Cleaning composition following CMP and methods related thereto
The invention provides a composition for cleaning contaminants from semiconductor wafers following chemical-mechanical polishing. The cleaning composition contains a bulky protecting ligand, an organic amine, an organic inhibitor, and water. The invention also provides methods for using the cleaning composition.
1. A composition for cleaning contaminants from semiconductor wafers following chemical-mechanical polishing, the composition comprising:
(a) a bulky protecting ligand selected from maleic acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethane diphosphoric acid (HEDA), ethylenediaminetetramethylene phosphoric acid, amino tris(methylene phosphoric acid) (ATMP), hydroxyethyliminodiacetic acid (HIDA), diethylenetriaminepentaacetic acid (DPTA), cysteine (Cys), ascorbic acid (Asc), choline hydroxide, quaternary ammonium hydroxide, and combinations thereof,
(b) one or more organic amines,
(c) one or more organic inhibitors, wherein the organic inhibitors are carbohydrazide (CHZ) and diethylhydroxylamine (DEHA), and
(d) water,
wherein the one or more organic amines are present in an amount of from about 0.01 wt. % to about 5 wt. % based on the total weight of the composition, the weight ratio of the bulky protecting ligand(s) to the organic amine(s) is about 1:1 or higher, and the composition has a pH of from about 9 to about 13.
2. The composition of claim 1 , wherein the contaminants include abrasive particles, organic residue, metal ions, polishing pad debris, CMP-byproducts, or any combination thereof.
3. The composition of claim 1 , wherein the weight ratio of the bulky protecting ligand(s) to the organic amine(s) is from about 1:1 to about 10:1.
4. The composition of claim 3 , wherein the weight ratio of the bulky protecting ligand(s) to the organic amine(s) is from about 1:1 to about 3:1.
5. The composition of claim 3 , wherein the weight ratio of the bulky protecting ligand(s) to the organic amine(s) is about 2.5:1.
6. The composition of claim 1 , wherein the bulky protecting ligand is a quaternary ammonium hydroxide having the formula:
wherein each of R 1 , R 2 , R 3 , and R 4 is independently an unsubstituted or substituted alkyl.
7. The composition of claim 5 , wherein the bulky protecting ligand is a quaternary ammonium hydroxide comprising tetraalkylammonium hydroxide, hydroxyalkylammonium hydroxide, trihydroxyalkylammonium hydroxide, or any combination thereof.
8. The composition of claim 5 , wherein the bulky protecting ligand is tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAM), tetrabutylammonium hydroxide (TBAH), cetyltrimetylammonium hydroxide, choline hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH), or any combination thereof.
9. The composition of claim 5 , wherein the bulky protecting ligand is tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH).
10. The composition of claim 1 , wherein the bulky protecting ligand is present in an amount of at least about 3 wt. % based on the total weight of the composition.
11. The composition of claim 10 , wherein the bulky protecting ligand is present in an amount of at least about 5 wt. % based on the total weight of the composition.
12. The composition of claim 1 , wherein the organic amine has the formula:
wherein R 1 is an unsubstituted or substituted alkyl, and each of R 2 and R 3 is independently H or R—OH, where R is an unsubstituted or substituted alkyl.
13. The composition of claim 1 , wherein the organic amine is an alkylamine, dialkylamine, trialkylamine, alkanolamine, or a combination thereof.
14. The composition of claim 13 , wherein the organic amine is methylamine, ethylamine, propylamine, isopropylamine, butylamine, dimethylamine, diethylamine, diisopropylamine, ethylmethylamine, butylmethylamine, propylethylamine, trimethylamine, triethylamine, ethyldimethyllamine, tributylamine, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), 3-amino-1-propanol, 2-dimethylaminoethanol, tris(hydroxymethyl)aminomethane (Tris), or a combination thereof.
15. The composition of claim 1 , wherein:
(a) the bulky protecting ligand is trihydroxyethylmethylammonium tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH) that is present in an amount of from about 0.01% to 0.2% by weight based on the total weight of the composition,
(b) the organic amine is monoethanolamine (MEA) that is present in an amount of from about 0.005% to 0.12% by weight based on the total weight of the composition,
(c) the organic inhibitor is (i) carbohydrazide (CHZ) that is present in an amount of from about 0.002% to 0.12% by weight based on the total weight of the composition and (ii) diethylhydroxylamine (DEHA) that is present in an amount of from about 0.002% to 0.06% by weight based on the total weight of the composition,
(d) water is present in an amount of from about 99.5 wt. % to about 99.98 wt. %; and
(e) the pH of the composition is from about 10 to about 13.
16. A composition for cleaning contaminants from semiconductor wafers following chemical-mechanical polishing, the composition comprising:
(a) a bulky protecting ligand selected from maleic acid, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), hydroxyethane diphosphoric acid (HEDA), ethylenediaminetetramethylene phosphoric acid, amino tris(methylene phosphoric acid) (ATMP), hydroxyethyliminodiacetic acid (HIDA), diethylenetriaminepentaacetic acid (DPTA), cysteine (Cys), ascorbic acid (Asc), choline hydroxide, quaternary ammonium hydroxide, and combinations thereof,
(b) one or more organic amines, wherein the weight ratio of the bulky protecting ligand(s) to the organic amine(s) is from about 1:1 to about 10:1,
(c) one or more dual organic inhibitors, wherein the dual organic inhibitors are carbohydrazide (CHZ) and diethylhydroxylamine (DEHA), and
(d) water,
wherein the composition has a pH of from about 9 to about 13.
17. The composition of claim 16 , wherein the chelating reducing agent is selected from CHZ, Asc, DMGO, Dihydroxybenzoic acid (DHBA), gallic acid, polyphenols, tannic acid and combinations thereof.
18. The composition of claim 16 , wherein the oxygen scavenger is selected from DEHA, MEKO, HQn, ammonium sulfite and combinations thereof.
19. The composition of claim 16 , wherein the contaminants include abrasive particles, organic residue, metal ions, pad debris, CMP-byproducts, or any combination thereof.
20. The composition of claim 16 , wherein the weight ratio of the bulky protecting ligand(s) to the organic amine(s) is from about 1:1 to about 3:1.
21. The composition of claim 16 , wherein the weight ratio of the bulky protecting ligand(s) to the organic amine(s) is about 2.5:1.
22. The composition of claim 16 , wherein the bulky protecting ligand is a quaternary ammonium hydroxide having the formula:
wherein each of R 1 , R 2 , R 3 , and R 4 is independent an unsubstituted or substituted alkyl.
23. The composition of claim 22 , wherein the bulky protecting ligand is ammonium hydroxide, tetraalkylammonium hydroxide, hydroxyalkylammonium hydroxide, trihydroxyalkylammonium hydroxide, or a combination thereof.
24. The composition of claim 23 , wherein the bulky protecting ligand is tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAM), tetrabutylammonium hydroxide (TBAH), cetyltrimetylammonium hydroxide, choline hydroxide, tris(2-hydroxyethyl)methylammonium hydroxide (THEMAH), or a combination thereof.
25. The composition of claim 23 , wherein the bulky protecting ligand is tris(2-hydroxyethyl)methyl ammonium hydroxide (THEMAH).
26. The composition of claim 16 , wherein the organic amine has the formula:
wherein R 1 is an unsubstituted or substituted alkyl, and each of R 2 and R 3 is independently H or R—OH, where R is an unsubstituted or substituted alkyl.
27. The composition of claim 16 , wherein the organic amine is an alkylamine, dialkylamine, trialkylamine, alkanolamine, or a combination thereof.
28. The composition of claim 27 , wherein the organic amine is methylamine, ethylamine, propylamine, isopropylamine, butylamine, dimethylamine, diethylamine, diisopropylamine, ethylmethylamine, butylmethylamine, propylethylamine trimethylamine, triethylamine, ethyldimethyllamine, tributylamine, monoethanolamine (MEA), diethanolamine (DEA), triethanolamine (TEA), 3-amino-1-propanol, 2-dimethylaminoethanol, tris(hydroxymethyl)aminomethane (Tris), or a combination thereof.