite and the B K-edge in hexagonal boron nitride, we demonstrate the impact of vibrational coupling and lattice distortions on the X-ray absorption near-edge structure (XANES) in two-dimensional layered materials. Theoretical XANES spectra are obtained by solving the Bethe–Salpeter equation of many-body perturbation theory, including excitonic effects through the correlated motion of the core hole and excited electron. We show that accounting for zero-point motion is important for the interpretation and understanding of the measured X-ray absorption fine structure in both materials, in particular for describing the σ*-peak structure.

tThe chemical bonding in the carbide core and the surface chemistry in a new group of transition-metalcarbides Tin+1Cn-Tx(n = 1,2) called MXenes have been investigated by surface-sensitive valence bandX-ray photoelectron spectroscopy. Changes in band structures of stacked nano sheets of different thick-nesses are analyzed in connection to known hybridization regions of TiC and TiO2that affect elastic andtransport properties. By employing high excitation energy, the photoelectron cross-section for the C 2s– Ti 3d hybridization region at the bottom of the valence band is enhanced. As shown in this work, theO 2p and F 2p bands strongly depend both on the bond lengths to the surface groups and the adsorptionsites. The effect of surface oxidation and Ar+sputtering on the electronic structure is also discussed.

The chemical bonding in an epitaxial ZrB₂ film is investigated by Zr K-edge (1s) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies and compared to the ZrB₂ compound target from which the film was synthesized as well as a bulk α-Zr reference. Quantitative analysis of X-ray Photoelectron Spectroscopy spectra reveals at the surface: ~5% O in the epitaxial ZrB₂ film, ~19% O in the ZrB₂ compound target and ~22% O in the bulk α-Zr reference after completed sputter cleaning. For the ZrB₂ compound target, X-ray diffraction (XRD) shows weak but visible   11, 111, and 220 peaks from monoclinic ZrO₂ together with peaks from ZrB₂ and where the intensity distribution for the ZrB₂ peaks show a randomly oriented target material.  For the bulk α-Zr reference no peaks from any crystalline oxide were visible in the diffractogram recorded from the 0001-oriented metal. The Zr K-edge absorption from the two ZrB₂ samples demonstrate more pronounced oscillations for the epitaxial ZrB₂ film than in the bulk ZrB₂ attributed to the high atomic ordering within the columns of the film. The XANES exhibits no pre-peak due to lack of p-d hybridization in ZrB₂, but with a chemical shift towards higher energy of 4 eV in the film and 6 eV for the bulk compared to α-Zr (17.993 keV) from the charge-transfer from Zr to B. The 2 eV larger shift in bulk ZrB₂ material suggests higher oxygen content than in the epitaxial film, which is supported by XPS. In EXAFS, the modelled cell-edge in ZrB₂ is slightly smaller in the thin film (a=3.165 Å, c=3.520 Å) in comparison to the bulk target material (a=3.175 Å, c=3.540 Å) while in hexagonal closest-packed metal (α-phase, a=3.254 Å, c=5.147 Å). The modelled coordination numbers show that the EXAFS spectra of the epitaxial ZrB₂ film is highly anisotropic with strong in-plane contribution, while the bulk target material is more isotropic. The Zr-B distance in the film of 2.539 Å is in agreement with the calculated value from XRD data of 2.542 Å. This is slightly shorter compared to that in the ZrB₂ compound target 2.599 Å, supporting the XANES results of a higher atomic order within the columns of the film compared to bulk ZrB₂.

We present a study on the high-Tc superconductor (HTSC) YBa2Cu3O7-x(YBCO) using polarization-dependent X-ray absorption and resonant inelastic X-ray scattering. High-resolution measurementsusing synchrotron-radiation are compared with calculations using a quasi-atomic multiplet approachperformed at the Cu 2p3/2-edge of YBCO. We use a multiplet approach within the single impurity Ander-son model to reproduce and understand the character of the localized low-energy excitations in YBCO.We observe a distinct peak at about 0.5 eV in O K RIXS. This peak shows dependence on doping, incidentenergy, and momentum transfer that suggests that it has a different origin than the previously discussedcuprate bimagnons. Therefore, we assign it to bimagnon excitations within the Zhang Rice bands and/orthe Upper Hubbard bands, respectively.

The variation in local atomic structure and chemical bonding of ZrH_x (x=0.15, 0.30, 1.16) magnetron sputtered thin films are investigated by Zr K-edge (1s) X-ray absorption near-edge structure and extended X-ray absorption fine structure spectroscopies. A chemical shift of the Zr K-edge towards higher energy with increasing hydrogen content is observed due to charge-transfer and an ionic or polar covalent bonding component between the Zr 4d and the H 1s states with increasing valency for Zr. We find an increase in the Zr-Zr bond distance with increasing hydrogen content from 3.160 Å in the hexagonal closest-packed metal (a-phase) to 3.395 Å in the understoichiometric d-ZrH_x film (CaF₂-type structure) with x=1.16 that largely resembles that of bulk d-ZrH₂. For yet lower hydrogen contents, the structures are mixed a- and d-phases, while sufficient hydrogen loading (x>1) yields a pure δ-phase that is understoichiometric, but thermodynamically stable. The change in the hydrogen content and strain is discussed in relation to the corresponding change of bond lengths, hybridizations, and trends in electrical resistivity.

The local structure and chemical bonding in two-phase amorphous Cr1−xCx nanocomposite thin films are investigated by Cr K-edge (1s) X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopies in comparison to theory. By utilizing the computationally efficient stochastic quenching (SQ) technique, we reveal the complexity of different Cr-sites in the transition metal carbides, highlighting the need for large scale averaging to obtain theoretical XANES and EXAFS spectra for comparison with measurements. As shown in this work, it is advantageous to use ab initio theory as an assessment to correctly model and fit experimental spectra and investigate the trends of bond lengths and coordination numbers in complex amorphous materials. With sufficient total carbon content (≥30 at. %), we find that the short-range coordination in the amorphous carbide phase exhibit similarities to that of a Cr7C3 ± y structure, while excessive carbons assemble in the amorphous carbon phase.

We investigate the amorphous structure, chemical bonding, and electrical properties ofmagnetron sputtered Fe1−xCx (0.21 < x < 0.72) thin films. X-ray, electron diffraction andtransmission electron microscopy show that the Fe1−xCx films are amorphousnanocomposites, consisting of a two-phase domain structure with Fe-rich carbidic FeCy , and acarbon-rich matrix. Pair distribution function analysis indicates a close-range order similar tothose of crystalline Fe3C carbides in all films with additional graphene-like structures at highcarbon content (71.8 at% C). From x-ray photoelectron spectroscopy measurements, we findthat the amorphous carbidic phase has a composition of 15–25 at% carbon that slightlyincreases with total carbon content. X-ray absorption spectra exhibit an increasing number ofunoccupied 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-transfereffects at the domain-size-dependent carbide/matrix interfaces. The four-point proberesistivity of the Fe1−xCx films increases exponentially with carbon content from ∼200μcm(x = 0.21) to ∼1200μcm (x = 0.72), and is found to depend on the total carbon contentrather than the composition of the carbide. Our findings open new possibilities for modifyingthe resistivity of amorphous thin film coatings based on transition metal carbides through thecontrol of amorphous domain structures.

The anisotropy in the electronic structure of the inherently nanolaminated ternary phase Cr2GeC is investigated by bulk-sensitive and element selective soft x-ray absorption/emission spectroscopy. The angle-resolved absorption/emission measurements reveal di erences between the in-plane and out-of-plane bonding at the (0001) interfaces of Cr2GeC. The Cr L2;3, C K, and Ge M1, M2;3 emission spectra are interpreted with rst-principles density-functional theory (DFT) including core-tovalence dipole transition matrix elements. For the Ge 4s states, the x-ray emission measurements reveal two orders of magnitude higher intensity at the Fermi level than DFT within the General Gradient Approximation (GGA) predicts. We provide direct evidence of anisotropy in the electronic structure and the orbital occupation that should a ect the thermal expansion coecient and transport properties. As shown in this work, hybridization and redistribution of intensity from the shallow 3d core levels to the 4s valence band explain the large Ge density of states at the Fermi level.