Electroless layer plating process and apparatus

• US 7,897,198 B1
• Filed: 09/03/2002
• Issued: 03/01/2011
• Est. Priority Date: 09/03/2002
• Status: Active Grant

• Current Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Original Assignee: Novellus Systems Incorporated (Lam Research Corporation)
• Inventors: Cleary, Timothy Patrick, Reid, Jonathan D., Webb, Eric G., Park, Heung L.
• Primary Examiner(s): Bareford; Katherine A
• Application Number:
  US10/235,420
• Time in Patent Office: 3,101 Days
• Field of Search: 427/404, 427/405, 427/304, 427/305, 427/58, 427/98, 427/123, 438/678
• US Class Current: 427/97.1
• CPC Class Codes: C23C 18/1651 Two or more layers only obtained by electroless plating
• CPC Class Codes: C23C 18/166 with two steps starting with addition of reducing agent followed by metal deposition
• CPC Class Codes: C23C 18/31 Coating with metals
• 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 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76849 the layer being positioned on top of the main fill metal
• CPC Class Codes: H01L 21/76873 for electroplating

Abstract

Electroless plating is performed to deposit conductive materials on work pieces such as partially fabricated integrated circuits. Components of an electroless plating bath are separately applied to a work piece by spin coating to produce a very thin conductive layer (in the range of a few hundred angstroms). The components are typically a reducing agent and a metal source.

Claims

1. A method of forming a metal layer on a surface of a partially fabricated semiconductor device substrate, the method comprising

(a) contacting the surface of the semiconductor device substrate with a liquid reducing agent solution, wherein the reducing agent solution comprises insufficient metal ion to permit electroless plating of the metal;

(b) contacting the surface of the semiconductor device substrate with a liquid metal ion solution, wherein the metal ion solution comprises insufficient reducing agent to permit electroless plating of the metal, whereby the metal ion reacts with the reducing agent at the substrate surface to electrolessly plate the metal on the substrate surface; and

(c) repeating (a) and (b) one or more times to gradually build up the metal layer, wherein each repetition of (a) and (b) generates a thin metal layer, on the order of about 1 to 50 atomic layers.

2. The method of claim 1, wherein the reducing agent solution is substantially free of the metal ions.

3. The method of claim 1, wherein the reducing agent solution comprises a reducing agent selected from the group consisting of glyoxylic acid, formaldehyde, hydrazine, dimethylamino borane, and ammonium hypophosphite.

4. The method of claim 1, wherein the reducing agent solution comprises reducing agent in a concentration ranging from between about 0.01 M to about 0.2 M.

5. The method of claim 1, wherein the metal ion is copper ion and the reducing agent is selected from the group consisting of glyoxylic acid and formaldehyde.

6. The method of claim 1, wherein the metal ion is cobalt ion and the reducing agent is selected from the group consisting of hydrazine, dimethylamineborane, and hypophosphite.

7. The method of claim 1, wherein the reducing agent solution contacts the substrate surface in a manner causing a saturated layer of reducing agent to adsorb to the substrate surface.

8. The method of claim 1, wherein the partially fabricated semiconductor device has comprises features having a principal dimension of at most about 1 micrometer.

9. The method of claim 1, wherein the metal layer comprises a seed layer for a Damascene structure.

10. The method of claim 1, wherein the metal layer comprises barrier-seed layer.

11. The method of claim 1, wherein the metal layer comprises a capping layer provided on top of a copper or aluminum conductive line.

12. The method of claim 11, wherein the capping layer comprises a material selected from the group consisting of Co, Cop, CoB, CoBP, CoBPW, CoWP, Ni, NiP, NiPW, and combinations thereof.

13. The method of claim 1, wherein the metal ion source comprises a salt of the metal ion.

14. The method of claim 13, wherein the metal ion is selected from the group consisting of cobalt, copper, nickel, and combinations thereof.

15. The method of claim 1, wherein the metal ion solution comprises metal ions in a concentration of between about 0.01 M and 0.5 M.

16. The method of claim 1, further comprising:

(d) contacting the substrate surface with a second reducing agent solution, wherein the reducing agent solution comprises insufficient concentration of a second metal ion to permit electroless plating of the second metal; and

(e) contacting the substrate surface with a solution of the second metal ion, whereby the second metal ion reacts with the second reducing agent on the substrate solution to electrolessly plate the second metal on the substrate surface.

17. The method of claim 1, further comprising contacting the substrate surface with deionized water.

18. The method of claim 1, wherein each repetition of (a) and (b) generates approximately one monolayer of metal.

19. A method of forming a metal layer on a surface of a partially fabricated semiconductor device substrate the method comprising

(a) delivering a liquid reducing agent solution to the surface of a semiconductor device substrate to cause said reducing agent to adsorb to the substrate surface;

(b) stopping or reducing delivery of the reducing agent solution to the substrate surface;

(c) delivering a liquid metal ion solution to the substrate surface, whereby the metal ion reacts with the adsorbed reducing agent at the substrate surface to electrolessly plate the metal on the substrate surface; and

(d) repeating (a) through (c) one or more times to gradually build up the metal layer, wherein each repetition of (a) through (c) generates a thin metal layer, on the order of about 1 to 50 atomic layers.

20. A method of forming a metal layer on a surface of a partially fabricated semiconductor device substrate, the method comprising

(a) delivering a metal source solution to the surface of a semiconductor device substrate to cause said metal source to adsorb to the substrate surface;

(b) stopping or reducing delivery of the metal source solution to the substrate surface;

(c) delivering a reducing agent solution to the substrate surface, whereby the reducing agent reacts with the adsorbed metal source at the substrate surface to electrolessly plate the metal on the substrate surface;

(d) repeating (a) through (c) one or more times to gradually build up the metal layer, wherein each repetition of (a) through (c) generates a thin metal layer, on the order of about 1 to 50 atomic layers, wherein repeating (a) comprises contacting the metal source solution to the metallic layer on the substrate.

21. The method of claim 20, wherein each repetition of (a) through (c) generates approximately one monolayer of metal.

22. A method of forming a composite metal layer on a surface of a semiconductor device substrate, the method comprising

(a) contacting the semiconductor device substrate surface with a liquid reducing agent solution, wherein the reducing agent solution comprises insufficient metal ion to permit electroless plating of the metal;

(b) contacting the substrate surface with a liquid first metal ion solution, wherein the first metal ion solution comprises insufficient reducing agent to permit electroless plating of the first metal, whereby the first metal ion reacts with the reducing agent at the substrate surface to electrolessly plate a first metal layer on the substrate surface;

(c) contacting the substrate surface with a liquid reducing agent solution, wherein the reducing agent solution comprises insufficient metal ion to permit electroless plating of the metal; and

(d) contacting the substrate surface with a liquid second metal ion solution, wherein the second metal ion is a different than the first metal ion and the second metal ion solution comprises insufficient reducing agent to permit electroless plating of the metal, whereby the second metal ion reacts with the reducing agent at the substrate surface to electrolessly plate the second metal on the first metal layer.

23. The method of claim 22, further comprising repeating (a) through (d) one or more times to gradually build up the composite metal layer, wherein each repetition of (a) and (b) and each repetition of (c) and (d) generates a thin metal layer, on the order of about 1 to 50 atomic layers.