Method and apparatus for removing organic films

• US 6,696,228 B2
• Filed: 10/21/2002
• Issued: 02/24/2004
• Est. Priority Date: 10/23/2001
• Status: Expired due to Fees

• Current Assignee: Nomura Micro Science Co.,Ltd., Ums Co., Ltd.
• Original Assignee: Nomura Micro Science Co.,Ltd., Ums Co., Ltd.
• Inventors: Endo, Mitsuru, Muraoka, Hisashi, Sato, Asuka, Muraoka, Rieko
• Primary Examiner(s): Schilling, Richard L.
• Application Number:
  US10/274,153
• Publication Number:
  US 20030108823A1
• Time in Patent Office: 491 Days
• Field of Search: 430/329, 134/2, 134/10, 134/13
• US Class Current: 430/329
• CPC Class Codes: B08B 2203/005 the liquid being ozonated
• CPC Class Codes: B08B 3/02 Cleaning by the force of jets or sprays
• CPC Class Codes: B08B 3/04 Cleaning involving contact with liquid
• CPC Class Codes: C09D 9/005 containing organic solvents
• CPC Class Codes: C11D 2111/22 Electronic devices, e.g. PCBs or semiconductors
• CPC Class Codes: C11D 7/266 Esters or carbonates
• CPC Class Codes: G03F 7/422 using liquids only G03F7/421 takes precedence
• CPC Class Codes: G03F 7/423 containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds

Abstract

A method and an apparatus for removing an organic film such as a resist film from a substrate surface are provided. These are very safe even at high temperatures, and use a treatment liquid which can be recycled and reused. A treatment liquid typically formed from liquid ethylene carbonate, propylene carbonate, or a liquid mixture of these two compounds, and in particular such a treatment liquid containing dissolved ozone, is contacted with a substrate with an organic film, and the organic film is removed. Furthermore, an apparatus of the present invention (A) a treatment liquid delivery device for transporting the treatment liquid to a treatment area, (B) a film contact device for bringing the treatment liquid into contacting with the organic film surface of the substrate within the treatment area, (C) a liquid circulation device for recycling treatment liquid discharged from the treatment area and returning the recycled liquid to the treatment area via one or more temporary storage devices, and (D) an ozone dissolution device for bringing ozone containing gas into contact with the treatment liquid either within the treatment area and/or within the temporary storage devices.

Claims

1. A method for removing an organic film on a surface of a substrate, comprising:

bringing a treatment liquid comprising liquid ethylene carbonate, propylene carbonate, or both of them into contact with said substrate to remove said organic film, thereby allowing material constituting said organic film to migrate into said treatment liquid,

decomposing said material in said treatment liquid into low molecular weight material by ozone, thereby said ozone treated treatment liquid being regenerated as a treatment liquid, and

recycling the treatment liquid thus regenerated for treating another substrate.

2. The method according to claim 1, wherein said treatment liquid comprises liquid ethylene carbonate, and during said contacting with said substrate said treatment liquid has a temperature within a range from 40 to 200°

C.

3. The method according to claim 1, wherein said treatment liquid comprises propylene carbonate or both of ethylene carbonate and propylene carbonate, and during said contacting with said substrate said treatment liquid has a temperature within a range from 20 to 200°

C.

4. The method according to claim 1, wherein the contacting of said treatment liquid with said substrate surface is effected by immersing said substrate with an organic film in said treatment liquid.

5. The method according claim 1, wherein the contacting of said treatment liquid with said substrate surface is effected by supplying said treatment liquid from a nozzle onto said substrate surface, and forming and then moving a liquid film of said liquid.

6. The method according claim 1, wherein the contacting of said treatment liquid with said substrate surface is effected by forming a liquid film of said treatment liquid on said substrate surface in an atmosphere of a gas containing a high concentration of ozone, and then moving said liquid film by either continuously or intermittently supplying fresh treatment liquid to said liquid film.

7. The method according to claim 1, which further comprises, after said contacting of said substrate and said treatment liquid, a step of rinsing said substrate either with ethylene carbonate liquid at a liquid temperature of 37 to 60°

C. containing dissolved ozone, or with propylene carbonate or a mixed liquid of ethylene carbonate and propylene carbonate at a liquid temperature of 20 to 50°

C. containing dissolved ozone.

8. The method according to claim 1, said step of decomposing the material which has migrated into said treatment liquid, is carried out at a different area from an area where said organic film removal treatment has been performed.

9. The method according to claim 1, wherein during contacting of said treatment liquid with said substrate surface, high frequency ultrasound is irradiated through said treatment liquid.

10. The method according to any one of claim 1, wherein said organic film is a resist film.

11. The method according to any one of claim 1, wherein said treatment liquid further comprises 0.01 to 2% by weight of an aliphatic carboxylic acid-based complexing agent.

12. The method according to claim 11, wherein said aliphatic carboxylic acid based-complexing agent is at least one compound selected from the group consisting of citric acid, oxalic acid and tartaric acid.

13. A method for removing an organic film on a surface of a substrate, comprising:

bringing a treatment liquid containing ozone dissolved in a liquid comprising ethylene carbonate, propylene carbonate, or both of them into contact with said substrate with an organic film on a surface thereof to remove said organic film, wherein said organic film is dissolved said treatment liquid and decomposed into low molecular weight material, and

using the treatment liquid after removal of said organic film for treating another substrate.

14. The method according to claim 13, wherein said treatment liquid after removal of said organic film is recycled as a treatment liquid as it is for treating another substrate.

15. The method according to claim 13, wherein said treatment liquid after removal of said organic film is further subjected to treatment with ozone, and then recycled as a treatment liquid for treating another substrate.

16. The method according to claim 15, said treatment with ozone is carried out at a different area from an area where said ozone-containing treatment liquid is brought into contact with said substrate.

17. The method according to claim 13, wherein said treatment liquid containing ozone is prepared by bringing a high concentration ozone-containing gas into contact with said liquid comprising ethylene carbonate, propylene carbonate, or both of them, wherein a distribution coefficient for a relationship between a concentration of ozone dissolved in said treatment liquid, and a concentration of ozone in said ozone containing gas is within a range from 0.05 to 0.4.

18. The method according to claim 13, wherein the contacting of said ozone-containing treatment liquid with said substrate surface is effected by immersing said substrate with an organic film in said treatment liquid.

19. The method according claim 13, wherein the contacting of said ozone-containing treatment liquid with said substrate surface is effected by supplying said ozone-containing treatment liquid from a nozzle onto said substrate surface, and forming and then moving a liquid film of said ozone-containing liquid.

20. The method according claim 13, wherein the contacting of said ozone-containing treatment liquid with said substrate surface is effected by forming a liquid film of said ozone-containing treatment liquid on said substrate surface in an atmosphere of a gas containing a high concentration of ozone, and then moving said liquid film by either continuously or intermittently supplying fresh ozone-containing treatment liquid to said liquid film.

21. The method according to claim 13, wherein during contacting of said treatment liquid with said substrate surface, high frequency ultrasound is irradiated through said treatment liquid.

22. The method according to claim 13, wherein said organic film is a resist film.

23. The method according to claim 13, wherein said treatment liquid further comprises 0.01 to 2% by weight of an aliphatic carboxylic acid-based complexing agent.

24. The method according to claim 23, wherein said aliphatic carboxylic acid based-complexing agent is at least one compound selected from the group consisting of citric acid, oxalic acid and tartaric acid.