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Ti-Si-C-N Thin Films Grown by Reactive Arc Evaporation from Ti3SiC2 Cathodes
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, Nanostructured Materials. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Nanostructured Materials. Linköping University, The Institute of Technology.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
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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. Vol. 26, 874-881 p.
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-61992DOI: 10.1557/jmr.2011.10OAI: oai:DiVA.org:liu-61992DiVA: diva2:370954
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
In thesis
1. Cathodic Arc Synthesis of Ti-Si-C-N Thin Films from Ternary Cathodes
Open this publication in new window or tab >>Cathodic Arc Synthesis of Ti-Si-C-N Thin Films from Ternary Cathodes
2010 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

Cathodic arc deposition is a powerful technique for thin film synthesis, associated with explosive phase transformations resulting in an energetic and highly ionized plasma. This Thesis presents film growth through arc deposition from compound cathodes of Ti3SiC2, providing source material for plasma and films rich in Si and C. The interest for the resulting Ti-Si-C-N films is inspired by the two ternaries Ti-Si-N and Ti-C-N, both successfully applied as corrosion  and wear resistant films, with a potential for synergistic effects in the quarternary system.

When using a rotating substrate fixture setup, which is common in high capacity commercial deposition systems, the repeated passage though the plasma zone results in growth layers in the films. This effect has been observed in several coating systems, in deposition of various materials, but has not been explained in detail. The here investigated layers are characterized by a compositional modulation in Si and Ti content, which is attributed primarily to preferential resputtering in segments of rotation when the plasma has high incidence angle towards the substrate normal. For depositions in a non-reactive environment, the films consist of primarily understoichiometric TiCx, Ti, and silicide phases, and display a modest hardness (20-30 GPa) slightly improved by a decreasing layer thickness. Hence, the side effects of artificial layering from substrate rotation in deposition systems should be recognized.

Adding N2 to the deposition process results in reactive growth of nitride material, formed in a wide range of compositions, and thereby enabling investigation of films in little explored parts of the Ti-Si-C-N system. The structure and properties of such films, comprising up to 12 at% Si and 16 at% C, is highly dependent on the supply of N2 during deposition. Superhard (45-50 GPa) cubic-phase (Ti,Si)(C,N) films with a nanocrystalline feathered structure is formed at N-content of 25-30 at%. At higher N2 deposition pressure, C and Si segregate to column and grain boundaries and the cubic phase assumes a more pronounced nitride character. This transformation is accompanied by substantially reduced film hardness to 20 GPa. Ti-Si-C-N films thus display a rich variety of structures with favorable mechanical properties, but in the regime of high Si and C content, the amount of N must be carefully controlled to avoid undesirable formation of weak grain boundary phases based on Si, C and N.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2010. 37 p.
Series
Linköping Studies in Science and Technology. Thesis, ISSN 0280-7971 ; 1456
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-61994 (URN)LIU-TEK-LIC-2010:27 (Local ID)978-91-7393-273-8 (ISBN)LIU-TEK-LIC-2010:27 (Archive number)LIU-TEK-LIC-2010:27 (OAI)
Presentation
2010-12-09, Planck, Fysikhuset, Campus Valla, Linköping University, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2010-12-01 Created: 2010-11-18 Last updated: 2010-12-01Bibliographically approved
2. Cathodic Arc Synthesis of Ti-Si-C-N Thin Films: Plasma Analysis and Microstructure Formation
Open this publication in new window or tab >>Cathodic Arc Synthesis of Ti-Si-C-N Thin Films: Plasma Analysis and Microstructure Formation
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:nbn:se:liu:diva-86259 (URN)978-91-7519-714-2 (ISBN)
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
3. Microstructure evolution of Ti-based and Cr cathodes during arc discharging and its impact on coating growth
Open this publication in new window or tab >>Microstructure evolution of Ti-based and Cr cathodes during arc discharging and its impact on coating growth
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis explores the microstructure evolution of cathodes with various material compositions and grain sizes during cathodic arc evaporation processes as well as the impact on the arc movement, and the microstructure and properties of the deposited nitride coatings. The studied cathode material systems include conventionally metal forged Ti and Ti -Si cathodes, novel Ti3SiC2 MAX-phase cathodes, and dedicatedly designed powder-metallurgical Ti-Si and Cr cathodes with different grain size. The microstructure and chemical composition of the virgin and arced cathodes together with the microstructure and mechanical properties of the deposited coatings were analyzed with various characterization techniques, including x-ray diffractometry, x-ray photoelectron spectroscopy, elastic recoil detection analysis, scanning electron microscopy, focused ion beam sample preparation technique, transmission electron microscopy, energy dispersive x-ray, electron energy loss spectroscopy, and nanoindentation.

In general, a converted layer forms on the cathode surfaces during cathodic arc evaporation. The thickness, the microstructure and the chemical composition of such layer are dependent on the composition and the grain size of the virgin cathodes, the nitrogen pressure, and the cathode fabrication methods.

For Ti based materials, the converted layer is 5-12 μm thick and consists of nanosized nitrided grains caused by the high reactivity of Ti to the ambient nitrogen gas. In comparison, the Cr cathode is covered with a 10-15 μm converted layer with micrometer/sub-micrometer sized grains. Only very limited amounts of nitrogen are detected within the layer due to the low reactivity of Cr to nitrogen.

For Ti-Si cathodes, the existence of multiple phases of Ti and Ti5Si3 with different work function renders preferential arc erosion on the Ti5Si3 phase during discharging. The preferential erosion generates higher roughness of the Ti-Si cathode surface compared with Ti. By increasing the grain size of the virgin Ti-Si cathodes from ~8 μm to ~620 μm, the average roughness  increases from 1.94±0.13 μm to 91±14 μm due to the amplified impact of preferential erosion of the enlarged Ti5Si3 grains. The variation of the preferential erosion affects the arc movement, the deposition rate, and the macroparticle distribution of the deposited Ti-Si-N coatings.

A novel Ti3SiC2 MAX phase is used as cathode material for the growth of Ti-Si-C-N coating. During arcing, the cathode surface forms a converted layer with two sublayers, consisting of a several-micrometer region with a molten and resolidified microstructure followed by a region with a decomposed microstructure. The microstructure and hardness of the deposited Ti -Si-C-N coatings is highly dependent on the wide range of coating compositions attained. In the coatings with abundance of N, the combined presence of Si and C strongly disturbs cubic phase growth and compromises their mechanical strength. At a nitrogen pressure of 0.25-0.5 Pa, 45-50 GPa superhard (Ti,Si)(C,N) coatings with a nanocrystalline feathered structure were obtained.

By increasing the grain size of the elemental Cr cathodes from ~10 μm and ~300 μm, the grain structure of the converted layer on the cathode surface varies from equiaxed grains to laminated grains after evaporating in a nitrogen atmosphere. When evaporated with a stationary fixture, the worn Cr cathode surface contains an organized pattern of deep ditches in the surface. The formation of such patterns is enhanced by increasing the cathode grain size. The fixture movement, which is either stationary or single rotating, affects the phase composition, the droplet density and the microstructure of the deposited Cr-N coatings, which consequently determines the mechanical properties of the coatings.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2013. 55 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1537
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-96790 (URN)978-91-7519-539-1 (ISBN)
Public defence
2013-09-20, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2013-08-27 Created: 2013-08-27 Last updated: 2016-08-31Bibliographically approved

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Eriksson, AndersZhu, JianqiangGhafoor, NaureenJensen, JensGreczynski, GrzegorzJohansson, MatsOdén, MagnusHultman, LarsRosén, Johanna

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