Methods, complexes, and system for forming metal-containing films

• US 20030119312A1
• Filed: 12/19/2002
• Published: 06/26/2003
• Est. Priority Date: 10/02/1996
• Status: Active Grant

• Current Assignee: Micron Technology, Inc.
• Original Assignee: Micron Technology, Inc.
• Inventors: Vaartstra, Brian A.
• Granted Patent: US 6,979,370 B2
• Time in Patent Office: Days
• US Class Current: 438/679
• CPC Class Codes: C07F 5/00 Compounds containing elements of Groups 3 or 13 of the Periodic Table
• CPC Class Codes: C07F 5/065 compounds with an Al-H linkage
• CPC Class Codes: C07F 5/066 compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/301 AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
• CPC Class Codes: H01L 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/76877 Filling of holes, grooves or trenches, e.g. vias, with conductive material

Abstract

A method of forming a film on a substrate using Group IIIA metal complexes. The complexes and methods are particularly suitable for the preparation of semiconductor structures using chemical vapor deposition techniques and systems.

Claims

1. A method of manufacturing a semiconductor structure, the method comprising:

providing a semiconductor substrate or substrate assembly;

providing a precursor comprising one or more complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein optionally R³ and R⁴ are joined to form a ring or rings with the metal and none of the other R groups are joined together to form ring systems; and

n=1 to 6; and

forming a metal-containing film from the precursor on a surface of the semiconductor substrate or substrate assembly;

wherein the metal-containing film is a Group IIIA metal film or a Group IIIA metal alloy film.

2. The method of claim 1 wherein the step of forming a metal-containing film comprises vaporizing the precursor to form vaporized precursor and directing the vaporized precursor toward the semiconductor substrate or substrate assembly using a chemical vapor deposition technique.

3. The method of claim 2 wherein the chemical vapor deposition technique comprises flash vaporization, bubbling, microdroplet formation, or combinations thereof.

4. The method of claim 1 wherein the semiconductor substrate is a silicon wafer.

5. The method of claim 1 wherein M is selected from the group consisting of Al, Ga, and In.

6. The method of claim 1 wherein at least one of R³ and R⁴ is H.

7. The method of claim 1 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₂₀)organic group.

8. The method of claim 1 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₄)alkyl moiety.

9. The method of claim 1 wherein the precursor is a liquid.

10. The method of claim 9 wherein the liquid precursor comprises one or more solid complexes dissolved in a liquid medium.

11. A method of manufacturing a semiconductor structure, the method comprising:

providing a semiconductor substrate or substrate assembly;

providing a precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵ is H; and

n=1 to 6;

forming a metal-containing film from the precursor on a surface of the semiconductor substrate or substrate assembly.

12. The method of claim 11 wherein the step of forming a metal-containing film comprises vaporizing the precursor to form vaporized precursor and directing the vaporized precursor toward the semiconductor substrate or substrate assembly using a chemical vapor deposition technique.

13. The method of claim 12 wherein the precursor is vaporized in the presence of a carrier gas.

14. The method of claim 12 wherein the precursor is vaporized in the presence of a reaction gas.

15. The method of claim 11 wherein the precursor further comprises one or more compounds containing a Group VA element.

16. The method of claim 11 wherein the precursor is a liquid.

17. The method of claim 11 wherein the metal-containing film is a Group IIIA metal film.

18. The method of claim 11 wherein the metal-containing film is a Group IIIA metal alloy film.

19. A method of manufacturing a semiconductor structure, the method comprising:

providing a semiconductor substrate or substrate assembly;

providing a liquid precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀) organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵ is H; and

n=1 to 6;

vaporizing the liquid precursor to form vaporized precursor; and

directing the vaporized precursor toward the semiconductor substrate or substrate assembly to form a metal-containing film on a surface of the semiconductor substrate or substrate assembly.

20. A method of forming a film on a substrate, the method comprising:

providing a substrate;

providing a precursor comprising one or more complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein optionally R³ and R⁴ are joined to form a ring or rings with the metal and none of the other R groups are joined together to form ring systems; and

n=1 to 6;

forming a metal-containing film from the precursor on a surface of the substrate;

wherein the metal-containing film is a Group IIIA metal film or a Group IIIA metal alloy film.

21. The method of claim 20 wherein the step of forming a metal-containing film comprises vaporizing the precursor to form vaporized precursor and directing the vaporized precursor toward the substrate using a chemical vapor deposition technique.

22. The method of claim 20 wherein the precursor is a liquid.

23. The method of claim 20 wherein the metal-containing film is a Group IIIA metal film.

24. The method of claim 20 wherein the metal-containing film is a Group IIIA metal alloy film.

25. The method of claim 20 wherein the step of forming a metal-containing film comprises vaporizing the precursor to form vaporized precursor and directing the vaporized precursor toward the substrate using a chemical vapor deposition technique.

26. The method of claim 25 wherein the precursor is vaporized in the presence of a carrier gas.

27. The method of claim 26 wherein the precursor is vaporized in the presence of a reaction gas.

28. The method of claim 20 wherein the precursor further comprises one or more compounds containing a Group VA element.

29. The method of claim 23 wherein the precursor is a liquid.

30. A method of forming a film on a substrate, the method comprising:

providing a substrate;

providing a precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵ is H; and

n=1 to 6;

forming a metal-containing film from the precursor on a surface of the substrate.

31. A method of forming a film on a substrate, the method comprising:

providing a substrate;

providing a liquid precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵ is H; and

n=1 to 6;

vaporizing the liquid precursor to form vaporized precursor; and

directing the vaporized precursor toward the substrate to form a metal-containing film on a surface of the substrate.

32. A hydride complex of the formula:

33. The complex of claim 32 wherein M is selected from the group consisting of Al, Ga, and In.

34. The complex of claim 32 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₂₀)organic group.

35. The complex of claim 32 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₈)organic group.

36. The complex of claim 32 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₄)alkyl moiety.

37. A chemical vapor deposition system comprising:

a deposition chamber having a substrate positioned therein;

a vessel containing a precursor comprising one or more complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein optionally R³ and R⁴ are joined to form a ring or rings with the metal and none of the other R groups are joined together to form ring systems; and

n=1 to 6; and

a source of an inert carrier gas for transferring the complex or complexes to the chemical vapor deposition chamber.

38. A chemical vapor deposition system comprising:

a deposition chamber having a substrate positioned therein;

a vessel containing a precursor comprising one or more complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein optionally R³ and R⁴ are joined to form a ring or rings with the metal and none of the other R groups are joined together to form ring systems; and

n=1 to 6; and

a source of an inert carrier gas for transferring the complex or complexes to the chemical vapor deposition chamber.

39. The system of claim 38 wherein M is selected from the group consisting of Al, Ga, and In.

40. The system of claim 38 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₂₀)organic group.

41. The system of claim 38 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₈)organic group.

42. The system of claim 38 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₄)alkyl moiety.

43. The system of claim 38 wherein the precursor is a liquid.

44. The system of claim 43 wherein the liquid precursor comprises one or more solid complexes dissolved in a liquid medium.

45. The system of claim 38 wherein the precursor further comprises one or more compounds containing a Group VA element.

46. A chemical vapor deposition system comprising:

a deposition chamber having a substrate positioned therein;

a vessel containing a precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵ is H; and

n=1 to 6; and

a source of an inert carrier gas for transferring the complex or complexes to the chemical vapor deposition chamber.

47. A chemical vapor deposition system comprising:

a deposition chamber having a substrate positioned therein;

a vessel containing a liquid precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵is H; and

n=1 to 6; and

a source of an inert carrier gas for transferring the complex or complexes to the chemical vapor deposition chamber.

48. A chemical vapor deposition system comprising:

a deposition chamber having a semiconductor substrate positioned therein;

a vessel containing a precursor comprising one or more complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein optionally R³ and R⁴ are joined to form a ring or rings with the metal and none of the other R groups are joined together to form ring systems; and

n=1 to 6; and

a source of an inert carrier gas for transferring the complex or complexes to the chemical vapor deposition chamber.

49. The system of claim 48 wherein the semiconductor substrate is a silicon wafer.

50. The system of claim 48 wherein M is selected from the group consisting of Al, Ga, and In.

51. The system of claim 48 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₂₀)organic group.

52. The system of claim 48 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₈)organic group.

53. The system of claim 48 wherein each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₄)alkyl moiety.

54. The system of claim 48 wherein the precursor is a liquid.

55. The system of claim 54 wherein the liquid precursor comprises one or more solid complexes dissolved in a liquid medium.

56. The system of claim 48 wherein the precursor further comprises one or more compounds containing a Group VA element.

57. A chemical vapor deposition system comprising:

a deposition chamber having a semiconductor substrate positioned therein;

a vessel containing a precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵ is H; and

n=1 to 6; and

a source of an inert carrier gas for transferring the complex or complexes to the chemical vapor deposition chamber.

58. A chemical vapor deposition system comprising:

a deposition chamber having a semiconductor substrate positioned therein;

a vessel containing a liquid precursor comprising one or more hydride complexes of the formulas;

 

wherein;

M is a Group IIIA metal;

each R¹, R², R³, R⁴, and R⁵ group is independently H or a (C₁-C₃₀)organic group, wherein none of the R groups are joined together to form ring systems, at least one of R³ and R⁴ is H, and R⁵ is H; and

n=1 to 6; and

a source of an inert carrier gas for transferring the complex or complexes to the chemical vapor deposition chamber.