Defectivity and process control of electroless deposition in microelectronics applications

• US 7,410,899 B2
• Filed: 09/20/2005
• Issued: 08/12/2008
• 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
• Primary Examiner(s): Fourson; George
• Assistant Examiner(s): Garcia; Joannie A
• Application Number:
  US11/230,912
• Publication Number:
  US 20070066057A1
• Time in Patent Office: 1,057 Days
• Field of Search: 438/678, 438/761, 438/778, 438/782, 438/FOR.390, 438/FOR.405, 257/635, 257/766, 257/E21.586, 204/157.45, 204/157.5, 204/633
• US Class Current: 438/678
• 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. 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 an electroless deposition composition comprising (a) a grain refiner comprising a grain refiner compound selected from the group consisting of a polyphosphoric acid, a polyphosphate salt, and a combination thereof wherein said grain refiner compound is a compound having a formula M_(n+2)P_nO_(3n+1) or (MPO₃)_n, where M represents a counter ion, and n=3 to 600; and

(b) a source of deposition ions selected from the group consisting of Co ions and Ni ions.

2. The method of claim 1 wherein the grain refiner compound is ammonium polyphosphate.

3. The method of claim 1 wherein the grain refiner compound is sodium polyphosphate.

4. The method of claim 1 wherein the grain refiner compound is polyphosphoric acid.

5. The method of claim 1 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 1 g/L and about 100 g/L.

6. The method of claim 1 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 4 g/L and about 50 g/L.

7. The method of claim 1 wherein the electroless deposition composition further comprises a reducing agent.

8. The method of claim 1 wherein the electroless deposition composition further comprises an oxygen scavenger compound selected from the group consisting of ascorbic acid, SO₃²⁻

, HSO₃⁻

, hydroquinone, catechol, resorcinol, hydrazine, and combinations thereof.

9. The method of claim 1 wherein the electroless deposition composition further comprises a stabilizer compound 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.

10. The method of claim 1 wherein the electroless deposition composition further comprises a leveler selected from the group consisting of diphenyl oxide disulfonic acids, triethanolamine salts of lauryl sulfate, ammonium laureth sulfates, alkylbenzene sulfonates, dodecylbenzene sulfonic acids, alkyldiphenyloxide disulfonate, low molecular weight polypropylene glycol, and combinations thereof.

11. The method of claim 1 wherein the substrate is a copper metal layer located in a semiconductor integrated circuit device.

12. The method of claim 1 wherein the electroless deposition composition further comprises an oxime-based stabilizer compound selected from the group consisting of salicylaldoxime, syn-2-pyridinealdoxime, dimethylglyoxime, 1,2-cyclohexanedione dioxime, diphenyl glyoxime, pyridyl diglyoxime, and combinations thereof.

13. An electroless plating solution for plating a metal capping layer onto a metal-filled interconnect in a microelectronic device, the solution comprising:

a source of deposition ions selected from the group consisting of Co ions and Ni ions;

a reducing agent; and

a grain refiner compound selected from the group consisting of a polyphosphoric acid, a polyphosphate salt, and a combination thereof wherein said grain refiner compound is a compound having a formula M_(n+2)P_nO_(3n+1) or (MPO₃)_n, where M represents a counter ion, and n=2 to 600.

14. The plating solution of claim 13 wherein the grain refiner compound is ammonium polyphosphate.

15. The plating solution of claim 13 wherein the grain refiner compound is sodium polyphosphate.

16. The plating solution of claim 13 wherein the grain refiner compound is polyphosphoric acid.

17. The plating solution of claim 13 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 1 g/L and about 100 g/L.

18. The plating solution of claim 13 wherein the grain refiner compound is present in the electroless deposition composition at a concentration between about 4 g/L and about 50 g/L.

19. The plating solution of claim 13 wherein the electroless deposition composition further comprises an oxygen scavenger compound selected from the group consisting of ascorbic acid, SO₃²⁻

, HSO₃⁻

, hydroquinone, catechol, resorcinol, hydrazine, and combinations thereof.

20. The plating solution of claim 13 wherein the electroless deposition composition further comprises a stabilizer compound selected from the group consisting of an aminobenzoic acid, an hydroxybenzoic acid, a molybdenum oxide, a vanadium oxide, rhenium oxide, salts thereof, derivatives thereof, and combinations thereof.

21. The plating solution of claim 13 wherein the electroless deposition composition further comprises a leveler selected from the group consisting of diphenyl oxide disulfonic acids, triethanolamine salts of lauryl sulfate, ammonium laureth sulfates, alkylbenzene sulfonates, dodecylbenzene sulfonic acids, alkyldiphenyloxide disulfonate, low molecular weight polypropylene glycol, and combinations thereof.

22. The electroless plating solution of claim 13 further comprising an oxime-based stabilizer compound selected from the group consisting of salicylaldoxime, syn-2-pyridinealdoxime, dimethylglyoxime, 1,2-cyclohexanedione dioxime, diphenyl glyoxime, pyridyl diglyoxime, and combinations thereof.