Nitride-based coatings are nowadays widely studied both from fundamental and technological point of views due to their unique physical and mechanical properties. Among the binary nitrides, TiN is the most stable thermodynamically and has been widely used due to the combination of its covalent and metal-like characteristics. Coatings produced by Physical Vapor Deposition (PVD) techniques generally exhibit a crystallographic texture, which in turn may strongly affect their properties, such as hardness, wear resistance, or diffusion barrier properties in microelectronic devices. Therefore great efforts have been made in recent years to understand the underlying mechanisms governing texture development in nitride thin films. In particular, the issue of stress build-up during PVD growth and its possible interplay with film preferred orientation is essential to address. We present a brief overview of stress and preferred orientation in nitride-based thin films, either in the form of single-, multi-layered or nanocomposite coatings. X-ray Diffraction (XRD) was used in the standard θ –2 θ configuration to study the texture development with film thickness, while the sin 2 ψ method combined with linear elasticity theory was employed to determine the complete strain/stress state. XRD measurements were made in the framework of the crystallite group method, which is of prime importance in thin films exhibiting a mixed texture, as it enables to selectively measure the elastic strain in a given subset of grains. For PVD films grown with energetic particles, the appropriate modeling requires the use of a triaxial stress tensor, including a hydrostatic stress component to take into account the local distortions induced by growth-defects. This approach enables us to determine the ‘stress-free and defect-free lattice parameter’, a 0 , solely linked to chemical effect. Illustrations will be given for fiber-textured TiN and ZrN films deposited on Si substrates, epitaxial TiN layers as well as epitaxial TiN sub-layers in TiN/Cu multilayers grown on (001) MgO single crystal substrates. Ternary TiN-based coatings, either in the form of solid solutions or nanocomposites will be also investigated.

Stress and preferred orientation in nitride-based PVD coatings

Stress and strain in polycrystalline thin films

This article reviews concepts and techniques for performing instrumented tensile testing of materials at small dimensions. State-of-the-art methods to probe tensile behavior of micro- and nanoscaled materials span many orders of magnitudes of force and displacement, often requiring a custom solution for each new material discovery. We discuss the experimental opportunities, challenges, and pitfalls in concert with the scientific insights revealed from tensile investigations at length scales where conventional wisdom is challenged on how materials deform.

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Micro- and nanoscale tensile testing of materials

Interfacial characterization, control and modification of carbon fiber reinforced polymer composites

Interface confined reactions, which can modulate the bonding of reactants with catalytic centres and influence the rate of the mass transport from bulk solution, have emerged as a viable strategy for achieving highly stable and selective catalysis. Here we demonstrate that 1T′-enriched lithiated molybdenum disulfide is a highly powerful reducing agent, which can be exploited for the in-situ reduction of metal ions within the inner planes of lithiated molybdenum disulfide to form a zero valent metal-intercalated molybdenum disulfide. The confinement of platinum nanoparticles within the molybdenum disulfide layered structure leads to enhanced hydrogen evolution reaction activity and stability compared to catalysts dispersed on carbon support. In particular, the inner platinum surface is accessible to charged species like proton and metal ions, while blocking poisoning by larger sized pollutants or neutral molecules. This points a way forward for using bulk intercalated compounds for energy related applications. Interface confined reactions are a viable strategy for achieving stable and selective catalysts. Here, the authors demonstrate that 1T'-enriched lithiated MoS2 can reduce metal ions in situ, forming zero valent platinum nanoparticle-intercalated MoS2, with enhanced hydrogen evolution activity.

Interface confined hydrogen evolution reaction in zero valent metal nanoparticles-intercalated molybdenum disulfide

The components of the macroscopic mechanical stress tensor of a stressed thin film, coating, multilayer or the region near the surface of a bulk material can in principle be determined by X-ray diffraction. The various analysis methods and measurement strategies, in dependence on specimen and measurement conditions, are summarized and evaluated in this paper. First, different X-ray diffraction geometries (conventional or grazing incidence) are described. Then, the case of macroscopically elastically isotropic, untextured specimens is considered: from the simplest case of a uniaxial state of stress to the most complicated case of a triaxial state of stress. The treatment is organized according to the number of unknowns to be determined (i.e. the state of stress, principal axes known or unknown), the use of one or several values of the rotation angle φ and the tilt angle ψ of the sample, and one or multiple hkl reflections. Next, the focus is on macroscopically elastically anisotropic (e.g. textured) specimens. In this case, the use of diffraction (X-ray) elastic constants is not possible. Instead, diffraction (X-ray) stress factors have to be used. On the basis of examples, it is demonstrated that successful diffraction stress analysis is only possible if an appropriate grain-interaction model is applied.

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A.C. Vermeulen

Papers

Stress analysis of polycrystalline thin films and surface regions by X-ray diffraction