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.

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 influence of B4C incorporation during magnetron sputter deposition of Cr/Sc multilayers intended for soft X-ray reflective optics is investigated. Chemical analysis suggests formation of metal: boride and carbide bonds which stabilize an amorphous layer structure, resulting in smoother interfaces and an increased reflectivity. A near-normal incidence reflectivity of 11.7%, corresponding to a 67% increase, is achieved at λ = 3.11 nm upon adding 23 at.% (B + C). The advantage is significant for the multilayer periods larger than 1.8 nm, where amorphization results in smaller interface widths, for example, giving 36% reflectance and 99.89% degree of polarization near Brewster angle for a multilayer polarizer. The modulated ion-energy-assistance during the growth is considered vital to avoid intermixing during the interface formation even when B + C are added.

We investigate the trends in mixing thermodynamics of Cr_1-xSc_xN solid solutions in the cubic B1 structure and their electronic density of state by first-principle calculations, and thin-film synthesis of Cr_1-xSc_xN solid solutions by reactive dc magnetron sputtering. Films with the composition Cr_0.92Sc_0.08N exhibit a thermoelectric power factor of about 8x10^-4 Wm^-1K^-2at 770 K, similar to CrN. The results show that the disordered Cr_1-xSc_xN solid solutions is thermodynamically stable in B1 solid solutions at T = 800°C rather than in the B1- L11 ordered solid solutions stable at 0 K. The calculated electronic density of state (DOS) indicates a positive bowing parameter for the electronic band gap of Cr1-xScxN solid solutions. The calculated DOS suggest possible improvement of power factor due to Sc 3d orbital delocalization on Cr 3d orbital gives decreasing electrical resistivity with retained Seebeck coefficient in Cr-rich regime, consistent with the experimentally observed high power factor for the solid solution.

Zirconium diboride (ZrB₂) exhibits high hardness and high melting point, which is beneficial for applications in for e.g. metal cutting. However, there is limited data on the mechanical properties of ZrB₂ films and no data on epitaxial films. In this study, ZrB₂(0001) thin films, with thicknesses up to 1.2 μm, have been deposited on Al₂O₃(0001) substrates by direct current magnetron sputtering from a compound target. X-ray diffraction and transmission electron microscopy show that the films grow epitaxially with two domain types exhibiting different in-plane epitaxial relationships to the substrate. The out-of-plane epitaxial relationship was determined to ZrB₂(0001)|Al₂O₃(0001) and the in-plane relationships of the two domains to ZrB₂[100]‖Al₂O₃[100] and ZrB₂[110]‖Al₂O₃[100]. Mechanical properties of the films, evaluated by nanoindentation, showed that all films exhibit hardness values above 45 GPa, a reduced Young's modulus in the range 350–400 GPa, and a high elastic recovery of 70% at an applied load of 9000 μN.

Multilayered thin films of Al/Cu/Fe have been prepared by magnetron sputtering and annealed into the quasicrystalline or approximant phases, for Al₂O₃ or Si substrates, respectively. The nanomechanical and nanotribological properties; hardness, elastic modulus, friction and toughness, have been measured using a triboindenter and analytical methods. The approximant phase, annealed at 600 °C for 4 h, proved to be harder and had higher elastic modulus values than the quasicrystalline phase, about, 15.6 GPa and 258 GPa, respectively. The fracture toughness of the approximant, <0.1 MPa/m^½, was however inferior to that of the quasicrystals with 1.5 MPa/m^½. The friction coefficients were measured in a range of 0.10-0.14 for the quasicrystalline and approximant thin films.

(Ti_0.25B_0.75)_1−xSi_xN_y, 0≤x≤0.89, 0.9≤y≤1.25, thin films were reactively grown on Si(001) substrates by dc magnetron sputtering from compound TiB2 and elemental Si targets. The films can be grown in a fully electron-diffraction amorphous state with x>0.46, as evidenced by XRD and HR-TEM investigations. With x=0, BN form onion-like sheets surrounding TiNnanograins. Substrate temperatures, Ts=100-600 ◦C, has a minor effect of the film structure and properties, due to limited surface diffusion.

Ion-assisted growth with substrate bias voltages, Vb, between -50 V and -200 V, favors densification of amorphous structures over nanocrystalline formation, and improves mechanical properties. A maximum hardness value of 26.8±0.7 GPa is found for an amorphous (Ti_0.25B_0.75)_0.39Si_0.61N_1.15 film grown with substrate temperature T_s=400 °C and substrate bias voltage V_b=-100 V.

Reactive sputtering by high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (DCMS) of a Zr target in Ar/H-2 plasmas was employed to deposit Zr-H films on Si(100) substrates, and with H content up to 61 at.% and O contents typically below 0.2 at.% as determined by elastic recoil detection analysis. X-ray photoelectron spectroscopy reveals a chemical shift of similar to 0.7 eV to higher binding energies for the Zr-H films compared to pure Zr films, consistent with a charge transfer from Zr to H in a zirconium hydride. X-ray diffraction shows that the films are single-phase delta-ZrH2 (CaF2 type structure) at H content greater thansimilar to 55 at.% and pole figure measurements give a 111 preferred orientation for these films. Scanning electron microscopy cross-section images show a glasslike microstructure for the HiPIMS films, while the DCMS films are columnar. Nanoindentation yield hardness values of 5.5-7 GPa for the delta-ZrH2 films that is slightly harder than the similar to 5 GPa determined for Zr films and with coefficients of friction in the range of 0.12-0.18 to compare with the range of 0.4-0.6 obtained for Zr films. Wear resistance testing show that phase-pure delta-ZrH2 films deposited by HiPIMS exhibit up to 50 times lower wear rate compared to those containing a secondary Zr phase. Four-point probe measurements give resistivity values in the range of similar to 100-120 mu Omega cm for the delta-ZrH2 films, which is slightly higher compared to Zr films with values in the range 70-80 mu Omega cm.

Multilayered Al/Cu/Fe thin films with composition close to the quasicrystalline phase have been prepared by magnetron sputtering. Annealing at 600 °C yields a homogeneous film of the cubic a-approximant phase by Si substrate diffusion, which prevents the formation of the quasicrystalline phase. After 4 h annealing the film contained 8 at.% Si, which corresponds to the expected value of the a-approximant. The amount of Si in the films was found to slowly increase to ~12 at.% during continued annealing (64 h) while the α-approximant phase was retained. The lattice parameter was found to  continuously decrease as Al became substituted with Si. The film is observed to be polycrystalline with individual grains being strained in varying magnitude, and with no preferential orientation relationship to the substrate or each other.

Ion assisted depositions have been used to grow the Al38Cu46Sc16 quasicrystalline phase directly from the vapor phase in thin film form. Diffraction experiments reveal that amorphous films are formed at room temperature. The quasicrystalline phase formed at a substrate temperature of 340 °C with an improved quality at higher temperatures up to 460 °C. The quasicrystal film quality is improved by increasing the ion flux during ion-assisted growth with ion energies of 26.7 eV. Increasing the ion energy further was however found to cause resputtering and defects in the film. Electron microscopy reveals a polycrystalline microstructure with crystal grains in the shape of thin needles.