TETRAHEDRAL AMORPHOUS CARBON FILMS: DEPOSITION METHODS, PROPERTIES AND APPLICATIONS

1. Koszalin University of Technology Institute of Mechatronics, Nanotechnology and Vacuum Technique TETRAHEDRAL AMORPHOUS CARBON FILMS: DEPOSITION METHODS, PROPERTIES AND APPLICATIONS Jan Walkowicz Vacuum and Plasma Surface EngineeringVaPSE 2009, October 22 - 26, 2009Hejnice, Czech Republic

2. Scope of the presentation Introduction: - types of diamond like carbon (DLC), - tetrahedral amorphous carbon (ta-C). Deposition methods and properties of ta-C films: - deposition mechanisms, - deposition methods, - correlation between growth conditions and properties. Application of ta-C films: - data storage devices, - medical implants, - antiwear applications. Summary.

3. Introduction

4. Introduction

5. Introduction • hydrogen-free amorphous carbon (a-C); • hydrogenated amorphous carbon (a-C:H); • tetrahedral hydrogen-free amorphous carbon (ta-C); • tetrahedral hydrogenated amorphous carbon (ta-C:H);

6. Introduction • The Association of German Engineers, Report VDI 2840, 2006:classification and nomenclature for diamond-like-carbon (DLC) and diamond films

7. Introduction Elastic properties of amorphous carbon and diamond [J. Robertson] Comparison of major properties of amorphous carbon and reference materials [J. Robertson]

8. Deposition methods and properties of ta-C films Subplantation model [J. Robertson] penetration direct knock-on (atomicpeening) relaxation • ion energy • substrate temperature

9. Deposition methods and properties of ta-C films [J. Robertson] • the energy and velocity distribution of thespecies; • the purity of the beam and nature of the species that bombard the target; • the ambient pressure during deposition.

10. Deposition methods and properties of ta-C films Plasma deposition Ion deposition Ion assisted sputtering Sputtering Cathodic Vacuum Arc Laser ablation

11. Deposition methods and properties of ta-C films Cathodic Vacuum Arc Ion deposition Laser ablation • Mass-Selected Ion Beam Deposition (MSIBD) • Pulsed laser deposition (PLD) • Filtered Cathodic Vacuum Arc (FCVA) • Filtered Pulsed Arc Discharge (FPAD) • Pulsed DC-Arc-Process (PDCAP)

12. Deposition methods and properties of ta-C films [M. Chhowalla] Ion energy range 30-400eV Max. sp3 content 90% Max. hardness70 Gpa Max. modulus 700 GPa Max. stress 10 GPa FCVA 6 GPa 10 GPa 10 GPa 30 eV 400 eV 25 nm 100 nm

13. Deposition methods and properties of ta-C films [M. Chhowalla] FCVA 75% 35% 50C 250C 110C 180C

14. Deposition methods and properties of ta-C films [M. Chhowalla] FCVA FCVA 75% FPAD ~250C 35% 50C 250C

15. Deposition methods and properties of ta-C films [N.A. Marks et al.] [B. Zheng et al.] 40 eV 80 eV 120 eV 1 eV 1 eV 70 eV • monoenergetic beams with energies of 1-100 eV, • 1 eV: a low-density film (mostly sp2 bonded atoms), • 70 eV: the majority of the bulk atoms are sp3 bonded, the density is noticeably higher, • transition from sp2-rich to sp3-rich material occurs between 7 and 30 eV, • the main growth mechanism of ta-C is atomic peening (subplantation is not the primary mechanism).

16. Deposition methods and properties of ta-C films

17. Deposition methods and properties of ta-C films • Substrate temperature and ion energy effect on the microstructure of carbon films produced using FCVA method[D.W.M. Lau et al.] • average ion energy: 10 eV – 820 eV, • DC BIAS voltage: from -25 V to -800 V, • substrate temperature: from room temperature to 640C, • deposition rate: 0.15 – 0.4 nm/s

18. Deposition methods and properties of ta-C films [D. Lau et al.] ta-C vertically oriented sp2 sheets(< 10 Ω/nm) sp3

19. Deposition methods and properties of ta-C films [D. Lau et al.] 240C

20. Deposition methods and properties of ta-C films [D. Lau et al.] 440C

21. Deposition methods and properties of ta-C films [D. Lau et al.] 640C

22. Deposition methods and properties of ta-C films [D. Lau et al.] • Temperatureinducedoriented growth of sp2-rich material • ion energy 40 eV ta-Condiamondsubstrate 120atomsdeposited 200atomsdeposited 500atomsdeposited [M. B. Taylor et al.]

23. Deposition methods and properties of ta-C films [D. Lau et al.] ta-C low stress ta-C a-C

24. Application of ta-C films DLC coatings for magnetic storage

25. Application of ta-C films Damping of surface fluctuations through impact-induced downhill currents MD simulation of the impact of 4000 atoms 0.12 [C. Casiraghi et al.]

26. Application of ta-C films DLC coatings as biocompatible materials • Blood interfacing implants: • minimal macrophage attachment, • maximal albumin/fibrinogen adsorption ratio. • Load bearing implants: • elimination of wear debris, • good biomechanical performance.

27. Application of ta-C films [W. J. Ma et al.] Macrophage morphology a-C:H (CH4) Ta-C a-C:H (C2H2) Albumin and fibrinogen adsorption Albumin/fibrinogen adsorption ratio

28. Application of ta-C films Wear debris Load bearing implant(hip joint) High energy FPAD (6 kV/13 kA/15 μs/600 eV) • acetabular caps and femoral heads made of AISI 316L, • mechanically polished (roughness of 5-10nm), • 40-100μm of ta-C (AD) deposited by FPAD, • 15 million cycles on hip joint simulator according to ISO9225 [E. Alakoski et al.]

29. Application of ta-C films DLC coatings for antiwear applications • Cutting and forming tools, automotive parts: • good hardness and adhesion, • good wear and corrosion resistance, • good high temperature toughness

30. Application of ta-C films Pulsed Arc Discharge on Carbon Target,50 Adc / 1600 A, 300 µsec

31. Application of ta-C films [W. Grimm] [A. Czyżniewski] Particle rich region Particle free region Running in process 0,5  0,15 ta-C  SHC Pulsed Arc Discharge on Carbon Target,50 Adc / 1600 A, 300 µsec

32. Application of ta-C films • Properties of SHC (ta-C) coatings [W. Grimm] • Coating thickness < 2.0 µm • Hydrogen content without H2 • Hardness: • Nano-Intender, L=10 mN > 4000 HV0.001 ...5000 HV0.001 • E-modulus > 450 GPa • Adhesion on HSS, VHM HF1 (VDI3824) • Structure ta-C • sp3-content > 70%  • Wear coefficient: • - calo, dry, WC-ball < 10-16 m3/Nm • with diamond emulsion < 10-15 m3/Nm • oscillating steel ball, dry < 10-16 m3/Nm  • Friction coefficient < 0.15

33. Application of ta-C films [W. Grimm] Tools for punching Motor components Drills

34. Application of ta-C films ta-C coatings for hardmetal woodcutting tools [M. Hakovirta] Cr/ta-Cmulti Cr/ta-Cmono Developmental Project No. UDA-POIG.01.03.01-32-052/08-00: „Hybrid technologies for woodworking tools modification”within the Operational Programme Innovative Economy POIG 2007-2013

35. Application of ta-C films [M. Hakovirta] Cr/ta-Cmulti Cr/ta-Cmono Developmental Project No. UDA-POIG.01.03.01-32-052/08-00: „Hybrid technologies for woodworking tools modification”within the Operational Programme Innovative Economy POIG 2007-2013

36. Application of ta-C films TiN/TiAlN 3,5 μm Cr/ta-Cmulti Cr/ta-Cmono Developmental Project No. UDA-POIG.01.03.01-32-052/08-00: „Hybrid technologies for woodworking tools modification”within the Operational Programme Innovative Economy POIG 2007-2013

37. Summary 1. The specific properties that distinguish the ta-C films from other DLC coatings are:- the highest content of sp3 bonding,- the highest hardness and Young modulus,- the highest level of intrinsic stress,- the highest thermal stability 2. For deposition of ta-C films the stream of energetic carbon ions is necessary. 3. The main mechanisms of ta-C growth are subplantation and atomic peening. 4. The critical parameters in ta-C films deposition is ion energy and substrate temperature. 5. Depending on deposition method ta-C films can possess properties required in electronic, biomedical and anti-wear applications.   

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