Significance of Al on the morphological and optical properties of Ti1−xAlxN thin films

TiN and Ti_1−xAl_xN thin films with different aluminum concentrations (x = 0.35, 0.40, 0.55, 0.64 and 0.81) were synthesized by reactive magnetron co-sputtering technique. The structure, surface morphology and optical properties were examined using Grazing Incidence X-ray Diffraction (GIXRD), Atomic Force Microscopy (AFM), Raman spectroscopy and spectroscopic ellipsometry, respectively. The structure of the films were found to be of rocksalt type (NaCl) for x = 0.0–0.64 and X-ray amorphous for x = 0.81. AFM topographies show continuous mound like structure for the films of x between 0.0 and 0.64, whereas the film with x = 0.81 showed smooth surface with fine grains. Micro-Raman spectroscopic studies indicate structural phase separation of AlN from TiAlN matrix for x > 0.40. Ti_1−xAl_xN has the tendency for decomposition with the increase of Al concentration whereas c-TiN and hcp-AlN are stable mostly. The optical studies carried out by spectroscopic ellipsometry measurements showed a change from metallic to insulating behavior with the increase in x. These films are found to be an insulator beyond x = 0.81.     

Influence of carbon chemical bonding on the tribological behavior of sputtered nanocomposite TiBC/a-C coatings

The tribological performance of nanocomposite coatings containing Ti-B-C phases and amorphous carbon (a-C) are studied. The coatings are deposited by a sputtering process from a sintered TiB₂:TiC target and graphite, using pulsed direct current and radio frequency sources. By varying the sputtering power ratio, the amorphous carbon content of the coatings can be tuned, as observed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The crystalline component consists of very disordered crystals with a mixture of TiB₂/TiC or TiB_xC_y phases. A slight increase in crystalline order is detected with the incorporation of carbon in the coatings that is attributed to the formation of a ternary TiB_xC_y phase. An estimation of the carbon present in the form of carbide (TiB_xC_y or TiC) and amorphous (a-C) is performed using fitting analysis of the C 1s XPS peak. The film hardness (22 to 31 GPa) correlates with the fraction of the TiB_xC_y phase that exists in the coatings. The tribological properties were measured by a pin-on-disk tribometer in ambient conditions, using 6 mm tungsten carbide balls at 1 N. The friction coefficients and the wear rates show similar behavior, exhibiting an optimum when the fraction of C atoms in the amorphous phase is near 50%. This composition enables significant improvement of the friction coefficients and wear rates (μ ∼ 0.1; k < 1 × 10⁻⁶ mm³/Nm), while maintaining a good value of hardness (24.6 GPa). Establishing the correlation between the lubricant properties and the fraction of a-C is very useful for purposes of tailoring the protective character of these nanocomposite coatings to engineering applications.     

Structure and optical properties of Zr1−xSixN thin films on sapphire

A series of zirconium silicon nitride (Zr_1−xSi_xN) thin films were grown on r-plane sapphire substrates using reactive RF magnetron co-sputtering of Zr and Si targets in a N₂/Ar plasma. X-ray diffraction pole figure analysis, X-ray reflectivity, X-ray photoelectron spectroscopy (XPS), optical microscopy, and optical absorption spectroscopy were used to characterize the film stoichiometries and structures after growth at 200 °C and post-deposition annealing up to 1000 °C in ultra-high vacuum. The atomically clean r-plane sapphire substrates induce high quality (100) heteroepitaxy of ZrN films rather than the (111) orientation observed on steel and silicon substrates, but the addition of Si yields amorphous films at the 200 °C growth temperature. After the annealing treatment, films with Si content x < 0.15 have compressive stress and crystallize into a polycrystalline structure with (100) fiber texture. For x > 0.15, the films are amorphous and remain so even after ultra-high vacuum annealing at 1000 °C. XPS spectra indicate that the bonding changes from covalent to more ionic in character as Si―N bonds form instead of Zr―N bonds. X-ray reflectivity, atomic force microscopy (AFM) and optical microscopy data reveal that after post-deposition annealing the 100 nm thick films have an average roughness < 2 nm, except for Si content near x = 0.15 corresponding to where the film becomes amorphous rather than being polycrystalline. At this stoichiometry, evidence was found for regions of film delamination and hillock formation, which is presumably driven by strain at the interface between the film and sapphire substrate. UV-visible absorption spectra also were found to depend on the film stoichiometry. For the amorphous Si-rich films (x > 0.15), the optical band gap increases with Si content, whereas for Zr-rich films (x < 0.15), there is no band gap and the films are highly conductive.     

Synthesis and characterisation of chromium lutetium gallium garnet solid solution

The chromium lutetium gallium garnet system has been studied. Samples with 2xCaOxCr₂O₃(3 − 2x)Lu₂O₃5Ga₂O₃ (x = 0.025, 0.05, 0.075, 0.1, 0.2 and 0.3,) and xCr₂O₃(3 − x)Lu₂O₃5Ga₂O₃ (x = 0, 0.05, 0.075 and 0.3) compositions have been prepared in Ca,Cr:LGG and Cr:LGG systems, respectively. Samples were prepared by ceramic method, fired at 1250 °C/6 h and characterised by XRD, lattice parameters, UV-vis-NIR spectroscopy, CIE L^*a^*b^* measurements and SEM/EDX. Results indicate that Ca,Cr:LGG and Cr:LGG solid solutions are obtained. In Cr:LGG system only Cr(III) is stabilised in octahedral positions substituting for Lu(III) and Ga(III). Both Cr(III) and Cr(IV) are present in Ca,Cr:LGG. The calcium is a charge compensator to stabilise Cr(IV) and this is the predominant oxidation state up to x = 0.075 composition. From this composition, Cr(III) becomes more stabilised in garnet lattice. Cr(IV) occupies generally tetrahedral and dodecahedral sites substituting for Ga(III) and Lu(III), while Cr(III) is in octahedral site substituting for Ga(III).     

A comparative study of CrNx coatings Synthesized by dc and pulsed dc magnetron sputtering

Chromium nitride (CrN_x) coatings were prepared by reactively sputtering chromium metal target with various nitrogen flow rate percentages (f_N2) using a closed field unbalanced magnetron sputtering system operated in dc and middle frequency pulsed condition (100 kHz and 50% duty cycle). In this study, plasma examination proved that a large amount of ions with a wide range of ion energies (up to 65 eV and mainly from 10-30 eV region) was identified in the pulsed plasma compared to the low ion flux and energy (0-10 eV) in a dc discharged plasma. The results showed that the phase structure of CrN_x coatings was changed from nitrogen doped Cr(N) to pure β-Cr₂N, and to a mixture of β-Cr₂N and c-CrN and then to pure c-CrN phases with an increase in the f_N2 in both dc and pulsed conditions. However, the pulsed CrN_x coatings exhibit lower N concentrations than dc CrN_x coatings prepared under the same f_N2, which leads to the existing of β-Cr₂N phase within a wide range of f_N2 (30-50%). In comparison with the typical large columnar structure in the dc sputtered coatings, the pulsed CrN_x coatings exhibit dramatic microstructure improvements which benefited from the improved plasma density and ion bombardment from the pulsed plasma, where the super dense and nearly equi-axial structures were observed in a wide range of f_N2. The microstructure improvements contributed to the enhancements in the hardness and wear resistance of pulsed CrN_x coatings. In the pulsed CrN_x coatings, the hardness values were above 30 GPa when the f_N2 is in the range of 30-40%, which is related to the formation of the β-Cr₂N phase. With the formation of a mixture of β-Cr₂N and c-CrN phases in the coatings deposited with 40-50% f_N2, a low COF of 0.36 and wear rate of 1.66 × 10^− 6 mm³ N^− 1 m^− 1 can be achieved.     

Influence of Cr deficiency on sintering character and properties of SOFC interconnect material La0.7Ca0.3Cr1−xO3−δ

The SOFC interconnect materials La_0.7Ca_0.3Cr_1−xO_3−δ (x = 0-0.09) were prepared using an auto-ignition process and characterized. XRD analysis indicated that all the samples displayed a pure perovskite phase after sintered at 1400 °C for 4 h. The relative density increased from 67% (x = 0) to 95.8% (x = 0.02) and reached to about 97% (x > 0.02), as sintered at 1400 °C for 4 h. The electrical conductivity in air dramatically increased and then lowered slowly with x values. The sample with 0.03 Cr deficiency got a maximum conductivity of 61.7 S cm⁻¹ at 850 °C in air, which is about three times as high as that of the sample with no Cr deficiency (20.6 S cm⁻¹). The sample with 0.06 Cr deficiency exhibited the highest electrical conductivity of 3.9 S cm⁻¹ at 850 °C in pure H₂. The thermal expansion coefficient (TEC) were below 11.8 × 10⁻⁶ K⁻¹ for samples of x = 0.02-0.09, that was of well compatibility with other components in SOFCs. Results indicate that the materials with 0.02-0.06 Cr deficiency have high properties and are much suitable for SOFC interconnect.     

Strong amorphization of high-entropy AlBCrSiTi nitride film

Amorphous coatings, particular nitride systems, are of interest for numerous practical applications. Nevertheless, at present only a few amorphous nitride coating systems have been considered, the most notably being the (TM, Si)N system (transition metal (TM) = Ti, Zr, W, Mo). The present study provides an alternative approach for producing amorphous nitride films with high thermal stability up to 700 °C for 2 h. Films are deposited from an equimolar AlBCrSiTi target in various argon/nitrogen atmospheres at different substrate temperatures. It is found that above the nitrogen flow ratio (i.e. R_N = N₂/N₂ + Ar) of 28.6% a near equal ratio between target elements and nitrogen is approached, thus indicating the coatings have the chemical formula of (AlBCrSiTi)N. The glancing-angle X-ray diffractometer and transmission electron microscope investigations indicate that the coatings, regardless of nitrogen concentration or deposition temperature (up to 500 °C), are amorphous. Thermal treatment shows that the amorphous structure of this (AlBCrSiTi)N coating is maintained up to 700 °C when annealing for 2 h in vacuum. At annealing temperatures of 800 °C and above, the amorphous films transform into a simple NaCl-type face-centered cubic solid solution. Even after annealing at 1000 °C for 2 h, the grain size is only 2 nm. High entropy effect, large lattice distortion effect, and sluggish diffusion effect are proposed to account for the formation of amorphous nitrides.     

A study of the nanostructure and hardness of electron beam evaporated TiAlBN Coatings

TiAlBN coatings have been deposited by electron beam (EB) evaporation from a single TiAlBN material source onto AISI 316 stainless steel substrates at a temperature of 450 °C and substrate bias of − 100 V. The stoichiometry and nanostructure have been studied by X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy. The hardness and elastic modulus were determined by nanoindentation. Five coatings have been deposited, three from hot-pressed TiAlBN material and two from hot isostatically pressed (HIPped) material. The coatings deposited from the hot-pressed material exhibited a nanocomposite nc-(Ti,Al)N/a-BN/a-(Ti,Al)B₂ structure, the relative phase fraction being consistent with that predicted by the equilibrium Ti-B-N phase diagram. Nanoindentation hardness values were in the range of 22 to 32 GPa. Using the HIPped material, coating (Ti,Al)B_0.29N_0.46 was found to have a phase composition of 72-79 mol.% nc-(Ti,Al)(N,B)_1 − x+ 21-28 mol.% amorphous titanium boride and a hardness of 32 GPa. The second coating, (Ti,Al)B_0.66N_0.25, was X-ray amorphous with a nitride+boride multiphase composition and a hardness of 26 GPa. The nanostructure and structure-property relationships of all coatings are discussed in detail. Comparisons are made between the single-EB coatings deposited in this work and previously deposited twin-EB coatings. Twin-EB deposition gives rise to lower adatom mobilities, leading to (111) (Ti,Al)N preferential orientation, smaller grain sizes, less dense coatings and lower hardnesses.     

Structure and mechanical properties of W-Se-C/diamond-like carbon and W-Se/diamond-like carbon bi-layer coatings prepared by pulsed laser deposition

Bi-layer W-Se-C/diamond-like carbon (DLC) and WSe_x/DLC coatings were obtained by standard and shadow-masked pulsed laser co-deposition from WSe₂ and graphite targets. W-Se-C coatings appeared as nanocomposites containing quasi-amorphous WSe₂, WC, spherical β-W nanocrystalline particles encapsulated in WSe₂ amorphous shell, and amorphous carbon phases. In WSe_x/DLC coatings, the formation of chemical bonds between W and C atoms was noticed at the interface. An increase of the C concentration over 40 at.% increases hardness and elasticity (up to 2 times at ~ 60 at.%C), and the Se/W ratio was always close to 1.4. The use of shadow-masked configuration avoids the deposition of micro- and nanoparticles. However, this method leads to a substantial increase of the Se content (Se/W ≥ 4), and the coatings became softer.     

Characterization of ZnO-In2O3 transparent conducting films by pulsed laser deposition

Transparent conducting oxide (TCO) films in the ZnO-In₂O₃ system were prepared by a pulsed laser deposition method. A target that consists of the mixture of ZnO and In₂O₃ powders was used. Influences of the target composition x (x = [Zn]/([Zn] + [In])) and heater temperature on structural, electrical and optical properties of the TCO films were examined. Introduction of oxygen gas into the chamber during the deposition was necessary for improvement in the transparency of the deposited films. The amorphous phase was observed for a wide range of x = 0.20-0.60 at 110 °C. Minimum resistivity was 2.65 × 10⁻⁴ Ω cm at x = 0.20. The films that showed the minimum resistivity had an amorphous structure and the composition shifted toward larger x, as the substrate temperature increased. The films were enriched in indium compared to the target composition and the cationic In/Zn ratio increased as the substrate temperature was increased.     

Structure and mechanical properties of low temperature magnetron sputtered nanocrystalline (nc-)Ti(N,C)/amorphous diamond like carbon (a-C:H) coatings

This paper reports on the structure and mechanical properties of ~ 2 μm thick nanocomposite (nc-) Ti(N,C)/amorphous diamond like carbon (a-C:H) coatings deposited on 100Cr6 steel substrates, using low temperature (~ 200 °C) DC reactive magnetron sputtering. The carbon content was varied with acetylene partial pressure in order to obtain single layer coatings with different a-C:H carbon phase fractions. The nanocrystalline Ti(N,C) phase is approximately stoichiometric for all coatings and the a-C:H phase fraction increases from 31 to 47 at.% as the coatings stoichiometry changed from TiC_1.34 N_0.51 to TiC_2.48 N_0.48, respectively. TiC_1.34 N_0.51 coatings showed the highest nanoindentation hardness (H) of ~ 14 GPa and a modulus (E_r) of ~ 144 GPa; H reduced to < 6 GPa and E_r to < 70 GPa for TiC_2.48 N_0.48 coatings. nc-Ti(N,C)/a-C:H coatings are promising candidates for applications where better matching of the modulus between a relatively low modulus substrate, hard loading support layer and low modulus-high H/E ratio top layer is required.     

Microstructure and mechanical properties of CrAlN/SiNx nanostructure multilayered coatings

Multilayered CrAlN and SiN_x films were deposited periodically by radio frequency reactive magnetron sputtering. In the CrAlN/SiN_x multilayered coatings, the thickness of CrAlN layer was fixed at 4 nm, while that of SiN_x layer was adjusted from 4 nm to 0.3 nm. The dependence of the SiN_x layer thickness on the preferred orientation, crystalline behavior and mechanical properties of multilayered coatings were discussed with the aid of XRD patterns and HRTEM. It was demonstrated that amorphous SiN_x layer transformed to a crystallized one when the thickness decreased from 4 nm to 0.3 nm. The crystalline SiN_x layer grew epitaxially, formed the coherent interface with the CrAlN layer, and the columnar structure was exhibited. The critical layer thickness for the transition from amorphous SiN_x to a crystallized one was found to be around 0.4 nm, and maximum hardness of 33 GPa was revealed.     

Characterization of TiCr(C,N)/amorphous carbon coatings synthesized by a cathodic arc deposition process

Ternary TiCrN and nanocomposite TiCr(C,N)/amorphous carbon (a-C) coatings with different carbon contents (0-26.6 at.%) were synthesized by cathodic arc evaporation with plasma enhanced duct equipment. The structural, chemical, and mechanical properties of the deposited films were studied by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), and nanoindentation measurement. The atomic content ratios of carbon/(Ti + Cr) and carbon/nitrogen increased with increasing C₂H₂ flow rate. A nanocomposite structure of coexisting metastable hard TiCr(C,N) crystallites and amorphous carbon phases was found in the TiCr(C,N)/a-C coatings, those possessed smaller crystallite sizes than the ternary TiCrN film. XPS analyses revealed the concentration of a-C increased with increasing carbon content from 8.9 at.% to 26.6 at.%. Exceeding the metastable solubility range of carbon within the TiCrN lattice, the carbon formed a-C phase in the deposited coatings. The nanocomposite TiCr(C,N)/a-C coatings exhibited higher hardness value of 29-31 GPa than the deposited TiCrN coating (26 ± 1 GPa). It has been found that the structural and mechanical properties of the films were correlated with the carbon content in the TiCr(C,N)/a-C coatings.     

Effects of BiAlO3 on structure and electrical properties of K0.5Na0.5NbO3-LiSbO3 lead-free piezoceramics

(1−x)(0.948 K_0.5Na_0.5NbO₃-0.052LiSbO₃)-xBiAlO₃ (KNNLS-xBA) lead-free piezoceramics were synthesized by conventional solid state reaction method. The compositional dependence of phase structure and electrical properties of the ceramics was systemically studied. XRD patterns revealed that all the ceramic samples possessed pure perovskite structure. In addition, polymorphic phase transition (PPT) for the ceramics with BA doping could not be observed in the measuring range from room temperature to 500 °C. Within the studied range of BA addition, the ceramics with x = 0.002 represented a relatively desirable balance between the degradation of the piezoelectric properties, improvement in temperature stability and mechanical quality factor. It was found that the KNNLS-0.002BA ceramics exhibited optimum overall properties (d₃₃ = 233 pC/N, k_p = 35%, tanδ = 0.047, P_r = 27.3 μC/cm², Q_m = 56 and T_c = 349 °C), suggesting that this material should be a promising lead-free piezoelectric candidate for piezoelectric applications.     

Ion sputtering rates of C, CrxCy, and Cr at different Ar ion incidence angles

To study the ion sputtering of a layered structure with different layer densities and ion sputtering yields a trilayer structure of C-graphite(46 nm)/Cr_xC_y(60 nm)/Cr(69 nm) was sputter deposited onto smooth silicon substrates. The ion sputtering rates of amorphous carbon, amorphous Cr_xC_y and polycrystalline Cr were determined by means of Auger electron spectroscopy depth profiling as a function of the angle of incidence of two symmetrically inclined 1 keV Ar⁺ ion beams in the range between 22° and 82°. The sputtering rates were calculated from the known thicknesses of the layers and the sputtering times necessary to remove the individual layers. It was found that the sputtering rates of C-graphite, Cr_xC_y carbide and Cr were strongly angle dependent. The experimental sputtering yields were in agreement with the theoretical results obtained by calculation of the transport of ions in solids, but the sputtering yields of C-graphite measured at ion incidence angles larger than 29° were smaller than the simulated ones.     

Effect of bias voltage on microstructure, mechanical and wear properties of Al-Si-N coatings deposited by cathodic arc evaporation

Al-Si-N coatings were deposited on tungsten carbide (WC-Co) and silicon wafer substrates using Cr and AlSi (12 at.% Si) alloy targets using a dual cathode source with short straight-duct filter in the cathode arc evaporation system. Al-Si-N coatings were synthesized under a constant flow of nitrogen, using various substrate bias voltages at a fixed AlSi cathode power. To enhance adhesive strength, the Cr/(Cr_xAl_ySi_z)N graduated layer between the top coating and the substrate was deposited as a buffer interlayer. The effects of bias voltage on the microstructure, mechanical and wear properties of the Al-Si-N films were investigated. Experimental results reveal that the Al-Si-N coatings exhibited a nanocomposite structure of nano-crystalline h-AlN, amorphous Si₃N₄ and a small amount of free Si and oxides. It was also observed that the deposition rate of as-deposited films gradually decreased from about 25.1 to 18.8 nm/min when the substrate bias was changed from − 30 to − 150 V. The XRD results revealed that h-AlN preferred orientation changed from (002) to (100) as the bias voltage increased. The maximum hardness of approximately 35 GPa was obtained at the bias voltage of −90 V. Moreover, the grain size was inversely proportional to the hardness of the film. Wear test results reveal that the Al-Si-N film had a lower coefficient of friction, between 0.5 and 0.7, than that 0.7 of the AlN film.     

Order-disorder phase transitions and high-temperature oxide ion conductivity of Er2+xTi2−xO7−δ (x = 0, 0.096)

The Er_2+xTi_2−xO_7−δ (x = 0.096; 35.5 mol% Er₂O₃) solid solution and the stoichiometric pyrochlore-structured compound Er₂Ti₂O₇ (x = 0; 33.3 mol% Er₂O₃) are characterized by X-ray diffraction (phase analysis and Rietveld method), thermal analysis and optical spectroscopy. Both oxides were synthesized by thermal sintering of co-precipitated powders. The synthesis study was performed in the temperature range 650-1690 °C. The amorphous phase exists below 700 °C. The crystallization of the ordered pyrochlore phase (P) in the range 800-1000 °C is accompanied by oxygen release. The ordered pyrochlore phase (P) exists in the range 1000−1200 °C. Heat-treatment at T ≥ 1600 °C leads to the formation of an oxide ion-conducting phase with a distorted pyrochlore structure (P2) and an ionic conductivity of about 10⁻³ S/cm at 740 °C. Complex impedance spectra are used to separately assess the bulk and grain-boundary conductivity of the samples. At 700 °C and oxygen pressures above 10⁻¹⁰ Pa, the Er_2+xTi_2−xO_7−δ (x = 0, 0.096) samples are purely ionic conductors.     

Structural and mechanical properties of multi-element (AlCrMoTaTiZr)Nx coatings by reactive magnetron sputtering

(AlCrMoTaTiZr)N_x high-entropy films were deposited on silicon wafer and cemented carbide substrates from a single alloy target by reactive RF magnetron sputtering under a mixed atmosphere of Ar and N₂. The effect of nitrogen flow ratio R_N on chemical composition, morphology, microstructure, and mechanical properties of the (AlCrMoTaTiZr)N_x films was investigated. Nitrogen-free alloy film had an amorphous structure, while nitride films with at least 37 at.% N exhibited a simple NaCl-type FCC (face-centered cubic) structure. Mixed structures occurred in films with lower nitrogen contents. Films with the FCC structure were thermally stable without phase decomposition at 1000 °C after 10 h. The (AlCrMoTaTiZr)N film deposited at R_N = 40% exhibited the highest hardness of 40.2 GPa which attains the superhard grade. The main strengthening mechanisms for this film were grain-size and solid-solution strengthening. A residual compressive stress of 1.04 GPa was small to account for the observed hardness. The nitride film was wear resistant, with a wear rate of 2.8 × 10^− 6 mm³/N m against a loaded 100Cr6 steel ball in the sliding wear test. These high-entropy films have potential in hard coating applications.     

SmAlO3-modified (K0.5Na0.5)0.95Li0.05Sb0.05Nb0.95O3 lead-free ceramics with a wide sintering temperature range

Lead-free ceramics (1 − x)(K_0.5Na_0.5)_0.95Li_0.05Sb_0.05Nb_0.95O₃-xSmAlO₃ (KNLNS-xSA) were prepared by conventional sintering technique. The phase structure, dielectric and piezoelectric properties of the ceramics were investigated. All compositions show a main perovskite structure, exhibiting room-temperature symmetries of tetragonal at x ≤ 0.0075, of pseudo-cubic at x = 0.0100. The Curie temperature of KNLNS-xSA ceramics decreases with increasing SmAlO₃ content. Moreover, the addition of SmAlO₃ can effectively broaden the sintering temperature range of the ceramics. The KNLNS-xSA ceramic with x = 0.0050 has an excellent electrical behavior of piezoelectric coefficient d₃₃ = 226 pC/N, planar mode electromechanical coupling coefficient k_p = 38%, dielectric loss tan δ = 3.0%, mechanical quality factor Q_m = 60, and Curie temperature T_C = 327 °C, suggesting that this material could be a promising lead-free piezoelectric candidate for piezoelectric applications.     

Toughness enhancement in TiAlN-based quarternary alloys

Improved toughness in hard and superhard thin films is a primary requirement for present day ceramic hard coatings, known to be prone to brittle failure during in-use conditions. We use density functional theory calculations to investigate a number of (TiAl)_1 − xM_xN thin films in the B1 structure, with 0.06 ≤ x ≤ 0.75, obtained by alloying TiAlN with M = V, Nb, Ta, Mo and W. Results show significant ductility enhancements, hence increased toughness, in these compounds. Importantly, these thin films are also predicted to be superhard, with similar or increased hardness values, compared to Ti_0.5Al_0.5 N. For (TiAl)_1 − xW_xN the results are experimentally confirmed. The ductility increase originates in the enhanced occupancy of d-t_2g metallic states, induced by the valence electrons of substitutional elements (V, Nb, Ta, Mo, W). This effect is more pronounced with increasing valence electron concentration, and, upon shearing, leads to the formation of a layered electronic structure in the compound material, consisting of alternating layers of high and low charge density in the metallic sublattice, which in turn, allows a selective response to normal and shear stresses.