Copper electroplating process for uniform across wafer deposition and void free filling on semi-noble metal coated wafers

• US 8,513,124 B1
• Filed: 05/21/2010
• Issued: 08/20/2013
• Est. Priority Date: 03/06/2008
• Status: Active Grant

• Current Assignee: Novellus Systems Incorporated (LAM Research Corporation)
• Original Assignee: Novellus Systems Incorporated (LAM Research Corporation)
• Inventors: Ponnuswamy, Thomas A., Reid, Jonathan D., Mayer, Steven T., Sukamto, John H.
• Primary Examiner(s): Maldonado, Julio J
• Assistant Examiner(s): McCall Shepard, Sonya D
• Application Number:
  US12/785,205
• Time in Patent Office: 1,187 Days
• Field of Search: 438/687, 257/E21.586, 257/E23.161, 257E23135-E23194, 257E21575-E21585
• US Class Current: 438/687
• CPC Class Codes: C25D 3/38 of copper
• CPC Class Codes: C25D 5/18 Electroplating using modulated, pulsed or reversing current
• CPC Class Codes: C25D 5/50 by heat-treatment
• CPC Class Codes: C25D 7/123 Semiconductors first coated with a seed layer or a conductive layer
• CPC Class Codes: H01L 21/2885 using an external electrical current, i.e. electro-deposition
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76864 Thermal treatment
• CPC Class Codes: H01L 21/76873 for electroplating
• CPC Class Codes: H01L 2221/1089 Stacks of seed layers

Abstract

Disclosed are methods of depositing a copper seed layer to be used for subsequent electroplating a bulk-layer of copper thereon. A copper seed layer may be deposited with different processes, including CVD, PVD, and electroplating. With electroplating methods for depositing a copper seed layer, disclosed are methods for depositing a copper alloy seed layer, methods for depositing a copper seed layer on the semi-noble metal layer with a non-corrosive electrolyte, methods of treating the semi-noble metal layer that the copper seed layer is deposited on, and methods for promoting a more uniform copper seed layer deposition across a semiconductor wafer.

Claims

1. A method for depositing a copper seed layer comprising:

providing a semiconductor wafer having a semi-noble metal layer thereon; and

depositing the copper seed layer on the semi-noble metal layer using an electroplating process with an electrolyte comprising a copper salt and a copper complexing agent, wherein the electrolyte is substantially free of chemical species that are corrosive to the metal layer, and wherein the electrolyte has a pH of about 8.5 to 13.5.

2. The method of claim 1, wherein a resistivity of the electrolyte is at least about 200 ohm cm.

3. The method of claim 1, wherein the semi-noble metal layer comprises cobalt or nickel.

4. The method of claim 1, wherein the chemical species that are corrosive to the semi-noble metal layer include oxygen.

5. The method of claim 1, wherein the chemical species that are corrosive to the semi-noble metal layer include halides.

6. The method of claim 1, wherein the electrolyte further comprises a corrosion inhibiting agent, wherein the corrosion inhibiting agent is selected from the group consisting of formaldehyde, glycolic acid, hydrazine, dimethylamine borane, and sodium hypophosphite.

7. The method of claim 1, further comprising:

depositing a partial copper seed layer on first regions of the semi-noble metal layer using a CVD or a PVD process before depositing the copper seed layer on second regions of the semi-noble metal layer using the electroplating process.

8. The method of claim 7, wherein the semiconductor wafer comprises field areas and features, wherein the field areas comprise the first regions, wherein the features comprise the second regions, and wherein depositing the partial copper seed layer on the first regions and depositing the copper seed layer on the second regions yields a continuous copper seed layer.

9. A method for depositing a copper seed layer comprising:

providing a semiconductor wafer having a semi-noble metal layer thereon;

applying forward and reverse current pulses to the semi-noble metal layer using a process with an electrolyte to treat the metal layer and thereby improve copper seed layer nucleation and coverage, wherein an efficiency of a forward current pulse is about 40% to 80%, wherein the forward current pulse deposits at least about 2.5 monolayers of copper on the metal layer, wherein an efficiency of a reverse current pulse is greater than about 80%, and wherein the reverse current pulse strips off substantially all of the copper deposited during the forward current pulse; and

depositing the copper seed layer on the semi-noble metal layer using an electroplating process with the electrolyte by applying a forward current.

10. The method of claim 9, wherein a resistivity of the electrolyte is at least about 200 ohm cm.

11. The method of claim 9, wherein a forward current passed in the forward current pulse is about 0.3 to 2 Coulombs.

12. The method of claim 9, wherein the electrolyte comprises a copper salt and a copper complexing agent.

13. A method for depositing a copper seed layer comprising:

providing a semiconductor wafer having a semi-noble metal layer thereon, the semiconductor wafer having an edge and a center;

depositing the copper seed layer on the semi-noble metal layer using an electroplating process with an electrolyte including a copper salt and a copper complexing agent, wherein a voltage across the metal layer is higher at the edge of the wafer than at the center of the wafer due to a terminal effect, and wherein a total current density approaches or surpasses a limiting copper current density at the edge of the wafer, a copper current density being a contribution of copper reduction to the total current density, thereby promoting a more uniform deposition rate across the metal layer.

14. The method of claim 13, wherein a resistivity of the electrolyte is at least about 200 ohm cm.

15. The method of claim 13, wherein the total current density surpasses the limiting copper current density at a point between the edge of the wafer and the center of the wafer.

16. The method of claim 13, wherein a current efficiency near the edge of the wafer is about 20% to 30%, and wherein a current efficiency near the center of the wafer is about 50% to 60%.

17. A method for depositing a copper alloy seed layer comprising:

providing a semiconductor wafer having a semi-noble metal layer thereon;

depositing the copper alloy seed layer on the semi-noble metal layer using an electroplating process with a first electrolyte including;

a copper salt and a copper complexing agent, and

a salt of an alloying element, the alloying element selected from;

cobalt, nickel, and silver; and

depositing a bulk-layer of copper on the copper alloy seed layer using an electroplating process with a second electrolyte.

18. The method of claim 17, further comprising:

treating the bulk-layer of copper and the copper alloy seed layer to cause at least some of the alloying element to move into the bulk-layer.

19. The method of claim 17, wherein the deposited copper alloy seed layer comprises about 0.1 to 5 weight percent of the alloying element.

20. The method of claim 17, wherein the copper complexing agent also complexes the alloying element.

21. The method of claim 17, wherein the copper complexing agent does not appreciably complex the alloying element.

22. The method of claim 17, wherein the first electrolyte further includes a second complexing agent, wherein the second complexing agent complexes the alloying element.