Method for depositing films using gas cluster ion beam processing

• US 7,794,798 B2
• Filed: 09/29/2007
• Issued: 09/14/2010
• Est. Priority Date: 09/29/2007
• Status: Active Grant

• Current Assignee: TEL Manufacturing and Engineering of America, Inc.
• Original Assignee: TEL Epion Inc. (Tokyo Electron Limited)
• Inventors: Hautala, John J.
• Primary Examiner(s): Vinh; Lan
• Assistant Examiner(s): Angadi; Maki A
• Application Number:
  US11/864,961
• Publication Number:
  US 20090087578A1
• Time in Patent Office: 1,081 Days
• Field of Search: 427/526, 427/585, 438 36- 37, 438/58, 438/87, 118/723, 118/726, 156/345.1
• US Class Current: 427/526
• CPC Class Codes: C23C 14/0605 Carbon
• CPC Class Codes: C23C 14/0635 Carbides
• CPC Class Codes: C23C 14/0652 Silicon nitride
• CPC Class Codes: C23C 14/221 Ion beam deposition C23C14/46, C23C14/48 take precedence
• CPC Class Codes: C23C 16/26 Deposition of carbon only
• CPC Class Codes: C23C 16/325 Silicon carbide
• CPC Class Codes: C23C 16/345 Silicon nitride
• CPC Class Codes: C23C 16/513 using plasma jets
• CPC Class Codes: H01J 2237/0812 Ionized cluster beam [ICB] sources

Abstract

A method for depositing material on a substrate is described. The method comprises maintaining a reduced-pressure environment around a substrate holder for holding a substrate having a surface, and holding the substrate securely within the reduced-pressure environment. Additionally, the method comprises providing to the reduced-pressure environment a gas cluster ion beam (GCIB) from a pressurized gas mixture, accelerating the GCIB, and irradiating the accelerated GCIB onto at least a portion of the surface of the substrate to form a thin film. In one embodiment, the pressurized gas mixture comprises a silicon-containing specie and at least one of a nitrogen-containing specie or a carbon-containing specie for forming a thin film containing silicon and at least one of nitrogen or carbon. In another embodiment, the gas mixture comprises a metal-containing specie for forming a thin metal-containing film. In yet another embodiment, the pressurized gas mixture comprises a fluorocarbon-containing specie for forming a thin fluorocarbon-containing film.

Claims

1. A method for depositing a thin film at a surface on a substrate, comprising:

maintaining a reduced-pressure environment around a substrate holder for holding a substrate having a surface;

holding said substrate securely within said reduced-pressure environment;

providing to said reduced-pressure environment a gas cluster ion beam (GCIB) from a pressurized gas mixture comprising a silicon-containing specie and at least two of a nitrogen-containing specie, an oxygen containing specie, or a carbon-containing specie;

accelerating said GCIB; and

irradiating said accelerated GCIB onto at least a portion of said surface of said substrate to deposit a thin film containing silicon and at least two of nitrogen, oxygen or carbon on said at least a portion of said surface of said substrate.

2. The method of claim 1, wherein said silicon-containing specie comprises silane (SiH₄), disilane (Si₂H₆), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiCl₃H), diethylsilane (C₄H₁₂Si), trimethylsilane (C₃H₁₀Si), silicon tetrachloride (SiCl₄), or silicon tetrafluoride (SiF₄), or a combination of two or more thereof.

3. The method of claim 1, wherein said nitrogen-containing specie comprises N₂, NH₃, NF₃, NO, N₂O, or NO₂, or a combination of two or more thereof.

4. The method of claim 1, wherein said carbon-containing specie comprises a hydrocarbon gas having the formula C_xH_y, wherein x and y are integers greater than or equal to unity.

5. The method of claim 1, wherein said carbon-containing specie comprises a fluorocarbon gas having the formula C_xF_y, wherein x and y are integers greater than or equal to unity.

6. The method of claim 1, wherein said carbon-containing specie comprises a hydrofluorocarbon gas having the formula C_xH_yF_z, wherein x, y and z are integers greater than or equal to unity.

7. The method of claim 1, wherein said carbon-containing specie comprises CO, CO₂, methane (CH₄) or carbon tetrafluoride (CF₄) or a combination thereof.

8. The method of claim 1, wherein said pressurized gas mixture further comprises a germanium-containing material, a hydrogen-containing material, a fluorine-containing material, a sulfur-containing material, a boron-containing material, a phosphorous-containing material, or an arsenic-containing material, or a combination of two or more thereof.

9. The method of claim 1, wherein said pressurized gas mixture further comprises sulfur hexafluoride (SF₆), boron trifluoride (BF₃), diborane (B₂H₆), phosphine (PH₃), PF₅, arsine (AsH₃), or AsF₅, or a combination of two or more thereof.

10. The method of claim 1, wherein said pressurized gas mixture further comprises germane (GeH₄), digermane (Ge₂H₆), dichlorogermane (GeH₂Cl₂), trichlorogermane (GeCl₃H), diethylgermane (C₄H₁₂Ge), trimethylgermane (C₃H₁₀Ge), germanium tetrachloride (GeCl₄), or germanium tetrafluoride (GeF₄), or a combination of two or more thereof.

11. The method of claim 1, wherein said pressurized gas mixture further comprises a noble gas.

12. The method of claim 1, further comprising:

annealing said thin film.

13. The method of claim 1, wherein the gas clusters of said GCIB are accelerated by an acceleration voltage between 1 and 70 kV.

14. The method of claim 1, further comprising:

filtering said GCIB to substantially reduce the number of gas clusters having 100 or less atoms or molecules or both.

15. The method of claim 1, further comprising:

scanning said accelerated GCIB onto at least a portion of said surface of said substrate.

16. The method of claim 15, further comprising:

adjusting the GCIB dose as a function of position on said surface of said substrate in order to vary the thickness of said thin film deposited on said surface of said substrate.

17. The method of claim 1, wherein the thickness of said thin film that is deposited on said surface is achieved by selecting a GCIB dose.

18. A method for depositing a thin film at a surface on a substrate, comprising:

maintaining a reduced-pressure environment around a substrate holder for holding a substrate having a surface;

holding said substrate securely within said reduced-pressure environment;

providing to said reduced-pressure environment a gas cluster ion beam (GCIB) from a pressurized gas mixture comprising a metal-containing specie;

accelerating said GCIB; and

irradiating said accelerated GCIB onto at least a portion of said surface of said substrate to deposit a metal-containing thin film on said at least a portion of said surface of said substrate.

19. The method of claim 18, wherein said metal-containing specie comprises a tungsten-containing material.

20. The method of claim 19, wherein said metal-containing specie comprises tungsten hexafluoride (WF₆).

21. The method of claim 18, wherein said pressurized gas mixture further comprises a silicon-containing material, a germanium-containing material, a carbon-containing material, an oxygen-containing material, a hydrogen-containing material, a nitrogen-containing material, a fluorine-containing material, a boron-containing material, a phosphorous-containing material, or an arsenic-containing material, or a combination of two or more thereof.

22. The method of claim 18, wherein said pressurized gas mixture further comprises silane (SiH₄), disilane (Si₂H₆), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiCl₃H), diethylsilane (C₄H₁₂Si), trimethylsilane (C₃H₁₀Si), silicon tetrachloride (SiCl₄), or silicon tetrafluoride (SiF₄), or a combination of two or more thereof.

23. The method of claim 22, wherein said pressurized gas mixture further comprises H₂, O₂, CO, CO₂, N₂, NH₃, NF₃, NO, N₂O, or NO₂, or a combination of two or more thereof.

24. The method of claim 18, wherein said pressurized gas mixture further comprises H₂, O₂, CO, CO₂, N₂, NH₃, NF₃, NO, N₂O, or NO₂, or a combination of two or more thereof.

25. The method of claim 18, wherein said metal-containing specie comprises a tungsten-containing material and wherein said pressurized gas mixture further comprises a silicon-containing material.

26. The method of claim 25, wherein said pressurized gas mixture further comprises a nitrogen-containing material or an oxygen-containing material or both.

27. The method of claim 18, wherein said metal-containing specie comprises a tungsten-containing material and wherein said pressurized gas mixture comprises a carbon-containing material.

28. The method of claim 18, wherein said pressurized gas mixture further comprises germane (GeH₄), digermane (Ge₂H₆), dichlorogermane (GeH₂Cl₂), trichlorogermane (GeCl₃H), diethylgermane (C₄H₁₂Ge), trimethylgermane (C₃H₁₀Ge), germanium tetrachloride (GeCl₄), or germanium tetrafluoride (GeF₄), or a combination of two or more thereof.

29. The method of claim 18, wherein said pressurized gas mixture further comprises a noble gas.

30. The method of claim 18, further comprising:

annealing said thin film.

31. The method of claim 18, wherein the gas clusters of said GCIB are accelerated by an acceleration voltage between 1 and 70 kV.

32. The method of claim 18, further comprising:

filtering said GCIB to substantially reduce the number of gas clusters having 100 or less atoms or molecules or both.

33. The method of claim 18, further comprising:

scanning said accelerated GCIB onto at least a portion of said surface of said substrate.

34. The method of claim 33, further comprising:

adjusting the GCIB dose as a function of position on said surface of said substrate in order to vary the thickness of said thin film deposited on said surface of said substrate.

35. The method of claim 18, wherein the thickness of said thin film that is deposited on said surface is achieved by selecting a GCIB dose.

36. A method for depositing a thin film at a surface on a substrate, comprising:

maintaining a reduced-pressure environment around a substrate holder for holding a substrate having a surface;

holding said substrate securely within said reduced-pressure environment;

providing to said reduced-pressure environment a gas cluster ion beam (GCIB) from a pressurized gas mixture comprising a fluorocarbon-containing specie;

accelerating said GCIB; and

irradiating said accelerated GCIB onto at least a portion of said surface of said substrate to deposit a fluorocarbon-containing thin film on said at least a portion of said surface of said substrate.

37. The method of claim 36, wherein said fluorocarbon-containing specie comprises a fluorocarbon gas having the formula C_xF_y, wherein x and y are integers greater than or equal to unity.

38. The method of claim 36, wherein said fluorocarbon-containing specie comprises a hydrofluorocarbon gas having the formula C_xH_yF_z, wherein x, y and z are integers greater than or equal to unity.

39. The method of claim 36, wherein said fluorocarbon-containing specie comprises CF₄, C₃F₈, C₃F₆, C₂F₆, C₄F₆, C₄F₈, C₅F₈, CH₂F₂, or CHF₃, or a combination of two or more thereof.

40. The method of claim 36, wherein said pressurized gas mixture further comprises a silicon-containing material, a germanium-containing material, a carbon-containing material, an oxygen-containing material, a hydrogen-containing material, a nitrogen-containing material, a fluorine-containing material, a boron-containing material, a phosphorous-containing material, or an arsenic-containing material, or a combination of two or more thereof.

41. The method of claim 36, wherein said pressurized gas mixture further comprises silane (SiH₄), disilane (Si₂H₆), dichlorosilane (SiH₂Cl₂), trichlorosilane (SiCl₃H), diethylsilane (C₄H₁₂Si), trimethylsilane (C₃H₁₀Si), silicon tetrachloride (SiCl₄), or silicon tetrafluoride (SiF₄), or a combination of two or more thereof.

42. The method of claim 36, wherein said pressurized gas mixture further comprises H₂, O₂, CO, CO₂, N₂, NH₃, NF₃, NO, N₂O, or NO₂, or a combination of two or more thereof.

43. The method of claim 36, wherein said pressurized gas mixture further comprises a noble gas.

44. The method of claim 36, further comprising:

providing a mask on at least a portion of said substrate.

45. The method of claim 36, further comprising:

controllably flowing said pressurized gas mixture so as to control nucleation of the gas mixture constituents into gas clusters.

46. The method of claim 36, wherein said substrate comprises a conductive material, a non-conductive material, or a semi-conductive material.

47. The method of claim 36, further comprising:

controlling the temperature of said substrate.

48. The method of claim 36, further comprising:

thermally treating said thin film.

49. The method of claim 36, wherein the gas clusters of said GCIB are accelerated by an acceleration voltage between 1 and 70 kV.

50. The method of claim 36, further comprising:

filtering said GCIB to substantially reduce the number of gas clusters having 100 or less atoms or molecules or both.

51. The method of claim 36, further comprising:

scanning said accelerated GCIB onto at least a portion of said surface of said substrate.

52. The method of claim 51, further comprising:

adjusting the GCIB dose as a function of position on said surface of said substrate in order to vary the thickness of said thin film deposited on said surface of said substrate.

53. The method of claim 36, wherein the thickness of said thin film that is deposited on said surface is achieved by selecting a GCIB dose.