Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology TETRAHEDRAL AMORPHOUS CARBON FILMS: DEPOSITION METHODS,

Institute of MechatronicsInstitute of Mechatronics,,Nanotechnology Nanotechnology and Vacuum Techniqueand Vacuum Technique

Koszalin University of Technology

TETRAHEDRAL AMORPHOUS CARBON FILMS:

DEPOSITION METHODS, PROPERTIES AND APPLICATIONS

Jan Walkowicz

Institute of Mechatronics, Institute of Mechatronics, NanotechnologyNanotechnologyand Vacuum Techniqueand Vacuum Technique

Koszalin University Koszalin University of Technologyof Technology

Vacuum and Plasma Surface Engineering VaPSE 2009, October 22 - 26, 2009 Hejnice, Czech Republic

Institute of Mechatronics, Nanotechnology and Vacuum Technique


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.



Introduction



Introduction



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);



Introduction

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



Introduction

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



ion energy substrate

temperature

Deposition methods and properties of ta-C films

Subplantation model[J. Robertson]

penetration

direct

knock-on(atomicpeening)

relaxation



[J. Robertson]


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.




Plasma deposition Ion deposition Ion assisted sputtering

Sputtering Cathodic Vacuum Arc Laser ablation




Ion depositionCathodic 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)



FCVA


Ion energy range 30-400 eVMax. sp3 content 90%Max. hardness 70 GpaMax. modulus 700 GPa

Max. stress 10 GPa

30 eV 400 eV

25 nm 100 nm

6 GPa 10 GPa

10 GPa

[M. Chhowalla]




FCVA

75%

35%

50C 250C

110C 180C

[M. Chhowalla]



FCVA

FPAD


~250C

FCVA

75%

35%

50C 250C

[M. Chhowalla]




1 eV

120 eV80 eV40 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).

[B. Zheng et al.] [N.A. Marks et al.]






Deposition methods and properties of ta-C filmsSubstrate 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 640C,

deposition rate: 0.15 – 0.4 nm/s



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

vertically oriented

sp2 sheets(< 10 Ω/nm)

ta-C

sp3




240C

[D. Lau et al.]




440C

[D. Lau et al.]




640C

[D. Lau et al.]




Temperature induced oriented growth of sp2-rich material

ion energy 40 eV

ta-Con

diamondsubstrate

120atoms

deposited

200atoms

deposited

500atoms

deposited

[D. Lau et al.]

[M. B. Taylor et al.]



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

ta-Clow stress ta-C

a-C



Application of ta-C films

DLC coatings for magnetic storage




Damping of surface fluctuations through impact-induced downhill

currents

MD simulation of the impact of 4000 atoms

[C. Casiraghi et al.]

0.12




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.



Ta-C a-C:H (CH4)

Albumin and fibrinogen adsorption Albumin/fibrinogen adsorption ratio

Macrophage morphology


a-C:H (C2H2)

[W. J. Ma et al.]



High energy FPAD (6 kV/13 kA/15 μs/600 eV)

Load bearing implant(hip joint)


[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




DLC coatings for antiwear applications

Cutting and forming tools, automotive parts:

good hardness and adhesion,

good wear and corrosion resistance,

good high temperature toughness




Pulsed Arc Discharge on Carbon Target, 50 Adc / 1600 A, 300 µsec



Running in process 0,5 0,15


Pulsed Arc Discharge on Carbon Target, 50 Adc / 1600 A, 300 µsec

1000 1200 1400 1600 18000

1000

2000

3000

4000

1562

1391ID/I

G = 1,25

inte

nsity

[a.u

.]

Raman schift [cm-1]

Particle free region

1000 1200 1400 1600 18000

1000

2000

3000

4000

5000

ID/I

G = 1,22

1581

1495

1346

inte

nsity

[a.u

.]

Raman schift [cm-1]

Particle rich region

ta-C SHC

[W. Grimm][A. Czyżniewski]




Properties of SHC (ta-C) coatings [W. Grimm] Coating thickness < 2.0 µmHydrogen content without H2

Hardness:Nano-Intender, L=10 mN > 4000 HV0.001 ...5000 HV0.001

E-modulus > 450 GPaAdhesion on HSS, VHM HF1 (VDI3824)Structure ta-Csp3-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




Toolsforpunching

Motor components

Drills

[W. Grimm]




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-CmonoCr/ta-Cmulti

[M. Hakovirta]






[M. Hakovirta]





TiN/TiAlN 3,5 μm




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.



References1. 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

Institute of MechatronicsInstitute of Mechatronics,,Nanotechnology Nanotechnology and Vacuum Techniqueand Vacuum Technique


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Institute of Mechatronics, Nanotechnology and Vacuum Technique Koszalin University of Technology TETRAHEDRAL AMORPHOUS CARBON FILMS: DEPOSITION METHODS,

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