Fluorine-doped diamond-like coatings

• US 6,468,642 B1
• Filed: 12/02/1998
• Issued: 10/22/2002
• Est. Priority Date: 10/03/1995
• Status: Expired due to Term

• Current Assignee: Sulzer Metaplas GmbH
• Original Assignee: NV Bekaert SA
• Inventors: Bray, Donald J., Venkatraman, Chandra, Goel, Arvind, Outten, Craig A., Halter, Christopher
• Primary Examiner(s): TURNER, ARCHENE A
• Application Number:
  US09/204,441
• Time in Patent Office: 1,420 Days
• Field of Search: 428/408, 428/336, 428/457, 428/216
• US Class Current: 428/216
• CPC Class Codes: B26B 21/60 by the coating material
• CPC Class Codes: C23C 16/0245 by etching with a plasma
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/26 Deposition of carbon only
• CPC Class Codes: Y10T 428/24975 No layer or component greater than 5 mils thick
• CPC Class Codes: Y10T 428/265 1 mil or less
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

The invention relates to fluorine-doped coatings which include a diamond-like composition containing carbon, silicon, oxygen, hydrogen, and fluorine on various substrates. Preferred substrates include flexible substrates, precision-edged substrates, and electrosurgical instruments. The present invention also relates to a method of making a substrate coated with a fluorine-doped diamond-like coating which includes positioning the substrate in a vacuum coating chamber and depositing a diamond-like composition containing carbon, silicon, oxygen, hydrogen, and fluorine onto the substrate by co-deposition of clusterless particle beams comprised of ions, atoms, or radicals of the carbon, silicon, oxygen, hydrogen, and fluorine, the mean free path of each particle species being in excess of the distance between its source and the growing particle coating surface of the substrate.

Claims

1. An article comprising a substrate coated with a fluorine-doped coating, wherein said coating comprises a diamond-like composition comprised of carbon, silicon, oxygen, hydrogen, and fluorine and wherein the coating has a hardness of from about 5 to about 32 GPa and a surface energy of from about 19 to about 29 dyne/cm.

2. An article according to claim 1, wherein the coating is amorphous.

3. An article according to claim 1, wherein the carbon is bonded to hydrogen or fluorine.

4. An article according to claim 1, wherein the silicon is bonded to oxygen.

5. An article according to claim 1, wherein the fluorine-doped coating has a surface energy of from about 19.5 dyne/cm to about 26 dyne/cm.

6. An article according to claim 5, wherein the flexible substrate is a polymeric film.

7. An article according to claim 6, wherein the polymeric film is selected from the group consisting of polyimide, polyester, polythermide, polyamide-imide and polyethylene terephthalate films.

8. An article according to claim 7, wherein the fluorine-doped coating further comprises an additional dopant.

9. An article according to claim 8, wherein the additional dopant is selected from the group consisting of elements from groups Ib-VIIb and VIII of the periodic table.

10. An article according to claim 9, wherein the additional dopant is selected from the group consisting of B, Si, Ge, Te, O, Mo, W, Ta, Nb, Pd, Ir, Pt, V, Fe, Co, Mg, Mn, Ni, Ti, Zr, Cr, Re, Hf, Cu, Al, N, Ag and Au.

11. An article according to claim 10, wherein the additional dopant is titanium.

12. An article according to claim 5, wherein the fluorine-doped coating has a thickness from about 0.005 micrometers to about 10 micrometers.

13. An article according to claim 5, wherein the carbon, hydrogen, silicon, oxygen and fluorine are obtained from the decomposition of an organosiloxane having from about 1 to about 10 silicon atoms.

14. An article according to claim 13, wherein the organosiloxane is polytrifluoropropylmethylsiloxane.

15. An article according to claim 13, wherein the organosiloxane is poly-3,3,3-trifluoropropylmethylsiloxane-(50%) dimethylsiloxane copolymer.

16. An article according to claim 5, wherein the carbon content of the fluorine-doped coating is from about 40 wt. % to about 98 wt. %.

17. An article according to claim 5, wherein the carbon to silicon weight ratio of the fluorine-doped coating is from about 4:

1 to about 9;

1.

18. An article according to claim 5, wherein the silicon to oxygen weight ratio of the fluorine-doped coating is from about 0.6:

1 to about 1.7;

1.

19. An article according to claim 5, wherein the carbon content of the fluorine-doped coating is at least 40 atomic % of the fluorine-doped coating, the hydrogen content is up to about 40 atomic % of the carbon, and the sum of the silicon, oxygen and dopants together is greater than about 2 atomic % of the coating.

20. An article according to claim 5, wherein the fluorine-doped coating has a dielectric strength from about 1 MV/cm to about 4 MV/cm.

21. An article according to claim 5, wherein the fluorine-doped coating has a resistivity from about 10¹⁴ ohm-cm to about 10⁻

2 ohm-cm.

22. An article according to claim 5, wherein the fluorine-doped coating has a surface energy from about 19.5 dyne/cm to about 26 dyne/cm.

23. An article according to claim 5, wherein the fluorine-doped coating has a water contact angle from about 80°

to about 101°

.

24. An article according to claim 1, wherein the substrate is a precision-edged substrate.

25. An article according to claim 24, wherein the precision-edged substrate comprises a metal.

26. An article according to claim 24, wherein the precision-edged substrate comprises a non-metal.

27. An article according to claim 24, wherein the substrate is selected from the group consisting of industrial tools, surgical instruments, knives and razors.

28. An article according to claim 27, wherein the substrate is a razor blade.

29. An article according to claim 24, wherein the fluorine-doped coating further comprises an additional dopant.

30. An article according to claim 29, wherein the additional dopant is selected from the group consisting of elements from groups Ib-VIIb and VIII of the periodic table.

31. An article according to claim 30, wherein the additional dopant is selected from the group consisting of B, Si, Ge, Te, O, Mo, W, Ta, Nb, Pd, Ir, Pt, V, Fe, Co, Mg, Mn, Ni, Ti, Zr, Cr, Re, Hf, Cu, Al, N, Ag, and Au.

32. An article according to claim 24, wherein the fluorine-doped coating is deposited on the substrate to a thickness from about 5 nm to about 12 micrometers.

33. An article according to claim 24, wherein the coating is deposited on the substrate to a thickness from about 5 nm to about 150 nm.

34. An article according to claim 24, wherein the fluorine-doped coating is deposited directly into the substrate without an interlayer.

35. An article according to claim 24, wherein the carbon, hydrogen, silicon, oxygen and fluorine are obtained from the decomposition of an organosiloxane having from about 1 to about 10 silicon atoms.

36. An article according to claim 35, wherein the organosiloxane is polytrifluoropropylmethylsiloxane.

37. An article according to claim 35, wherein the organosiloxane is poly-3,3,3-trifluoropropylmethylsiloxane-(50%) dimethylsiloxane copolymer.

38. An article according to claim 24, wherein the carbon content of the fluorine-doped coating is from about 40 wt. % to about 98 wt. %.

39. An article according to claim 24, wherein the carbon to silicon weight ratio of the fluorine-doped coating is from about 2:

1 to about 8;

1.

40. An article according to claim 24, wherein the silicon to oxygen weight ratio of the fluorine-doped coating is from about 0.5:

1 to about 3;

1.

41. An article according to claim 24, wherein the carbon content of the fluorine-doped coating is at least 40 atomic % of the fluorine-doped coating, the hydrogen content is up to about 40 atomic % of the carbon, and the sum of the silicon, oxygen and dopants together is greater than about 2 atomic % of the coating.

42. An article according to claim 24, wherein the fluorine-doped coating has a resistivity from about 10¹⁴ ohm-cm to about 10⁻

2 ohm-cm.

43. An article according to claim 24, wherein the fluorine-doped coating has a water contact angle from about 80°

to about 101°

.

44. An article according to claim 1, wherein the substrate is an electrosurgical instrument.

45. An article according to claim 44, wherein the electrosurgical instrument is selected from the group consisting of electrosurgical blades, bipolar forceps, laparoscopic instruments, dental brackets, and biomedical devices.

46. An article according to claim 44, wherein the electrosurgical instrument is a precision-edged substrate.

47. An article according to claim 44, wherein the fluorine-doped coating further comprises an additional dopant.

48. An article according to claim 47, wherein the additional dopant is selected from the group consisting of elements from groups Ib-VIIb and VIII of the periodic table.

49. An article according to claim 48, wherein the additional dopant is selected from the group consisting of B, Li, Na, Si, Ge, Te, O, Mo, W, Ta, Nb, Pd, Ir, Pt, V, Fe, Co, Mg, Mn, Ni, Ti, Zr, Cr, Re, Hf, Cu, Al, N, Ag, Au, TiN, BN, AlN, ZrN and CrN.

50. An article according to claim 44, wherein the fluorine-doped coating is deposited to a thickness from about 0.5 μ

m to about 5 μ

m.

51. An article according to claim 44, wherein the fluorine-doped coating is deposited to a thickness from about 2 μ

m to about 3 μ

m.

52. An article according to claim 44, wherein the carbon, hydrogen, silicon and oxygen are obtained from the decomposition of an organosiloxane having from about 1 to about 10 silicon atoms.

53. An article according to claim 52, wherein the organosiloxane is polytrifluoropropylmethylsiloxane.

54. An article according to claim 52, wherein the organosiloxane is poly-3,3,3-trifluoropropylmethylsiloxane-(50%) dimethylsiloxane copolymer.

55. An article according to claim 44, wherein the carbon content of the fluorine-doped coating is from about 40 wt. % to about 98 wt. %.

56. An article according to claim 44, wherein the carbon to silicon weight ratio of the fluorine-doped coating is from about 2:

1 to about 8;

1.

57. An article according to claim 44, wherein the silicon to oxygen weight ratio of the fluorine-doped coating is from about 0.5:

1 to about 3;

1.

58. An article according to claim 44, wherein the carbon content of the fluorine-doped coating is at least 40 atomic % of the fluorine-doped coating, the hydrogen content is up to about 40 atomic % of the carbon, and the sum of the silicon, oxygen and dopants together is greater than about 2 atomic % of the coating.

59. An article according to claim 44, wherein the article has an impedance from about 1 ohm to about 1000 ohms.

60. An article according to claim 44, wherein the fluorine-doped coating has a resistivity from about 10⁻

2 ohm-cm to about 10¹⁵ ohm-cm.

61. An article according to claim 44, wherein the fluorine-doped coating has a water contact angle from about 80°

to about 101°

.