Crystallite size-dependent metastable phase formation of TiAlN coatings.

It is well known that surface energy differences thermodynamically stabilize nanocrystalline γ-Al2O3 over α-Al2O3. Here, through correlative ab initio calculations and advanced material characterization at the nanometer scale, we demonstrate that the metastable phase formation of nanocrystalline TiAlN, an industrial benchmark coating material, is crystallite size-dependent. By relating calculated surface and volume energy contributions to the total energy, we predict the chemical composition-dependent phase boundary between the two metastable solid solution phases of cubic and wurzite Ti1-xAlxN. This phase boundary is characterized by the critical crystallite size d critical . Crystallite size-dependent phase stability predictions are in very good agreement with experimental phase formation data where x was varied by utilizing combinatorial vapor phase condensation. The wide range of critical Al solubilities for metastable cubic Ti1-xAlxN from x max = 0.4 to 0.9 reported in literature and the sobering disagreement thereof with DFT predictions can at least in part be rationalized based on the here identified crystallite size-dependent metastable phase formation. Furthermore, it is evident that predictions of critical Al solubilities in metastable cubic TiAlN are flawed, if the previously overlooked surface energy contribution to the total energy is not considered.

Silicon etch with chromium ions generated by a filtered or non-filtered cathodic arc discharge.

The pre-treatment of substrate surfaces prior to deposition is important for the adhesion of physical vapour deposition coatings. This work investigates Si surfaces after the bombardment by energetic Cr ions which are created in cathodic arc discharges. The effect of the pre-treatment is analysed by X-ray diffraction, Rutherford backscattering spectroscopy, scanning electron microscopy and in-depth X-ray photoemission spectroscopy and compared for Cr vapour produced from a filtered and non-filtered cathodic arc discharge. Cr coverage as a function of ion energy was also predicted by TRIDYN Monte Carlo calculations. Discrepancies between measured and simulated values in the transition regime between layer growth and surface removal can be explained by the chemical reactions between Cr ions and the Si substrate or between the substrate surface and the residual gases. Simulations help to find optimum and more stable parameters for specific film and substrate combinations faster than trial-and-error procedure.

Density measurement of thin layers by electron energy loss spectroscopy (EELS).

A method to measure the density of thin layers is presented which utilizes electron energy loss spectroscopy (EELS) techniques within a transmission electron microscope. The method is based on the acquisition of energy filtered images in the low loss region as well as of an element distribution map using core loss edges. After correction of multiple inelastic scattering effects, the intensity of the element distribution map is proportional to density and thickness. The dependence of the intensities of images with low energy loss electrons on the density is different from that. This difference allows the calculation of the relative density pixel by pixel and to determine lateral density gradients or fluctuations in thin films without relying on a constant specimen thickness. The method is demonstrated at thin carbon layers produced with density gradients.