Process for removing material from substrates

• US 20070161248A1
• Filed: 11/22/2006
• Published: 07/12/2007
• Est. Priority Date: 11/23/2005
• Status: Active Grant

• Current Assignee: TEL Manufacturing and Engineering of America, Inc.
• Original Assignee: FSI International, Inc. (Tokyo Electron Limited)
• Inventors: Christenson, Kurt, Ruether, Patricia, Hanestad, Ronald, Wagener, Thomas
• Granted Patent: US 7,592,264 B2
• Time in Patent Office: Days
• US Class Current: 438/689
• CPC Class Codes: B05B 1/00 Nozzles, spray heads or other outlets, with or without auxiliary devices such as valves, heating means B05B3/00, B05B5/00, B05B7/00 take precedence; nozzles for baths with water or gas jets A61H33/00, e.g. A61H33/6063, A61H33/6021, A61H33/026 or A61H33/027; Nozzles specially adapted for fire-extinguishing A62C31/02; Nozzles for generating high velocity abrasive fluid jets B24C5/04; nozzles for jet-ink printing mechanisms B41J2/135; nozzles for filling containers B65B39/00; nozzles for liquid-dispensing, e.g. in vehicle service stations B67D7/42
• CPC Class Codes: B05B 7/1209 the controlling means for each liquid or other fluent material being manual and interdependent
• CPC Class Codes: B08B 2230/01 Cleaning with steam
• CPC Class Codes: B08B 3/08 the liquid having chemical or dissolving effect substances used, see the relevant classes
• CPC Class Codes: B08B 7/00 Cleaning by methods not provided for in a single other subclass or a single group in this subclass
• CPC Class Codes: G03F 7/423 containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
• CPC Class Codes: H01L 21/02063 the processing being the formation of vias or contact holes
• CPC Class Codes: H01L 21/02071 the processing being a delineation, e.g. RIE, of conductive layers
• CPC Class Codes: H01L 21/30604 Chemical etching
• CPC Class Codes: H01L 21/31105 Etching inorganic layers
• CPC Class Codes: H01L 21/31133 by chemical means
• CPC Class Codes: H01L 21/6708 using mainly spraying means, e.g. nozzles

Abstract

A method of removing materials, and preferably photoresist, from a substrate comprises dispensing a liquid sulfuric acid composition comprising sulfuric acid and/or its desiccating species and precursors and having a water/sulfuiric acid molar ratio of no greater than 5:1 onto an material coated substrate in an amount effective to substantially uniformly coat the material coated substrate. The substrate is preferably heated to a temperature of at least about 90° C., either before, during or after dispensing of the liquid sulfuric acid composition. After the substrate is at a temperature of at least about 90° C., the liquid sulfuric acid composition is exposed to water vapor in an amount effective to increase the temperature of the liquid sulfuric acid composition above the temperature of the liquid sulfuric acid composition prior to exposure to the water vapor. The substrate is then preferably rinsed to remove the material.

Claims

1. A method of removing material from a substrate, comprising

a) placing a substrate having material on a surface thereof in a treatment chamber;

b) dispensing a liquid sulfuric acid composition comprising sulfuric acid and/or its desiccating species and precursors onto the substrate surface in an amount effective to substantially uniformly coat the substrate surface; and

c) exposing the liquid sulfuric acid composition to water vapor in an amount effective to increase the temperature of the liquid sulfuric acid composition above the temperature of the liquid sulfuric acid composition prior to exposure to the water vapor;

wherein the liquid sulfuric acid composition at the time of exposure to water vapor has a water/sulfuric acid molar ratio of no greater than about 5;

1.

2. The method of claim 1, wherein the liquid sulfuric acid composition is exposed to water vapor in an amount effective to increase the temperature of the liquid sulfuric acid composition on the substrate surface above both (i) the temperature of the on-substrate liquid sulfuric acid composition prior to exposure to the water vapor and (ii) the temperature of the water vapor.

3. The method of claim 1, wherein the liquid sulfuric acid composition at the time of exposure to water vapor has a water/sulfuric acid molar ratio of no greater than about 2:

1.

4. The method of claim 1, wherein the liquid sulfuric acid composition at the time of exposure to water vapor has a water/sulfuric acid molar ratio of no greater than about 1:

2.

5. The method of claim 1, wherein an oxidizing agent is introduced into the treatment chamber during or after dispense of the liquid sulfuric acid composition.

6. The method of claim 5, wherein the oxidizing agent is hydrogen peroxide.

7. The method of claim 5, wherein the oxidizing agent is ozone

8. The method of claim 1, wherein the substrate surface is treated with a surfactant containing composition prior to dispensing the liquid sulfuric acid composition thereon.

9. The method of claim 1, wherein either before, during or after dispensing of the liquid sulfuric acid composition but prior to exposing the liquid sulfuric acid composition to water vapor, the substrate is heated to a temperature of at least about 90°

C.

10. The method of claim 1, wherein the water vapor is provided at a temperature of from about 80°

C. to about 110°

C.

11. The method of claim 1, wherein the water vapor is provided at a temperature of about 100°

C.

12. The method of claim 1, wherein the water vapor is provided at a temperature greater than the temperature of the liquid sulfuric acid composition prior to exposure to the water vapor.

13. The method of claim 1, wherein the liquid sulfuric acid composition is dispensed at a temperature of at least about 130°

C. prior to exposure to the water vapor.

14. The method of claim 1, wherein the liquid sulfuric acid composition is dispensed at a temperature of from about 130°

C. to about 200°

C. prior to exposure to the water vapor.

15. The method of claim 1, wherein the material is a photoresist.

16. The method of claim 1, wherein the dispense of the liquid sulfuric acid composition is stopped prior to exposure of the liquid sulfiric acid composition to the water vapor.

17. The method of claim 1, wherein the liquid sulfiric acid composition is dispensed onto the substrate surface in a plurality of discrete pulses.

18. The method of claim 1, wherein the substrate is not moving or is rotating at a rate of less than about 20 rpm during and/or after dispense of the liquid sulfuric acid composition, and during exposure of the liquid sulfuric acid composition to the water vapor.

19. The method of claim 1, wherein the substrate is rotating during dispense of the liquid sulfuric acid composition onto the surface of the substrate, and the liquid sulfuric acid composition is dispensed by spraying the liquid at an angle that is off normal from the center of rotation of the substrate.

20. The method of claim 1, wherein the substrate is rotating during dispense of the liquid sulfuric acid composition onto the surface of the substrate, and the liquid sulfuric acid composition is dispensed by spraying the liquid at a varying angle relative to the center of rotation of the substrate in a sweeping motion.

21. The method of claim 1, wherein the angle of spray varies during a single dispense of the liquid sulfuric acid composition.

22. The method of claim 1, wherein the angle of spray varies from one dispense of the liquid sulfuric acid composition to the next when a plurality of liquid dispenses are carried out in a treatment cycle.