1. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 1 Witold Gulbiński Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology, PL Carbon-based nanocomposite thin films – deposition, structure and properties Carbon-Based Nanostructured Composite and Nanolaminated Films

2. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 2 Carbon-based nanocomposite thin films – deposition, structure and properties OUTLINE Carbon films – DLC: taC, aC, aC:H Carbon films – DLC: taC, aC, aC:H Carbon-based nanocomposite thin films (CBNTF) – the design concept Carbon-based nanocomposite thin films (CBNTF) – the design concept Deposition methods Deposition methods Structure and properties of nanocomposite thin films Structure and properties of nanocomposite thin films Carbide containing MeC x -taC and MeC x -aC:H films (Me = Si, Ti, V, W, Mo…) Carbide containing MeC x -taC and MeC x -aC:H films (Me = Si, Ti, V, W, Mo…) Metal containing Me-taC:H and Me-aC:H (Me=Co, Ni, Cu, Ag, Au…) Metal containing Me-taC:H and Me-aC:H (Me=Co, Ni, Cu, Ag, Au…) Comments on applications Comments on applications Concluding remarks Concluding remarks

3. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 3 A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and amorphous carbon, Phys. Rev. B 61 (20) (2000) 14095. Carbon-based nanocomposite thin films – deposition, structure and properties The bombardment of energetic carbon species during deposition is critical for the growth of DLC films. The ion energy is the most important parameter for determining the characteristics of DLC films. The ion bombardment tends to result in the highly-dense packing of carbon atoms in the film, yielding a very high compressive stress therein. A very high compressive stress tends to detach the film from the substrate, when the film thickness increases above a critical value. The internal stress can be reduced by different mechanisms.

4. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 4 A.C. Ferrari, J. Robertson, Interpretation of Raman spectra of disordered and amorphous carbon, Phys. Rev. B 61 (20) (2000) 14095. G peak position and I(D)/I(G) ratio vs sp 3 fraction for as-deposited a-C:H. Carbon-based nanocomposite thin films – deposition, structure and properties

5. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 5 Carbon-based nanocomposite thin films – deposition, structure and properties taC Al Ni Co Cu Ag, Au Ti Cr V Mo Ta Zr W MeC x -taC Me-taC Si taC:H aC:H Ti Cr V Mo Ta Zr W Me-taC:H MeC x -taC:H Me-aC:H MeC x -aC:H Al Ni Co Cu Ag, Au Si

6. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 6 Carbon-based nanocomposite thin films – deposition, structure and properties REQUIREMENTS for tribological coatings -high toughness (high strength + ductility): ability to support high loads in sliding/rolling contact -low friction -high hardness -high adhesion -chemical and tribochemical stability

7. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 7 Carbon-based nanocomposite thin films – deposition, structure and properties How to do that? - Embed grains of hard phase (TM carbides) in a softer matrix (aC or aC:H), allowing for high ductility due to grain boundary sliding Carbon based nanocomposite coatings - the way to increase toughness and wear resistance accompanied by low friction

8. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 8 Carbon-based nanocomposite thin films – deposition, structure and properties Design concepts of tough nanocomposite coatings: Encapsulation of 3-10 nm sized hard crystalline grains in an amorphous matrix restricts dislocation activity, diverts and arrests macro-crack development. A large volume fraction of grain boundaries provides ductility through grain boundary sliding and nano-cracking along grain/matrix interfaces. A graded interface layer is usually applied between the substrate and crystalline/amorphous composite coating to enhance adhesion strength and relieve stresses (combination of functional gradient and nanocomposite design) A.A. Voevodin, Tsinghua Science and Technology, 10 (2005) 665-679

9. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 9 Carbon-based nanocomposite thin films – deposition, structure and properties (111) (200) (220) (311) (222) (400) (420) (422) (111) (200) (220) (311) (222) (400) (420) Nanocrystalline MeC x x crystallites < 20 nm Nanocomposite MeC-aC;H x crystallites < 10 nm Nanocomposite MeC-aC;H x crystallites < 4 nm Powłoki nanokompozytowe typu XC/a-C:H krystality < 10 nm b) d) c) a) Up to 10 % a-C:H 10- 70 % a-C:H 70- 95 % a-C:H MeC x aC:H TiC d = 8-10nm TiC-aC:H d = 4-6nm H = 32 GPa, μ = 0.35 Ti48C40H9(O,N.Ar)3 TiC-aC:H d = <4nm H = 42 GPa, μ = 0.26 Ti38C52H6(O,N.Ar)4 H = 15 GPa, μ = 0.06 Ti6C72H21(O,N.Ar)1 A. Czyżniewski et al., Journal of Materials Processing Technology 157–158 (2004) 274–283

10. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 10 Carbon-based nanocomposite thin films – deposition, structure and properties 3-10 nm crystalline grains (TiC) embedded in an amorphous matrix (aC). The grains are separated by 1-3 nm. A.A. Voevodin, Tsinghua Science and Technology, 10 (2005) 665-679 From scratch test Film thickness: 1 μm Load: 10N! Indentation depth: 9 μm! TiC-aC restriction of dislocation activity, macro-cracking blocked, ductility through grain boundary sliding, nanocracking along grain-matrix interfaces

11. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 11 Carbon-based nanocomposite thin films – deposition, structure and properties MeC x - or Me-taC Magnetron sputtering (multisource: Me & C or segment targets) Ion beam sputtering (multitarget) Filtered cathodic vacuum arc Pulsed laser ( ns, fs) - segment targets or multitarget geometries taC Al Ni Co Cu Ag, Au Ti Cr V Mo Ta Zr W MeC x -taC Me-taC Si Deposition of CBNTF

12. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 12 Carbon-based nanocomposite thin films – deposition, structure and properties MeC x - or Me-aC:H CVD, PECVD (RF, MV-ECR) Reactive magnetron sputtering (multisource: Me targets) Other techniques usually linking two or more techniques listed above (DMWECR + Sputtering) taC:H aC:H Ti Cr V Mo Ta Zr W Me-taC:H MeC x -taC:H Me-aC:H MeC x -aC:H Al Ni Co Cu Ag, Au Si Deposition of CBNTF

13. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 13 Carbon-based nanocomposite thin films – deposition, structure and properties Filtered vacuum arc of graphite with simultaneous magnetron sputtering of Si. Si-taC films Churl Seung Lee et al., Diamond and Related Materials 11 (2002) 198–203

14. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 14 Si incorporated into tetrahedral amorphous carbon (aSiC-taC) Churl Seung Lee et al., Diamond and Related Materials 11 (2002) 198–203 sp 3 /sp 2 Carbon-based nanocomposite thin films – deposition, structure and properties

15. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 15 B.K. Tay et al., Diamond and Related Materials 10 (2001) 1082-1087 (Al or Ti – taC) D. Sheeja et al., Diamond and Related Materials 12 (2003) 2032–2036 (Al -taC) S. Zhang et al., Thin Solid Films 482 (2005) 138– 144 (Ti+Al – taC) Me-taC, Me =Al, Ti films Carbon films were deposited by the off-plane double- bend filtered cathodic vacuum arc from metal doped graphite target. sp 3 /sp 2 ncTiC-taC Al-taC Carbon-based nanocomposite thin films – deposition, structure and properties

16. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 16 WC x -WS 2 -aC adaptive nanocomposite films (for vacuum applications) Andrey A. Voevodin et al., Surface and Coatings Technology 116–119 (1999) 36–45 KrF excimer laser + MS S - 0 at.% S - 15 at.% S - 29 at.% PLD: Graphite + MS: (W, WS 2 ) Carbon-based nanocomposite thin films – deposition, structure and properties

17. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 17 WS 2 lubrication Graphite lubrication Carbon-based nanocomposite thin films – deposition, structure and properties

18. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 18 A. Czyżniewski et al., Journal of Materials Processing Technology 157–158 (2004) 274–283 Ti, W, Si – aC:H nanocomposite films Carbon-based nanocomposite thin films – deposition, structure and properties

19. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 19 A. Czyżniewski et al., Journal of Materials Processing Technology 157–158 (2004) 274–283 Ti, W, Si – aC:H nanocomposite films Carbon-based nanocomposite thin films – deposition, structure and properties

20. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 20 C 1s C-C C-Ti W. Gulbiński et al., Applied Surface Science 239 (2005) 302–310 TiC– aC:H nanocomposite films Carbon-based nanocomposite thin films – deposition, structure and properties

21. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 21 W. Gulbiński et al., Applied Surface Science 239 (2005) 302–310 Carbon-based nanocomposite thin films – deposition, structure and properties TiC– aC:H nanocomposite films

22. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 22 P. Zhang, Diamond and Related Materials 13 (2004) 459–464 Me-aC where Me = Al, Ti, Ni, Si, were prepared by the filtered cathodic vacuum arc technique with metal-carbon (5 at.% metal) composite targets.Hydrophobic Θ>70 0 Hydrophilic Θ<70 0 aC Carbon-based nanocomposite thin films – deposition, structure and properties

23. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 23 Q.F. Huang et al., Diamond and Related Materials 9 (2000) 534–538 MoC x -aC:H nanocomposite films Carbon-based nanocomposite thin films – deposition, structure and properties

24. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 24 Ion beam co-sputtering of graphite target having a nickel chip attached to its surface. F. C. Fonseca et al., JOURNAL OF APPLIED PHYSICS 97 (2005) 044313 Films were deposited on polished Si wafers heated to 350 °C. (above Ni 3 C decomposition temperature) Ni concentration: 5 to 22 wt % Ni-aC films with superparamagnetic properties Carbon-based nanocomposite thin films – deposition, structure and properties

25. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 25 F. C. Fonseca et al., JOURNAL OF APPLIED PHYSICS 97 (2005) 044313 Normalized magnetization as a function of H/T at temperatures of 100, 150, 200, 250 and 300 K Ni grain size distribution Carbon-based nanocomposite thin films – deposition, structure and properties T B = 13K H c =0

26. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 26 The films deposited below 400 C showed a columnar structure of hexagonal Ni 3 C type crystalline grains embedded in a matrix consisting of an amorphous and/or graphite-like carbon. T s = 20 0 C K. Sedlackova, P. Lobotka, I. Vavra, G. Radnoczi, Carbon 43 (2005) 2192–2198 Ni 3 C-aC films by DC MS of Ni and C 30 at% Ni 18 at% Ni Carbon-based nanocomposite thin films – deposition, structure and properties

27. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 27 Above T S = 400 C the composite consists of globular fcc Ni grains sized between 50 and 100 nm that were separated by the Fullerene-like carbon phase. T s = 400 0 C K. Sedlackova, P. Lobotka, I. Vavra, G. Radnoczi, Carbon 43 (2005) 2192–2198 Ni-aC films 30 at% Ni Carbon-based nanocomposite thin films – deposition, structure and properties

28. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 28 Co-taC nanocomposite films (Co 65 at.% -taC) with ferromagnetic properties Hao Wang et al., Materials Science and Engineering C 16 (2001) 147–151 Carbon-based nanocomposite thin films – deposition, structure and properties

29. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 29 Co-taC nanocomposite films (Co: 65 at.%) with ferromagnetic properties The most important advantage of carbon encapsulation is the increase of the effective distance of neighbouring magnetic grains so that the exchange coupling between them is weakened or eliminated. As dep. 350 0 C 400 0 C Hao Wang et al., Materials Science and Engineering C 16 (2001) 147–151 C 1s XPS Carbon-based nanocomposite thin films – deposition, structure and properties

30. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 30 As deposited 300 0 C 350 0 C 400 0 C Magnetic Force Microscopy Hao Wang et al., Materials Science and Engineering C 16 (2001) 147–151 Co-taC nanocomposite films Magnetization loop Carbon-based nanocomposite thin films – deposition, structure and properties

31. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 31 0 at.% Cu σ = 2.9 GPa μH = 22 GPa 0.7 GPa 16 GPa 11 at.% Cu C.-C. Chen, F.C.-N. Hong, Applied Surface Science 242 (2005) 261–269 Cu-aC:H nc thin films (RF PECVD + Cu sputtering) Copper was used to: -prevent the formation of bonds between the nanocrystallite and the carbon matrix, -facilitate grain–matrix interface sliding, which increases the films ductility. Carbon-based nanocomposite thin films – deposition, structure and properties

32. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 32 Cu-aC:H 16 at.% Cu C.-C. Chen, F.C.-N. Hong, Applied Surface Science 242 (2005) 261–269 Carbon-based nanocomposite thin films – deposition, structure and properties

33. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 33 Ag-aC:H nanocomposite films Silver within a diamondlike carbon–silver nanocomposite film may provide antimicrobial functionality to a medical devices. Silver nanoparticles are highly toxic to microorganisms, and demonstrate biocidal effects against: Staphylococcus aureus, Escherichia coli, Pseudomonas aeruginosa, Listeria monocytogenes and other species of bacteria. The exact mechanism of action of silver is unknown, but it is believed that silver ions act by binding to DNA, interfering with electron transport within cells, and injuring bacterial enzymes. R.B. Thurman, C.P. Gerba, CRC Crit. Rev. Environ. Control 18 (2000) 295 Carbon-based nanocomposite thin films – deposition, structure and properties

34. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 34 R.J. Narayan, Diamond & Related Materials 14 (2005) 1319–1330 10 nm self-assembled morphology Ag-taC TiC-taC 32 GPa μ = 0.15 29 GPa μ = 0.10 Excimer laser KrF, 248nm, 25ns, 10Hz, 5J/cm 2 Ag Ti Coalescence of Ag clusters Carbon-based nanocomposite thin films – deposition, structure and properties

35. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 35 Pulsed laser deposition of Ag-taC nanocomposites Graphite Ag Laser beam P.A. Patsalas, ESF Exploratory Workshop, Carbon-based nanostructured composite films August 2006, Gdansk, Poland Carbon-based nanocomposite thin films – deposition, structure and properties

36. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 36 P.A. Patsalas, ESF Exploratory Workshop, Carbon-based nanostructured composite films August 2006, Gdansk, Poland Pulsed laser deposition of Ag-taC nanocomposites Ag _ + Carbon-based nanocomposite thin films – deposition, structure and properties

37. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 37 Ag P.A. Patsalas, ESF Exploratory Workshop, Carbon-based nanostructured composite films August 2006, Gdansk, Poland Pulsed laser deposition of Ag-taC nanocomposites Carbon-based nanocomposite thin films – deposition, structure and properties

38. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 38 Ag P.A. Patsalas, ESF Exploratory Workshop, Carbon-based nanostructured composite films August 2006, Gdansk, Poland Pulsed laser deposition of Ag-taC nanocomposites Carbon-based nanocomposite thin films – deposition, structure and properties

39. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 39 MeSi-aC:H; Me=Mo, Cr V.K. Dmitriev et al.. Diamond and Related Materials 10 (2001) 1007-1010 Silicon-organic liquid – Plasma Polymerized Methyl Silane (PPMS) was used as a plasma-forming substance of the open plasmatron. (C 2 H 5 ) 3 SiO[CH 3 C 6 H 5 SiO] 3 Si(CH 3 ) 3 Mo, Cr IR radiation source or thermostable resistors CrSi-aC:H Carbon-based nanocomposite thin films – deposition, structure and properties

40. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 40 MeSi-aC:H; Me=Mo, Cr V.K. Dmitriev et al., Diamond and Related Materials 10 (2001) 1007-1010 Mo, Cr Stability test: 1 year at 800 0 C in air Carbon-based nanocomposite thin films – deposition, structure and properties

41. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 41 SEM micrograph of two-level Cu wiring with DLC dielectric ρ = 10 16 Ωcm ULSI chips Films with dielectric constant values between 3.3 and 2.7. Incorporation of fluorine in FDLC films produces a material of apparently higher thermal stability and further reduced dielectric constant, to values even lower then 2.4 A. Grill, Diamond and Related Materials 10 (2001) 234-239 R.F. plasma-assisted PACVD in a parallel plate reactor. P = CV 2 f Low-k interconnect dielectric Carbon-based nanocomposite thin films – deposition, structure and properties a-C:(H+F)

42. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 42 Microwave radiation absorption Co-aC:H films deposited by magnetron sputtering on aramide tissue (20-61 at.% Co) up to percolation threshold. Superparamagnetic state at RT Co-aC:H sputtering on aramide (aromatic polymer - polyamide) tissues provides flexible and durable electromagnetic absorption coverings. L.V. Lutsev et al., JOURNAL OF APPLIED PHYSICS 97 (2005) 104327 Al 2 O 3 Substrate aramide tissue Co(60 at.%)-aC:H Carbon-based nanocomposite thin films – deposition, structure and properties

43. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 43 Concluding remarks CBNTF can be deposited by well known PVD (MS, VArc, PLD) and CVD (PACVD) methods In tribological applications CBNTF show: friction coefficient below 0.1 - can be achieved in vacuum and under humid conditions, low wear, hardness in the range from 10-40GPa, low residual stresses and good adhesion, high cohesive toughness. For CBNTF containing ferromagnetic metals (Ni, Co), superparamagnetic as well as ferromagnetic behaviour is observed dependent on metal cluster size. Dielectric properties of CBNTF can be tuned form low to high k values. Surface wetting properties of CBNTF can be modified by metal doping. Silver conataining CBNTF show a potential for antibacterial applications. Due to chemical inertness and biocompatibility, CBNTF are candidates for medical applications. Carbon-based nanocomposite thin films – deposition, structure and properties

44. Hybrid technologies for woodworking tools modification within the Operational Programme Innovative Economy POIG 2007-2013 Koszalin University of Technology 44 Thank you for your kind attention Carbon-based nanocomposite thin films – deposition, structure and properties