Microelectronic cleaning composition containing halogen oxygen acids, salts and derivatives thereof
View Patent ↗Microelectronic cleaning compositions for cleaning microelectronic substrates, and particularly cleaning compositions useful with and having improved compatibility with microelectronic substrates characterized by silicon dioxide, sensitive low-κ or high-κ dielectrics and copper, tungsten, tantalum, nickel, gold, cobalt, palladium, platinum, chromium, ruthenium, rhodium, iridium, hafnium, titanium, molybdenum, tin and other metallization, as well as substrates of Al or Al(Cu) metallizations and advanced interconnect technologies, are provided by microelectronic cleaning compositions comprising halogen acids, salts and derivatives thereof.
1. A composition for cleaning photoresist or residue from a microelectronic substrate, the cleaning composition comprising:
(a) an oxidizer selected from the group consisting of an alkyl hypochlorite and a tetraalkylammonium hypochlorite, and
(b) a solvent for component (a),
(c) a stabilizer for available hydrogen from the oxidizer, the stabilizer being selected from the group consisting of triazoles, thiazoles, tetrazoles and imidazoles; and, optionally one or more of the following components:
(d) an non ammonium-producing alkaline base,
(e) an acid,
(f) a metal chelating or complexing agent,
(g) a cleaning performance enhancing additive,
(h) a metal corrosion inhibitor,
(i) a non ammonium-producing fluoride, and
(j) a surfactant;
with the proviso that when the oxidizer component (a) is an alkyl hypochlorite, the component (b) solvent is not an amide, sulfone, sulfolene, selenone or a saturated alcohol solvent.
2. A composition according to claim 1 wherein the oxidizer component (a) is tetramethylammonium hypochlorite.
3. A composition according to claim 2 wherein the component (b) solvent comprises water, and the composition also comprises a tetramethylammonium hydroxide as component (d).
4. A composition according to claim 3 additionally comprising a component (j) surfactant.
5. A composition according to claim 3 comprising benzotriazole as component (c).
6. A composition according to claim 2 wherein the component (b) solvent comprises sulfolane, and the composition also comprises tetramethylammonium fluoride as component (i).
7. A composition according to claim 6 wherein the composition comprises benzotriazole as component (c).
8. A composition according to claim 1 wherein the component (b) solvent comprises water, and the composition also comprises tetramethylammonium fluoride as component (i).
9. A composition according to claim 8 wherein the composition comprises benzotriazole as component (c).
10. A composition for cleaning photoresist or residue from a microelectronic substrate and stabilized as to the amount of available halogen, the cleaning composition comprising:
(a) an oxidizer selected from the group consisting of a halogen oxygen acid, a salt of said acid, or derivative thereof wherein the derivative is selected from the group consisting of halogenated isocyanates, chlorine dioxide, chlorine monoxide, and hypochlorite-phosphite complexes, and
(b) a solvent for component (a),
(c) a stabilizing effective amount of a stabilizer for available hydrogen from the oxidizer, the stabilizer being selected from the group consisting of triazoles, thiazoles, tetrazoles and imidazoles in an amount of from about 0.1% to about 5% by weight of the composition and having been incorporated with the oxidizer component during synthesis of the oxidizer;
and, optionally one or more of the following components:
(d) an non ammonium-producing alkaline base,
(e) an acid,
(f) a metal chelating or complexing agent,
(g) a cleaning performance enhancing additive,
(h) a metal corrosion inhibitor,
(i) a non ammonium-producing fluoride, and
(j) a surfactant;
with the provisos that when the oxidizer component (a) is an alkyl hypochlorite, the component (b) solvent is not an amide, sulfone, sulfolene, selenone or a saturated alcohol solvent, and when the oxidizer component (a) is hypochlorous acid the cleaning composition also must contain the non-ammonium-producing alkaline base.
11. A composition according to claim 10 wherein the composition comprises a halogen oxy acid or salt or derivative thereof in an amount, based on the total weight of the composition, of from about 0.001% to about 30% and provides from about 0.001% to about 30% available halogen.
12. A composition according to claim 10 the oxidizer is selected from the group consisting of a halogen oxy-acid, salt or derivative thereof wherein the derivative is a hypochlorite-phosphite complex and wherein the stabilizer (c) is present in an amount up to about 0.5% by weight.
13. A composition according to claim 10 wherein the stabilizer is benzotriazole.
14. A composition according to claim 10 wherein the oxidizer component (a) is selected from the group consisting of an alkyl chlorite, an alkyl hypochlorite, a tetraalkylammonium chlorite, a tetraalkylammonium hypochlorite, a substituted trialkylammonium chlorite and a substituted trialkylammonium hypochlorite, and wherein said oxidizer provides from about 0.001 to about 30% available halogen.
15. A composition according to claim 10 wherein the oxidizer component (a) is selected from the group consisting of hypochlorous acid, chloric acid, alkali and alkaline earth salts of said acids, alkyl hypochlorites and tetraalkylammonium hypochlorites.
16. A composition of claim 10 wherein the oxidizer component (a) is selected from the group consisting of sodium hypochlorite.
17. A composition according to claim 16 wherein the solvent is water.
18. A composition according to claim 10 wherein the oxidizer component (a) comprise HClO 3 .
19. A composition according to claim 18 wherein the component (b) solvent comprises water, and the composition comprises a component (j) surfactant.
20. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 10 .
21. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 11 .
22. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 12 .
23. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 13 .
24. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 14 .
25. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 15 .
26. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 16 .
27. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 17 .
28. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 18 .
29. The process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 19 .
30. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 1 .
31. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 2 .
32. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 3 .
33. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 4 .
34. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 5 .
35. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 6 .
36. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 7 .
37. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 8 .
38. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 9 .
39. A composition stabilized as to the amount of available halogen comprising:
(a) an oxidizer selected from the group consisting of an organic salt of a halogen oxygen acid selected from the group consisting of alkyl chlorites alkyl hypochlorites, tetraalkylammonium chlorites, tetraalkylammonium hypochlorites, substituted tetraalkylammonium chlorites, and substituted tetraalkylammonium hypochlorites; and
(b) a stabilizing effective amount of a stabilizer selected from the group consisting of triazoles, thiazoles, tetrazoles and imidazoles in an amount of from about 0.1% to about 5% by weight of the composition and having been incorporated with the organic salt of the halogen oxygen acid during synthesis of the organic salt of the halogen oxygen acid.
40. The composition of claim 39 wherein the stabilizer is a triazole.
41. The composition of claim 40 wherein the stabilizer is benzotriazole.
42. The composition of claim 39 wherein the oxidizer component (a) is selected from the group consisting of alkyl hypochlorites and tetralkylammonium hypochlorites.
43. The composition of claim 39 wherein the oxidizer component (a) is selected from the group consisting of t-butyl hypochlorite and tetramethylammonium hypochlorite.
44. The composition of claim 41 wherein the oxidizer component (a) is selected from the group consisting of t-butyl hypochlorite and tetramethylammonium hypochlorite.
45. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 39 .
46. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 40 .
47. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 41 .
48. process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 42 .
49. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 43 .
50. A process for cleaning photoresist or residue from a microelectronic substrate, the process comprising contacting the substrate with a cleaning composition for a time sufficient to clean the photoresist or residue from the substrate, wherein the cleaning composition comprises a composition of claim 44 .
51. A process according to claim 30 wherein the composition comprises an organic salt of a halogen oxy acid in an amount, based on the total weight of the composition, of from about 0.001% to about 30% and provides from about 0.001% to about 30% available halogen.
52. A process according to claim 51 wherein the composition comprises benzotriazole as component (c).
53. A process according to claim 51 wherein-the stabilizer (c) is present in an amount up to about 0.5% by weight.
54. A process according to claim 53 wherein the composition comprises benzotriazole as component (c).
55. A process according to any one of claims 30 , 31 or 32 - 54 wherein the microelectronic substrate being cleaned is characterized by the presence of at least one of a copper, tantalum, tungsten, nickel, gold, cobalt, palladium, platinum, chromium, ruthenium, rhodium, iridium, hafnium, titanium, molybdenum, and tin metallization, and sensitive low-κ or high-κ dielectrics.