Solvated ruthenium precursors for direct liquid injection of ruthenium and ruthenium oxide and method of using same

• US 6,541,067 B1
• Filed: 02/18/2000
• Issued: 04/01/2003
• Est. Priority Date: 08/27/1998
• Status: Expired due to Fees

• Current Assignee: MOSAID Technologies Inc. (f/k/a Conversant Intellectual Property Management)
• Original Assignee: Micron Technology, Inc.
• Inventors: Uhlenbrock, Stefan, Marsh, Eugene P.
• Primary Examiner(s): Meeks, Timothy
• Application Number:
  US09/506,962
• Time in Patent Office: 1,138 Days
• Field of Search: 427/99, 427/124, 427/250, 427/252, 427/255.31, 427/901, 438/681, 438/686, 438/758, 438/778
• US Class Current: 427/252
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/40 Oxides
• 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 28/60 Electrodes
• CPC Class Codes: Y10S 427/101 Liquid Source Chemical Depostion, i.e. LSCVD or Aerosol Chemical Vapor Deposition, i.e. ACVD

Abstract

A method is provided for forming a film of ruthenium or ruthenium oxide to the surface of a substrate by employing the techniques of chemical vapor deposition to decompose ruthenium precursor formulations. The ruthenium precursor formulations of the present invention include a ruthenium precursor compound and a solvent capable of solubilizing the ruthenium precursor compound. A method is further provided for making a vaporized ruthenium precursor for use in the chemical vapor deposition of ruthenium and ruthenium-containing materials onto substrates, wherein a ruthenium precursor formulation having a ruthenium-containing precursor compound and a solvent capable of solubilizing the ruthenium-containing precursor compound is vaporized.

Claims

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

providing a semiconductor substrate;

providing a ruthenium precursor formulation comprising tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium dissolved in a solvent capable of solubilizing said ruthenium-containing precursor compound;

vaporizing said ruthenium precursor formulation to form a vaporized precursor compound; and

directing said vaporized precursor compound toward said semiconductor substrate or to form a ruthenium film on a surface of the semiconductor substrate.

2. The method of claim 1, further comprising providing said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium as a liquid.

3. The method of claim 1, further comprising providing said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium to have a freezing point around room temperature.

4. The method of claim 1, wherein said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium decomposes at a temperature greater than room temperature.

5. The method of claim 1, further comprising selecting the semiconductor substrate from the group consisting of a semiconductor wafer, a semiconductor on an insulator substrate, a semiconductor on a sapphire substrate, a semiconductor on a metal substrate, a semiconductor on a nitride, and a semiconductor on a conducting layer.

6. The method of claim 1, further comprising vaporizing the ruthenium precursor formulation using a hot wall type chemical deposition technique.

7. The method of claim 1, further comprising vaporizing the ruthenium precursor formulation using a cold wall type chemical deposition technique.

8. The method of claim 1, further comprising containing the semiconductor substrate within a reaction chamber having a pressure of about 0.1 torr to about 10 torr.

9. The method of claim 1, further comprising containing the semiconductor substrate within a reaction chamber having a pressure of about 1 atmosphere.

10. The method of claim 1, further comprising providing said ruthenium precursor formulation to further contain an oxidizing agent.

11. The method of claim 1, further comprising providing said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium to further contain oxygen.

12. The method of claim 1, further comprising directing said vaporized tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium in combination with at least one oxidizing gas toward the semiconductor substrate to form a ruthenium oxide film on a surface of the semiconductor substrate.

13. The method of claim 12, further comprising providing oxygen as said at least one oxidizing gas.

14. The method of claim 12, further comprising selecting said at least one oxidizing gas from the group of O₂, N₂O, O₃, NO, NO₂, H₂O₂, H₂O, SO₂, SO₃, organic peroxides, and combinations thereof.

15. The method of claim 1, further comprising injecting said ruthenium precursor formulation into a vaporizer to vaporize said ruthenium precursor formulation.

16. The method of claim 1, further comprising injecting said ruthenium precursor formulation into a flash vaporizer to vaporize said ruthenium precursor formulation.

17. The method of claim 1, further comprising selecting said solvent from the group consisting of hexane, hexanes, pentane, heptane, and butylacetate.

18. A method of making a vaporized ruthenium precursor for use in chemical vapor deposition of ruthenium films onto substrates comprising:

providing a ruthenium precursor formulation comprising tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium and a solvent capable of solubilizing said ruthenium-containing precursor compound; and

vaporizing said ruthenium precursor formulation to form a vaporized precursor compound.

19. The method of claim 18, further comprising providing said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium as a liquid.

20. The method of claim 18, further comprising selecting said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium to have a freezing point around room temperature.

21. The method of claim 18, further comprising selecting said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium to have a temperature of decomposition greater than room temperature.

22. The method of claim 18, further comprising providing said ruthenium precursor formulation to contain an oxidizing agent.

23. The method of claim 18, further comprising providing said tricarbonyl(1,2,3,4-η

)-1,3-cyclohexadiene ruthenium to further contain oxygen.

24. The method of claim 18, further comprising injecting said ruthenium precursor formulation into a vaporizer to vaporize said ruthenium precursor formulation.

25. The method of claim 18, further comprising injecting said ruthenium precursor formulation into a flash vaporizer to vaporize said ruthenium precursor formulation.

26. The method of claim 18, further comprising selecting said solvent from the group consisting of hexane, hexanes, pentane, heptane, and butylacetate.

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

providing a semiconductor substrate or substrate assembly;

providing a ruthenium precursor formulation comprising cyclohexadienetricarbonyl ruthenium dissolved in a solvent capable of solubilizing said cyclohexadienetricarbonyl ruthenium;

vaporizing said ruthenium precursor formulation to form a vaporized precursor compound; and

directing said vaporized precursor compound toward said semiconductor substrate or substrate assembly to form a ruthenium film on a surface of the semiconductor substrate or substrate assembly.

28. The method of claim 27, further comprising injecting said ruthenium precursor formulation into a flash vaporizer to vaporize said ruthenium precursor formulation.

29. The method of claim 27, further comprising selecting said solvent from the group consisting of hexane, hexanes, pentane, heptane, and butylacetate.

30. The method of claim 27, further comprising selecting the semiconductor substrate from the group consisting of a semiconductor wafer, a semiconductor on an insulator substrate, a semiconductor on a sapphire substrate, a semiconductor on a metal substrate, a semiconductor on a nitride, and a semiconductor on a conducting layer.

31. The method of claim 27, further comprising selecting said ruthenium precursor formulation to contain an oxidizing agent.

32. The method of claim 27, further comprising providing said ruthenium precursor formulation to further contain oxygen.

33. The method of claim 27, further comprising directing said vaporized precursor compound in combination with at least one oxidizing gas toward the semiconductor substrate to form a ruthenium oxide film on a surface of the semiconductor substrate or substrate assembly.

34. The method of claim 33, further comprising providing oxygen as said at least one oxidizing gas.

35. The method of claim 33, further comprising selecting said at least one oxidizing gas from the group of O₂, N₂O, O₃, NO, NO₂, H₂O₂, H₂O, SO₂, SO₃, organic peroxides, and combinations thereof.

36. The method of claim 27, further comprising injecting said ruthenium precursor formulation into a vaporizer to vaporize said ruthenium precursor formulation.

37. The method of claim 27, wherein vaporizing said ruthenium precursor formulation comprises injecting said ruthenium precursor formulation into a flash vaporizer.

38. A method of making a vaporized ruthenium precursor for use in chemical vapor deposition of ruthenium films onto substrates comprising:

providing a ruthenium precursor formulation comprising cyclohexadienetricarbonyl ruthenium and a solvent capable of solubilizing said cyclohexadienetricarbonyl ruthenium; and

vaporizing said ruthenium precursor formulation to form a vaporized precursor compound.

39. The method of claim 38, further comprising selecting said ruthenium precursor formulation to contain an oxidizing agent.

40. The method of claim 38, further comprising selecting said ruthenium precursor formulation to further contain oxygen.

41. The method of claim 38, further comprising injecting said ruthenium precursor formulation into a vaporizer to vaporize said ruthenium precursor formulation.

42. The method of claim 38, further comprising injecting said ruthenium precursor formulation into a flash vaporizer to vaporize said ruthenium precursor formulation.

43. The method of claim 38, further comprising selecting said solvent from the group consisting of hexane, hexanes, pentane, heptane, and butylacetate.