liu.seSearch for publications in DiVA
Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Fullerene-like CNx and CPx Thin Films; Synthesis, Modeling, and Applications
Linköping University, Department of Physics, Chemistry and Biology, Thin Film Physics. Linköping University, The Institute of Technology.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This Thesis concerns the development of fullerene-like (FL) carbon nitride (CNx) thin films and the discovery of phosphorus-carbide (CPx) compounds. The work dedicated to CPx include first-principles theoretical simulations of the growth and properties of FL-CPx structures. I have employed DC magnetron sputtering methods to synthesize both CNx and CPx thin films. The deposition conditions for CPx films were chosen on the basis of the theoretical results as well as from the experience from the deposition of FL-CNx thin films.

The characterization of the CPx films is divided into three main directions: structural characterization by transmission electron microscopyand scanning electron microscopy, analysis of the amount of elements and chemical bonds presentin the structure by X-ray photoelectron spectroscopy and Auger spectroscopy, and mechanicalproperty analysis by nanoindentation. The CPx films exhibit a short range orderedstructure with FL characteristics for substrate temperature of 300 °C and for a phosphorus content of 10-15 at.%, which isconsistent with the theoretical findings. These films also displayed the best mechanical properties in terms of hardness and resiliency, which are better than those of the corresponding FL-CNx films.

For the FL-CNx thin film material, I find that the surface water adsorption is lower compared to commercial computer hard disk top coatings. Following that line the dangling bonds in FL-CNx coatings have been investigated  by electron spin resonance (ESR). The absence of ESR signal for FL-CNx indicates very low density of dangling bonds in the material, which explains the low water adsorption tendency.

The potential for using highly elastic FL-CNx coatings in an automotive valve-train environment has also been investigated. CNx coatings of different nitrogen content were investigated using microscopy, wear testing, nanoindentation testing, and in an experimental cam-tappet testing rig. The FL-CNx coating with the higher value of hardness/elastic modulus showed greater durability in cam-tappet wear testing.

Place, publisher, year, edition, pages
Linköping: Linköping University Electronic Press , 2009. , 60 p.
Series
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1247
Keyword [en]
Phosphorus-carbide (CPx), carbon nitride (CNx), thin films, resilient coatings, magnetron sputtering, theoretical modeling
National Category
Other Engineering and Technologies not elsewhere specified
Identifiers
URN: urn:nbn:se:liu:diva-17126ISBN: 978-91-7393-676-7 (print)OAI: oai:DiVA.org:liu-17126DiVA: diva2:202070
Public defence
2009-03-30, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Opponent
Supervisors
Available from: 2009-03-24 Created: 2009-03-06 Last updated: 2016-08-31Bibliographically approved
List of papers
1. Fullerene–like CPx: A first–principles study of the relative stability of precursors and defect energetics during synthetic growth
Open this publication in new window or tab >>Fullerene–like CPx: A first–principles study of the relative stability of precursors and defect energetics during synthetic growth
Show others...
2006 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 515, no 3, 1028-1032 p.Article in journal (Refereed) Published
Abstract [en]

Inherently nanostructured CPx compounds were studied by first-principles calculations. Geometry optimizations and cohesive energy comparisons show stability for C3P, C2P, C3P2, CP, and P4 (P2) species in isolated form as well as incorporated in graphene layers. The energy cost for structural defects, arising from the substitution of C for P and intercalation of P atoms in graphene, was also evaluated. We find a larger curvature of the graphene sheets and a higher density of cross-linkage sites in comparison to fullerene-like (FL) CNx, which is explained by differences in the bonding between P and N. Thus, the computational results extend the scope of fullerene-like thin film materials with FL-CPx and provide insights for its structural properties.

Keyword
Fullerene-like materials; Phosphorus carbide (CPx); First-principles calculations; Thin films; Precursors
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-14230 (URN)10.1016/j.tsf.2006.07.176 (DOI)
Available from: 2007-01-26 Created: 2007-01-26 Last updated: 2017-12-13Bibliographically approved
2. First–principles calculations on the structural evolution of solid fullerene–like CPx
Open this publication in new window or tab >>First–principles calculations on the structural evolution of solid fullerene–like CPx
Show others...
2006 (English)In: Chemical Physics Letters, ISSN 0009-2614, E-ISSN 1873-4448, Vol. 426, no 4-6, 374-379 p.Article in journal (Refereed) Published
Abstract [en]

The formation and structural evolution of fullerene-like (FL) carbon phosphide (CPx) during synthetic growth were studied by first-principles calculations. Geometry optimizations and comparison between the cohesive energies suggest stability for solid FL-CPx compounds. In comparison with fullerene-like carbon nitride, higher curvature of the graphene sheets and higher density of cross-linkages between them is predicted and explained by the different electronic properties of P and N. Cage-like and onion-like structures, both containing tetragons, are found to be typical for fullerene-like CPx. Segregation of P is predicted at fractions exceeding ~20 at.%.

National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-14231 (URN)10.1016/j.cplett.2006.05.087 (DOI)
Available from: 2007-01-26 Created: 2007-01-26 Last updated: 2017-12-13Bibliographically approved
3. Synthesis of phosphorus-carbide thin films by magnetron sputtering
Open this publication in new window or tab >>Synthesis of phosphorus-carbide thin films by magnetron sputtering
Show others...
2008 (English)In: physica status solidi (RRL) - Rapid Research Letters, ISSN 1862-6254, Vol. 2, no 4, 191-193 p.Article in journal (Refereed) Published
Abstract [en]

Phosphorus-carbide, CPx (0.025≤x≤0.1) thin films have beensynthesized by magnetron sputtering from pressed graphite-phosphorustargets. The films were characterized by X-ray photoelectron spectroscopy,transmission electron microscopy and diffraction, andnanoindentation. CP0.02 exhibits C-P bonding in an amorphous structure with elements of curved grapheneplanes, yielding a material with unique short range order. These features are consistent with what has been predicted by our results of theoreticallymodeled synthetic growth of CPx. The films are mechanicallyresilient with hardness up to 24 GPa and elastic recovery upto 72%.

Place, publisher, year, edition, pages
Wiley InterScience, 2008
Keyword
Phosphorus-carbide (CPx), thin films, magnetron sputtering, resilient material
National Category
Other Engineering and Technologies not elsewhere specified
Identifiers
urn:nbn:se:liu:diva-17114 (URN)
Available from: 2009-03-06 Created: 2009-03-06 Last updated: 2016-08-31Bibliographically approved
4. Structure and properties of phosphorus-carbide thin solid films
Open this publication in new window or tab >>Structure and properties of phosphorus-carbide thin solid films
Show others...
2013 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 548, no 2, 247-254 p.Article in journal (Refereed) Published
Abstract [en]

Phosphorus-carbide (CPx) thin films have been deposited by unbalanced reactive magnetron sputtering and investigated by TEM, XPS, SEM, ERDA, Raman scattering spectroscopy, nanoindentation testing, and four-point electrical probe techniques. As-deposited films with x=0.1 are electron amorphous with elements of FL structure and high mechanical resiliency with hardness of 34.4 GPa and elastic recovery of 72%. The electrical resistivity of the films are in the range 0.4-1.7 Ωcm for CP0.027, 1.4-22.9 Ωcm for CP0.1, and lower than the minimal value the four-point probe is able to detect for CPx with x≥0.2.

Keyword
Phosphorus carbide, thin films, magnetron sputtering
National Category
Other Engineering and Technologies not elsewhere specified
Identifiers
urn:nbn:se:liu:diva-17058 (URN)10.1016/j.tsf.2013.10.010 (DOI)000327530300039 ()
Available from: 2009-03-04 Created: 2009-03-04 Last updated: 2017-12-13Bibliographically approved
5. Water adsorption on lubricated fullerene-like CNx films
Open this publication in new window or tab >>Water adsorption on lubricated fullerene-like CNx films
Show others...
2006 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 515, no 3, 979-983 p.Article in journal (Refereed) Published
Abstract [en]

Humidity influences the tribological performance of the head–disk interface in magnetic data storage devices. In this work we compare the uptake of water of amorphous hydrogenated carbon (a-CHy) and carbon nitride (a-CNx) films, widely used as protective overcoats in computer disk drive systems, with two types of amorphous non-hydrogenated carbon (a-C and a-Csp2) films, and fullerene-like carbon nitride (FL-CNx) films. Carbon films were deposited on quartz crystal substrates by reactive dc magnetron sputtering in Ar/N2 discharges. After deposition, some of the films were coated with a 2-nm-thick layer of Z-tetraol, a lubricant used in hard disk devices. A quartz crystal microbalance placed in a vacuum chamber was used to measure the adsorption of water at room temperature and at pressures of water corresponding to relative humidities in the range RH = 0 to 90%. Water adsorption and desorption is fast, indicating that equilibrium with ambient humidity is reached on time scales of minutes, much faster than the time scales for fluctuations in ambient humidity. The amount of water adsorbed on the non-lubricated amorphous carbon films is significantly higher than that on the fullerene-like films. The presence of the lubricant influences water adsorption but its impact differs on different carbon films.

Keyword
Carbon nitride, Water, Adsorption, Sputtering, Fullerene-like
National Category
Engineering and Technology
Identifiers
urn:nbn:se:liu:diva-14229 (URN)10.1016/j.tsf.2006.07.065 (DOI)
Available from: 2007-01-26 Created: 2007-01-26 Last updated: 2017-12-13Bibliographically approved
6. Water adsorption on fullerene-like carbon nitride overcoats
Open this publication in new window or tab >>Water adsorption on fullerene-like carbon nitride overcoats
Show others...
2008 (English)In: Thin Solid Films, ISSN 0040-6090, E-ISSN 1879-2731, Vol. 517, no 3, 1106-1110 p.Article in journal (Refereed) Published
Abstract [en]

Humidity influences the tribological performance of the head-disk interface in magnetic data storage devices. In this work we compare the uptake of water of amorphous carbon nitride (a-CNx) films, widely used as protective overcoats in computer disk drive systems, with fullerene-like carbon nitride (FL-CNx) and amorphous carbon (a-C) films. Films with thickness in the range 10-300 run were deposited on quartz crystal substrates by reactive DC magnetron sputtering. A quartz crystal microbalance placed in a vacuum chamber was used to measure the water adsorption. Electron paramagnetic resonance (EPR) has been used to correlate water adsorption with film microstructure and surface defects (dangling bonds). Measurements indicate that the amount of adsorbed water is highest for the pure a-C films and that the FL-CNx films adsorbed less than a-CNx. EPR data correlate the lower water adsorption on FL-CNx films with a possible lack of dangling bonds on the film surface. To provide additional insight into the atomic structure of defects in the FL-CNx, a-CNx and a-C compounds, we performed first-principles calculations within the framework of Density Functional Theory. Emphasis was put on the energy cost for formation of vacancy defects and dangling bonds in relaxed systems. Cohesive energy comparison reveals that the energy cost formation for dangling bonds in different configurations is considerably higher in FL-CNx than for the amorphous films. These simulations thus confirm the experimental results showing that dangling bonds are much less likely in FL-CNx than in a-CNx and a-C films.

Keyword
Carbon nitride, CNx, dangling bonds, water adsorption, QCM, EPR, DFT
National Category
Natural Sciences
Identifiers
urn:nbn:se:liu:diva-16402 (URN)10.1016/j.tsf.2008.07.022 (DOI)
Note
Presented at the 35th International Conference on Metallurgical Coatings and Thin Films (ICMCTF), San Diego, USAAvailable from: 2009-01-23 Created: 2009-01-23 Last updated: 2017-12-14Bibliographically approved
7. Performance of fullerene-like CNx coatings for automotive valve-train applications
Open this publication in new window or tab >>Performance of fullerene-like CNx coatings for automotive valve-train applications
(English)Manuscript (Other academic)
Abstract [en]

The design of internal combustion engines is evolving in order to provide greater efficiency and lower harmful emissions. There has been a move to lower component masses, higher engine temperatures, lower viscosity oils and low SAPS (sulphated ash, phosphor and sulphur) oils. With the transition to low density, low hardness materials and new lubrication conditions, come issues of component wear. Surface engineering techniques such as thin-film coating technologies present a possible solution. Thin-film coating development in recent years has often focused on achieving a high hardness, which often leads to high elastic modulus. However, there are potential benefits of less stiff and more elastic coatings. A number of wear mechanism are directly related to the ratio of hardness (H) and elastic modulus (E) and higher H/E ratios can be beneficial. This work therefore investigates the potential for using a highly elastic, experimental fullerene-like carbon nitride (FL-CNx) coating in a valve-train environment. Two FL-CNx coatings of differing nitrogen content were investigated using microscopy, wear testing, nanoindentation testing and in an experimental cam-tappet testing rig. The two FL-CNx coatings had similar adhesion to the substrate and hardness. The FL-CNx coating with the higher value of H/E also showed greater durability in the valve-train testing.

Keyword
Fullerene-like materials, automotive valve-train, applications
National Category
Other Engineering and Technologies not elsewhere specified
Identifiers
urn:nbn:se:liu:diva-17060 (URN)
Available from: 2009-03-04 Created: 2009-03-04 Last updated: 2016-08-31Bibliographically approved

Open Access in DiVA

fulltext(1675 kB)936 downloads
File information
File name FULLTEXT01.pdfFile size 1675 kBChecksum SHA-512
c7c0d477ba79a859f0538c81d5e0151bd4a51a11e196c8cf3ed9a4e0790a93b44973d52732661418c743eb6dfda57ec42d730fc66c03cf5b66079292097500dc
Type fulltextMimetype application/pdf
cover(1539 kB)131 downloads
File information
File name COVER01.pdfFile size 1539 kBChecksum SHA-512
24c0eda93117dabc493282ea9e0d174559cfd47c9ae76153488563ace7a2c1b6aabd269bec31e74c1eede9264de80e502f8609ae4a31eae20df19c6d58e4a538
Type coverMimetype application/pdf

Authority records BETA

Furlan, Andrej

Search in DiVA

By author/editor
Furlan, Andrej
By organisation
Thin Film PhysicsThe Institute of Technology
Other Engineering and Technologies not elsewhere specified

Search outside of DiVA

GoogleGoogle Scholar
Total: 936 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 2391 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • oxford
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf