Use of silyating agents

• US 7,425,505 B2
• Filed: 07/19/2004
• Issued: 09/16/2008
• Est. Priority Date: 07/23/2003
• Status: Expired due to Fees

• Current Assignee: Tel Fsi, Inc. (Tokyo Electron Limited)
• Original Assignee: FSI International, Inc. (Tokyo Electron Limited)
• Inventors: Christenson, Kurt Karl, Clark, Philip G., Schwab, Brent D.
• Primary Examiner(s): Sarkar; Asok K.
• Assistant Examiner(s): Yevsikov; Victor V.
• Application Number:
  US10/894,319
• Publication Number:
  US 20050032293A1
• Time in Patent Office: 1,520 Days
• Field of Search: 438/689, 438/725, 438/780, 438/787
• US Class Current: 438/689
• CPC Class Codes: H01L 21/02063 the processing being the formation of vias or contact holes
• CPC Class Codes: H01L 21/02137 the material comprising alkyl silsesquioxane, e.g. MSQ
• CPC Class Codes: H01L 21/02203 the layer being porous
• CPC Class Codes: H01L 21/02337 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/02343 treatment by exposure to a liquid
• CPC Class Codes: H01L 21/02348 treatment by exposure to UV light
• CPC Class Codes: H01L 21/3105 After-treatment
• CPC Class Codes: H01L 21/31058 of organic layers
• CPC Class Codes: H01L 21/31138 by dry-etching
• CPC Class Codes: H01L 21/3122 layers comprising polysiloxane compounds
• CPC Class Codes: H01L 21/3124 layers comprising hydrogen silsesquioxane
• CPC Class Codes: H01L 21/3125 layers comprising silazane compounds
• CPC Class Codes: H01L 21/31695 Deposition of porous oxides or porous glassy oxides or oxide based porous glass
• CPC Class Codes: H01L 21/76814 post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
• CPC Class Codes: H01L 21/76826 by contacting the layer with gases, liquids or plasmas
• CPC Class Codes: H01L 23/3171 the coating being directly applied to the semiconductor body, e.g. passivation layer H01L23/3178 takes precedence
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Abstract

The present invention provides improvements to the use of silyating agents in semiconductor processing. More particularly, the silyating agents may be provided in combination with a substantially non-flammable ether, so that the combination is substantially non-flammable. Additionally, the silyating agent may be utilized in vapor form, or applied in conjunction with the electromagnetic radiation. Each of these embodiments can enhance the usability of the silyating agent, i.e., by rendering the silyating agent more safe, more easily utilized in a variety of processing equipment and/or by enhancing the passivation efficacy/efficiency of the silyating agent.

Claims

1. A method of passivating a semiconductor substrate comprising a dielectric film to moisture absorption comprising:

processing the dielectric film of the substrate in manner that causes the dielectric constant of the dielectric film to increase; and

after said processing, exposing the dielectric film of the substrate to a composition in a manner so as to reduce the dielectric constant of the dielectric film, wherein the composition comprises at least one silyating agent and at least one substantially non-flammable ether.

2. The method of claim 1, wherein the substrate is exposed to the composition at ambient pressure.

3. The method of claim 1, wherein the silyating agent is hexamethyldisilazane.

4. The method of claim 1, wherein said processing comprises the step of treating the substrate with a post-ash residue removal composition in a manner so as to expose the dielectric film.

5. The method of claim 1, wherein the ether comprises a hydrofluoroether.

6. The method of claim 5, wherein the hydrofluoroether comprises a segregated hydrofluoroether.

15. The method of claim 1, wherein the ether comprises a hydrofluoroether.

16. The method of claim 15, wherein the hydrofluroether comprises a segregated hydrofluoroether.

7. A method of passivating a semiconductor substrate comprising a dielectric film to moisture absorption comprising:

processing the dielectric film of the substrate in manner that causes the dielectric constant of the dielectric film to increase; and

after said processing, exposing the dielectric film of the substrate to a vapor in a manner so as to reduce the dielectric constant of the dielectric film, wherein the vapor comprises at least one silyating agent and at least one substantially non-flammable ether.

8. The method of claim 7 wherein the vapor further comprises an inert carrier gas.

9. The method of claim 7, further comprising the step of exposing the substrate to electromagnetic radiation.

10. The method of claim 9, wherein the electromagnetic radiation comprises broadband ultraviolet radiation.

11. The method of claim 10, wherein the ultraviolet radiation is applied to the substrate substantially simultaneously with the at least one silyating agent and at least one substantially non-flammable ether.

12. The method of claim 10, wherein the ultraviolet radiation is applied to the substrate sequentially with respect to the at least one silyating agent and at least one substantially non-flammable ether.

13. The method of claim 10, wherein the ultraviolet radiation is applied to the substrate in an overlapping fashion with respect to the at least one silyating agent and at least one substantially non-flammable ether.

14. The method of claim 7, wherein said processing comprises the step of exposing the substrate to a post-ash residue removal composition in a manner so as to expose the dielectric film.

17. A method of passivating a semiconductor substrate comprising a dielectric film having an upper and a lower surface to moisture absorption comprising:

processing the dielectric film of the substrate in manner that causes the dielectric constant of the dielectric film to increase; and

after said processing, performing the steps comprising;

exposing the dielectric film of the substrate to at least one silyating agent; and

exposing the substrate to broadband ultraviolet radiation, wherein said exposing steps are performed in a manner so as to reduce the dielectric constant of the dielectric film.

18. The method of claim 17, wherein the at least one silyating agent comprises hexamethyldisilazane.

19. The method of claim 18, wherein the hexamethyldisilazane is provided as a fluid composition.

20. The method of claim 19, wherein the fluid composition further comprises a substantially non-flammable ether.

21. The method of claim 20, wherein the substantially non-flammable ether comprises a segregated hydrofluoroether.

22. The method of claim 17, wherein the substrate is exposed to broadband ultraviolet radiation via an ultraviolet lamp.

23. The method of claim 17, wherein the broadband ultraviolet radiation is caused to be incident upon the upper surface of the semiconductor substrate.

24. The method of claim 17, wherein the broadband ultraviolet radiation is caused to be incident upon the lower surface of the semiconductor substrate.

25. The method of claim 17, wherein said processing comprises the step of exposing the substrate to a post-ash residue removal composition in a manner so as to expose the dielectric film.

26. A single processing chamber method for passivating a semiconductor substrate comprising a dielectric film to moisture absorption following a residue removal step comprising:

placing the substrate within the processing chamber, wherein while the substrate is positioned in the processing chamber performing steps comprising;

a first exposing step comprising exposing at least a portion of the substrate to a residue removal composition in a manner so as to expose the dielectric film, wherein the dielectric film has an increased dielectric constant due to processing; and

after said first exposing a second exposing step comprising exposing at least a portion of the dielectric film of the substrate to a silvating composition comprising at least one silyating agent in a manner so as to reduce the dielectric constant of the dielectric film.

27. The method of claim 26, wherein the contact angle of the dielectric film is less than about 10°

after being exposed to the residue removal composition.

28. The method of claim 27, wherein the contact angle of the dielectric film is at least about 60°

after being exposed to the at least one silyating agent.

29. The method of claim 26, further comprising the step of exposing at least a portion of the substrate to electromagnetic radiation within the processing chamber.

30. The method of claim 26, wherein the silyating composition further comprises at least one substantially non-flammable ether.