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

2. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Scope of the presentation 2.Deposition methods and properties of ta-C films: - deposition mechanisms, - deposition methods, - correlation between growth conditions and properties. 3.Application of ta-C films: - data storage devices, - medical implants, - antiwear applications. 1.Introduction: -types of diamond like carbon (DLC), -tetrahedral amorphous carbon (ta-C). 4.Summary.

3. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Introduction

4. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Introduction

5. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology 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. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Introduction The Association of German Engineers, Report VDI 2840, 2006: classification and nomenclature for diamond-like-carbon (DLC) and diamond films

7. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Introduction Comparison of major properties of amorphous carbon and reference materials [J. Robertson] Elastic properties of amorphous carbon and diamond [J. Robertson]

8. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology ion energy substrate temperature Deposition methods and properties of ta-C films Subplantation model [J. Robertson] penetration direct knock-on (atomic peening) relaxation

9. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology [J. Robertson] Deposition methods and properties of ta-C films the energy and velocity distribution of the species; the purity of the beam and nature of the species that bombard the target; the ambient pressure during deposition.

10. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films Plasma deposition Ion depositionIon assisted sputtering Sputtering Cathodic Vacuum Arc Laser ablation

11. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films Ion deposition Cathodic Vacuum Arc Laser ablation Mass-Selected Ion Beam Deposition (MSIBD) Filtered Cathodic Vacuum Arc (FCVA) Filtered Pulsed Arc Discharge (FPAD) Pulsed DC-Arc- Process (PDCAP) Pulsed laser deposition (PLD)

12. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology FCVA Deposition methods and properties of ta-C films Ion energy range 30-400 eV Max. sp 3 content 90% Max. hardness 70 Gpa Max. modulus 700 GPa Max. stress 10 GPa 30 eV 400 eV 25 nm 100 nm 6 GPa 10 GPa [M. Chhowalla]

13. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films FCVA 75% 35% 50 C 250 C 110 C 180 C [M. Chhowalla]

14. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology FCVA FPAD Deposition methods and properties of ta-C films ~250 C FCVA 75% 35% 50 C 250 C [M. Chhowalla]

15. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films 1 eV 120 eV 80 eV 40 eV 1 eV 70 eV monoenergetic beams with energies of 1-100 eV, 1 eV: a low-density film (mostly sp 2 bonded atoms), 70 eV: the majority of the bulk atoms are sp 3 bonded, the density is noticeably higher, transition from sp 2 -rich to sp 3 -rich material occurs between 7 and 30 eV, the main growth mechanism of ta-C is atomic peening (subplantation is not the primary mechanism). [B. Zheng et al.] [N.A. Marks et al.]

16. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films

17. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology 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. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films [D. Lau et al.] vertically oriented sp 2 sheets (< 10 Ω/nm) ta-C sp 3

19. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films 240 C [D. Lau et al.]

20. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films 440 C [D. Lau et al.]

21. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films 640 C [D. Lau et al.]

22. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films Temperature induced oriented growth of sp 2 -rich material ion energy 40 eV ta-C on diamond substrate 120 atoms deposited 200 atoms deposited 500 atoms deposited [D. Lau et al.] [M. B. Taylor et al.]

23. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Deposition methods and properties of ta-C films [D. Lau et al.] ta-C low stress ta-C a-C

24. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films DLC coatings for magnetic storage

25. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films Damping of surface fluctuations through impact-induced downhill currents MD simulation of the impact of 4000 atoms [C. Casiraghi et al.] 0.12

26. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology 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. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Ta-C a-C:H (CH 4 ) Albumin and fibrinogen adsorption Albumin/fibrinogen adsorption ratio Macrophage morphology Application of ta-C films a-C:H (C 2 H 2 ) [W. J. Ma et al.]

28. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology High energy FPAD (6 kV/13 kA/15 μs/600 eV) Load bearing implant (hip joint) Application of ta-C films [E. Alakoski et al.] 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 Wear debris

29. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology 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. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films Pulsed Arc Discharge on Carbon Target, 50 Adc / 1600 A, 300 µsec

31. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Running in process 0,5 0,15 Application of ta-C films Pulsed Arc Discharge on Carbon Target, 50 Adc / 1600 A, 300 µsec Particle free region Particle rich region ta-C SHC [W. Grimm] [A. Czyżniewski]

32. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films Properties of SHC (ta-C) coatings [W. Grimm] Coating thickness < 2.0 µm Hydrogen content without H 2 Hardness: Nano-Intender, L=10 mN > 4000 HV 0.001...5000 HV 0.001 E-modulus > 450 GPa Adhesion on HSS, VHM HF1 (VDI3824) Structure ta-C sp 3 -content > 70% Wear coefficient: - calo, dry, WC-ball < 10 -16 m 3 /Nm - with diamond emulsion < 10 -15 m 3 /Nm - oscillating steel ball, dry < 10 -16 m 3 /Nm Friction coefficient < 0.15

33. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films Tools for punching Motor components Drills [W. Grimm]

34. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films ta-C coatings for hardmetal woodcutting tools 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 Cr/ta-C mono Cr/ta-C multi [M. Hakovirta]

35. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films 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 Cr/ta-C mono Cr/ta-C multi [M. Hakovirta]

36. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Application of ta-C films 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 TiN/TiAlN 3,5 μm Cr/ta-C mono Cr/ta-C multi

37. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Summary 1. The specific properties that distinguish the ta-C films from other DLC coatings are: - the highest content of sp 3 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.

38. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology References 1.S. Aisenberg and R. Chabot, Journal of Applied Physics 42 (1971) 2953-2958. 2.J. Robertson, Materials Science and Engineering R 37 (2002) 129-281. 3.The Association of German Engineers, Report VDI 2840, 2006. 4.Y. Lifshitz, Diamond and Related Materials 5 (1996) 388-400. 5.M. Kamiya et al., Vacuum 83 (2009) 510–514. 6.D. W. M. Lau et al., Journal of Applied Physics 105 (2009) 084302-1-6. 7.D. W. M. Lau et al., Carbon 47 (2009) 3263–3270. 8.V-M. Tiainen, Diamond & Related Materials 17 (2008) 2071–2074. 9.M. B. Taylor et al., J. Phys.: Condens. Matter 21 (2009) 225003 (9pp). 10.B. Zheng et al., Carbon 43 (2005) 1976–1983. 11.M. Hakovirta et al., Diamond and Related Materials 4 (1995) 1335-1339. 12.M. Chhowalla, Diamond and Related Materials 10 (2001) 1011-1016. 13.J. Zhu et al., Vacuum 72 (2004) 285–290. 14.V. N. Inkin et al., Diamond and Related Materials 10 (2001) 1003-1108. 15.A. C. Ferrari et al., Diamond and Related Materials 11 (2002) 994-999. 16.E. Alakoski et al., Diamond and Related Materials 12 (2003) 2115-2118. 17.E. Alakoski et al., Diamond and Related Materials 15 (2006) 34-37. 18.J. Filik, Spectroscopy Europe 17 (2005) 10-17. 19.A. C. Ferrari and J. Robertson, Physical Review B 61 (2000) 14 095-14 107. 20.A. C. Ferrari, Diamond and Related Materials 11 (2002) 1053-1061. 21.C. Casiraghi et al., Materials Today 10 (2007) 44-53. 22.C. Casiraghi et al., Diamond and Related Materials 14 (2005) 913-920. 23.A. C. Ferrari, Surface and Coatings Technology 180 –181 (2004) 190–206. 24.J. Robertson, Tribology International 36 (2003) 405–415. 25.A. Grill, Diamond and Related Materials 12 (2003) 166–170. 26.Q. Zhao et al. Journal of Colloid and Interface Science 280 (2004) 174-183. 27.W. J. Ma et al. Biomaterials 28 (2007) 1620-1628. 28.E. Alakoski et al., The Open Orthopaedics Journal, 2008, 2, 43-50. 29.M. Hakovirta, Diamond and Related Materials 8 (1999) 1225–1228. 30.M. G. Faga and L. Settineri, Surface and Coatings Technology 201 (2006) 3002–3007. Acknowledgements: Publication part-financed by the European Union within the European Regional Development Fund

39. Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology Thank you for your attention!