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Dynamics of Ti, N, and TiNx (x=1-3) admolecule transport on TiN(001) surfaces
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.ORCID iD: 0000-0002-2837-3656
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
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2012 (English)In: Physical Review B. Condensed Matter and Materials Physics, ISSN 1098-0121, E-ISSN 1550-235X, Vol. 86, no 15, 155443- p.Article in journal (Refereed) Published
Abstract [en]

We use classical molecular dynamics and the modified embedded atom method formalism to investigate the dynamics of atomic-scale transport on a low-index model compound surface, TiN(001). Our simulations, totaling 0.25 mu s for each case study, follow the pathways and migration kinetics of Ti and N adatoms, as well as TiNx complexes with x = 1-3, which are known to contribute to the growth of TiN thin films by reactive deposition from Ti, N-2, and N precursors. The simulations are carried out at 1000 K, within the optimal range for TiN(001) epitaxial growth. We find Ti adatoms to be the highest-mobility species on TiN(001), with the primary migration path involving jumps of one nearest-neighbor distance d(NN) between adjacent fourfold hollow sites along in-plane andlt; 100 andgt; channels. Long jumps, 2d(NN), are also observed, but at much lower frequency. N adatoms, which exhibit significantly lower migration rates than Ti, diffuse along in-plane andlt; 110 andgt; directions and, when they intersect other N atoms, associatively form N-2 molecules, which desorb at kinetic rates. As expected, TiN and TiN3 complexes migrate at even lower rates with complex diffusion pathways involving rotations, translations, and rototranslations. TiN2 trimers, however, are shown to have surprisingly high diffusion rates, above that of N adatoms and almost half that of Ti adatoms. TiN3 motion is dominated by in-place rotation with negligible diffusion.

Place, publisher, year, edition, pages
American Physical Society , 2012. Vol. 86, no 15, 155443- p.
National Category
Engineering and Technology
Identifiers
URN: urn:nbn:se:liu:diva-86129DOI: 10.1103/PhysRevB.86.155443ISI: 000310130800008OAI: oai:DiVA.org:liu-86129DiVA: diva2:574952
Note

Funding Agencies|Swedish Research Council (VR)|2008-6572|Swedish Government Strategic Research Area Grant in Materials Science|Mat-LiU 2009-00971|

Available from: 2012-12-07 Created: 2012-12-07 Last updated: 2017-12-07
In thesis
1. Transition Metal Nitrides: Alloy Design and Surface Transport Properties using Ab-initio and Classical Computational Methods
Open this publication in new window or tab >>Transition Metal Nitrides: Alloy Design and Surface Transport Properties using Ab-initio and Classical Computational Methods
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Enhanced toughness in brittle ceramic materials, such as transition metal nitrides (TMN), is achieved by optimizing the occupancy of shear-sensitive metallic electronic-states. This is the major result of my theoretical research, aimed to solve an inherent long-standing problem for hard ceramic protective coatings: brittleness. High hardness, in combination with high toughness, is thus one of the most desired mechanical/physical properties in modern coatings. A significant part of this PhD Thesis is dedicated to the density functional theory (DFT) calculations carried out to understand the electronic origins of ductility, and to predict novel TMN alloys with optimal hardness/toughness ratios. Importantly, one of the TMN alloys identified in my theoretical work has subsequently been synthesized in the laboratory and exhibits the predicted properties.

The second part of this Thesis concerns molecular dynamics (MD) simulations of Ti, N, and TiNx adspecies diffusion on TiN surfaces, chosen as a model material, to provide unprecedented detail of critical atomic-scale transport processes, which dictate the growth modes of TMN thin films. Even the most advanced experimental techniques cannot provide sufficient information on the kinetics and dynamics of picosecond atomistic processes, which affect thin films nucleation and growth. Information on these phenomena would allow experimentalists to better understand the role of deposition conditions and fine tune thin films growth modes, to tailor coatings properties to the requirements of different applications. The MD simulations discussed in the second part of this PhD Thesis, predict that Ti adatoms and TiN2 admolecules are the most mobile species on TiN(001) terraces. Moreover, these adspecies are rapidly incorporated at island descending steps, and primarily contribute to layer-by-layer growth. In contrast, TiN3 tetramers are found to be essentially stationary on both TiN(001) terraces and islands, and thus constitute the critical nuclei for three-dimensional growth.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2013. 75 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1513
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-91379 (URN)978-91-7519-638-1 (ISBN)
Public defence
2013-05-23, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2013-04-23 Created: 2013-04-23 Last updated: 2016-08-31Bibliographically approved
2. A theoretical study of mass transport processes on TiN(001) and mechanical properties of TiN- and VN-based ternaries
Open this publication in new window or tab >>A theoretical study of mass transport processes on TiN(001) and mechanical properties of TiN- and VN-based ternaries
2014 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns computer simulations, using classical molecular dynamics, of transport processes related to TiN(001) growth. It is motivated from the challenge to understand transport processes at the atomic scale responsible for crystal and film growth and their different growth modes. Not even the most advanced experimental techniques are capable of resolving the sub ps time and sub-Ångström length-scales required. TiN belongs to an important class of transition metal nitrides, and is chosen here as a model system for such fundamental studies of surface transport. The simulations show that on terraces, Ti adatoms exhibit much higher migration rates than N adatoms. For TiNx complexes, as x increases from 1 to 3, rotation becomes increasingly more prevalent than translation. This leads to surprisingly high mobilities of TiN2 trimers, higher than that of N adatoms. On islands, Ti adatoms experience a significant funneling effect, resulting in short residence times. TiN dimers and TiN2 trimers exhibit surprisingly high diffusivities and residence times even shorter than Ti adatoms. TiN3 trimers, however, are essentially stationary on both terraces and islands and serve as nucleation clusters. Overall, Ti adatoms and TiN2 trimers are the most efficient carriers of Ti and N atoms with and between TiN(001) surface layers. These results indicate that Ti/N flux ratios close to one promote layer-by-layer TiN(001) growth, whereas lower ratios result in surface roughening. Understanding of these phenomena enables experimentalists to tune  the growth processes to optimize material properties.

In this thesis I also carry out theoretical calculations to investigate the role of configurational order on the metallic sublattice in relation to toughness enhancement. My studies set out from the recent understanding that the toughness of transition metal nitrides can be enhanced by tuning the valence electron concentration. My results show that ordered alloys exhibit lower resistance to shear deformations than disordered alloys, and higher resistance to tensile deformation. The lower resistance to shear deformations is explained by the formation of fully bonding electronic states perpendicular to the applied stress. Using the Pugh-Pettifor criterion, it is shown that while configurational order has an effect on the ductility of the material, this is primarily governed by the valence electron concentration.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2014. 22 p.
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1686
National Category
Physical Sciences
Identifiers
urn:nbn:se:liu:diva-111950 (URN)10.3384/lic.diva-111950 (DOI)978-91-7519-197-3 (ISBN)
Supervisors
Available from: 2014-11-11 Created: 2014-11-11 Last updated: 2016-08-31Bibliographically approved
3. Growth and Mechanical Properties of Transition Metal Nitrides and Carbides
Open this publication in new window or tab >>Growth and Mechanical Properties of Transition Metal Nitrides and Carbides
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The atomic-scale dynamical processes at play during film growth cannot be resolved by even the most advanced experimental methods. As such, computational methods, and chiefly classical molecular dynamics, are the only available research tools to study these processes. The investigation of key dynamical processes during thin film growth yields a deeper understanding of the film growth evolution, ultimately allowing for the optimization of experimental parameters and tailoring of film properties. This thesis details the study of fundamental surface dynamics processes, and the role played by primary diffusing species, during TiN film growth, here employed as a model system for transition metal nitrides in general. It is found that Ti adatoms and TiN2 admolecules are the fastest diffusing species, and the species which most rapidly descend from islands onto the growing film. Thus, they are the main contributors and players in driving the layer-by-layer growth mode. TiN3 admolecules, in contrast, are essentially stationary and thereby promote multilayer growth. Large-scale growth simulations reveal that tailoring the incident N/Ti ratio and N kinetic energy significantly affects the growth mode and film microstructure.

The mechanical properties of ternary transition metal nitride and carbide alloys, investigated using density functional theory, are also discussed herein, in comparison to recent experimental results. By optimizing the valence electron concentration in these compounds, the occupation of shear-compliant d‑t2g electronic states can be maximized. The investigation of M1M2N alloys, where M1 = Ti or V and M2 = W or Mo, with different structures demonstrates that this optimization leads to enhanced ductility, and thereby toughness, in transition metal nitride alloys regardless of the degree of ordering on the metal sublattice. Estimations based on the calculation of the mechanical properties of the corresponding M1M2C transition metal carbide alloys indicate that these materials remain brittle. However, charge density analysis and calculations of stress/strain curves reveal features commonly associated with ductile materials.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2016. 48 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1791
National Category
Condensed Matter Physics
Identifiers
urn:nbn:se:liu:diva-132272 (URN)10.3384/diss.diva-132272 (DOI)9789176856840 (ISBN)
Public defence
2016-11-30, Planck, Fysikhuset, Campus Valla, Linköping, 10:15 (English)
Opponent
Supervisors
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2016-11-11 Created: 2016-10-25 Last updated: 2016-11-11Bibliographically approved

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Sangiovanni, DavideEdström, DanielHultman, LarsChirita, ValeriuPetrov, IvanGreene, Joseph E

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