CVD RUTHENIUM SEED FOR CVD RUTHENIUM DEPOSITION

• US 20020146513A1
• Filed: 04/05/2001
• Published: 10/10/2002
• Est. Priority Date: 04/05/2001
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: Zhao, Jun, Wang, Yaxin, Wade, Christopher P., Tao, Xianzhi, Jin, Xiaoliang, Pao, Elaine
• Granted Patent: US 6,479,100 B2
• Time in Patent Office: Days
• US Class Current: 427/255.28
• CPC Class Codes: C08F 14/06 Vinyl chloride
• CPC Class Codes: C23C 16/0281 of metallic sub-layers C23C16/029 takes precedence
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/56 After-treatment

Abstract

The present invention provides a method of forming a ruthenium seed layer on a substrate comprising the steps of introducing a ruthenium-containing compound into a CVD apparatus; introducing oxygen into the CVD apparatus; maintaining an oxygen rich environment in the process chamber for the initial formation of a ruthenium oxide seed layer; vaporizing the ruthenium-containing compound; depositing the ruthenium oxide seed layer onto the substrate by chemical vapor deposition; and annealing the deposited ruthenium oxide seed layer in a gas ambient forming a ruthenium seed layer. Also provided is a method of depositing a ruthenium thin metal film using a metalorganic precursor onto a CVD ruthenium seed layer by metalorganic chemical vapor deposition.

Claims

1. A method of forming a ruthenium seed layer on a substrate comprising the steps of:

(a) vaporizing a ruthenium-containing compound;

(b) introducing the vaporized ruthenium-containing compound into a CVD apparatus;

(c) introducing oxygen into the CVD apparatus;

(d) maintaining an oxygen rich environment in a process chamber of the CVD apparatus for the initial formation of a ruthenium oxide seed layer;

(e) depositing the ruthenium oxide seed layer onto the substrate by chemical vapor deposition; and

(f) annealing the deposited ruthenium oxide seed layer in a gas ambient thus forming a ruthenium seed layer.

2. The method of claim 1, wherein the substrate is selected from the group consisting of silicon, silicon dioxide, titanium nitride, titanium aluminum nitride, tantalum nitride, tantalum pentoxide and barium strontium titanate.

3. The method of claim 1, wherein said ruthenium-containing compound is selected from the group consisting of ruthenium bis-(ethylcyclopentadienyl) and ruthenium octanedionate.

4. The method of claim 1, wherein the oxygen to ruthenium ratio in said oxygen rich environment is from about 1:

1 to about 100;

1.

5. The method of claim 4, wherein the oxygen to ruthenium ratio in said oxygen rich environment is about 14:

1.

6. The method of claim 1, wherein the heater temperature is from about 200°

C. to about 400°

C.

7. The method of claim 1, wherein the initially deposited ruthenium oxide is RuOx wherein x is 2.

8. The method of claim 7, wherein the percentage of oxygen in the RuOx compound is about 60%.

9. The method of claim 1, wherein said annealing occurs in a gas ambient selected from the group consisting of H₂/N₂, H₂ and H₂/Ar.

10. The method of claim 9, wherein the percentage of hydrogen gas in the ambient is from about 10% to 100%.

11. The method of claim 1, wherein said annealing occurs at a temperature from about 200°

C. to about 600°

C.

12. The method of claim 1, wherein the annealed ruthenium seed layer comprises RuOy wherein y is less than 2.

13. The method of claim 12, wherein the percentage of oxygen in RuOy is less than about 20%.

14. The method of claim 12, wherein the ruthenium seed layer has a thickness of about 100 Å

or less.

15. The method of claim 1, wherein the ruthenium seed layer is used for the subsequent metalorganic chemical vapor deposition of a ruthenium film thereon.

16. The method of claim 15, wherein said ruthenium film is deposited via a metalorganic precursor selected from the group consisting of ruthenium bis-(ethylcyclopentadienyl) and ruthenium octanedionate.

18. The method of claim 17, wherein the substrate is selected from the group consisting of silicon, silicon dioxide, titanium nitride, titanium aluminum nitride, tantalum nitride, tantalum pentoxide and barium strontium titanate.

19. The method of claim 17, wherein said ruthenium-containing compound is selected from the group consisting of ruthenium bis-(ethylcyclopentadienyl) and ruthenium octanedionate.

20. The method of claim 17, wherein the oxygen to ruthenium ratio is about 14:

1.

21. The method of claim 17, wherein the initially deposited ruthenium oxide is RuOx wherein x is about 2.

22. The method of claim 21, wherein the percentage of oxygen in RuOx is about 60%.

23. The method of claim 17, wherein the percentage of hydrogen gas in the ambient is from about 10% to 100%.

24. The method of claim 17, wherein the annealed ruthenium seed layer is RuOy wherein y is less than 2.

25. The method of claim 24, wherein the percentage of oxygen in RuOy is less than about 20%.

26. The method of claim 24, wherein the ruthenium seed layer has a thickness of about 100 Å

or less.

27. The method of claim 17, wherein the ruthenium seed layer is used for the subsequent metalorganic chemical vapor deposition of a ruthenium film thereon.

28. The method of claim 27, wherein said ruthenium film is deposited via a metalorganic precursor selected from the group consisting of ruthenium bis-(ethylcyclopentadienyl) and ruthenium octanedionate.

30. The method of claim 29, wherein the substrate is selected from the group consisting of silicon, silicon dioxide, titanium nitride, titanium aluminum nitride, tantalum nitride, tantalum pentoxide and barium strontium titanate.

31. The method of claim 29, wherein said ruthenium-containing compound is selected from the group consisting of ruthenium bis-(ethylcyclopentadienyl) and ruthenium octanedionate.

32. The method of claim 29, wherein the percentage of oxygen in RuOx is about 60%.

33. The method of claim 29, wherein the percentage of oxygen in RuOy is less than about 20%.

34. The method of claim 29, wherein the ruthenium seed layer has a thickness of about 100 Å

or less.

35. The method of claim 29, wherein the ruthenium seed layer is used for the subsequent metalorganic chemical vapor deposition of a ruthenium film thereon.

36. The method of claim 35, wherein the ruthenium film is deposited via a metalorganic precursor selected from the group consisting of ruthenium bis-(ethylcyclopentadienyl) and ruthenium octanedionate.

37. A method of forming a ruthenium thin metal film using a metalorganic precursor comprising the steps of:

forming a ruthenium seed layer on a substrate by the method of claim 1;

vaporizing the metalorganic precursor; and

depositing the ruthenium thin metal film on the ruthenium seed layer by metalorganic chemical vapor deposition.

38. The method of claim 37, wherein said metalorganic precursor is selected from the group consisting of ruthenium bis-(ethylcyclopentadienyl) and ruthenium octanedionate.

17. A method of forming a ruthenium seed layer on a substrate comprising the steps of:

(a) vaporizing a ruthenium-containing compound at a temperature of about 200°

C. to about 400°

C.;

(b) introducing the vaporized ruthenium-containing compound into a CVD apparatus;

(c) introducing oxygen into the CVD apparatus;

(d) maintaining an oxygen rich environment in a process chamber of the CVD apparatus for the initial formation of a ruthenium oxide seed layer wherein the oxygen to ruthenium ratio in said environment is from about 1;

1 to about 100;

1;

(e) depositing the ruthenium oxide seed layer onto the substrate by chemical vapor deposition; and

(f) annealing the deposited ruthenium oxide seed layer in a gas ambient selected from the group consisting of H₂/N₂, H₂ and H₂/Ar and wherein said annealing occurs at about 200°

C. to about 600°

C. thereby forming a ruthenium seed layer.

29. A method of forming a ruthenium seed layer on a substrate comprising the steps of:

(a) vaporizing a ruthenium-containing compound at a temperature of about 200°

C. to about 400°

C.;

(b) introducing the vaporized ruthenium-containing compound into a CVD apparatus;

(c) introducing oxygen into the CVD apparatus;

(d) maintaining an oxygen rich environment in a process chamber of the CVD apparatus for the initial formation of a ruthenium oxide seed layer wherein the oxygen to ruthenium ratio in said environment is from about 1;

1 to about 100;

1;

(e) depositing the ruthenium oxide seed layer onto the substrate by chemical vapor deposition such that the ruthenium oxide is RuOx wherein x is about 2; and

(f) annealing the deposited ruthenium oxide seed layer in a gas ambient selected from the group consisting of H₂/N₂, H₂ and H₂/Ar;

wherein said annealing occurs from about 200°

C. to about 600°

C. wherein the ruthenium is RuOy with y less than 2 thereby forming a ruthenium seed layer.