USRE42128EExpiredUtility

Compositions for removing residue from a substrate and use thereof

Assignee: AIR PROD & CHEMPriority: Sep 26, 2002Filed: Jan 22, 2009Granted: Feb 8, 2011

Est. expirySep 26, 2022(expired)· nominal 20-yr term from priority

Inventors:Matthew I. Egbe

H10P 70/273H10P 50/287H10P 70/234G03F 7/42G03C 5/00C23G 1/14G03F 7/425

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Claims

Abstract

Compositions containing certain organic solvents and a fluorine source are capable of removing photoresist and etching residue.

Claims

exact text as granted — not AI-modified

1. A composition suitable for removing photoresist and etching residue which comprises:
a) at least about 50% by weight of a solvent which is tetrahydrofurfuryl alcohol;
b) about 0.005 to about 0.8 by weight of a source of fluorine.
c) up to about 49.9% by weight of water; and
d) up to about 20% by weight of a corrosion inhibitor.

2. The composition of claim 1 wherein the fluorine source is selected from the group consisting of hydrofluoric acid, ammonium fluoride, quaternary ammonium fluorides, fluoroborates, fluoroboric acid, tin bifluoride, antimony fluoride, tetrabutylammonium tetrafluoroborate, aluminum hexafluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the following formula:
R 1 N(R 3 )R 2

wherein R 1 , R 2 and R 3 each individually represent H or an alkyl group.

3. The composition of claim 1 wherein the fluorine source comprises ammonium fluoride or teframethylammonium fluoride.

4. The composition of claim 1 wherein said corrosion inhibitor comprises a hydroxylamine.

5. The composition of claim 4 wherein said hydroxy amine comprises diethyl hydroxylamine.

6. The composition of claim 1 wherein the amount of said solvent is about 50% by weight to about 75 by weight;
said source of fluorine is about 0.05 to about 0.5% by weight, and said water is about 25 to about 35% by weight.

7. The composition of claim 6 wherein the amount of said corrosion inhibitor is about 0.5 to about 20% by weight.

8. The composition of claim 6 wherein the amount of said corrosion inhibitor is about 10 to about 14% by weight.

9. The composition of claim 1 being free of organic carboxylic acids.

10. A method for removing photoresist or etching residue or both from a substrate wherein comprises contacting said substract with a composition comprising:
a) at least about 50% by weight of a solvent which is tetrahydrofurfuryl alcohol;
b) about 0.005 to about 0.8 by weight of a source of fluorine
c) up to about 49.9% by weight of water; and
d) up to about 20% by weight of a corrosion inhibitor.

11. The method of claim 10 wherein the fluorine source is selected from the group consisting of hydrofluoride, quaternary ammonium fluorides, fluoroborates, fluoroboric acid, tin bifluoride, antimony fluoride, tetrabutylammonium tetrafluoroborate, aluminum hexafluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the following formula:
R 1 N(R 3 )R 2 F

wherein R 1 , R 2 and R 3 each individually represent H or an alkyl group.

12. The method of claim 10 wherein the fluorine source comprises ammonium fluoride or tetramethylammonium fluoride.

13. The method of claim 10 wherein said corrosion inhibitor comprises a hydroxylamine.

14. The method of claim 13 wherein said hydroxy amine comprises diethyl-hydroxylamine.

15. The method of claim 10 wherein the amount of said solvent is about 50% by weight to about 75% by weight; source of fluorine is about 0.05 to about 0.5% by weight, and said water is about 25 to about 35% by weight.

16. The method of claim 15 wherein the amount of said corrosion inhibitor is about 0.5 to about 20% by weight.

17. The method of claim 15 wherein the amount of said corrosion inhibitor is about 10 to about 14% by weight.

18. The method of claim 10 wherein said composition is free of organic carboxylic acids.

19. The method of claim 10 wherein the substrate also includes a material selected from the group consisting of metal, silicon, silicate and interlevel dielectric material.

20. The method of claim 19 wherein the interlevel dielectric material comprises silicon oxides.

21. The method of claim 19 wherein The metal is selected from the group consisting of copper, copper alloy, titanium, titanium nitride, tantalum, tantalum nitride, tantalum, tantalum nitride, aluminum and/or aluminum alloy.

22. A composition for removing residues comprising at least one residue selected from photoresist residues, etch residues, and mixtures thereof, the composition comprising:
at least about 50 % by weight of an organic solvent comprising: an alkylene glycol ether; and at least one solvent selected from propylene glycol, ethylene glycol, glycerol, polyvinyl alcohol, ethyl lactate, and N - N - dimethylacetamide; a source of fluorine; up to about 49 . 9 % by weight of water; and optionally up to about 20 % by weight of a corrosion inhibitor.

23. The composition of claim 22 wherein the source of fluorine comprises at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, quaternary ammonium fluorides, fluoroborates, fluoroboric acid, tin bifluoride, antimony fluoride, tetrabutylammonium tetrafluoroborate, aluminum hexafluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the following formula:
R 1 N ( R 3 ) R 2

wherein R
1
, R
2
and Ra each individually represent H or an alkyl group.

24. The composition of claim 23 wherein the source of fluorine comprises ammonium fluoride.

25. The composition of claim 23 wherein the source of fluorine comprises the fluoride salt of an aliphatic primary, secondary or tertiary amine having the following formula:
R 1 N ( R 3 ) R 2

wherein R
1
, R
2
and R
3
each individually represent H or an alkyl group.

26. The composition of claim 22 wherein the at least one solvent comprises propylene glycol.

27. The composition of claim 22 wherein the at least one solvent comprises ethylene glycol.

28. The composition of claim 22 wherein the at least one solvent comprises glycerol.

29. The composition of claim 22 wherein the at least one solvent comprises polyvinyl alcohol.

30. The composition of claim 22 wherein the at least one solvent comprises N- N - dimethylacetamide.

31. The composition of claim 22 wherein the composition comprises a corrosion inhibitor.

32. The composition of claim 31 wherein the corrosion inhibitor comprises a hydroxylamine.

33. The composition of claim 32 wherein the corrosion inhibitor further comprises an acid.

34. The composition of claim 33 wherein the corrosion inhibitor comprises lactic acid.

35. A composition for removing residues comprising at least one residue selected from photoresist residues, etch residues, and mixtures thereof, the composition comprising:
at least about 50 % by weight of an organic solvent comprising: an alkylene glycol ether; and at least one solvent selected from propylene glycol and glycerol; about 0 . 005 to about 0 . 8 % by weight of a source of fluorine; up to about 49 . 9 % by weight of water; and up to about 20 % by weight of a corrosion inhibitor.

36. The composition of claim 35 wherein the corrosion inhibitor comprises a hydroxylamine.

37. The composition of claim 36 wherein the corrosion inhibitor further comprises an acid.

38. The composition of claim 36 wherein the corrosion inhibitor comprises lactic acid.

39. The composition of claim 35 wherein the at least one solvent comprises propylene glycol.

40. The composition of claim 35 wherein the at least one solvent comprises glycerol.

41. A method for removing residues comprising at least one residue selected from photoresist residues, etch residues, and mixtures thereof from a substrate, the method comprising:
contacting the substrate with a composition comprising: at least about 50 % by weight of an organic solvent comprising: an alkylene glycol ether; and at least one solvent selected from propylene glycol, ethyl glycol, glycerol, polyvinyl alcohol, ethyl lactate, and N - N - dimethylacetamide; a source of fluorine; up to about 49 . 9 % by weight of water; and optionally up to about 20 % by weight of a corrosion inhibitor.

42. The method of claim 41 wherein the wherein the source of fluorine comprises at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, quaternary ammonium fluorides, fluoroborates, fluoroboric acid, tin bifluoride, antimony fluoride, tetrabutylammonium tetrafluoroborate, aluminum hexafluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the following formula:
R 1 N ( R 3 ) R 2

wherein R
1
, R
2
and R
3
each individually represent H or an alkyl group.

43. The method of claim 42 wherein the source of fluorine comprises ammonium fluoride.

44. The method of claim 41 wherein the source of fluorine comprises the fluoride salt of an aliphatic primary, secondary or tertiary amine having the following formula:
R 1 N ( R 3 ) R 2

wherein R
1
, R
2
and R
3
each individually represent H or an alkyl group.

45. The method of claim 41 wherein the at least one solvent comprises propylene glycol.

46. The method of claim 41 wherein the at least one solvent comprises ethylene glycol.

47. The method of claim 41 wherein the at least one solvent comprises glycerol.

48. The method of claim 41 wherein the at least one solvent comprises polyvinyl alcohol.

49. The method of claim 41 wherein the at least one solvent comprises N- N - dimethylacetamide.

50. The method of claim 41 wherein the composition comprises a corrosion inhibitor.

51. The method of claim 50 wherein the corrosion inhibitor comprises a hydroxylamine.

52. The method of claim 51 wherein the corrosion inhibitor further comprises an acid.

53. The composition of claim 52 wherein the corrosion inhibitor comprises lactic acid.

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