High modulus, low dielectric constant coatings

• US 6,576,300 B1
• Filed: 03/20/2000
• Issued: 06/10/2003
• Est. Priority Date: 03/20/2000
• Status: Expired due to Fees

• Current Assignee: Axcelis Technologies Incorporated, Dow, Inc.
• Original Assignee: Axcelis Technologies Incorporated, Dow, Inc.
• Inventors: Chung, Kyuha, Spaulding, Michael John, Liu, Youfan, Berry, Ivan Louis III, Moyer, Eric Scott, Han, Qingyuan
• Primary Examiner(s): PADGETT, MARIANNE L
• Application Number:
  US09/528,835
• Time in Patent Office: 1,177 Days
• Field of Search: 427/489,536,539,397.7,397.8,535,493 438/789,793
• US Class Current: 427/489
• CPC Class Codes: C01B 33/126 Preparation of silica of undetermined type
• CPC Class Codes: H01L 21/02126 the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
• CPC Class Codes: H01L 21/02134 the material comprising hydrogen silsesquioxane, e.g. HSQ
• CPC Class Codes: H01L 21/02203 the layer being porous
• CPC Class Codes: H01L 21/02216 the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
• CPC Class Codes: H01L 21/02282 liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/0234 treatment by exposure to a plasma
• CPC Class Codes: H01L 21/3122 layers comprising polysiloxane compounds
• CPC Class Codes: H01L 21/31695 Deposition of porous oxides or porous glassy oxides or oxide based porous glass
• CPC Class Codes: Y10T 428/31663 As siloxane, silicone or silane

Abstract

Low dielectric constant films with improved elastic modulus. The method of making such coatings involves providing a porous network coating produced from a resin containing at least 2 Si—H groups where the coating has been thermally cured and has a dielectric constant in the range of from about 1.1 to about 3.5, and plasma treating the coating to convert the coating into porous silica. Plasma treatment of the network coating yields a coating with improved modulus, but with a higher dielectric constant. The coating is plasma treated for between about 15 and 120 seconds at a temperature less than or about 350° C. The plasma treated coating can optionally be annealed. Rapid thermal processing (RTP) of the plasma treated coating reduces the dielectric constant of the coating while maintaining an improved elastic modulus as compared to the initial porous coating. The annealing temperature is preferably in excess of or about 350° C., and the annealing time is preferably at least or about 120 seconds. The annealed, plasma treated coating has a dielectric constant in the range of from about 1.1 to about 2.4 and an improved elastic modulus.

Claims

1. A method of making a plasma treated coating comprising:

providing a thermally cured porous network coating produced from a resin containing at least 2 Si—

H groups, wherein the porous network coating has an initial dielectric constant and an initial elastic modulus; and

plasma treating the porous network coating to reduce an amount of SiH bonds and to provide a plasma treated coating having a second dielectric constant which is greater than the initial dielectric constant, and a second elastic modulus which is greater than the initial elastic modulus.

2. The method of claim 1 further comprising annealing the plasma treated coating to provide an annealed, plasma treated coating having a third dielectric constant which is less than the second dielectric constant and a third elastic modulus which is greater than the initial elastic modulus.

3. The method of claim 2 wherein the plasma treated coating is annealed at a temperature in excess of or about 350°

C.

4. The method of claim 2 wherein the plasma treated coating is annealed at a temperature in the range of about 350°

C. to about 450°

C.

5. The method of claim 2 wherein the plasma treated coating is annealed for at least or about 120 seconds.

6. The method of claim 1 wherein the second elastic modulus of the plasma treated coating is at least 50% greater than the initial elastic modulus.

7. The method of claim 1 wherein the second elastic modulus of the plasma treated coating is at least 100% greater than the initial elastic modulus.

8. The method of claim 2 wherein the third elastic modulus of the annealed, plasma treated coating is at least 50% greater that the initial elastic modulus.

9. The method of claim 2 wherein the third elastic modulus of the annealed, plasma treated coating is at least 100% greater than the initial elastic modulus.

10. The method of claim 1 wherein the thermally cured porous network coating is cured by heating to a temperature sufficient to convert the porous network coating into a ceramic.

11. The method of claim 10 wherein the thermally cured porous network coating is cured by heating to a temperature of about 50°

C. to about 1000°

C. for up to or about 6 hours.

12. The method of claim 11 wherein the thermally cured porous network coating is cured by heating to a temperature in the range of about 50°

C. to about 500°

C. for between 10 minutes and about 2 hours.

13. The method of claim 11 wherein the thermally cured porous network coating is cured by heating to a temperature in the range of about 350°

C. to about 450°

C. for between 10 minutes and about 1 hour.

14. The method of claim 1 wherein the thermally cured porous network coating is plasma treated for a time in the range of about 15 to about 120 seconds.

15. The method of claim 1 wherein the thermally cured porous network coating is plasma treated at a temperature less than or about 350°

C.

16. The method of claim 1 wherein the thermally cured porous network coating is plasma treated at a temperature in the range of about 80°

C. to about 280°

C.

17. The method of claim 2 wherein the third dielectric constant of the annealed, plasma treated coating is in the range of from about 1.1 to about 3.5.

18. The method of claim 2 wherein the third elastic modulus of the annealed, plasma treated coating is greater than or about 4 GPa.

19. The method of claim 2 wherein the third elastic modulus of the annealed, plasma treated coating is greater than or about 10 GPa.