Compositions for processing of semiconductor substrates
View Patent ↗Compositions useful in semiconductor manufacturing for surface preparation and/or cleaning of wafer substrates such as semiconductor device precursor structures. The compositions can be employed for processing of wafers that have, or are intended to be further processed to include, copper metallization, e.g., in operations such as surface preparation, pre-plating cleaning, post-etching cleaning, and post-chemical mechanical polishing cleaning of semiconductor wafers. The compositions contain (i) alkanolamine, (ii) quaternary ammonium hydroxide and (iii) a complexing agent, and are storage-stable, as well as non-darkening and degradation-resistant in exposure to oxygen.
1. A composition comprising (i) alkanolamine, (ii) quaternary ammonium hydroxide and (iii) a complexing agent, wherein the complexing agent includes at least one component selected from the group consisting of glyoxylic acid, 2-mercaptobenzimidazole, proline, and derivatives of the foregoing amino acids, with the provision that the complexing agent does not include citric acid, and wherein the composition has a pH greater than 9.
2. The composition of claim 1 , wherein components (i), (ii), and (iii) are in effective relative proportions to one another for surface preparation and/or cleaning of a semiconductor substrate.
3. The composition of claim 1 , including about 0.001 to about 90 wt. % alkanolamine, about 0.00001 to about 40 wt. % quaternary ammonium hydroxide, and about 0.00001 about 20 wt. % complexing agent, based on total weight of the composition.
4. The composition of claim 1 , wherein the alkanolamine is present in an amount of from about 0.001 wt. % to about 90 wt. %, based on the weight of the composition.
5. The composition of claim 1 , wherein the quaternary ammonium hydroxide is present in an amount of from about 0.005 wt. % to about 40 wt. % based on the weight of the composition.
6. The composition of claim 1 , wherein the complexing agent is present in an amount of from about 0.001 wt. % to about 20 wt. %, based on the weight of the composition.
7. The composition of claim 1 , further comprising water.
8. The composition of claim 7 , containing less than 20 wt. % water, based on total weight of the composition.
9. The composition of claim 7 , wherein water is present in an amount of from about 95 wt. % to about 99.999 wt. %, based on the weight of the composition.
10. The composition of claim 1 , wherein the alkanolamine includes at least one species selected from the group consisting of aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, and C 1 -C 8 alkanolamines.
11. The composition of claim 1 , wherein the quaternary ammonium hydroxide is selected from the group consisting of choline, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, tetramethylammonium hydroxide, tetrapropylammoniumhydroxide, and combinations thereof.
12. The composition of claim 1 , having a pH greater than 10.
13. The composition of claim 1 , wherein components (i), (ii), and (iii) are in relative proportions rendering the composition non-darkening and degradation-resistant in exposure to oxygen.
14. The composition of claim 1 , wherein the complexing agent further includes at least one species selected from the group consisting of lactic acid, glycine, succinic acid and oxalic acid.
15. A method of processing a semiconductor substrate to remove undesired material therefrom or to prepare a surface of said semiconductor substrate for subsequent treatment, said method comprising contacting the semiconductor substrate with an effective amount of a composition comprising (i) alkanolamine, (ii) quaternary ammonium hydroxide and (iii) a complexing agent, wherein the complexing agent includes at least one component selected from the group consisting of glyoxylic acid, 2-mercaptobenzimidazole, proline, and derivatives of the foregoing amino acids, with the provision that the complexing agent does not include citric acid, and wherein the composition has a pH greater than 9.
16. The method of claim 15 , comprising processing the semiconductor substrate to remove etch residue or chemical mechanical polishing residue therefrom.
17. The method of claim 15 , comprising processing the semiconductor substrate to remove BTA therefrom.
18. The method of claim 15 , comprising processing the semiconductor substrate to prepare it for subsequent deposition of material thereon.
19. The method of claim 18 , wherein said deposition of material comprises cobalt plating.
20. The method of claim 15 , wherein components (i), (ii), and (iii) are in effective relative proportions to one another for surface preparations and/or cleaning of a semiconductor substrate.
21. The method of claim 15 , wherein the composition includes about 0.001 to about 90 wt. % alkanolamine, about 0.00001 to about 40 wt. % quaternary ammonium hydroxide, and about 0.00001 to about 20 wt. % complexing agent, based on total weight of the composition.
22. The method of claim 15 , wherein the composition includes alkanolamine in an amount of from about 0.001 wt. % to about 90 wt. %, based on the weight of the composition.
23. The method of claim 15 , wherein the composition includes quaternary ammonium hydroxide in an amount of from about 0.005 wt. % to about 40 wt. %, based on the weight of the composition.
24. The method of claim 15 , wherein the composition includes complexing agent in an amount of from about 0.001 wt. % to about 20 wt. % based on the weight of the composition.
25. The method of claim 15 , wherein the composition includes water.
26. The method of claim 25 , wherein the composition includes less than 20 wt. % water, based on total weight of the composition.
27. The method of claim 25 , wherein the composition includes water in an amount of from about 95 wt. % to about 99.999 wt. %, based on the weight of the composition.
28. The method of claim 15 , wherein the composition comprises alkanolamine including at least one species selected from the group consisting of aminoethylethanolamine, N-methylaminoethanol, aminoethoxyethanol, dimethylaminoethoxyethanol, diethanolamine, N-methyldiethanolamine, monoethanolamine, triethanolamine, and C 1 -C 8 alkanolamines.
29. The method of claim 15 , wherein the composition comprises quaternary ammonium hydroxide selected from the group consisting of choline, tetrabutylammoniumhydroxide, tetraethylammionium hydroxide, tetramethylammonium hydroxide, tetrapropylammoniumhydroxide, and combinations thereof.
30. The method of claim 15 , wherein the pH is greater than 10.
31. The method of claim 15 , wherein the composition comprises components (i), (ii), and (iii) in relative proportions rendering the composition non-darkening and degradation-resistant in exposure to oxygen.
32. The method of claim 15 , wherein the composition further comprises complexing agent including at least one species selected from the group consisting of lactic acid, glycine, succinic acid and oxalic acid.
33. The composition of claim 1 , comprising monoethanolamine, tetramethylammonium hydroxide, 2-mercaptobenzimidazole and water.
34. The composition of claim 1 , comprising monoethanolamine, tetramethylammonium hydroxide, 2-mercaptobenzimidazole, lactic acid, and water.
35. A composition comprising (i) alkanolamine, (ii) quaternary ammonium hydroxide, (iii) a complexing agent and (iv) water, wherein the complexing agent includes at least one component selected from the group consisting of 2-mercaptobenzimidazole, proline, and derivatives of the foregoing amino acids, with the provision that the complexing agent does not include citric acid, and wherein the composition has a pH greater than 9.