Activation-free electroless solution for deposition of cobalt and method for deposition of cobalt capping/passivation layer on copper

• US 6,902,605 B2
• Filed: 03/06/2003
• Issued: 06/07/2005
• Est. Priority Date: 03/06/2003
• Status: Active Grant

• Current Assignee: Lam Research Corporation
• Original Assignee: Blue29, LLC
• Inventors: Petrov, Nicolai, Kolics, Artur, Ivanov, Igor, Ting, Chiu
• Primary Examiner(s): KLEMANSKI, HELENE G
• Application Number:
  US10/379,692
• Publication Number:
  US 20040175509A1
• Time in Patent Office: 824 Days
• Field of Search: 106/1.22, 106/1.27, 427/443.1, 427/437
• US Class Current: 106/1.22
• CPC Class Codes: C23C 18/36 using hypophosphites
• CPC Class Codes: C23C 18/50 with alloys based on iron, cobalt or nickel
• CPC Class Codes: H01L 21/288 from a liquid, e.g. electrolytic deposition
• CPC Class Codes: H01L 21/76849 the layer being positioned on top of the main fill metal

Abstract

The present invention relates to compositions and a method for electroless formation of alkaline-metal-free coatings on the basis of cobalt and composition of cobalt with tungsten and phosphorus, which have high resistance to oxidation and stability of electrical characteristics, when the Co—Cu system layer is used in IC chips. The composition of the electroless solution contains more than one reducing agents, one of which can catalyze the initial electroless deposition layer of cobalt on copper (called initiator), while the other maintains deposition of cobalt on the aforementioned initial layer as the process is continued. Small amount (100-5000 ppm) of elements from the initiator also builds into the electroless film, which is expected to further improve the barrier properties of the resultant film compared to the deposition bath without initiator. Such coating may find application in semiconductor manufacturing where properties of deposited films and controllability of the composition and physical and chemical characteristics of the deposited films may be critically important.

Claims

1. An electroless deposition solution for deposition of cobalt onto a substrate, comprising:

at least one cobalt ion source; and

at least two reducing agents for reducing ions of said at least one cobalt ion source, wherein the at least two reducing agents comprise;

a first reducing agent for initiating deposition of a first layer of cobalt on said substrate; and

a second distinct reducing agent for continuing the deposition of cobalt above said substrate, wherein the second reducing agent is substantially absent of alkali metals.

2. The electroless deposition solution of claim 1, wherein said source of cobalt is selected from salts of cobalt (II).

3. The electroless deposition solution of claim 1, wherein said first reducing agent comprises at least one aminoborane.

4. The electroless deposition solution of claim 3, wherein said at least one aminoborane is a dimethylaminoborane.

5. The electroless deposition solution of claim 4, wherein said at least one aminoborane is a dimethylaminoborane used in concentration within the range of approximately 1 g/l to approximately 2 g/l.

6. The electroless deposition solution of claim 1, wherein said electroless deposition solution has a pH value not exceeding 10.

8. The method of claim 4, wherein the step of preparing the electroless deposition solution comprises preparing an electroless deposition comprising a concentration of aminoboranes between approximately 100 ppm and approximately 5,000 ppm.

9. The method of claim 8, wherein the step of exposing the copper surface comprises maintaining the electroless deposition solution at a temperature between approximately 20°

C. and approximately 110°

C.

10. The electroless deposition solution of claim 1, wherein a concentration of the second reducing agent is at least approximately 20 times larger than a concentration of the first reducing agent.

11. The electroless deposition solution of claim 1, wherein the second reducing agent comprises hypophosphorous acid.

12. The electroless deposition solution of claim 1, wherein the second reducing agent comprises ammonium hypophosphite.

13. The electroless deposition solution of claim 1, wherein the second reducing agent comprises hydrazine.

14. The method of claim 9, wherein the step of exposing the copper surface comprises maintaining the electroless deposition solution at a temperature between approximately 75°

C. and approximately 100°

C.

7. A single-stage method for electroless deposition of a cobalt layer on a copper surface, comprising:

preparing an electroless deposition solution by mixing at least one cobalt ion source with a first reducing comprising boron and a second reducing agent substantially free of alkali metals and distinct from the first reducing agent; and

exposing the copper surface to the electroless deposition solution to form the cobalt layer.

15. The method of claim 7, wherein the method is substantially absent of catalytic activation process on the copper surface prior to the step of exposing the copper surface to the electroless deposition solution.

16. The method of claim 7, wherein the step of preparing the electroless deposition solution comprises preparing an electroless deposition comprising a concentration of the second reducing agent between approximately 2000 ppm and approximately 500,000 ppm.

17. The method of claim 7, wherein the step of exposing the copper surface comprises depositing a cobalt film having a negligible amount of boron.

18. The method of claim 7, wherein the step of exposing the copper surface comprises depositing a cobalt film having a concentration of alkali metals less than approximately 2 ppm.

19. The method of claim 7, wherein the step of exposing the copper surface comprises depositing the cobalt film at a rate between approximately 180 angstroms/minute and approximately 220 angstroms/minute.

20. The method of claim 7, wherein the first reducing agent comprises dimethylaminoborane.

21. The method of claim 7, wherein the second reducing agent comprises hypophosphorous acid.

22. The method of claim 7, wherein the second reducing agent comprises ammonium hypophosphite.

23. The method of claim 7, wherein the second reducing agent comprises hydrazine.

24. An electroless deposition solution, comprising:

cobalt ions;

at least two reducing agents configured to reduce the cobalt ions to a cobalt film, wherein the at least two reducing agents comprise;

a first reducing agent comprising an aminoborane; and

a second distinct reducing agent comprising phosphorous and substantially absent of an alkali metal.

25. The electroless deposition solution of claim 24, wherein the first reducing agent comprises dimethylaminoborane.

26. The electroless deposition solution of claim 24, wherein the second reducing agent comprises hypophosphorous acid.

27. The electroless deposition solution of claim 24, wherein the second reducing agent comprises ammonium hypophosphite.

28. The electroless deposition solution of claim 24, wherein the second reducing agent comprises hydrazine.

29. The electroless deposition solution of claim 24, wherein a concentration of the second reducing agent is at least approximately 20 times larger than a concentration of the first reducing agent.

30. The electroless deposition solution of claim 24, wherein a concentration of the first reducing agent is between approximately 0.001 mol/L and approximately 0.01 mol/L.

31. The electroless deposition solution of claim 24, comprising a pH less than or equal to 10.

32. The electroless deposition solution of claim 24, further comprising metal ions other than the cobalt ions.

33. The electroless deposition solution of claim 32, wherein the metal ions other than the cobalt ions are selected from the group of metal ions consisting of chromium ions, molybdenum ions, and tungsten ions.

34. The electroless deposition solution of claim 33, wherein a source of the tungsten ions comprise a tungsten (VI) compound.