Coated article including titanium oxycarbide and method of making same

• US 20040180216A1
• Filed: 03/11/2003
• Published: 09/16/2004
• Est. Priority Date: 03/11/2003
• Status: Active Grant

• Current Assignee: Guardian Glass LLC (KOCH Industries Incorporated)
• Original Assignee: Guardian Industries Corporation (KOCH Industries Incorporated)
• Inventors: Thomsen, Scott V., Petrmichl, Rudolph Hugo, Veerasamy, Vijayen S.
• Granted Patent: US 7,052,585 B2
• Time in Patent Office: Days
• US Class Current: 428/432
• CPC Class Codes: C03C 17/22 with other inorganic material C03C17/34, C03C17/44 take precedence
• CPC Class Codes: C03C 17/2456 Coating containing TiO2
• CPC Class Codes: C03C 2217/212 TiO2
• CPC Class Codes: C03C 2217/282 Carbides, silicides
• CPC Class Codes: C03C 2218/154 by sputtering
• CPC Class Codes: C03C 2218/32 After-treatment
• CPC Class Codes: C23C 14/06 characterised by the coating material C23C14/0021 , C23C14/04 take precedence
• CPC Class Codes: C23C 14/083 of refractory metals or yttrium
• CPC Class Codes: C23C 14/48 Ion implantation
• CPC Class Codes: C23C 14/5833 Ion beam bombardment
• CPC Class Codes: Y10T 428/30 Self-sustaining carbon mass or layer with impregnant or other layer
• CPC Class Codes: Y10T 428/31 Surface property or characteristic of web, sheet or block

Abstract

A coated article is provided which includes a layer including titanium oxycarbide. In order to form the coated article, a layer of titanium oxide is deposited on a substrate by sputtering or the like. After sputtering of the layer including titanium oxide, an ion beam source(s) is used to implant at least carbon ions into the titanium oxide. When implanting, the carbon ions have sufficient ion energy so as to knock off oxygen (O) from TiO_x molecules so as to enable a substantially continuous layer comprising titanium oxycarbide to form near a surface of the previously sputtered layer.

Claims

1. A method of making a coated article, the method comprising:

providing a glass substrate;

sputtering a layer comprising titanium oxide TiO_x (where x is from 1 to

     3) on the substrate, thereby forming a sputtered layer; and

utilizing at least one ion source using anode-cathode voltage of at least about 1,500 V to cause at least carbon ions to be directed toward the sputtered layer comprising titanium oxide so that at least some of the carbon ions are implanted into the sputtered layer to a depth of at least 25 Å

below a surface of the sputtered layer.

2. The method of claim 1, wherein said carbon ions are implanted into the sputtered layer so as to form a substantially continuous layer comprising titanium oxycarbide proximate the surface of the sputtered layer.

3. The method of claim 1, wherein said ion source uses anode-cathode voltage of at least about 2,000 V to cause said carbon ions to be directed toward the sputtered layer.

4. The method of claim 1, wherein said ion source uses anode-cathode voltage of at least about 3,500 V to cause said carbon ions to be directed toward the sputtered layer.

5. The method of claim 1, wherein said ion source uses anode-cathode voltage sufficient to cause at least some of the carbon ions directed toward the sputtered layer to have an ion energy of at least about 200 eV per carbon ion.

6. The method of claim 1, wherein said ion source uses anode-cathode voltage sufficient to cause at least some of the carbon ions directed toward the sputtered layer to have an ion energy of at least about 375 eV per carbon ion.

7. The method of claim 1, wherein said ion source uses anode-cathode voltage sufficient to cause at least some of the carbon ions directed toward the sputtered layer to have an ion energy of at least about 500 eV per carbon ion.

8. The method of claim 1, wherein said ion source uses anode-cathode voltage sufficient to cause at least some of the carbon ions directed toward the sputtered layer to have an ion energy of at least about 625 eV per carbon ion.

9. The method of claim 1, wherein said ion source uses anode-cathode voltage sufficient to cause at least some of the carbon ions to be implanted into the sputtered layer at a depth of at least 50 Å

below the surface of the sputtered layer.

10. The method of claim 1, wherein said ion source uses anode-cathode voltage sufficient to cause at least some of the carbon ions to be implanted into the sputtered layer at a depth of at least 100 Å

below the surface of the sputtered layer.

11. The method of claim 1, wherein the coated article has a contact angle θ

of no greater than about 20 degrees.

12. The method of claim 1, wherein the coated article has a contact angle θ

of no greater than about 15 degrees.

13. The method of claim 1, further comprising directing visible light toward the coated article which visible light causes a contact angle θ

of the coated article to decrease.

14. The method of claim 1, wherein at least a hydrocarbon gas is used in the ion source, so that at least carbon ions and hydrogen ions are directed toward the sputtered layer in an ion beam.

15. The method of claim 1, wherein at least one additional layer is provided on the substrate between the sputtered layer comprising TiO_x and the substrate.

16. The method of claim 1, further comprising ion beam depositing a layer comprising amorphous diamond-like carbon (DLC) on the substrate over the sputtered layer and over the carbon ions that are implanted into the sputtered layer.

17. The method of claim 16, wherein the layer comprising DLC is from about 1-40 Å

thick, and wherein the layer comprising titanium oxide is amorphous.

40. A coated article made according to the method of claim 1.

18. A method of making a coated article, the method comprising:

providing a substrate;

sputtering a layer comprising titanium oxide on the substrate, thereby forming a sputtered layer; and

directing at least carbon ions toward the sputtered layer comprising titanium oxide, at least some of the carbon ions having an ion energy of at least 200 eV per carbon ion so that at least some of the carbon ions implant in the sputtered layer thereby forming a layer comprising titanium oxycarbide.

19. The method of claim 18, wherein at least some of the carbon ions implant into the sputtered layer to a depth of at least 25 Å

below a surface of the sputtered layer.

20. The method of claim 18, wherein said carbon ions are implanted into the sputtered layer so as to form a substantially continuous layer comprising titanium oxycarbide proximate a surface of the sputtered layer.

21. The method of claim 18, further comprising using an ion source using anode-cathode voltage of at least about 2,000 V in directing said carbon ions toward the sputtered layer.

22. The method of claim 18, further comprising using an ion source using anode-cathode voltage of at least about 3,500 V in directing said carbon ions toward the sputtered layer.

23. The method of claim 18, wherein at least some of said carbon ions directed toward the sputtered layer have an ion energy of at least about 375 eV per carbon ion.

24. The method of claim 18, wherein at least some of said carbon ions directed toward the sputtered layer have an ion energy of at least about 500 eV per carbon ion.

25. The method of claim 18, wherein at least some of said carbon ions directed toward the sputtered layer have an ion energy of at least about 625 eV per carbon ion.

26. The method of claim 18, wherein at least some of the carbon ions implant into the sputtered layer to a depth of at least 50 Å

below a surface of the sputtered layer.

27. The method of claim 18, wherein an ion source uses anode-cathode voltage sufficient to cause at least some of the carbon ions to be implanted into the sputtered layer at a depth of at least 100 Å

below a surface of the sputtered layer.

28. The method of claim 18, wherein the coated article has a contact angle 0 of no greater than about 20 degrees.

29. The method of claim 18, wherein the coated article has a contact angle 0 of no greater than about 15 degrees.

30. The method of claim 18, further comprising directing visible light toward the coated article which visible light causes a contact angle θ

of the coated article to decrease.

31. The method of claim 18, wherein at least a hydrocarbon gas is used in the ion source, so that at least carbon ions and hydrogen ions are directed toward the sputtered layer in an ion beam.

32. The method of claim 18, wherein at least one additional layer is provided on the substrate between the sputtered layer comprising titanium oxide and the substrate.

33. The method of claim 18, further comprising ion beam depositing a layer comprising amorphous diamond-like carbon (DLC) with a density of at least 2.4 gm/cm³ on the substrate over the sputtered layer after and/or while said carbon ions are implanted in the sputtered layer.

34. A method of making a coated article, the method comprising:

providing a substrate;

forming a layer comprising a metal oxide on the substrate; and

directing at least carbon ions toward the layer comprising the metal oxide, at least some of the carbon ions having an ion energy of at least 200 eV per carbon ion so that at least some of the carbon ions implant in the layer thereby forming a layer comprising an oxycarbide.

35. The method of claim 34, wherein at least some of the carbon ions implant into the layer to a depth of at least 25 Å

below a surface of the layer.

36. The method of claim 34, wherein at least some of said carbon ions directed toward the layer have an ion energy of at least about 375 eV per carbon ion.

37. The method of claim 34, wherein at least some of said carbon ions directed toward the layer have an ion energy of at least about 500 eV per carbon ion.

38. The method of claim 34, wherein at least some of said carbon ions directed toward the layer have an ion energy of at least about 625 eV per carbon ion.

39. The method of claim 34, wherein said metal comprises Ti.

41. A coated article made according to the method of claim 34.

51. The method of claim 34, further comprising heating the layer comprising the metal oxide in order to enhance formation of oxycarbide.

42. A coated article comprising a coating supported by a glass substrate, the coating comprising:

a layer comprising titanium oxide, and

at least carbon atoms implanted in the layer comprising titanium oxide,

at least some of the carbon ions being implanted to a depth of at least 25 Å

below a surface of the layer comprising titanium oxide, thereby forming a layer comprising titanium oxycarbide.

43. The coated article of claim 42, wherein the coated article has a contact angle of no greater than 20 degrees.

44. The coated article of claim 42, wherein the coated article has a contact angle of no greater than 15 degrees after at least 50 hours of exposure to UV radiation and water.

45. The coated article of claim 42, wherein the layer comprising titanium oxycarbide further comprises from 1 to 25% H.

46. The coated article of claim 42, wherein the layer comprising titanium oxycarbide further comprises from 5 to 15% H.

47. The coated article of claim 42, wherein at least some of the carbon atoms are implanted to a depth of at least 50 Å

below the surface of the layer.

48. The coated article of claim 42, wherein at least some of the carbon atoms are implanted to a depth of at least 100 Å

below the surface of the layer.

49. The coated article of claim 42, wherein the layer comprising titanium oxide is amorphous.

50. A coated article comprising a coating supported by a substrate, the coating comprising:

a sputtered layer comprising a metal oxide, and

at least carbon atoms which are ion beam implanted in the sputtered layer comprising the metal oxide, at least some of the carbon ions being implanted to a depth of at least 25 Å

below a surface of the sputtered layer, thereby forming a layer comprising an oxycarbide.

52. A method of making a coated article, the method comprising:

providing a glass substrate;

sputtering a layer comprising a metal (M) oxide MO_x (where x is from 1 to

     3) on the substrate, thereby forming a sputtered layer; and

utilizing at least one ion source using anode-cathode voltage of at least about 1,500 V to cause at least carbon ions to be directed toward the sputtered layer comprising the metal oxide so that at least some of the carbon ions are implanted into the sputtered layer to a depth of at least 25 Å

below a surface of the sputtered layer thereby forming a layer comprising oxycarbide; and

ion beam depositing a layer of diamond-like carbon (DLC) over the layer comprising oxycarbide.

53. The method of claim 52, wherein a heterojunction is formed at the interface between the layer comprising oxycarbide and the layer comprising DLC.

54. The method of claim 53, wherein when incident visible light hits charge accumulated at the heterojunction, electron hole pairs form and cause contact angle θ

to decrease.