We use Density Functional Theory (DFT) calculations in the generalized gradient approximation (GGA) to predict the properties of a number of novel Ti-M-N and V-M-N thin films in the B1 (NaCl) structure. The new compounds are obtained by alloying TiN and VN, with Ta, Nb, V, Mo and W, respectively Nb and W, in concentrations of 50 %. We evaluate the elastic moduli and constants for all these ternaries, perform a detailed analysis of their electronic structure, and compare these results with the corresponding properties of TiN and Ti_0.5Al_0.5N. Our calculations show that, in terms of hardness, these ternaries compare with TiN and Ti_0.5Al_0.5N, as we obtain comparable, respectively increased values, for the Young and bulk moduli, in most cases. Significantly, however, these novel compounds exhibit substantially lower values of the C₄₄ elastic constant and positive Cauchy pressures, i.e. they are considerably more ductile than TiN and Ti_0.5Al_0.5N. This unique combination of increased hardness and ductility, which is in contrast to the hardness/brittleness relationship typically found in hard coatings, is certainly relevant for applications in which high strength thin films/coatings are desired. In terms of electronic structure, our results reveal a layered charge density for all these ternaries, consisting in alternating high and low electron density regions, similar to that reported for MAX phase materials and other nanolaminates. This combination of metallic and ceramic properties is also evident in the density of states analysis we report. In order to fully understand the mechanism responsible for this interleaved arrangement of electrons, we carry out an improved crystal orbital overlap population (COOP) calculation and succeed in resolving energetically the bonding and antibonding contributions, of the first and second neighbors, to the chemical bonds in these compounds. Herein, we present the results of our COOP analysis, and based on this, we explain the observed trend in hardness and ductility as a result of the interaction between the e_g and t_2g sets of d orbitals characteristic to these ternaries.

The influence of ballistic and diffusive particles on the development of the surface morphology of plasma-assisted sputtered thin films is studied. Ballistic particles are sputtered from the cathode and are characterized by their high directionality towards the film surface as well as by typical kinetic energies in the order of 1 eV, whereas thermal diffusive particles follow the Maxwell velocity distribution function, with typical kinetic energies in the order of 0.01 eV. These factors influence the role of non-local surface shadowing and the surface sticking probability of the deposition particles, which, along with other fundamental mechanisms, strongly condition the development of the film morphology. In order to carry out this research, a combined theoretical and experimental approach has been followed: on one hand several thin films have been deposited in different experimental conditions which allow differentiating ballistic and diffusive contributions to the film growth, and, on the other hand, we have developed a basic Monte Carlo model of the depositions process. The comparison between experimental and theoretical results provides fundamental understanding about the influence of ballistic and diffusive particles on the development of the thin film nanostructure.

Lack of detailed process conditions knowledge remains a key challenge in magnetron sputtering, both for chamber design and for process development. Fundamental information such as the pressure and temperature distribution of the sputter gas, and the energies and arrival angles of the sputtered atoms and other energetic species is often missing, or is only estimated from general formulas. However, open-source or low-cost tools are available for modeling all the physics of the sputter process, which can give more accurate data from desktop computations than traditional empirical approaches.

To get a better understanding of magnetron sputtering, we have collected existing models for the 4 main physics steps: 1) dynamics of the plasma using Particle In Cell-Monte Carlo Collision (PIC-MCC), 2) impact of ions on the target using molecular dynamics (MD), 3) transport of sputtered atoms to the substrate using Direct Simulation Monte Carlo (DSMC), and 4) growth of the film using hybrid Kinetic Monte Carlo (KMC) and MD methods. All the models have been tested against experimental measurements. The spatial distribution and electron temperature T_e of the plasma have been reproduced within ~25% for a scaled model of an example magnetron system. The rarefaction of the neutral gas in front of a magnetron observed by Rossnagel and others has been reproduced, and it is associated with a local pressure increase of ~50% which may strongly influence film properties such as stress and film density. Results on energies and arrival angles of sputtered atoms and reflected gas neutrals are applied to the Kinetic Monte Carlo simulation of film growth. Model results and applications to growth of Cu, Zr and Be films will be presented. Work underway on increasing computation speed with parallelization will also be discussed.