Method for forming a conductive copper structure

• US 6,743,719 B1
• Filed: 01/22/2003
• Issued: 06/01/2004
• Est. Priority Date: 01/22/2003
• Status: Active Grant

• Current Assignee: Texas Instruments, Inc.
• Original Assignee: Texas Instruments, Inc.
• Inventors: Xia, Changfeng, Lu, Jiong-Ping, Chen, Linlin
• Primary Examiner(s): GURLEY, LYNNE ANN
• Application Number:
  US10/348,821
• Time in Patent Office: 496 Days
• Field of Search: 438/635, 438/658, 438/660, 438/674, 438/677-679, 438/687, 438/908, 438/913
• US Class Current: 438/658
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76861 Post-treatment or after-treatment not introducing additional chemical elements into the layer
• CPC Class Codes: H01L 21/76874 for electroless plating
• CPC Class Codes: H01L 21/76877 Filling of holes, grooves or trenches, e.g. vias, with conductive material
• CPC Class Codes: Y10S 438/908 Utilizing cluster apparatus

Abstract

The present invention provides, in one embodiment, a method of forming a metal layer over a semiconductor wafer. The method includes the chemical reduction of copper oxide (105) over the deposited copper seed layer (110) by exposure to a substantially copper-free reducing agent solution (120), such that the copper oxide (105) is substantially converted to elemental copper, followed by electrochemical deposition of a second copper layer (125) over the copper seed layer (110). Such methods and resulting conductive structures thereof may be advantageously used in methods to make integrated circuits comprising interconnection metal lines.

Claims

1. A method of forming a metal layer over a semiconductor wafer, comprising:

exposing a copper oxide on a copper seed layer located over a semiconductor substrate to a substantially copper-free reducing agent solution, such that said copper oxide is substantially converted to elemental copper, wherein said substantially copper-free reducing agent solution comprises a reducing agent selected from the group consisting of formate, formaldehyde, dimethylamine borane, ammonium hypophosphite, and hydrazine sulfate; and

electrochemically depositing a second copper layer over said copper seed layer.

2. The method as recited in claim 1 wherein said exposing and said electrochemically depositing is conducted in a same deposition tool.

3. The method as recited in claim 1, further includes drying said copper seed layer after said exposing said copper seed layer to a substantially copper-free reducing agent solution wherein said drying and said exposing are performed in the same tool.

4. The method as recited in claim 1, further includes a time window between said exposing and said electrochemically depositing, of less than about 4 hours.

5. The method as recited in claim 1, wherein said reducing agent has a reduction potential that is less than a reduction potential of a copper-containing solution having essentially the same composition as the copper-free reducing agent solution.

6. The method as recited in claim 1, wherein said substantially copper-free reducing agent is dissolved in an aqueous solution.

7. The method as recited in claim 1, wherein said substantially copper-free reducing agent has a concentration less than about 1 molar.

8. The method as recited in claim 1, wherein a thickness of said copper seed layer after said exposing to said substantially the same as compared to a deposited copper seed layer.

9. The method as recited in claim 1, wherein said thickness of said copper seed layer after said exposing to said substantially copper-free reducing agent is at least about 20 Angstroms.

10. A method of making an integrated circuit comprising:

forming active devices over or in a semiconductor substrate;

forming interconnect metals lines on a dielectric layer located over said active devices including;

exposing a copper oxide on a copper seed layer located over said semiconductor substrate to a substantially copper-free reducing agent solution, such that said copper oxide is substantially converted to elemental copper, wherein said substantially copper-free reducing agent solution comprises a reducing agent selected from the group consisting of formate, formaldehyde, dimethylamine borane, ammonium hypophosphite, and hydrazine sulfate;

depositing, using an electrochemical deposition tool, a second copper layer over said seed layer;

connecting said interconnects with said active devices to form an operative integrated circuit.

11. The method as recited in claim 10 wherein said exposing is conducted in said electrochemical deposition tool.

12. The method as recited in claim 10, further includes drying said copper seed layer after said exposing said copper seed layer to a substantially copper-free reducing agent solution wherein said drying and said exposing are performed in the same tool.

13. The method as recited in claim 10, further includes a time window between said exposing and said electrochemically depositing, of less than about 4 hours.

14. The method as recited in claim 10, wherein said reducing agent has a reduction potential of a copper-containing solution having essentially the same composition as the copper-free reducing agent solution.

15. The method as recited in claim 10, wherein said substantially copper-free reducing agent is dissolved in an aqueous solution.

16. The method as recited in claim 10, wherein said substantially copper-free reducing agent has a concentration of less than about 1 molar.

17. The method as recited in claim 10, wherein a thickness of said copper seed layer after said exposing is substantially the same as compared to a deposited copper seed layer.

18. The method as recited in claim 10, wherein said thickness of said copper seed layer after said exposing to said substantially copper-free reducing agent is at least about 20 Angstroms.