Defectivity and process control of electroless deposition in microelectronics applications

• US 20070062408A1
• Filed: 10/05/2005
• Published: 03/22/2007
• Est. Priority Date: 09/20/2005
• Status: Active Grant

• Current Assignee: MacDermid Enthone Inc. (Element Solutions Inc)
• Original Assignee: Enthone Incorporated (Element Solutions Inc)
• Inventors: Chen, Qingyun, Hurtubise, Richard, Paneccasio, Vincent, Stritch, Daniel, Valverde, Charles, Witt, Christian, Petrov, Nicolai
• Granted Patent: US 7,611,988 B2
• Time in Patent Office: Days
• US Class Current: 106/1.260
• CPC Class Codes: C09D 5/10 containing metal dust
• CPC Class Codes: C23C 18/34 using reducing agents
• 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
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

Methods and compositions for electrolessly depositing Co, Ni, or alloys thereof onto a substrate in manufacture of microelectronic devices. Grain refiners, levelers, oxygen scavengers, and stabilizers for electroless Co and Ni deposition solutions.

Claims

1. An electroless deposition composition for electrolessly depositing Co, Ni, or alloys thereof onto a substrate in manufacture of microelectronic devices, the deposition composition comprising (a) a source of deposition ions selected from the group consisting of Co ions and Ni ions, (b) a reducing agent for reducing said deposition ions onto the substrate, and (c) a stabilizer selected from the group consisting of an aminobenzoic acid, an hydroxybenzoic acid, a molybdenum oxide, a vanadium oxide, a rhenium oxide, salts thereof, derivatives thereof, and combinations thereof.

2. The electroless deposition composition of claim 1 wherein the stabilizer comprises the aminobenzoic acid.

3. The electroless deposition composition of claim 2 wherein the aminobenzoic acid is selected from the group consisting of 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 5-aminosalicylic acid, 2-amino-5-hydroxybenzoic acid, salts thereof, derivatives thereof, and combinations thereof.

4. The electroless deposition composition of claim 2 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 2 ppm and about 1500 ppm.

5. The electroless deposition composition of claim 2 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 5 ppm and about 30 ppm.

6. The electroless deposition composition of claim 3 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 2 ppm and about 1500 ppm.

7. The electroless deposition composition of claim 3 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 5 ppm and about 30 ppm.

8. The electroless deposition composition of claim 1 wherein the stabilizer comprises the hydroxybenzoic acid.

9. The electroless deposition composition of claim 8 wherein the hydroxybenzoic acid is selected from the group consisting of salicylic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, 2,3,6-trihydroxybenzoic acid, 2,4,5-trihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 3,4,5-trihydroxybenzoic acid, salts thereof, derivatives thereof, and combinations thereof.

10. The electroless deposition composition of claim 8 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 2 ppm and about 1500 ppm.

11. The electroless deposition composition of claim 8 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 5 ppm and about 30 ppm.

12. The electroless deposition composition of claim 9 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 2 ppm and about 1500 ppm.

13. The electroless deposition composition of claim 9 wherein the stabilizer is present in the electroless deposition composition at a concentration between about 5 ppm and about 30 ppm.

14. The electroless deposition composition of claim 1 wherein the stabilizer comprises the molybdenum oxide present in the electroless deposition composition at a concentration between about 10 ppm and about 800 ppm.

15. The electroless deposition composition of claim 1 wherein the stabilizer comprises the molybdenum oxide;

wherein the molybdenum oxide is selected from the group consisting of MoO₃ predissolved with TMAH;

(NH₄)₂MoO₄;

(NH₄)₂Mo₂O₇;

(NH₄)₆Mo₇O₂₄.4H₂O;

(NH₄)₂Mo₃O₁₀.2H2O;

(NH₄)₆Mo₈O₂₇.4H2O;

dimolybdatesi (Me₂Mo₂O₇.nH₂O);

trimolybdates (Me₂Mo₃O₁₀.nH₂O) ;

tetramolybdates (Me₂Mo₄O₁₃);

metamolybdates (Me₂H_10-m[H₂(M₂O₇)₆].nH₂O);

hexamolybdates (Me₂Mo₆O₁₉.nH₂O);

octamolybdates (Me₂Mo₈O₂₅.nH₂O);

paramolybdates (Me₂Mo₇O₂₂.nH₂O and Me₁₀Mo₁₂O₄₁.nH₂O);

molybdic acids;

molybdic acid salts of ammonium, tetramethylammonium and alkali metals;

heteropoly acids of molybdenum; and

combinations thereof;

wherein Me is a counterion selected from among ammonium, tetramethylammonium, and alkali metal cations;

m is less than 10; and

n is an integer having a value corresponding to a stable or metastable form of the hydrated oxide;

wherein the stabilizer is present in the electroless deposition composition at a concentration between about 10 ppm and about 800 ppm.

16. The electroless deposition composition of claim 14 wherein the molybdenum oxide is present in the electroless deposition composition at a concentration between about 10 ppm and about 30 ppm.

17. The electroless deposition composition of claim 15 wherein the molybdenum oxide is present in the electroless deposition composition at a concentration between about 10 ppm and about 30 ppm.

18. The electroless deposition composition of claim 14 wherein the molybdenum oxide is present in the electroless deposition composition at a concentration between about 100 ppm and about 500 ppm.

19. The electroless deposition composition of claim 15 wherein the molybdenum oxide is present in the electroless deposition composition at a concentration between about 100 ppm and about 500 ppm.

20. The electroless deposition composition of claim 1 wherein the stabilizer comprises the vanadium oxide.

21. The electroless deposition composition of claim 20 wherein the vanadium oxide is selected from the group consisting of vanadate salts, triammonium vanadate salts, metavanadate salts, pyrovanadates (V₂O⁴⁻

), hexavanadates (HV₆O₁,³⁻

), V₂O₃, V₂O₄, V₂O₅, and combinations thereof.

22. The electroless deposition composition of claim 21 wherein the vanadium oxide is present in the electroless deposition composition at a concentration between about 1 ppm and about 100 ppm.

23. The electroless deposition composition of claim 21 wherein the vanadium oxide is present in the electroless deposition composition at a concentration between about 2 ppm and about 5 ppm.

24. The electroless deposition composition of claim 21 wherein the vanadium oxide is present in the electroless deposition composition at a concentration between about 5 ppm and about 20 ppm.

25. The electroless deposition composition of claim 1 wherein the stabilizer comprises the rhenium oxide in cl concentration between about 2 ppm and about 300 ppm.

26. The electroless deposition composition of claim 25 wherein the rhenium oxide is selected from the group consisting of rhenium trioxides, perrhenic acids, ammonium perrhenic acid salts, tetramethylammonium perrhenic acid salts, alkali metal perrhenic acid salts, heteropolyacids of rhenium, and combinations thereof.

27. The electroless deposition composition of claim 26 wherein the rhenium oxide is present in a concentration between about 5 ppm and about 10 ppm.

28. The electroless deposition composition of claim 26 wherein the rhenium oxide is present in a concentration between about 10 ppm and about 100 ppm.

29. A method for electrolessly depositing Co, Ni, or alloys thereof onto a substrate in manufacture of microelectronic devices, the method comprising contacting the substrate with the electroless deposition composition of claim 1.