Low temperature growth strategies for Mo₂BC coatings are reviewed and initial theoretical and experimental data pertaining to the applicability of these coatings during forming of Al based alloys are discussed. A Mo₂BC(040) surface was exposed to O₂. The gas interaction was investigated using ab initio molecular dynamics and x-ray photoelectron spectroscopy (XPS) of air exposed surfaces. The calculations suggest that the most dominating physical mechanism is dissociative O₂ adsorption whereby Mo – O, O – Mo – O and Mo₂ – C – O bond formation is observed. To validate these results, Mo₂BC thin films were synthesised utilizing high power pulsed magnetron sputtering and air exposed surfaces were probed by XPS. MoO₂ and MoO₃ bond formation is observed and is consistent with here obtained ab initio data. Additionally, the interfacial interactions of O₂ exposed Mo₂BC(040) surface with an Al nonamer is studied with ab initio molecular dynamics to describe on the atomic scale the interaction between this surface and Al to mimic the interface present during cold forming processes of Al based alloys. The Al nonamer was disrupted and Al forms chemical bonds with oxygen contained in the O₂ exposed Mo₂BC(040) surface. Based on the comparison of here calculated adsorption energy with literature data, Al – Al bonds are shown to be significantly weaker than the Al – O bonds formed across the interface. Hence, Al-Al bond rupture is expected for a mechanically loaded interface. Therefore the adhesion of a residual Al on the native oxide layer is predicted. This is consistent with experimental observations. The data presented here may also be relevant for other oxygen containing surfaces in a contact with Al or Al based alloys for example during forming operations.

The Modified Embedded Atom Method (MEAM) interatomic potential within the classical Molecular Dynamics (MD) framework enables realistic, large-scale simulations of important model materials such as TiN. As a step toward s understanding atomistic processes controlling the growth of TiN on a fundamental level, we perform large-scale simulations of TiN/TiN(001) deposition using a TiN MEAM parameterization which reproduces experimentally-observed surface diffusion trends, correctly accounts for Ehrlich barriers at island step edges [1], [2], and has been shown to give results in excellent qualitative and good quantitative agreement with Ab Initio MD based on Density Functional Theory (DFT) [3], [4]. 85% of a monolayer of TiN is deposited on 100x100 atom TiN(001) substrates at a rate of 1 Ti atom per 50 ps, resulting in simulation times of 212.5 ns. The TiN substrate is maintained at a typical epitaxial growth temperature, 1200 K during deposition using N:Ti flux ratios of 1:1, 2:1, and 4:1 and incident energies of 2 and 10 Ev to probe the effects of N₂ partial pressure and substrate bias on TiN(001) growth modes. We observe nucleation of Ti_xN_y molecules; N₂ desorption; the formation, growth and coalescence of mixed <100>, <110>, and <111> faceted islands; as well as intra- and interlayer mass transport mechanisms. For equal flux ratios at 2 Ev incidence energy, islands begin to form atop existing islands at coverages ≳ 0.25 ML, leading to 3D multilayer growth. Increasing the N:Ti flux ratio shifts the growth mode to layer-by-layer growth and changes the stoichiometry from under- to over-stoichiometric. We discuss the implications of these results on thin film growth and process tailoring. Our classical MD predictions are supported and complemented by DFT-MD simulations.

[1] D. G. Sangiovanni, D. Edström, L. Hultman, V. Chirita, I. Petrov, and J. E. Greene, “Dynamics of Ti, N, and TiNx (x=1–3) admolecule transport on TiN(001) surfaces,” Phys. Rev. B, vol. 86, no. 15, p. 155443, 2012.

[2] D. Edström, D. G. Sangiovanni, L. Hultman, V. Chirita, I. Petrov, and J. E. Greene, “Ti and N adatom descent pathways to the terrace from atop two-dimensional TiN/TiN(001) islands,” Thin Solid Films, vol. 558, pp. 37–46, 2014.

[3] D. G. Sangiovanni, D. Edström, L. Hultman, I. Petrov, J. E. Greene, and V. Chirita, “Ab initio and classical molecular dynamics simulations of N₂ desorption from TiN(001) surfaces,” Surf. Sci., vol. 624, pp. 25–31, 2014.

[4] D. G. Sangiovanni, D. Edström, L. Hultman, I. Petrov, J. E. Greene, and V. Chirita, “Ti adatom diffusion on TiN(001): Ab initio and classical molecular dynamics simulations,” Surf. Sci., vol. 627, pp. 34-41, 2014.

Residual stresses within physical vapour deposited coatings are a major concern, as they are often the origin of failure and delamination. Furthermore, stresses, which typically scale with the thickness, limit the thickness of the coating. With increasing stresses, the interface region is increasingly stressed and weakened, promoting delamination and buckling effects. CrN coatings are known to allow for moderate compressive or even tensile stresses, enabling the preparation of coating thicknesses above 20 μm. Although CrN coatings exhibit excellent tribological and wear resistance properties, their thermal stability with respect to Cr-N dissociation is limited to 900 °C, which limits their application field. However, several applications require higher thermal stability in combination with relatively thick ceramic coatings. Therefore, we study in detail the requirements to develop nitride-based coatings with thicknesses exceeding 20 μm.

The residual stresses of arc evaporated TiN, CrN, TiAlN, CrAlN, and TiAlTaN coatings, prepared with an industrial sized coating plant (Balzers Oerlikon INNOVA), are investigated as a function of their thicknesses by measuring the curvature of one-side coated Si(100) cantilevers. Based on these studies we developed multilayer arrangements of TiN/CrN, TiAlN/CrN, TiAlN/CrAlN, and TiAlTaN/CrAlN thick coatings. Their stresses are designed through variations in bilayer period and arrangements of the cathodes at the sidewalls of the industrial chamber.

The individual coatings and multilayers are additionally investigated with respect to growth morphology (by cross sectional scanning electron microscopy), hardness and indentation moduli (by nanoindentation), structure and crystallographic phases (by X-ray diffraction).

This work summarizes recent developments on applying thin film structure and architecture concepts to hard coatings for optimized performance in various application fields.

The hardness of materials rapidly decreases at elevated temperatures as generally the density of structural defects, such as point defects, dislocations, and grain boundaries, decreases. Additional strengthening can be provided by age-hardening mechanisms, which originate from decomposition-processes of supersaturated phases to form new obstacles retarding plastic deformation. Furthermore important is the resistance against oxidation and corrosive attack.

By using ab initio calculations and sophisticated experimental methods we will have a detailed insight into various mechanisms responsible for excellent mechanical strength, thermal stability and oxidation resistance properties of Ti–Al–N based hard coatings. For these materials we will also compare the effect of various architecture and alloying concepts with e.g., Y, Zr, Hf, Nb, and Ta.

Another important class of hard coatings is based on the material systems CrN and Cr–Al–N. After a short overview on ab inito and experimental studies in comparison to their sister system Ti–Al–N, we will have a small excursion on the influence of architecture – using the model system CrN/AlN multilayers or their superlattices – on the mechanical properties and especially fracture toughness. Furthermore, based on recent ab initio investigations suggesting that the inherent fracture toughness of CrN can be increased by alloying with Mo or W, we will explore in detail the challenges in studying Cr–Mo–N or Cr–W–N materials by ab inito and experiments.

WN_x layers, 1.45-μm-thick, were deposited by reactive magnetron sputtering on MgO(001), MgO(111), and Al₂O₃(0001) in 20 mTorr N₂ at T_s = 500-800 °C. X-ray diffraction ω-2θ scans, ω-rocking curves, φ scans, and reciprocal space maps show that all layers deposited from 500-700 °C exhibit the cubic rock-salt structure, with a relaxed lattice constant that decreases from 4.299 to 4.171 Å as the N-to-W ratio decreases from x = 1.20 for T_s = 500 °C to x = 0.83 for T_s = 700 °C, as measured by energy dispersive and photoelectron spectroscopies. T_s = 500-600 °C yields a polycrystalline 111-textured microstructure on all substrates. In contrast, deposition at 700 °C results in epitaxial growth of WN(111) and WN(001) on MgO(111) and MgO(001), respectively, while deposition on Al₂O₃(0001) yields a 111-preferred orientation, misoriented cubic WN grains as well as N-deficient BCC W. T_s = 800 °C causes nitrogen loss and WN_x layers with primarily BCC W grains and x = 0.04-0.06. The measured elastic modulus ranges from 110-260 GPa for T_s = 500-700 °C and decreases with increasing N-content, and increases to 350 GPa for T_s = 800 °C. For samples deposited at T_s = 700 °C, nanoindentation on WN on MgO(001), MgO(111), and Al₂O₃(0001) provides hardness values of 9.8 ± 2.0, 12.5 ± 1.0, and 10.3 ± 0.4 GPa, and elastic moduli of 240±40, 257±13, and 242±10 GPa, respectively. The corresponding shear moduli measured by Brillouin light scattering are 127±2 GPa, 121±2 GPa and 115±2 GPa. MoN_x layers, 1- μm-thick, deposited on MgO(001) also exhibit a cubic rock salt structure with x decreasing from 1.18 for T_s = 500 and 600 °C to x = 0.76 for T_s = 800 °C but remaining approximately constant for T_s = 800-1000 °C. Layers with T_s > 700 °C contain both epitaxial MoN_x(001) and 111-oriented grains. The out-of-plane lattice constant decreases from 4.22 to 4.18 Å for 111 oriented grains and from 4.17 to 4.06 Å for epitaxial 001-oriented grains, as T_s is increased from 700 °C to 1000 °C.

As the length scale of individual layers are reduced in a Cu/Nb multilayer, fcc to bcc and bcc to fcc transformations were noted for Cu and Nb respectively. These transitions have been modeled using a thermodynamic phase diagram where interfacial and volumetric energy considerations determine stability and the bilayer thickness of the multilayer is a state variable for predicting those transformations. Using HRTEM, the evolution of the interface from incoherent-to-semicoherent-to-coherent is determined and related to the structural component of the interfacial energy reduction that drives the crystalline transformations. When equal thicknesses of each layer were < 1 nm, the layers underwent an additional transformation from a crystalline to amorphous structure. This has been rationalized by the positive enthalpy of mixing between these two species as they intermixed during the sputter deposition process. The chemical intermixing and local clustering at and near the interface has been quantified by atom probe tomography. These phase transformations have been related to real-time, intrinsic growth stress measurements. All of the multilayers were in a compressive stress state, but a notable reduction in the compressive stress value occurred with each transformation. The collective characterization of the film, via TEM, atom probe, and stress evolution, have provided insights into the structural stability of crystalline phases at the nanoscale.

Corundum-type Al₂O₃ coatings demonstrate excellent thermo-mechanical properties, giving rise to widespread applications as protective films on, e.g., cutting inserts or components. These coatings are typically synthesised by chemical vapour deposition (CVD) at temperatures of 900 °C or higher, which excludes temperature sensitive substrates. Physical vapour deposition (PVD) proved to be a suitable method for low temperature synthesis of nitrides with excellent properties. However, the growth of single-phased corundum-type α-Al₂O₃ by PVD is still a difficult task under standard production conditions. In general, a mixed phase composition of metastable cubic phases is observed, which influence the thermo-mechanical performance of the coating. The utilisation of targets produced by powder metallurgical methods allows for the combination of aluminium with other elements, suitable to promote dedicated crystal structures as demonstrated by AlCr and more recently AlCrFe, where dense crystalline coatings with an increased amount of hexagonal phase fractions were realised. Although the alloying with Cr and Fe is a promising concept with good prospects, the mechanism to form the hexagonal structure in these materials is yet not understood. Therefore, the aspect of layer-nucleation is investigated in more detail. A significant part of hexagonal crystallites in (Al,Cr,Fe)₂O₃ coatings is triggered by nucleation onto small particles incorporated in the coating. They originate from the cathode surface and are generated during the cathodic arc process. Cathode surface modifications, macroparticle incorporation and the associated coating microstructures are elucidated by detailed X-ray diffraction and electron microscopy studies. Implications on the coatings’ properties and possible technological concepts are discussed.