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Influence of Ar and N2 Pressure on Plasma Chemistry, Ion Energy, and Thin Film Composition during Filtered Arc Deposition from Ti3SiC2 Cathodes
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
Materials Chemistry, RWTH Aachen University, Aachen, Germany.
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
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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. Vol. 42, no 11, 3498-3507 p.
National Category
Physical Sciences
Identifiers
URN: urn:nbn:se:liu:diva-86252DOI: 10.1109/TPS.2014.2361867ISI: 000345067700008OAI: oai:DiVA.org:liu-86252DiVA: diva2:576078
Available from: 2012-12-12 Created: 2012-12-12 Last updated: 2017-12-07Bibliographically approved
In thesis
1. 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)
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Available from: 2012-12-12 Created: 2012-12-12 Last updated: 2016-08-31Bibliographically approved

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Eriksson, AndersJensen, JensHultman, LarsRosén, Johanna

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