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The Influence of Inert Gases on the a-C and CNx Thin Film Deposition: A Comparison between DCMS and HiPIMS Processes
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
Research Institute for Technical Physics and Materials Science, Hungarian Academy of Sciences, Budapest, Hungary.
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics.ORCID iD: 0000-0002-4898-5115
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

DCMS and HiPIMS discharges of C in Ne, Ar, and Kr as well as their reactive counterparts (N2/Ne, N2/Ar, and N2/Kr) were investigated for the growth of carbon and carbon-nitride (CNx) thin films. The thin films were synthesized in an industrial deposition chamber from a pure graphite target. Time averaged plasma mass spectroscopy showed that the energies of the most abundant plasma cations depend on the inert gas and the amount of N2 in the sputter gas rather than the sputter modes. The ion species population in the plasma, on the other hand, was found to depend heavily on the sputter mode; HiPIMS processes yield approximately ten times higher flux ratios of ions originating from the target to ions originating from the process gas. Exceptional cases are the discharges in Ne or N2/Ne mixtures containing up to 20% N2. Here, no influence of the sputter mode on cation energies and population was found. CNx and a-C thin films deposited in 14% N2/inert gas mixture and pure inert gas, respectively, were characterized regarding the chemical composition, chemical bonding and microstructure as well as their mechanical properties using elastic recoil detection analysis, X-ray photoelectron spectroscopy, transmission electron microscopy in combination with selected area electron diffraction, and nanoindentation, respectively. The thin film characteristics showed strong correlations to the energies of abundant plasma cations (namely C+, Ar+, Ar++, Ne+,22Ne+, Ne++, 82Kr+, 84Kr+, 86Kr+, Kr++, N+, N2+, CN+ as well as C2N2+)and cation population of the corresponding deposition process. High amounts of C bond in sp3 hybridization state were found for thin films sputtered in Ne, accounting for their elevated hardness and amorphous microstructure. With increasing inert gas atomic number the a-C and CNx thin films show an increasingly distinct near range ordered microstructural evolution. This effect is more pronounced for HiPIMS processes and accompanied by a lowered hardness, but elevated elastic properties.

National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:liu:diva-90910OAI: oai:DiVA.org:liu-90910DiVA: diva2:615012
Available from: 2013-04-08 Created: 2013-04-08 Last updated: 2016-08-31Bibliographically approved
In thesis
1. Carbon Nitride and Carbon Fluoride Thin Films Prepared by HiPIMS
Open this publication in new window or tab >>Carbon Nitride and Carbon Fluoride Thin Films Prepared by HiPIMS
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The present thesis focuses on carbon based thin films prepared by high power impulse magnetron sputtering (HiPIMS) and direct current magnetron sputtering (DCMS). Carbon nitride (CNx: 0 < x < 0.20) as well as carbon fluoride (CFx: 0.16 < x < 0.35) thin films were synthesized in an industrial deposition chamber by reactive magnetron sputtering of graphite in Ne/N2, Ar/N2, Kr/N2, Ar/CF4, and Ar/C4F8 ambients. In order to increase the understanding of the deposition processes of C in the corresponding reactive gas mixture plasmas, ion mass spectroscopy was carried out. A detailed evaluation of target current and target voltage waveforms was performed when graphite was sputtered in HiPIMS mode. First principle calculations targeting the growth of CFx thin films revealed most probable film forming species as well as CFx film structure defining defects. In order to set different process parameters into relation with thin film properties, the synthesized carbon based thin films were characterized with regards to their chemical composition, chemical bonding, and microstructure. A further aspect was the thin film characterization for possible applications. For this, mainly nanoindentation and contact angle measurements were performed. Theoretical calculations and the results from the characterization of the deposition processes were successfully related to the thin film properties.

The reactive graphite/N2/inert gas HiPIMS discharge yielded high ion energies as well as elevated C+ and N+ abundances. Under such conditions, amorphous CNx thin films with hardnesses of up to 40 GPa were deposited. Elastic, fullerene like CNx thin films, on the other hand, were deposited at increased substrate temperatures in HiPIMS discharges exhibiting moderate ion energies. Here, a pulse assisted chemical sputtering at the target and the substrate was found to support the formation of a fullerene-like microstructure.

CFx thin films were found to have surface energies equivalent to super-hydrophobic materials for x > 0.26 while such films were polymeric in nature accounting for hardnesses below 1 GPa. Whereas, an amorphous structure for carbon-based films with fluorine contents ranging between 16 % and 23 % was observed. For those films, the hardness increased with decreasing fluorine content and ranged between 16 GPa and 4 GPa. The HiPIMS process in fluorinecontaining atmosphere was found to be a powerful tool in order to change the surface properties of carbon based thin films.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press, 2013. 82 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1512
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-90912 (URN)978-91-7519-642-8 (ISBN)
Public defence
2013-05-08, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
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Available from: 2013-04-08 Created: 2013-04-08 Last updated: 2016-08-31Bibliographically approved

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Schmidt, SusannGreczynski, GrzegorzJensen, JensHultman, Lars

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