Method for preventing and cleaning ruthenium-containing deposits in a CVD apparatus

• US 7,107,998 B2
• Filed: 10/16/2003
• Issued: 09/19/2006
• Est. Priority Date: 10/16/2003
• Status: Active Grant

• Current Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Original Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Inventors: Draeger, Nerissa Sue, Greer, Harold F. R., Fair, James A., Sung, Junghwan
• Primary Examiner(s): Barr, Michael
• Assistant Examiner(s): CHAUDHRY, SAEED T
• Application Number:
  US10/687,318
• Publication Number:
  US 20050081882A1
• Time in Patent Office: 1,069 Days
• Field of Search: 134/1.1, 134/1.2, 216/67, 216/76, 438/720
• US Class Current: 134/22.1
• CPC Class Codes: C23C 16/16 from metal carbonyl compounds
• CPC Class Codes: C23C 16/4405 Cleaning of reactor or parts inside the reactor by using reactive gases
• CPC Class Codes: C23G 5/00 Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents

Abstract

Carbon monoxide gas is provided in a ruthenium-deposition apparatus to clean undesired ruthenium-containing deposits from apparatus surfaces. Carbon monoxide gas is mixed with reactant gases in apparatus tubing and in a ruthenium-deposition reaction chamber to inhibit formation of undesired ruthenium deposits on apparatus surfaces and to remove ruthenium deposits.

Claims

1. A method of cleaning a ruthenium-containing deposit from a ruthenium-deposition apparatus, comprising processes of:

providing carbon monoxide (CO) gas in at least a portion of said ruthenium-deposition apparatus during cleaning; and

during cleaning, maintaining at least said portion substantially free of an activated oxygen species and an oxygen-atom donating gas.

2. A method as in claim 1, further comprising:

avoiding formation of RuO₄.

3. A method as in claim 1 wherein:

said maintaining at least said portion substantially free comprises purging at least said portion with a purge gas comprising CO; and

wherein said purge gas contains substantially no oxygen-containing oxidizing species except carbon monoxide.

4. A method as in claim 1 wherein:

said maintaining at least said portion substantially free comprises supplying during cleaning in said portion substantially no species selected from the group consisting of ozone, radical oxygen, a halogen-containing species, nitrogen oxide, and an activated oxygen species.

5. A method as in claim 4, further comprising:

during cleaning, maintaining at least said portion substantially free of a strong oxidizer.

6. A method as in claim 1 wherein:

said ruthenium-deposition apparatus comprises at least a portion selected from the group consisting of a ruthenium-deposition reaction chamber, a ruthenium-precursor inlet tube, an inlet manifold, and a reaction-chamber exhaust.

7. A method as in claim 1, further comprising:

maintaining the temperature of at least said portion of said ruthenium-deposition apparatus in a range of about from 150°

C. to 250°

C.

8. A method of cleaning a ruthenium-containing deposit from a ruthenium-deposition apparatus, comprising processes of:

providing carbon monoxide gas in at least a portion of said ruthenium-deposition apparatus; and

avoiding formation of RuO₄.

9. A method as in claim 8, wherein said avoiding formation of RuO₄ comprises:

during cleaning, maintaining at least said portion substantially free of an activated oxygen species and an oxygen-atom donating gas.

10. A method as in claim 9, wherein:

said providing carbon monoxide gas in at least said portion comprises flowing carbon monoxide gas through said portion; and

said avoiding formation of RuO₄ comprises supplying during cleaning in said portion substantially no species selected from the group consisting of ozone, radical oxygen, halogen-containing species, nitrogen oxide, and an activated oxygen species.

11. A method as in claim 10, wherein said avoiding formation of RuO₄ further comprises:

maintaining during cleaning at least said portion substantially free of a strong oxidizer.

12. A method as in claim 8, further comprising:

during cleaning, maintaining at least said portion substantially free of a ruthenium-containing precursor.

13. A method of inhibiting formation of a ruthenium-containing deposit on an apparatus surface of a ruthenium-deposition apparatus during deposition of a ruthenium-containing film on a wafer substrate, comprising:

providing a ruthenium-containing precursor gas proximate to a wafer substrate surface in a ruthenium-deposition apparatus to deposit a ruthenium-containing film on said wafer substrate surface; and

providing carbon monoxide (CO) gas proximate to an apparatus surface of said ruthenium-deposition apparatus during said providing said ruthenium-containing precursor gas proximate to said wafer substrate surface.

14. A method as in claim 13, further comprising:

avoiding formation of RuO₄.

15. A method as in claim 13, further comprising:

maintaining said apparatus proximate to said apparatus surface substantially free of an activated oxygen species and an oxygen-atom donating gas.

16. A method as in claim 15 wherein:

said providing carbon monoxide gas proximate to said apparatus surface comprises flushing said surface with carbon monoxide gas; and

said maintaining said apparatus proximate to said apparatus surface substantially free comprises supplying proximate to said apparatus surface substantially no species selected from the group consisting of ozone, radical oxygen, halogen-containing species, nitrogen oxide and activated oxygen species.

17. A method as in claim 16 wherein said maintaining said apparatus proximate to said apparatus surface substantially free further comprises:

supplying proximate to said apparatus surface substantially no strong oxidizer.

18. A method as in claim 13 wherein:

said ruthenium-deposition apparatus comprises a ruthenium-deposition reaction chamber and a ruthenium-precursor inlet tube having inlet tube wall surfaces; and

said providing carbon monoxide gas comprises flowing carbon monoxide gas through said ruthenium-precursor inlet tube while flowing a ruthenium-containing precursor gas through said ruthenium-precursor inlet tube.

19. A method as in claim 18 wherein:

said flowing carbon monoxide gas through said ruthenium-precursor inlet tube comprises flowing a carrier gas comprising carbon monoxide at a carrier gas flow rate;

said flowing a ruthenium-containing precursor gas comprises flowing a ruthenium-containing precursor gas at a ruthenium precursor flow rate; and

a ratio of said ruthenium precursor flow rate divided by said carrier gas flow rate has a value in a range of about from 1/5 to 1/100.

20. A method as in claim 19, further comprising:

flowing a reactant gas at a reactant gas flow rate through a reactant inlet tube, said reactant gas comprising a gas selected from the group consisting of a strong oxidizer and a reducing gas; and

wherein;

said flowing said carrier gas and said ruthenium-containing precursor gas through said ruthenium precursor inlet tube comprises flowing said carrier gas and said ruthenium-containing precursor gas at a combined flow rate; and

a ratio of said combined flow rate divided by said reactant gas flow rate flow rate has a value in a range of about from 1/1 to 1/10.

21. A method as in claim 13 wherein:

said ruthenium-deposition apparatus comprises a ruthenium-deposition reaction chamber and an inlet manifold connected to said reaction chamber; and

said providing carbon monoxide gas comprises flowing carbon monoxide gas through said inlet manifold while flowing a ruthenium-containing precursor gas through said inlet manifold.

22. A method as in claim 13, further comprising:

maintaining said apparatus proximate to said apparatus surface substantially free of a ruthenium-containing precursor gas.

23. A method as in claim 22 wherein:

said ruthenium-deposition apparatus comprises a ruthenium-deposition reaction chamber and a substrate holder having a substrate holder surface located in said reaction chamber; and

said providing carbon monoxide gas comprises flushing said substrate holder surface with carbon monoxide gas while providing a ruthenium-containing precursor gas in said reaction chamber.

24. A method as in claim 22 wherein:

said ruthenium-deposition apparatus comprises a ruthenium-deposition reaction chamber having reaction chamber walls; and

said providing carbon monoxide gas comprises flushing said reaction chamber walls with carbon monoxide gas while providing a ruthenium-containing precursor gas in said reaction chamber.

25. A method as in claim 13, further comprising:

maintaining said apparatus proximate to said apparatus surface substantially free of a reducing agent.

26. A method as in claim 13, wherein said providing carbon monoxide (CO) gas proximate to an apparatus surface comprises:

providing substantially no oxygen-containing oxidizing species except carbon monoxide proximate to said apparatus surface.

27. A method as in claim 13, further comprising:

maintaining the temperature of said apparatus surface in a range of about from 150°

C. to 250°

C.