Cyclic amino compounds for low-k silylation

• US 8,999,734 B2
• Filed: 03/10/2010
• Issued: 04/07/2015
• Est. Priority Date: 03/10/2009
• Status: Active Grant

• Current Assignee: American Air Liquide Incorporated (L'Air Liquide SA)
• Original Assignee: American Air Liquide Incorporated (L'Air Liquide SA)
• Inventors: McAndrew, James J. F., Anderson, Curtis, Dussarrat, Christian
• Primary Examiner(s): Abdelaziez, Yasser A
• Application Number:
  US12/721,362
• Publication Number:
  US 20100233829A1
• Time in Patent Office: 1,854 Days
• Field of Search: None
• US Class Current: 438/4
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• CPC Class Codes: H01L 21/02343 treatment by exposure to a liquid
• CPC Class Codes: H01L 21/02359 treatment to change the surface groups of the insulating layer

Abstract

Disclosed herein are mono-functional silylating compounds that may exhibit enhanced silylating capabilities. Also disclosed are method of synthesizing and using these compounds. Finally methods to determine effective silylation are also disclosed.

Claims

1. A method of repairing a dielectric film previously damaged by a processing step(s), the method comprising the step of:

contacting the dielectric film with a repair agent having a formula R₃SiL, wherein each R is independently selected from the group consisting of H, methyl, and ethyl;

L is a nitrogen-containing ring selected from the group consisting of 1,2,3-triazole, piperidine, 1-methylpiperazine, pyrolidine, and pyrazole; and

one nitrogen in the nitrogen-containing ring is bonded directly to the Si atom, whereby the dielectric film is completely or partially restored.

2. The method of claim 1, further comprising heating the dielectric film after introduction into the chamber and prior to introduction of the repair agent.

3. The method of claim 1, further comprising annealing the dielectric film following the reaction contacting step.

4. The method of claim 1, wherein the repair agent is selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilyl-1,2,3-triazole, trimethylsilylpiperidine, and trimethylsilyl-4-methylpiperazine.

5. The method of claim 4, wherein the repair agent has a total concentration of metal contaminants of less than 10 ppmw.

6. The method of claim 4, wherein the dielectric film is porous.

7. The method of claim 6, wherein the porous dielectric film is nanoporous silica.

8. The method of claim 6, wherein the porous dielectric film has a dielectric constant of 2.0 to 3.0.

9. The method of claim 8, wherein the porous dielectric film has a dielectric constant of 2.2 or smaller.

10. The method of claim 1, wherein the dielectric film comprises a hydrogenated carbon-doped silicon oxide.

11. The method of claim 1, wherein the restoration comprises an improvement of a repair depth and/or a wet etch rate.

12. The method of claim 1, wherein the repair agent is a vapor.

13. The method of claim 1, wherein the repair agent is a liquid.

14. The method of claim 1, wherein the processing step comprises an etching or a chemical mechanical polishing step which removed dielectric film methyl terminations to leave either dangling bonds or Si—

OH groups.

15. The method of claim 1, wherein the repair agent is selected from the group consisting of trimethylsilylpyrrolidine, trimethylsilylpyrazole, trimethylsilylpiperidine, and combinations thereof.