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MAB phases (MABs) are atomically-thin laminates of ceramic/metallic-like layers, having made a breakthrough in the development of 2D materials. Though theoretically offering a vast chemical and phase space, relatively few MABs have yet been synthesised. To guide experiments, we perform a systematic high-throughput {\it{ab initio}} screening of MABs that combine group 4--7 transition metals (M); Al, Si, Ga, Ge, or In (A); and boron (B) focusing on their phase stability trends and mechanical properties. Considering the 1:1:1, 2:1:1, 2:1:2, 3:1:2, 3:1:3, and 3:1:4 M:A:B ratios and 10 phase prototypes, possible stabilisation of a single-phase compound for each elemental combination is assessed through formation energy spectra of the competing mechanically and dynamically stable MABs. Based on the volumetric proximity of energetically-close phases, we identify systems in which volume-changing deformations may facilitate transformation toughening. Subsequently, chemistry- and phase-structure-related trends in the elastic stiffness and ductility are predicted using elastic-constants-based descriptors. The analysis of directional Cauchy pressures and Young's moduli allows comparing mechanical response parallel and normal to M--B/A layers. Among the suggested most promising MABs are Nb$_3$AlB$_4$, Cr$_2$SiB$_2$, Mn$_2$SiB$_2$ or the already synthesised MoAlB.

Machine-learning interatomic potentials (MLIPs) offer a powerful avenue for simulations beyond length and timescales of ab initio methods. Their development for investigation of mechanical properties and fracture, however, is far from trivial since extended defects -- governing plasticity and crack nucleation in most materials -- are too large to be included in the training set. Using TiB$_2$ as a model ceramic material, we propose a strategy for fitting MLIPs suitable to simulate mechanical response of monocrystals until fracture. Our MLIP accurately reproduces ab initio stresses and failure mechanisms during room-temperature uniaxial tensile deformation of TiB$_2$ at the atomic scale ($\approx{10}^3$ atoms). More realistic tensile tests (low strain rate, Poisson's contraction) at the nanoscale ($\approx{10}^4$--10$^6$ atoms) require MLIP up-fitting, i.e. learning from additional ab initio configurations. Consequently, we elucidate trends in theoretical strength, toughness, and crack initiation patterns under different loading directions. To identify useful environments for further up-fitting, i.e., making the MLIP applicable to a wider spectrum of simulations, we asses transferability to other deformation conditions and phases not explicitly trained on.

Transition metal diborides crystallise in the $\alpha$, $\gamma$, or $\omega$ type structure, in which pure transition metal layers alternate with pure boron layers stacked along the hexagonal [0001] axis. Here we view the prototypes as different stackings of the transition metal planes and suppose they can transform from one into another by a displacive transformation. Employing first-principles calculations, we simulate sliding of individual planes in the group IV-VII transition metal diborides along a transformation pathway connecting the $\alpha$, $\gamma$, and $\omega$ structure. Chemistry-related trends are predicted in terms of energetic and structural changes along a transformation pathway, together with the mechanical and dynamical stability of the different stackings. Our results suggest that MnB$_2$ and MoB$_2$ possess the overall lowest sliding barriers among the investigated TMB$_2$s. Furthermore, we discuss trends in strength and ductility indicators, including Young's modulus or Cauchy pressure, derived from elastic constants., Comment: 12 pages, 6 figures, accepted for publication in Vacuum, before proof

Superlattice architecture represents an effective strategy to improve performance of hard protective coatings. Our model system, MoN/TaN, combines materials well-known for their high ductility as well as a strong driving force for vacancies. In this work, we reveal and interpret peculiar structure-stability-elasticity relations for MoN/TaN combining modelling and experimental approaches. Chemistry of the most stable structural variants depending on various deposition conditions is predicted by Density Functional Theory calculations using the concept of chemical potential. Importantly, no stability region exists for the defect-free superlattice. The X-ray Diffraction and Energy-dispersive $\text{X-ray}$ Spectroscopy experiments show that MoN/TaN superlattices consist of distorted fcc building blocks and contain non-metallic vacancies in MoN layers, which perfectly agrees with our theoretical model for these particular deposition conditions. The vibrational spectra analysis together with the close overlap between the experimental indentation modulus and the calculated Young's modulus points towards MoN$_{0.5}$/TaN as the most likely chemistry of our coatings.

High-entropy materials often outperform their lower-entropy relatives in various aspects, such as thermal stability and fracture toughness. While there are extensive research activities in the field of high-entropy alloys, comparably little is performed for high-entropy ceramics, and especially for high-entropy diborides. Here we show, that not only the hardness of ZrB2 layers can be improved from 43.2 to 45.8 to 47.2 GPa through the formation of solid solution ternary diborides (Zr0.61Ti0.39B2) and high-entropy diborides (Zr0.23Ti0.20Hf0.19V0.14Ta0.24B2), respectively, but especially their thermal stability against structural rearrangements and decomposition towards the constituting binary diborides., Comment: Viewpoint article

Quantum mechanical calculations had been previously applied to predict phase stability in many ternary and multinary nitride systems. While the predictions were very accurate for the Ti-Al-N system, some discrepancies between theory and experiment were obtained in the case of other systems. Namely, in the case of Ta-Al-N, the calculations tend to overestimate the minimum Al content necessary to obtain a metastable solid solution with a cubic structure. In this work, we present a comprehensive study of the impact of vacancies on the phase fields in quasi-binary TaN-AlN and NbN-AlN systems. Our calculations clearly show that presence of point defects strongly enlarges the cubic phase field in the TaN-AlN system, while the effect is less pronounced in the NbN-AlN case. The present phase stability predictions agree better with experimental observations of physical vapour deposited thin films reported in the literature than that based on perfect, non-defected structures. This study shows that a representative structural model is crucial for a meaningful comparison with experimental data., Comment: 15 pages, 7 figures, submitted to S&CT

Employing ab initio calculations, we discuss chemical, mechanical, and dynamical stability of MoN-TaN solid solutions together with cubic-like MoN/TaN superlattices, as another materials design concept. Hexagonal-type structures based on low-energy modifications of MoN and TaN are the most stable ones over the whole composition range. Despite being metastable, disordered cubic polymorphs are energetically significantly preferred over their ordered counterparts. An in-depth analysis of atomic environments in terms of bond lengths and angles reveals that the chemical disorder results in (partially) broken symmetry, i.e., the disordered cubic structure relaxes towards a hexagonal NiAs-type phase, the ground state of MoN. Surprisingly, also the superlattice architecture is clearly favored over the ordered cubic solid solution. We show that the bi-axial coherency stresses in superlattices break the cubic symmetry beyond simple tetragonal distortions and lead to a new tetragonal $\zeta$-phase (space group P4/nmm), which exhibits a more negative formation energy than the symmetry-stabilized cubic structures of MoN and TaN. Unlike cubic TaN, the $\zeta\text{-TaN}$ is elastically and vibrationally stable, while $\zeta$-MoN is stabilized only by the superlattice structure. To map compositional trends in elasticity, we establish mechanical stability of various Mo$_{1-x}$Ta$_x$N systems and find the closest high-symmetry approximants of the corresponding elastic tensors. According to the estimated polycrystalline moduli, the hexagonal polymorphs are predicted to be extremely hard, however, less ductile than the cubic phases and superlattices. The trends in stability based on energetics and elasticity are corroborated by density of electronic states.

We employ \textit{ab initio} calculations to investigate energetics of point defects in metastable rocksalt cubic Ta-N and Mo-N. Our results reveal a strong tendency to off-stoichiometry, i.e. defected structures are predicted to be more stable than perfect ones with 1:1 metal-to-nitrogen stoichiometry, in agreement with previous literature reports. While Ta-N significantly favours metal vacancies, Mo-N exhibits similar energies of formation regardless of the vacancy type ($V_\text{Mo}$, $V_\text{N}$) as long as their concentration is below $\approx15\,\text{at.\%}$. The overall lowest energy of formation were obtained for $\text{Ta}_{0.78}\text{N}$ and $\text{Mo}_{0.91}\text{N}$, which are hence predicted to be the most stable compositions. To account for various experimental condition during synthesis, we further evaluated the phase stability as a function of chemical potential of individual species. The proposed phase diagrams reveal four stable compositions, $\text{Mo}_{0.84}\text{N}$, $\text{Mo}_{0.91}\text{N}$, $\text{MoN}_{0.69}$ and $\text{MoN}_{0.44}$, in the case of Mo-N and nine stable compositions in the case of Ta-N indicating the crucial role of metal under-stoichiometry, since $\text{Ta}_{0.75}\text{N}$ and $\text{Ta}_{0.78}\text{N}$ significantly dominate the diagram. These results are important for understanding and designing experiments using non-equilibrium deposition techniques. Finally, we discuss a role of defects ordering and estimate a cubic lattice parameter as a function of a defect contents., Comment: 9 pages, 6 figures, 2 tables

The tendency for nitrogen deficiency in cubic Cr-Mo-N and Cr-W-N solid solutions is predicted by a comprehensive evaluation of the lattice spacing, mixing thermodynamics, and elastic properties using first-principles calculations and experimentally confirmed by means of X-ray diffraction. A major conclusion is that these systems exhibit significant amount of N vacancies whose amount scales linearly with the TM content, hence making the Cr1-xTMxN1-0.5x chemical formula more precise and informative to describe the chemical composition of cubic Cr-Mo-N and Cr-W-N solid solutions as compared with the conventionally used Cr1-xTMxN. The cubic Cr1-xMoxN1-0.5x and Cr1-xWxN1-0.5x solid solutions exhibit large positive mixing enthalpies towards isostructural phase decomposition into cubic B1-CrN and {\gamma}-Mo2N or {\gamma}-W2N, respectively. Their ductility increases with increasing Mo or W content and both systems exhibit significantly direction-dependent Young's moduli over the entire composition range, even when using the approach to study their polycrystalline behavior. The excellent agreement between experimentally obtained lattice parameters, Mo- and W-dependent nitrogen content, elastic properties and their calculated values for our model descriptions, Cr1-xMoxN1-0.5x and Cr1-xWxN1-0.5x, allows to understand these complex material systems. Based on our results, we can conclude that their content of nitrogen vacancies scales with half of the alloying content Mo or W., Comment: 5 figures

This paper presents first principles calculations of paramagnetic cubic CrN$_x$ with the aim to provide deeper insight into recently published transmission electron microscopy-based study on this material. Among several types of point defects which may result in N-deficient material, N vacancy is found to be energetically preferred to Cr interstitial and anti-sites. Electron Energy Loss Near Edge Structure of N K-edge transition is calculated for various concentrations of N vacancies in CrN$_x$, yielding the same trends as experimentally observed. Analysis of the electronic structure reveals decreased charge transfer from Cr sites with increased N vacancy content, hence increasing the metallic character of the defected material. Finally, the electronic structure is found to be strongly dependent on the local environment (i.e. presence of the N vacancies)., Comment: 5 pages, 4 figures

The dynamical and thermodynamic phase stabilities of the stoichiometric compound CrN including different structural and magnetic configurations are comprehensively investigated using a first-principles density-functional-theory (DFT) plus U approach in conjunction with experimental measurements of the thermal expansion. Comparing DFT and DFT+U results with experimental data reveals that the treatment of electron correlations using methods beyond standard DFT is crucial. The non-magnetic face-centered cubic B1-CrN phase is both, elastically and dynamically unstable, even under high pressure, while CrN phases with non-zero local magnetic moments are predicted to be dynamically stable within the framework of the DFT+U scheme. Furthermore, the impact of different treatments for the exchange-correlation (xc)-functional is investigated by carrying out all computations employing the local density approximation and generalized gradient approximation. To address finite-temperature properties, both, magnetic and vibrational contributions to the free energy have been computed employing our recently developed spin-space averaging method. The calculated phase transition temperature between low-temperature antiferromagnetic and high-temperature paramagnetic (PM) CrN variants is in excellent agreement with experimental values and reveals the strong impact of the choice of the xc-functional. The temperature-dependent linear thermal expansion coefficient of CrN is experimentally determined by the wafer curvature method from a reactive magnetron sputter deposited single-phase B1-CrN thin film with dense film morphology. A good agreement is found between experimental and ab initio calculated linear thermal expansion coefficients of PM B1-CrN. Other thermodynamic properties, such as the specific heat capacity, have been computed as well and compared to previous experimental data., Comment: 10 figures

Alloying Ti-Al-N coatings with Ta has proven to enhance their hardness, thermal stability, and oxidation resistance. However, especially for arc-evaporated Ti-Al-Ta-N coatings only limited information on the detailed influence of the elements on various properties is available. Therefore, we have developed arc-evaporated Ti1-x-yAlxTayN coatings with various Al (x = 0.50 - 0.65) and Ta (y = 0.00 - 0.15) contents. While the thermal stability of our coatings during annealing in inert He atmosphere increases with increasing Ta content, best results are obtained for specific Ta-Al ratios during oxidation. Single phase cubic Ti0.32Al0.60Ta0.08N yields a mass-gain of only ~5 % after 5 h at 950 {\deg}C in synthetic air, whereas Ti0.35Al0.65N is completely oxidized after 15 min. This is in part based on the suppressed anatase and direct rutile TiO2 formation at a defined Ta-Al content. Consequently, the anatase-to-rutile transformation, generally observed for Ti1-xAlxN, is absent. This reduces the generation of pores and cracks within the oxide scale and especially at the nitride-oxide interface, leading to the formation of a protective rutile and corundum based oxide scale. This is also reflected in the pronounced decrease in activation energy for the protective scale formation from 232 kJ/mol for Ti0.35Al0.65N down to 14.5 kJ/mol for Ti0.32Al0.60Ta0.08N. Based on our results we can conclude that especially phase transformations within the oxide scale need to be suppressed, as the connected volume changes lead to the formation of cracks and pores.

Numerous different crystal structures of Ta2O5 are reported in literature. Although experimentally and computationally obtained lattice parameters and mechanical properties are in excellent agreement there is a pronounced deviation when it comes to electronic structures of Ta2O5. Based on ab initio studies and nano-beam X-ray diffraction of sputtered Ta2O5 thin films, we introduce an orthorhombic basic structure with a = 0.6425, b = 0.3769, and c = 0.7706 nm, which is stabilized by flipping of an oxygen atom in neighboring c-planes. The calculated energy of formation is with -3.209 eV/atom almost as low as -3.259 eV/atom for the well-known Stephenson superstructure. We propose the new structure based on the fact that it allows for a good description of orthorhombic Ta2O5 even with a small and simple unit cell, which is especially advantageous for computational studies.

Despite the fast development of computational materials modelling, theoretical description of macroscopic elastic properties of textured polycrystalline aggregates starting from basic principles remains a challenging task. In this communication we use a supercell-based approach to obtain the elastic properties of random solid solution cubic ZrAlN system as a function of the metallic sublattice composition and texture descriptors. The employed special quasi-random structures are optimised not only with respect to short range order parameters, but also to make the three cubic directions $[1\,0\,0]$, $[0\,1\,0]$, and $[0\,0\,1]$ as similar as possible. In this way, only a small spread of elastic constants tensor components is achieved and an optimum trade-off between modelling of chemical disorder and computational limits regarding the supercell size is achieved. The single crystal elastic constants are shown to vary smoothly with composition, yielding $x\approx0.4$-0.5 an alloy constitution with an almost isotropic response. Consequently, polycrystals with this composition are suggested to have Young's modulus independent on the actual microstructure. This is indeed confirmed by explicit calculations of polycrystal elastic properties, both within the isotropic aggregate limit, as well as with fibre textures with various orientations and sharpness. It turns out, that for low AlN mole fractions, the spread of the possible Young's moduli data caused by the texture variation can be larger than 100 GPa. Consequently, our discussion of Young's modulus data of cubic ZrAlN contains also the evaluation of the texture typical for thin films., Comment: 10 pages, 6 figures, 3 tables

The alloying effect on the lattice parameters, isostructural mixing enthalpies and ductility of the ternary nitride systems Cr1-xTMxN (TM=Sc, Y; Ti, Zr, Hf; V, Nb, Ta; Mo, W) in the cubic B1 structure has been investigated using first-principles calculations. Maximum mixing enthalpy due to large lattice mismatch in Cr1-xYxN solid solution shows a strong preference for phase separation, while Cr1-xTaxN exhibits a negative mixing enthalpy in the whole compositional range with respect to cubic B1 structured CrN and TaN, thus being unlikely to decompose spinodally. The near-to-zero mixing enthalpies of Cr1-xScxN and Cr1-xVxN are ascribed to the mutually counteracted electronic and lattice mismatch effects. Additions of small amounts of V, Nb, Ta, Mo or W into CrN coatings increase its ductility., Comment: 19 pages, 3 figures

Tailoring and improving material properties by alloying is a long-known and used concept. Recent research has demonstrated the potential of ab initio calculations in understanding the material properties at the nanoscale. Here we present a systematic overview of alloying trends when early-transition metals (Y, Zr, Nb, Hf, Ta) are added in the Ti$_{1-x}$Al$_x$N system, routinely used as a protective hard coating. The alloy lattice parameters tend to be larger than the corresponding linearised Vegard's estimation, with the largest deviation more than 2.5% obtained for Y$_{0.5}$Al$_{0.5}$N. The chemical strengthening is most pronounced for Ta and Nb, although also causing smallest elastic distortions of the lattice due to their atomic radii being comparable with Ti and Al. This is further supported by the analysis of the electronic density of states. Finally, mixing enthalpy as a measure of the driving force for decomposition into the stable constituents, is enhanced by adding Y, Zr and Nb, suggesting that the onset of spinodal decomposition will appear in these cases for lower thermal loads than for Hf and Ta alloyed Ti$_{1-x}$Al$_x$N., Comment: 9 pages, 6 figures

Reactive magnetron sputtering enables the deposition of various thin films to be used for protective as well as optical and electronic applications. However, progressing target erosion during sputtering results in increased magnetic field strengths at the target surface. Consequently, the glow discharge, the target poisoning, and hence the morphology, crystal structure and stoichiometry of the prepared thin films are influenced. Therefore, these effects were investigated by varying the cathode current Im between 0.50 and 1.00 A, the magnetic field strength B between 45 and 90 mT, and the O2/(Ar+O2) flow rate ratio between 0 and 100%. With increasing oxygen flow ratio a sub-stoichiometric TaOx oxide forms at the metallic Ta target surface which further transfers to a non-conductive tantalum pentoxide Ta2O5, impeding a stable DC glow discharge. These two transition zones (from Ta to TaOx and from TaOx to Ta2O5) shift to higher oxygen flow rates for increasing target currents. Contrary, increasing the magnetic field strength (e.g., due to sputter erosion) mainly shifts the TaOx to Ta2O5 transition to lower oxygen flow rates while marginally influencing the Ta to TaOx transition. To allow for a stable DC glow discharge (and to suppress the formation of non-conductive Ta2O5 at the target) even at a flow rate ratio of 100% either a high target current (Im >= 1 A) or a low magnetic field strength (B <= 60 mT) is necessary. These conditions are required to prepare stoichiometric and fully crystalline Ta2O5 films. Our investigations clearly demonstrate the importance of the magnetic field strength, which changes during sputter erosion, on the target poisoning and the resulting film quality., Comment: 10 pages, 9 figures, 1 table

The elastic properties of paramagnetic cubic B1 (c-) Cr1-xAlxN ternary alloys are studied using stress-strain and energy-strain methods within the framework of Density Functional Theory (DFT). A strong compositional dependence of the elastic properties is predicted. Young's modulus, E, and shear modulus, G, exhibit the same compositional trends as experimentally measured hardness values (i.e. increasing with Al content), while bulk modulus, B, remains almost constant. The isotropic elastic response in the c-Cr1-xAlxN is predicted for concentrations around x=0.50. Brittle behavior and directional bonding characteristics are predominant in the c-Cr1-xAlxN coatings in the whole composition range, and become more pronounced with increasing Al content., Comment: 24 pages, 4 figures, submitted to PRB

In this Letter we present first principle calculation of surface energies of rock-salt (B1), zinc-blende (B3), and wurtzite (B4) AlN allotropes. Out of several low-index facets, the highest energies are obtained for mono-atomic surfaces (i.e. only by either Al or N atoms): $\gamma_{\{111\}}^{\rm B1}=410\uu{meV/\AA}^2$, $\gamma_{\{100\}}^{\rm B3}=346\uu{meV/\AA}^2$, $\gamma_{\{111\}}^{\rm B3}=360\uu{meV/\AA}^2$, and $\gamma_{\{0001\}}^{\rm B4}=365\uu{meV/\AA}^2$. The difference between Al- and N-terminated surfaces in these cases is less then $20\uu{meV/\AA}^2$. The stoichiometric facets have energies lower by $100\uu{meV/\AA}^2$ or more. The obtained trends could be rationalised by a simple nearest-neighbour broken-bond model., Comment: 7 pages, 2 figures

Recently, we have reported on low friction CrN/TiN coatings deposited using a hybrid sputtering technique. These multilayers exhibit friction coefficients $\mu$ below 0.1 when tested in atmosphere with a relative humidity $\approx25%$, but $\mu$ ranges between 0.6-0.8 upon decreasing the humidity below 5%. Here we use first principle calculations to study O and H adatom energetics on TiN and CrN (001) surfaces. The diffusional barrier of H on TiN(001) is about half of the value on CrN(001) surface, while both elements are stronger bonded on CrN. Based on these results we propose a mechanism for a water-based self-assembled nanobearing., Comment: 4 pages, 3 figures

Although electron energy loss near edge structure analysis provides a tool for experimentally probing unoccupied density of states, a detailed comparison with simulations is necessary in order to understand the origin of individual peaks. This paper presents a density functional theory based technique for predicting the N K-edge for ternary (quasi-binary) nitrogen alloys by adopting a core hole approach, a methodology that has been successful for binary nitride compounds. It is demonstrated that using the spectra of binary compounds for optimising the core hole charge ($0.35\,\mathrm{e}$ for cubic Ti$_{1-x}$Al$_x$N and $0.45\,\mathrm{e}$ for wurtzite Al$_x$Ga$_{1-x}$N), the predicted spectra evolutions of the ternary alloys agree well with the experiments. The spectral features are subsequently discussed in terms of the electronic structure and bonding of the alloys., Comment: 11 pages, 9 figures, 1 table

Motivated by an increasing demand for coherent data that can be used for selecting materials with properties tailored for specific application requirements, we studied elastic response of nine binary early transition metal nitrides (ScN, TiN, VN, YN, ZrN, NbN, LaN, HfN, and TaN) and AlN. In particular, single crystal elastic constants, Young's modulus in different crystallographic directions, polycrystalline values of shear and Young's moduli, and the elastic anisotropy factor were calculated. Additionally, we provide estimates of the third order elastic constants for the ten binary nitrides., Comment: 10 pages, 7 figures