ICMCTF2016 Session B7: Computational Design and Experimental Development of Functional Thin Films
Tuesday, April 26, 2016 8:00 AM in Room San Diego
Time Period TuM Sessions | Abstract Timeline | Topic B Sessions | Time Periods | Topics | ICMCTF2016 Schedule
B7-1 Molecular Simulations of TiN/TiN(001) Growth
Daniel Edström, DavideG. Sangiovanni, Lars Hultman (Thin Film Physics Division, IFM, Linköping University, Sweden); Ivan Petrov, Joseph Greene (University of Illinois at Urbana-Champaign, USA); Valeriu Chirita (Thin Film Physics Division, IFM, Linköping University, Sweden)
The Modified Embedded Atom Method (MEAM) interatomic potential is used within the classical Molecular Dynamics (MD) framework to perform simulations of important model materials such as TiN, in order to understand the processes which control TiN growth modes on a fundamental level. We report the results of 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 , , and has been shown to give results in good qualitative and quantitative agreement with Ab Initio MD based on Density Functional Theory , . We deposit 85% of a monolayer of TiN on 100x100 atom TiN(001) substrates maintained at 1200 K, at a rate of 1 Ti atom per 50 ps, for total simulation times of 212.5 ns. We use N/Ti flux ratios of 1, 2, and 4, and incident N 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 TixNy molecules; N2 desorption; formation, growth and coalescence of mixed <100>, <110>, and <111> faceted islands; as well as intra- and interlayer mass transport mechanisms. For N/Ti flux ratios of 1 at 2 eV incidence energy, films exhibit Ti-rich surface regions which serve as traps to nucleate higher layers, leading to multilayer growth. Increasing the N/Ti flux ratio shifts the growth mode to layer-by-layer and modifies the overall film composition from under- to over-stoichiometric. As the N content of films is increased, N-terminated <110>-oriented island edges become increasingly dominant and the substrate vacancy concentration changes from being N- to Ti-dominated. We discuss the implications of these results on thin film growth and process tailoring.
 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.
 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.
 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.
 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.
B7-2 High-Temperature Evolution of the 3D-Microstructure of Ti(1-x)AlxN
Jennifer Ullbrand, Ferenc Tasnadi, Magnus Odén (IFM Linköpings Universitet, Sweden)
Ti(1-x)AlxN coatings are of great interest in the cutting tool industry as hard and wear resistant coatings. It is possible to grow thermodynamically metastable c-Ti(1-x)AlxN (B1 structure) for a wide range of compositions (typically x < 0.75) with a low temperature (~ 400 °C) coating synthesis, e.g. arc deposition. During cutting, the coating is subjected to elevated temperatures (900-1200°C) and c-TiAlN tend to spinodal decompose and form alternating coherent domains of c-TiN and c-AlN. Accompanying this decomposition is a well-known age hardening. Despite the experimental efforts spent on investigating TiAlN there is a need for a detailed description of the rapid microstructure evolution, its impact on mechanical properties at high temperature such as elastic properties, and gain understanding of the underlying contributions to the observed age hardening.
In order to address these issues, we simulate the microstructure, stress and strain evolution, and Young’s modulus evolution during spinodal decomposition for a range of global compositions (x = 0.3, 0.5, 0.67, 0.75) in 3D at 900°C. The microstructure is analyzed by the auto correlation function revealing a refinement of the structure as well as an increased morphological anisotropy for higher Al content samples. The refinement is explained by the critical wavelength variation and the increased anisotropy is discussed in terms of spatial variation in elastic properties with composition.
The microstructure simulations are based on the Cahn Hilliard partial differential equation (PDE), extended to include the elastic energy contribution. The finite element program package FiPy  parallelized on a supercomputer is used to solve the PDE equations. The enthalpy of mixing , the elastic compliance tensor , and the lattice parameter, are determined by first-principles density-functional theory (DFT) calculations over the entire compositional range of Ti(1-x)AlxN and used as input parameters.
 J.E. Guyer, D. Wheeler, J. A Warren, FiPy: Partial Differential Equations with Python, Comput. Sci. Eng. 11 (2009) 6–15. doi:10.1109/MCSE.2009.52.
 B. Alling, A. Ruban, A. Karimi, L. Hultman, I. Abrikosov, Unified cluster expansion method applied to the configurational thermodynamics of cubic Ti(1-x)AlxN, Phys. Rev. B. 83 (2011) 104203. doi:10.1103/PhysRevB.83.104203.
 F. Tasnádi, I. A. Abrikosov, L. Rogström, J. Almer, M.P. Johansson, M. Odén, Significant elastic anisotropy in Ti(1-x)AlxN alloys, Appl. Phys. Lett. 97 (2010) 231902. doi:10.1063/1.3524502.
B7-3 Nitrogen Vacancies – a Key Factor in Synthesis of c-Mo–Al–N Hard Coatings
Fedor F. Klimashin, Holger Euchner, Paul Mayrhofer (TU Wien, Austria)
Here we show that cubic-structured Mo–Al–N coatings have a high potential to be used as wear protection for various high-demanding applications. We have found that within this material system, nitrogen vacancies have a significant and determining role for the stabilization of the cubic structure – a necessary prerequisite for high thermal stability and strength. While for solid solutions without N-vacancies the wurtzite-type structure is always energetically preferred, nitrogen vacancies favor the formation of the cubic phase. These ab initio predictions were experimentally verified with the help of magnetron sputtered Mo1-xAlxNy coatings. We could show for the first time, that the cubic phase can be maintained up to the very high Al-content of Al/(Mo+Al) ≈ 0.57. The significantly increased Al-content within the cubic phase for our sputtered Mo1-xAlxNy coatings suggests for an increased thermal stability and also helps to increase their hardness up to 38 GPa. (Further addition of Al results in a substantial softening to ~22 GPa as a consequence of the evolving wurtzite-type structure.) The study shows the extremely important role of vacancies, here nitrogen vacancies, which are often neglected.
B7-4 Vacancies as the Key to Excellent Properties Within Mo–Cr–N
Paul Mayrhofer, Fedor F. Klimashin, Nikola Koutna, Holger Euchner (TU Wien, Austria); David Holec (Montanuniversität Leoben, Austria)
Although many research activities concentrate on transition metal nitrides, due to their excellent properties, only little is known on the pronounced effect of vacancies on their structure evolution and mechanical properties. We investigate in detail – by ab initio and experimental studies – the influence of vacancies on the structural evolution and mechanical properties of Mo–N based coatings. The chemical composition as well as the structural development of coatings prepared with N2-to-total pressure ratios (pN2/pT) of 0.32 and 0.44 can best be described by the quasi-binary Mo2N–CrN tie line. Mo2N and CrN are face centred cubic (fcc), only that for Mo2N half of the N-sublattice is vacant. Consequently, with increasing Cr content also the N-sublattice becomes less vacant and the chemical composition of fcc single-phase ternaries can be described as Mo1-xCrxN0.5(1+x). These coatings exhibit an excellent agreement between experimentally and ab initio obtained lattice parameters of fcc Mo1-xCrxN0.5(1+x). When increasing the N2-to-total pressure ratio to pN2/pT = 0.69, the N-sublattice is already fully occupied for Cr-additions of x ≥ 0.4, as suggested by elastic recoil detection analysis and lattice parameter variations. The latter follows the ab initio obtained lattice parameters along the quasi-binary MoN–CrN tie line for x ≥ 0.5. The single-phase fcc coating with Cr/(Mo+Cr) of x ~0.2, prepared with pN2/pT = 0.32, exhibits the highest hardness of ~34 GPa among all coatings studied.