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Cathodic Arc Synthesis of Ti-Si-C-N Thin Films: Plasma Analysis and Microstructure Formation
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This Thesis explores the arc deposition process and films of Ti-Si-C-N, inspired by the two ternary systems Ti-Si-N and Ti-C-N, both successfully applied as corrosion and wear resistant films. The correlation between cathode, plasma, and film properties are studied for a comprehensive view on film formation. Novel approaches to adapt arc deposition to form multi-element films are investigated, concluding that the source of C is not a determining factor for film growth. Thus, cubic-phase films of similar properties can be synthesized from processes with either 1) ternary Ti-Si-C cathodes, including the Ti3SiC2 MAX phase, in N2 atmosphere or 2) Ti-Si cathodes in a mixture of N2 and CH4. With the Ti3SiC2 cathodes, superhard (45-50 GPa) cubic-phase (Ti,Si)(C,N) films can be deposited. The structure is nanocrystalline and feather-like, with high Si and C content of 12 and 16 at%, respectively. To isolate the effects of Si on film structure, magnetron sputtered Ti-Si-N films of comparatively low defect density was studied. These films show a strong preference for {200}  growth orientation, and can be grown as a single phase solid solution on MgO(001) substrates up to ~9 at% Si, i.e. considerably higher than the ~5 at% Si above which a feather-like nanocrystalline structure forms in arc deposited films. On (011) and (111) growth surfaces, the films self-organize into TiN columns separated by segregated crystalline-to-amorphous SiNx. The conditions for film growth by arc were investigated through plasma studies, showing that plasma properties are dependent on cathode composition as well as phase structure. Plasma generation from Ti-Si cathodes, with up to 25 at% Si, show higher average ion charge states of Ti and Si compared to plasma from elemental cathodes, which may be related to TiSix phases of higher cohesive energies. The ion energy distributions range up to 200 eV. Furthermore, compositional discrepancies between plasma ions and film infer significant contributions to film growth from Si rich neutral species. This is further supported by depositions with a macroparticle filter, intended for growth of films with low surface roughness, where Si and C contents lower than the stoichiometry of Ti3SiC2 cathodes was measured in both plasma and films. Also the substrate geometry is critical for the film composition in plasma based film deposition, as evidenced by the formation of artificial layering from rotating substrate fixtures common in high capacity arc deposition systems. The layers are characterized by modulations in composition and crystallinity, primarily attributed to preferential resputtering in high ion incidence angle segments repeated through rotation.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2013. , 55 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1495
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-86259ISBN: 978-91-7519-714-2 (print)OAI: oai:DiVA.org:liu-86259DiVA: diva2:576126
Public defence
2013-01-14, Visionen, B-huset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2012-12-12 Created: 2012-12-12 Last updated: 2016-08-31Bibliographically approved
List of papers
1. Layer Formation by Resputtering in Ti-Si-C Hard Coatings during Large Scale Cathodic Arc Deposition
Open this publication in new window or tab >>Layer Formation by Resputtering in Ti-Si-C Hard Coatings during Large Scale Cathodic Arc Deposition
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2011 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 205, no 15, 3923-3930 p.Article in journal (Refereed) Published
Abstract [en]

This paper presents the physical mechanism behind the phenomenon of self-layering in thin films made by industrial scale cathodic arc deposition systems using compound cathodes and rotating substrate fixture. For Ti-Si-C films, electron microscopy and energy dispersive x-ray spectrometry reveals a trapezoid modulation in Si content in the substrate normal direction, with a period of 4 to 23 nm dependent on cathode configuration. This is caused by preferential resputtering of Si by the energetic deposition flux incident at high incidence angles when the substrates are facing away from the cathodes. The Ti-rich sub-layers exhibit TiC grains with size up to 5 nm, while layers with high Si-content are less crystalline. The nanoindentation hardness of the films increases with decreasing layer thickness.

Place, publisher, year, edition, pages
Elsevier, 2011
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-61991 (URN)10.1016/j.surfcoat.2011.02.007 (DOI)000289606000004 ()
Note

Original Publication: Anders Eriksson, Jianqiang Zhu, Naureen Ghafoor, Mats Johansson, Jacob Sjölen, Jens Jensen, Magnus Odén, Lars Hultman and Johanna Rosén, Layer Formation by Resputtering in Ti-Si-C Hard Coatings during Large Scale Cathodic Arc Deposition, 2011, Surface & Coatings Technology, (205), 15, 3923-3930. http://dx.doi.org/10.1016/j.surfcoat.2011.02.007 Copyright: Elsevier Science B.V., Amsterdam. http://www.elsevier.com/

Available from: 2010-11-18 Created: 2010-11-18 Last updated: 2017-12-12
2. Ti-Si-C-N Thin Films Grown by Reactive Arc Evaporation from Ti3SiC2 Cathodes
Open this publication in new window or tab >>Ti-Si-C-N Thin Films Grown by Reactive Arc Evaporation from Ti3SiC2 Cathodes
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2011 (English)In: Journal of Materials Research, ISSN 0884-2914, E-ISSN 2044-5326, Vol. 26, 874-881 p.Article in journal (Refereed) Published
Abstract [en]

Ti-Si-C-N thin films were deposited onto WC-Co substrates by industrial scale arc evaporation from Ti3SiC2 compound cathodes in N2 gas. Microstructure and hardness were found to be highly dependent on the wide range of film compositions attained, comprising up to 12 at.% Si and 16 at.% C. Nonreactive deposition yielded films consisting of understoichiometric TiCx, Ti and silicide phases with high (27 GPa) hardness. At a nitrogen pressure of 0.25-0.5 Pa, below that required for N saturation, superhard, 45-50 GPa, (Ti,Si)(C,N) films with a nanocrystalline feathered structure were formed. Films grown above 2 Pa displayed crystalline phases of more pronounced nitride character, but with C and Si segregated to grain boundaries to form weak grain boundary phases. In abundance of N, the combined presence of Si and C disturb cubic phase growth severely and compromises the mechanical strength of the films.

Place, publisher, year, edition, pages
Cambrdige University Press, 2011
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-61992 (URN)10.1557/jmr.2011.10 (DOI)
Note

Original Publication: Anders Eriksson, Jianqiang Zhu, Naureen Ghafoor, Jens Jensen, Grzegorz Greczynski, Mats Johansson, Jacob Sjölen, Magnus Odén, Lars Hultman and Johanna Rosén, Ti-Si-C-N Thin Films Grown by Reactive Arc Evaporation from Ti3SiC2 Cathodes, 2011, Journal of Materials Research, (26), 874-881. http://dx.doi.org/10.1557/jmr.2011.10 Copyright: Mrs Materials Research Society http://www.mrs.org/

Available from: 2010-11-18 Created: 2010-11-18 Last updated: 2017-12-12
3. Influence of Ar and N2 Pressure on Plasma Chemistry, Ion Energy, and Thin Film Composition during Filtered Arc Deposition from Ti3SiC2 Cathodes
Open this publication in new window or tab >>Influence of Ar and N2 Pressure on Plasma Chemistry, Ion Energy, and Thin Film Composition during Filtered Arc Deposition from Ti3SiC2 Cathodes
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2014 (English)In: IEEE Transactions on Plasma Science, ISSN 0093-3813, E-ISSN 1939-9375, Vol. 42, no 11, 3498-3507 p.Article in journal (Refereed) Published
Abstract [en]

Arc plasma from Ti3SiC2 compound cathodes used in a filtered dc arc system has been characterized with respect to plasma chemistry and charge-state resolved ion energies. In vacuum, the plasma composition is dominated by Ti ions, with concentrations of 84.3, 9.3, and 6.4 at% for Ti, Si, and C ions, respectively. The reduced amount of Si and most notably C compared with the cathode composition is confirmed by analysis of film composition in corresponding growth experiments. The deposition of light-element deficient films is thus related to plasma generation or filter transport. The ion energy distributions in vacuum range up to 140, 90, and 70 eV for Ti, Si, and C, respectively. Corresponding average ion energies of 48, 36, and 27 eV are reduced upon introduction of gas, down to around 5 eV at 0.6 Pa Ar or 0.3 Pa N2 for all species. In vacuum, the charge state distributions of Si and C are shifted to higher values compared with corresponding elemental cathodes, likely caused by changed effective electron temperature of the plasma stemming from compound cathode material and/or by electron impact ionization in the filter. The average ion charge states are reduced upon addition of Ar, ranging between 1.97 and 1.48 for Ti, 1.91 and 1.46 for Si, and 1.25 and 1.02 for C. Similar effects are observed upon introduction of N2, though with more efficient charge state reduction with pressure. It is conceivable that the pressure-induced changes in ion energy and charge state are crucial for the film synthesis from a microstructure evolution point of view, as they affect the ion-surface interactions through supply of energy, especially when substrate biasing is employed during arc deposition from a compound cathode.

Place, publisher, year, edition, pages
IEEE Press, 2014
National Category
Physical Sciences
Identifiers
urn:nbn:se:liu:diva-86252 (URN)10.1109/TPS.2014.2361867 (DOI)000345067700008 ()
Available from: 2012-12-12 Created: 2012-12-12 Last updated: 2017-12-07Bibliographically approved
4. Arc deposition of Ti–Si–C–N thin films from binary and ternary cathodes — Comparing sources of C
Open this publication in new window or tab >>Arc deposition of Ti–Si–C–N thin films from binary and ternary cathodes — Comparing sources of C
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2012 (English)In: Surface & Coatings Technology, ISSN 0257-8972, E-ISSN 1879-3347, Vol. 213, 145-154 p.Article in journal (Refereed) Published
Abstract [en]

Ti–Si–C–N thin films with composition of 1–11 at.% Si and 1–20 at.% C have been deposited onto cemented carbide substrates by arcing Ti–Si cathodes in a CH4 + N2 gas mixture and, alternatively, through arcing Ti–Si–C cathodes in N2. Films of comparable compositions from the two types of cathodes have similar structure and properties. Hence, C can be supplied as either plasma ions generated from the cathode or atoms from the gas phase with small influence on the structural evolution. Over the compositional range obtained, the films were dense and cubic-phase nanocrystalline, as characterized by X-ray diffraction, ion beam analysis, and scanning and transmission electron microscopy. The films have high hardness (30–40 GPa by nanoindentation) due to hardening from low-angle grain boundaries on the nanometer scale and lattice defects such as growth-induced vacancies and alloying element interstitials.

Place, publisher, year, edition, pages
Elsevier, 2012
Keyword
Cathodic arc deposition; Reactive deposition; Hard coatings; Compound cathodes; Ti–Si–C–N
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-86253 (URN)10.1016/j.surfcoat.2012.10.038 (DOI)000314081200020 ()
Available from: 2012-12-12 Created: 2012-12-12 Last updated: 2017-12-07Bibliographically approved
5. Characterization of plasma chemistry and ion energy in cathodic arc plasma from Ti-Si cathodes of different compositions
Open this publication in new window or tab >>Characterization of plasma chemistry and ion energy in cathodic arc plasma from Ti-Si cathodes of different compositions
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2013 (English)In: Journal of Applied Physics, ISSN 0021-8979, E-ISSN 1089-7550, Vol. 113, no 16Article in journal (Refereed) Published
Abstract [en]

Arc plasma from Ti-Si compound cathodes with up to 25 at. % Si was characterized in a DC arc system with respect to chemistry and charge-state-resolved ion energy. The plasma ion composition showed a lower Si content, diverging up to 12 at. % compared to the cathode composition, yet concurrently deposited films were in accordance with the cathode stoichiometry. Significant contribution to film growth from neutrals is inferred besides ions, since the contribution from macroparticles, estimated by scanning electron microscopy, cannot alone account for the compositional difference between cathode, plasma, and film. The average ion charge states for Ti and Si were higher than reference data for elemental cathodes. This result is likely related to TiSix phases of higher cohesive energies in the compound cathodes and higher effective electron temperature in plasma formation. The ion energy distributions extended up to ∼200 and ∼130 eV for Ti and Si, respectively, with corresponding average energies of ∼60 and ∼30 eV. These averages were, however, not dependent on Si content in the cathode, except for 25 at. % Si where the average energies were increased up to 72 eV for Ti and 47 eV for Si.

National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-91729 (URN)10.1063/1.4802433 (DOI)000318550300012 ()
Available from: 2013-04-30 Created: 2013-04-30 Last updated: 2017-12-06
6. Nanocolumnar Epitaxial Ti1-xSixN (0 ≤ x ≤ 0.18) Thin Films Grown by Dual Reactive Magnetron Sputtering on MgO (001), (011), and (111) Substrates
Open this publication in new window or tab >>Nanocolumnar Epitaxial Ti1-xSixN (0 ≤ x ≤ 0.18) Thin Films Grown by Dual Reactive Magnetron Sputtering on MgO (001), (011), and (111) Substrates
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2012 (English)Manuscript (preprint) (Other academic)
Abstract [en]

Ti1-xSixNy thin films and multilayers have been grown on single-crystal TiN-templated MgO (001), (011), and (111) substrates kept at 550 °C. Elemental Ti and Si targets were used in UVH reactive dual magnetron sputtering in a mixed Ar/N2 discharge. Composition analysis by time-of-flight energy elastic recoil detection analysis show that the films are close to stoichiometric (0.95 ≤ y ≤ 1.00) with respect to TiN over the wide range of Si concentrations 0 ≤ x ≤ 0.22. High-resolution transmission electron microscopy (TEM) combined with scanning TEM and energy dispersive Xray analysis show that all films grow epitaxially for x ≤ 0.18 and that as much as every fifth Ti atom can be replaced by Si (~10 at.%) in Ti1-xSixN(001). For the (011) and (111)-oriented films, however, only 1-2 at.% Si substitutes for Ti. Instead, Si segregates to form crystalline-to-amorphous SiNz (z ≈ 1) tissue phases, which promote the formation of epitaxial TiN nanocolumns. The nanocolumns have preferred {110} interfaces and {200} top facets and grow several hundreds  of nm in length.

National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-86256 (URN)
Available from: 2012-12-12 Created: 2012-12-12 Last updated: 2016-08-31

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