Methods for preparing ruthenium metal films

• US 6,074,945 A
• Filed: 08/27/1998
• Issued: 06/13/2000
• Est. Priority Date: 08/27/1998
• Status: Expired due to Term

• Current Assignee: Conversant Intellectual Property Management Inc (MOSAID Technologies Inc. (f/k/a Conversant Intellectual Property Management))
• Original Assignee: Micron Technology, Inc.
• Inventors: Vaartstra, Brian A., Marsh, Eugene P.
• Primary Examiner(s): MEEKS, TIMOTHY HOWARD
• Application Number:
  US09/140,878
• Time in Patent Office: 656 Days
• Field of Search: 427/99, 427/124, 427/576, 427/584, 427/585, 427/250, 427/252, 427/253, 427/383.1, 427/383.3, 438/681, 438/686
• US Class Current: 438/681
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• 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

Abstract

The present invention provides methods for the preparation of ruthenium metal films from liquid ruthenium complexes of the formula (diene)Ru(CO)₃ wherein "diene" refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, fluorinated derivatives thereof, derivatives thereof additionally containing heteroatoms such as halide, Si, S, Se, P, As, N, or 0, or combinations thereof.

Claims

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

providing a semiconductor substrate or substrate assembly;

providing a liquid precursor composition comprising one or more compounds of the formula;

space="preserve" listing-type="equation">(diene)Ru(CO).sub.3

wherein "diene" refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, derivatives thereof comprising halide, Si, S, Se, P, As, N, or O heteroatoms, or combinations of said heteroatoms;

vaporizing the liquid precursor composition to form vaporized precursor composition; and

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

2. The method of claim 1 wherein the temperature of the substrate or substrate assembly is about 150°

C. to about 350°

C.

3. The method of claim 1 wherein the temperature of the substrate or substrate assembly is about 200°

C. to about 250°

C.

4. The method of claim 3 wherein the substrate or substrate assembly is contained within a reaction chamber having a pressure of about 10^-3 torr to about 1 atmosphere.

5. The method of claim 4 wherein the substrate or substrate assembly is contained within a reaction chamber having a pressure of about 0.1 torr to about 10 torr.

6. The method of claim 1 wherein the substrate or substrate assembly is contained within a reaction chamber having a pressure of about 0.1 torr to about 10 torr.

7. The method of claim 1 wherein the step of vaporizing the liquid precursor comprises using a technique selected from the group consisting of flash vaporization, bubbling, microdroplet formation, and combinations thereof.

8. The method of claim 1 wherein the semiconductor substrate or substrate assembly comprises a silicon wafer.

9. The method of claim 1 wherein the precursor composition is vaporized in the presence of at least one carrier gas.

10. The method of claim 1 wherein the precursor composition is vaporized in the presence of at least one reducing gas.

11. The method of claim 10 wherein the precursor composition is vaporized in the presence of a reducing gas selected from the group consisting of H₂, NH₃, and combinations thereof.

12. The method of claim 1 wherein the diene derivative is a fluorinated diene.

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

providing a semiconductor substrate or substrate assembly, which is at a temperature of about 150°

C. to about 350°

C., contained within a reaction chamber having a pressure of about 10^-3 torr to about 1 atmosphere;

providing a liquid precursor composition at a temperature of about 20°

C. to about 50°

C., the precursor composition comprising one or more compounds of the formula;

space="preserve" listing-type="equation">(diene)Ru(CO).sub.3

wherein "diene" refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, derivatives thereof comprising halide, Si, S, Se, P, As, N, or O heteroatoms, or combinations of said heteroatoms;

vaporizing the liquid precursor composition to form vaporized precursor composition; and

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

14. The method of claim 13 wherein the diene derivative is a fluorinated diene.

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

providing a semiconductor substrate or substrate assembly;

providing a liquid precursor composition comprising one or more compounds of the formula;

space="preserve" listing-type="equation">(diene)Ru(CO).sub.3

wherein "diene" refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, derivatives thereof comprising halide, Si, S, Se, P, As, N, or O heteroatoms, or combinations of said heteroatoms;

vaporizing the liquid precursor composition to form vaporized precursor composition;

directing the vaporized precursor composition toward the semiconductor substrate or substrate assembly to form a ruthenium metal film on a surface of the semiconductor substrate or substrate assembly; and

annealing the ruthenium metal film.

16. The method of claim 15 wherein the annealing step is carried out at a temperature of about 300°

C. to about 1000°

C.

17. The method of claim 15 wherein the diene derivative is a fluorinated diene.

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

providing a semiconductor substrate or substrate assembly comprising a surface having one or more small high aspect ratio openings;

providing a liquid precursor composition comprising one or more compounds of the formula;

space="preserve" listing-type="equation">(diene)Ru(CO).sub.3

wherein "diene" refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, derivatives thereof comprising halide, Si, S, Se, P, As, N, or O heteroatoms, or combinations of said heteroatoms;

vaporizing the liquid precursor composition to form vaporized precursor composition; and

directing the vaporized precursor composition toward the semiconductor substrate or substrate assembly to form a ruthenium metal film on the surface of the semiconductor substrate or substrate assembly having the one or more high aspect ratio openings.

19. The method of claim 18 wherein the diene derivative is a fluorinated diene.

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

providing a substrate;

providing a liquid precursor composition comprising one or more compounds of the formula;

space="preserve" listing-type="equation">(diene)Ru(CO).sub.3

wherein "diene" refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, derivatives thereof comprising halide, Si, S, Se, P, As, N, or O heteroatoms or combinations of said heteroatoms;

vaporizing the liquid precursor composition to form vaporized precursor composition; and

directing the vaporized precursor composition toward the substrate to form a ruthenium metal film on a surface of the substrate.

21. The method of claim 20 wherein the diene derivative is a fluorinated diene.

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

providing a semiconductor substrate or substrate assembly comprising a surface having one or more small high aspect ratio openings, which is at a temperature of about 150°

C. to about 350°

C., wherein the semiconductor substrate or substrate assembly is contained within a reaction chamber having a pressure of about 10^-3 torr to about 1 atmosphere;

providing a liquid precursor composition at a temperature of about 20°

C. to about 50°

C., the precursor composition comprising one or more compounds of the formula;

space="preserve" listing-type="equation">(diene)Ru(CO).sub.3

wherein "diene" refers to linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, derivatives thereof comprising halide, Si, S, Se, P, As, N, or O heteroatoms or combinations of said heteroatoms;

vaporizing the liquid precursor composition to form vaporized precursor composition; and

directing the vaporized precursor composition toward the semiconductor substrate or substrate assembly to form a ruthenium metal film on the surface of the semiconductor substrate or substrate assembly having the one or more small high aspect ratio openings.

23. The method of claim 22 wherein the diene derivative is a fluorinated diene.