Thin films and methods and machines for forming the thin films

• US 8,329,002 B1
• Filed: 03/10/2009
• Issued: 12/11/2012
• Est. Priority Date: 03/10/2009
• Status: Expired due to Fees

• Current Assignee: 4Wave, Inc.
• Original Assignee: 4Wave, Inc.
• Inventors: Baldwin, David A., Githinji, Anthony, Antrazi, Sami C.
• Primary Examiner(s): Booth, Richard A.
• Application Number:
  US12/382,192
• Time in Patent Office: 1,372 Days
• Field of Search: 438/104, 438785-786, 204/192.21, 204/192.22
• US Class Current: 204/192.21
• CPC Class Codes: C23C 14/0042 Controlling partial pressure or flow rate of reactive or inert gases with feedback of measurements
• CPC Class Codes: C23C 14/0676 Oxynitrides
• CPC Class Codes: C23C 14/083 of refractory metals or yttrium
• CPC Class Codes: C23C 14/46 by ion beam produced by an external ion source
• CPC Class Codes: C23C 14/54 Controlling or regulating the coating process

Abstract

Methods for depositing an amorphous vanadium oxide (VO_x) film include vaporizing vanadium from a vanadium source while the a gas containing an oxygen species and a process modifying additive are in the chamber so as to deposit an amorphous VO_x film on the substrate, where x>0. The process modifying additive includes a gas flowing into the chamber or vaporized material from a target source. The additive may stabilize the deposition rate of VO_x, reduce resistivity, improve thickness control, and improve uniformity of thickness and resistivity. The thin film may be a nitrogen-enhanced, amorphous vanadium oxide (VO_xN_y) film formed on a substrate, where x>y>0, and the film contains at least 0.2 atomic % nitrogen. The film may be used in a device, such as a thermal or infrared sensor, or more particularly a bolometer.

Claims

1. A method for manufacturing an amorphous vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a first gas into the chamber, the first gas containing a reactive oxygen species;

flowing nitrogen gas into the chamber; and

vaporizing vanadium from a vanadium source while the first gas and the nitrogen gas are flowing into the chamber so as to deposit an amorphous VO_x film on the substrate, where x>

0.

2. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein during deposition the substrate is maintained at a temperature no greater than 100°

C.

3. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein:

the step of flowing the first gas into the chamber comprises flowing the first gas at a first regulated flow rate; and

the step of flowing nitrogen gas into the chamber comprises flowing the nitrogen gas at a second regulated flow rate, wherein the first flow rate is greater than the second flow rate.

4. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the step of vaporizing vanadium from the vanadium target is performed by physical vapor deposition.

5. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 4, wherein the step of physical vapor deposition comprises plasma ion sputtering.

6. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 4, wherein the step of physical vapor deposition comprises ion beam sputtering.

7. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 4, wherein the step of physical vapor deposition comprises arc vaporization.

8. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 4, wherein the step of physical vapor deposition comprises biased target deposition.

9. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the first gas comprises oxygen (O₂).

10. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein substrate comprises silicon.

11. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein substrate comprises glass.

12. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein substrate comprises plastic.

13. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film is characterized by 0.5≦

x<

2.0.

14. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 2, wherein the deposited VO_x film is characterized by 0.5≦

x<

2.0.

15. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film comprises nitrogen.

16. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film comprises at least 0.2 atomic % nitrogen.

17. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film comprises at least 0.5 atomic % nitrogen.

18. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film comprises at least 0.7 atomic % nitrogen.

19. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film comprises at least 1 atomic % nitrogen.

20. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film comprises at least 3 atomic % nitrogen.

21. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein the deposited VO_x film comprises argon.

22. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, further comprising:

supplying a second gas and a third gas to an ion source associated with the deposition chamber, wherein the second gas comprises an inert gas and the third gas comprises a reactive oxygen species; and

activating the ion source; and

wherein the step of vaporizing vanadium comprises vaporizing vanadium from the vanadium source using the ion source while the first gas and the nitrogen gas are flowing into the chamber and the second gas and the third gas are supplied to the ion source.

23. The method for manufacturing an amorphous vanadium oxide (VO_x) film according to claim 1, wherein at least one substrate dimension is 150 mm or greater and wherein the VO_x film has a resistivity of at most 0.5 ohm-centimeters and a non-uniformity of resistivity of less than 3.0% over a region over a region having a diameter of at least a 130 mm.

24. A method for manufacturing a vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a gas into the chamber, wherein the gas comprises molecules with at least nitrogen and oxygen in the same molecule; and

vaporizing vanadium from a vanadium target while the gas is flowing into the chamber so as to deposit a VO_x film on the substrate, where x>

0.

25. A method of manufacturing a vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a first gas into the chamber, the first gas containing a reactive oxygen species; and

vaporizing vanadium and nitrogen from a vanadium nitride target while the first gas is flowing into the chamber so as to deposit a VO_x film on the substrate, where x>

0.

26. The method of manufacturing a vanadium oxide (VO_x) film according to claim 25, wherein the deposited VO_x film comprises nitrogen.

27. The method of manufacturing a vanadium oxide (VO_x) film according to claim 25, further comprising flowing nitrogen gas into the chamber during the step of vaporizing the target.

28. A method for depositing an amorphous vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a first gas into the chamber at a first regulated flow rate, the first gas containing a reactive oxygen species;

flowing a process modifying additive gas into the chamber at a second regulated flow rate, wherein the first flow rate is greater than the second flow rate; and

vaporizing vanadium from a vanadium source while the first gas and the process modifying additive gas are flowing into the chamber so as to deposit an amorphous VO_x film on the substrate, where x>

0.

29. The method for depositing according to claim 28, wherein the deposited VO_x film comprises at least 0.5 atomic % nitrogen.

30. The method for depositing according to claim 28, wherein the VO_x film comprises at least 0.7 atomic % nitrogen.

31. The method for depositing according to claim 28, wherein the VO_x film comprises at least 1 atomic % nitrogen.

32. The method for depositing according to claim 28, wherein the VO_x film comprises at least 3 atomic % nitrogen.

33. The method for depositing according to claim 29, wherein the deposition rate of VO_x film is at least 20 Å

per minute.

34. The method for depositing according to claim 33, wherein the deposition rate of VO_x film is at least 50 Å

per minute.

35. A method of manufacturing an amorphous vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a first gas into the chamber, the first gas containing a reactive oxygen species;

flowing nitrogen gas into the chamber; and

vaporizing vanadium from a vanadium source while the first gas and the nitrogen gas are flowing into the chamber so as to deposit an amorphous VO_x film on the substrate, where x>

0.

36. The method of manufacturing according to claim 35, wherein the deposition rate of VO_x film is at least 20 Å

per minute.

37. The method of manufacturing according to claim 36, wherein the deposited VO_x film comprises at least 0.5 atomic % nitrogen.

38. The method of manufacturing according to claim 36, wherein the VO_x film comprises at least 0.7 atomic % nitrogen.

39. The method of manufacturing according to claim 36, wherein the VO_x film comprises at least 1 atomic % nitrogen.

40. The method of manufacturing according to claim 36, wherein the VO_x film comprises at least 3 atomic % nitrogen.

41. The method of manufacturing according to claim 37, wherein the substrate is not heated during the deposition of VO_x.

42. The method of manufacturing according to claim 35, wherein the step of flowing a first gas into the chamber comprises flowing the first gas at a first regulated flow rate, and the step of flowing process controlling gas into the chamber comprises flowing the process controlling gas at a second regulated flow rate, wherein the first flow rate is greater than the second flow rate.

43. A method of manufacturing an amorphous vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a first gas into the chamber, the first gas containing a reactive oxygen species;

flowing nitrogen gas into the chamber; and

vaporizing vanadium from a vanadium source while the first gas and the nitrogen gas are flowing into the chamber so as to deposit an amorphous VO_x film on the substrate, where x>

0, wherein the nitrogen gas stabilizes the deposition rate of VO_x.

44. The method of manufacturing according to claim 43, wherein the deposition rate of VO_x film is at least 20 Å

per minute.

45. The method of manufacturing according to claim 43, wherein the deposited VO_x film comprises at least 0.5 atomic % nitrogen.

46. The method of manufacturing according to claim 43, wherein the VO_x film comprises at least 0.7 atomic % nitrogen.

47. The method of manufacturing according to claim 43, wherein the VO_x film comprises at least 1 atomic % nitrogen.

48. The method of manufacturing according to claim 43, wherein the VO_x film comprises at least 3 atomic % nitrogen.

49. The method of manufacturing according to claim 46, wherein the substrate is not heated during the deposition of VO_x.

50. A method for manufacturing an amorphous vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a first gas into the chamber, the first gas containing a reactive oxygen species; and

vaporizing vanadium from a vanadium source while the first gas is flowing into the chamber so as to deposit an amorphous VO_x film on the substrate, where x>

0 and wherein the VO_x film has a resistivity of at most 0.3 ohm-centimeters and a non-uniformity of resistivity of less than 1.0% over a region having a diameter of at least a 130 mm.

51. The method for manufacturing according to claim 50, further comprising flowing nitrogen gas into the chamber during the step of vaporizing the vanadium source.

52. The method for manufacturing according to claim 51, wherein the step of flowing a first gas into the chamber comprising flowing the first gas at a first regulated flow rate and the step of flowing nitrogen gas in to the chamber comprises flowing the nitrogen gas a second regulated flow rate, the first flow rate being greater than the second flow rate.

53. The method for manufacturing according to claim 50, wherein the VO_x film has a resistivity is less than 0.2 ohm-centimeters over a region having a diameter of at least a 130 mm.

54. The method for manufacturing according to claim 50, wherein the deposited VO_x film comprises at least 1.0 atomic % nitrogen.

55. The method for manufacturing according to claim 50, wherein the substrate is not heated during the deposition of the VO_x film.

56. The method for manufacturing according to claim 50, wherein the deposition rate of VO_x film is at least 20 Å

per minute.

57. The method for manufacturing according to claim 50, wherein the VO_x film has a non-uniformity of resistivity of less than 1.0% over a region having a diameter of at least a 180 mm.

58. The method for manufacturing according to claim 50, wherein the VO_x film has a resistivity of less than 0.2 ohm-centimeters over a region having a diameter of at least a 180 mm.

59. A method for manufacturing an amorphous vanadium oxide (VO_x) film, comprising:

loading a substrate into a deposition chamber;

flowing a first gas into the deposition chamber, the first gas comprising a reactive oxygen species;

supplying a second gas and a third gas to an ion source associated with the deposition chamber, wherein the second gas comprises an inert gas and the third gas comprises a reactive oxygen species;

activating the ion source; and

vaporizing vanadium from an vanadium source using the ion source while the first gas is flowing into the chamber and the second gas and the third gas are supplied to the ion source so as to deposit a VO_x film on the substrate, where x>

0 and wherein the VO_x film has a resistivity of at most 0.3 ohm-centimeters and a non-uniformity of resistivity of less than 3.0% over a region having a diameter of at least a 130 mm.

60. The method for manufacturing according to claim 59, further comprising flowing nitrogen gas into the chamber during the step of vaporizing the vanadium source.

61. The method for manufacturing according to claim 60, wherein:

the step of flowing a first gas into the chamber comprises flowing the first gas at a first regulated flow rate; and

the step of flowing nitrogen gas in to the chamber comprises flowing the nitrogen gas at a second regulated flow rate, the first flow rate combined with the flow rate of the third gas comprising a reactive oxygen species flowing through the ion source being greater than the second flow rate.

62. The method for manufacturing according to claim 59, wherein the VO_x film has a non-uniformity of resistivity between 0.50% and 2.00% a region having a diameter of at least a 130 mm.

63. The method for manufacturing according to claim 59, wherein the deposited VO_x film comprises at least 0.5 atomic % nitrogen.

64. The method for manufacturing according to claim 59, wherein the deposition rate of VO_x film is at least 20 Å

per minute.

65. The method for manufacturing according to claim 59, wherein the VO_x film has a non-uniformity of resistivity of less than 3.0% over a region having a diameter of at least a 180 mm.

66. The method for manufacturing according to claim 59, wherein the VO_x film has a non-uniformity of resistivity of between 0.5% and 2.0% over a region having a diameter of at least a 180 mm.