Method and apparatus for treating a substrate with an ozone-solvent solution

• US 6,982,006 B1
• Filed: 10/19/2000
• Issued: 01/03/2006
• Est. Priority Date: 10/19/1999
• Status: Expired due to Fees

• Current Assignee: David G. Boyers, Jay Theodore Jr. Cremer
• Original Assignee: David G. Boyers, Jay Theodore Jr. Cremer
• Inventors: Boyers, David G., Cremer, Jay Theodore Jr.
• Primary Examiner(s): CARRILLO, BIBI SHARIDAN
• Application Number:
  US09/693,012
• Time in Patent Office: 1,902 Days
• Field of Search: 134/1, 134/1.1, 134/1.2, 134 2- 3, 134/1.3, 134/19, 134/21, 134/24, 134/26, 134/28, 134/30, 134 34- 37, 134/41, 134/42, 134/902
• US Class Current: 134/3
• CPC Class Codes: A61L 2/183 Ozone dissolved in a liquid
• CPC Class Codes: A61L 2202/122 Chambers for sterilisation
• CPC Class Codes: A61L 2202/24 Medical instruments, e.g. endoscopes, catheters, sharps
• CPC Class Codes: B08B 2203/005 the liquid being ozonated
• CPC Class Codes: B08B 3/04 Cleaning involving contact with liquid
• CPC Class Codes: C01B 13/10 Preparation of ozone
• CPC Class Codes: G03F 7/40 Treatment after imagewise removal, e.g. baking
• CPC Class Codes: H01L 21/0206 during, before or after processing of insulating layers
• CPC Class Codes: H01L 21/02071 the processing being a delineation, e.g. RIE, of conductive layers
• CPC Class Codes: H01L 21/31133 by chemical means
• CPC Class Codes: Y10S 134/902 Semiconductor wafer

Abstract

A general method and apparatus for treating materials at high speed comprises the steps of dissolving a relatively high concentration ozone gas in a solvent at a relatively low predetermined temperature T1 to form an ozone-solvent solution with a relatively high dissolved ozone concentration, and heating either the ozone-water solution or the material to be treated or both, the ozone-solvent solution and the material to be oxidized with a point-of-use heater to quickly increase the temperature to a predetermined higher temperature T2>T1, and applying the ozone-solvent solution to said material(s) whereby the heated ozone-water solution will have a much higher dissolved ozone concentration at said higher temperature, than could be achieved if the ozone gas was initially dissolved in water at said higher temperature.

Claims

1. A method for treating a material, comprising:

forming an ozone-solvent solution at a first temperature;

passing said ozone-solvent solution through a heater to heat said ozone-solvent solution from said first temperature to form a heated [−

]ozone-solvent solution relative to said first temperature, such that said heated ozone-solvent solution is supersaturated with ozone; and

reacting the supersaturated heated ozone-solvent solution with the material at a second temperature;

wherein the first temperature is less than the second temperature.

2. The method of claim 1, wherein said ozone-solvent solution is formed at said first temperature by dissolving an ozone gas in solvent at said first temperature to form a first concentration of dissolved ozone.

3. The method of claim 1, wherein the second temperature is at least 5 degrees Celsius greater than the first temperature.

4. The method of claim 1, wherein reacting said supersaturated heated ozone-solvent solution with the material comprises applying the supersaturated heated ozone-solvent solution to the material using at least one nozzle.

5. The method of claim 1, wherein reacting the supersaturated heated ozone-solvent solution with the material comprises immersing the material within the supersaturated heated ozone-solvent solution.

6. The method of claim 1, wherein said step of reacting said supersaturated heated ozone-solvent solution with said material has at least one point of reaction, and wherein the heater comprises using a liquid-to-liquid heat exchanger placed just upstream of the at least one point of reaction of said supersaturated heated ozone-solvent solution with said material.

7. The method of claim 1, wherein said step of reacting said supersaturated heated ozone-solvent solution with said material has at least one point of reaction, and wherein the heater comprises an in-line heater placed just upstream of the at least one point of reaction of said supersaturated heated ozone-solvent solution with said material.

8. The method of claim 1, further comprising:

injecting a chemical into said supersaturated heated ozone-solvent solution prior to reacting said supersaturated heated ozone-solvent solution with said material.

9. The method of claim 1, wherein said material comprises a substrate, and wherein the step of reacting said supersaturated heated ozone-solvent solution with said substrate comprises:

spinning said substrate to achieve a rotational speed about an axis; and

dispensing said supersaturated heated ozone-solvent solution over at least a portion of at least one surface of the spinning substrate using at least one nozzle.

10. The method of claim 1, wherein said material comprises a substrate, said method further comprising the step of rinsing the substrate after the substrate is reacted with said supersaturated heated ozone-solvent solution.

11. The method of claim 1, wherein the material comprises a planar substrate selected from the group consisting of semiconductor wafers, flat panel displays, memory discs, substrates for use in an electronic device.

12. The method of claim 1, wherein the material is selected from the group consisting of photoresist, post etch resist residue, post etch residue, anti-reflective coating, organic contamination.

13. The method of claim 1, wherein said step of reacting said supersaturated heated ozone-solvent solution with said material comprises passing said supersaturated heated ozone-solvent solution through an orifice that directs said supersaturated heated ozone-solvent solution toward said material, and wherein the heater is placed just upstream of said orifice.

14. The method of claim 1, further comprising:

injecting a chemical into said ozone-solvent solution prior to passing said ozone-solvent solution through said heater.

15. The method of claim 1, further comprising passing said supersaturated heated ozone-solvent solution through at least one element selected from the group consisting of a back pressure regulator, a pressure dropping nozzle, and a valve, prior to applying the supersaturated heated ozone-solvent solution to the material.

16. The method of claim 2, wherein said supersaturated heated ozone-solvent solution is reacted with the material within a time period after heat is first applied to said ozone-solvent solution in said heater to minimize a decrease in the concentration of the dissolved ozone in the supersaturated heated ozone-solvent solution.

17. The method of claim 3, wherein the first temperature is between 1 and 30 degrees Celsius.

18. The method of claim 3, wherein the first temperature is between 1 and 10 degrees Celsius.

19. The method of claim 3, wherein the second temperature is between 30 and 95 degrees Celsius.

20. The method of claim 3, wherein the second temperature is between 35 and 65 degrees Celsius.

21. The method of claim 8, wherein the chemical comprises a hydroxyl radical scavenger.

22. The method of claim 8, wherein the chemical comprises an element selected from the group consisting of a pH buffer, an acid, and a base.

23. The method of claim 8, wherein the chemical comprises a corrosion inhibitor.

24. The method of claim 8, wherein the chemical comprises a surfactant.

25. The method of claim 9, wherein said at least one nozzle is positioned on said axis.

26. The method of claim 9, wherein a plurality of nozzles are positioned in a plurality of positions over the substrate.

27. The method of claim 9, further comprising the step of moving said nozzle relative to said substrate.

28. The method of claim 9 wherein said at least one nozzle is successively positioned at one or more positions relative to the center of rotation of said substrate.

29. The method of claim 16, wherein the time period is such that the concentration of the supersaturated heated ozone-solvent solution at said second temperature is greater than if said ozone-solvent solution had been formed at said second temperature.

30. The method of claim 16, wherein the time period corresponds to no more than a 20 percent decrease in the concentration of the dissolved ozone in the supersaturated heated ozone-solvent solution from said first concentration.

39. The method of any one of claims 1–

21, claims 17–

6, claim 8, claims 22–

25, claims 9–

12, claims 32–

37, claim 38, claim 28, claim 13, claims 38–

29, and claim 15 further comprising;

removing undissolved ozone gas prior to the step of passing said ozone solvent solution through said heater.

31. A method for oxidizing a material, comprising:

forming an ozone-solvent solution at a first temperature;

passing the ozone-solvent solution through a heater to heat said ozone-solvent solution from the first temperature to form a supersaturated heated ozone-solvent solution; and

after the step of heating the ozone-solvent solution, reacting the supersaturated heated ozone-solvent solution with the material at approximately a second temperature to oxidize the material wherein the first temperature is less than the second.

32. The method of claim 31, further comprising rinsing the material.

33. The method of claim 31, wherein the second temperature is at least 5 degrees Celsius greater than the first temperature.

34. The method of claim 31, wherein the first temperature is between 1 and 30 degrees Celsius.

35. The method of claim 31, wherein the second temperature is between 30 and 95 degrees Celsius.

36. The method of claim 31, wherein reacting the ozone-solvent solution with the material comprises applying the supersaturated heated ozone-solvent solution to the material.

37. The method of claim 31, further comprising:

injecting a chemical into the supersaturated heated ozone-solvent solution prior to applying the supersaturated heated ozone-solvent solution to the material.

38. The method of claim 31, further comprising:

injecting a chemical into said supersaturated heated ozone-solvent solution prior to reacting said supersaturated heated ozone-solvent solution with said material.