Cleaning formulations
A composition useful for removing residue from a semiconductor substrate comprising in effective cleaning amounts: from about 55 to 80% by weight of water; from about 0.3 to about 5.0% by weight of EDTA; from about 10.0 to about 30.0% by weight of an amine compound wherein the amine compound is selected from the group consisting of a secondary amine, a tertiary amine, and mixtures thereof; from about 0.1 to about 5.0% by weight of a polyfunctional organic acid; from about 0.01 to about 8.0% by weight of a fluoride ion source; from about 0 to about 60% by weight of a water-miscible organic solvent; and from about 0 to about 15% by weight of a corrosion inhibitor.
1. A composition useful for removing residue from a semiconductor substrate consisting of, in effective cleaning amounts:
from about 0.3 to about 5.0% by weight of EDTA;
from about 10.0 to about 30.0% by weight of an amine compound wherein the amine compound is selected from the group consisting of a secondary amine, a tertiary amine, and mixtures thereof;
from about 0.1 to about 5.0% by weight of a polyfunctional organic acid;
from about 0.01 to about 8.0% by weight of a fluoride ion source selected from the group consisting of ammonium fluoride, a quaternary ammonium fluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the formula:
R 1 NR 2 R 3 R 4 F
wherein R 1 , R 2 , R 3 and R 4 each individually represent H or a (C 1 -C 4 ) alkyl group;
from about 0 to about 60% by weight of a water-miscible organic solvent;
from about 0 to about 15% by weight of a corrosion inhibitor; and
remainder is water.
2. The composition of claim 1 wherein the amine compound is selected from the group consisting of triethanolamine (TEA), diethanolamine, N-methyl diethanolamine, diisopropanolamine, N-methyl ethanol amine, and mixtures thereof.
3. The composition of claim 1 wherein the polyfunctional organic acid is selected from the group consisting of malonic acid, malic acid, phthalic acid, citric acid, trimellitic acid, and combinations thereof.
4. The composition of claim 1 wherein the corrosion inhibitor is present and is a triazole compound.
5. The composition of claim 4 wherein the triazole compound is selected from the group consisting of benzotriazole, o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, and dihydroxypropylbenzotriazole.
6. The composition of claim 5 wherein the triazole compound is selected from the group consisting of o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, and mixtures thereof.
7. The composition of claim 1 wherein the water-miscible organic solvent is present and is selected from the group consisting of dimethylacetamide (DMAC), N-methyl pyrrolidinone (NMP), dimethylsulfoxide (DMSO), dimethylformamide, N-methylformamide, formamide, dimethyl-2-piperidone (DMPD), tetrahydrofurfuryl alcohol, glycerol, ethylene glycol, an amide, an alcohol, a sulfoxide, a hydroxyamide, an amino alcohols, a (C 2 -C 20 ) alkanediol, a (C 3 -C 20 ) alkanetriol, a cyclic alcohol, propylene glycol, tetrahydrofurfuryl alcohol, diacetone alcohol, 1,4-cyclohexanedimethanol.
8. The composition of claim 7 wherein the water-miscible organic solvent is selected from the group consisting of DMSO, NMP, and DMAC.
9. The composition of claim 1 wherein the water-miscible organic solvent is present and is a glycol ether selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl either, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol, monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene monobutyl ether, dipropylene glycol diisopropyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane, and 2-(2-butoxyethoxy) ethanol.
10. The composition of claim 1 consisting essentially of:
from about 0.3 to about 3.5% by weight of EDTA;
from about 20.0 to about 30.0% by weight of an amine compound wherein the amine compound is selected from the group consisting of a secondary amine, a tertiary amine, and mixtures thereof;
from about 0.5 to about 2.0% by weight of a polyfunctional organic acid;
from about 0.025 to about 5.0% by weight of a fluoride ion source selected from the group consisting of ammonium fluoride, a quaternary ammonium fluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the formula:
R 1 NR 2 R 3 R 4 F
wherein R 1 , R 2 , R 3 and R 4 each individually represent H or a (C 1 -C 4 ) alkyl group;
from about 20 to about 40% by weight of a water-miscible organic solvent; and
from about 0.3 to about 1.5% by weight of a corrosion inhibitor selected from the group consisting of o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, and mixtures thereof.
11. A method for removing residue from a substrate optionally comprising aluminum, the method comprising the steps of:
contacting the substrate at a temperature of from about 25° C. to about 85° C. for a period of time ranging from about 1 minute to about 1 hour with a composition consisting of:
from about 0.3 to about 5.0% by weight of EDTA;
from about 10.0 to about 30.0% by weight of an amine compound wherein the amine compound is selected from the group consisting of a secondary amine, a tertiary amine, and mixtures thereof;
from about 0.1 to about 5.0% by weight of a polyfunctional organic acid;
from about 0.01 to about 8.0% by weight of a fluoride ion source selected from the group consisting of ammonium fluoride, a quaternary ammonium fluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the formula:
R 1 NR 2 R 3 R 4 F
wherein R 1 , R 2 , R 3 and R 4 each individually represent H or a (C 1 -C 4 ) alkyl group;
from about 0 to about 60% by weight of a water-miscible organic solvent;
from about 0 to about 15% by weight of a corrosion inhibitor; and
remainder water;
rinsing the substrate with water; and
drying the substrate, wherein the method excludes an intermediate IPA rinse step prior to the step of rinsing the substrate with water.
12. The method of claim 11 wherein the substrate is a semiconductor substrate.
13. The method of claim 11 wherein the amine compound is selected from the group consisting of triethanolamine (TEA), diethanolamine, N-methyl diethanolamine, diisopropanolamine, N-methyl ethanol amine, and mixtures thereof.
14. The method of claim 11 wherein the polyfunctional organic acid is selected from the group consisting of malonic acid, malic acid, phthalic acid, citric acid, trimellitic acid, and combinations thereof.
15. The method of claim 11 wherein the corrosion inhibitor is present and is a triazole compound.
16. The method of claim 15 wherein the triazole compound is selected from the group consisting of benzotriazole, o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, carboxybenzotriazole, 1-hydroxybenzotriazole, nitrobenzotriazole, and dihydroxypropylbenzotriazole.
17. The method of claim 16 wherein the triazole compound is selected from the group consisting of o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, and mixtures thereof.
18. The method of claim 11 wherein the water-miscible organic solvent is present and is selected from the group consisting of dimethylacetamide (DMAC), N-methyl pyrrolidinone (NMP), dimethylsulfoxide (DMSO), dimethylformamide, N-methylformamide, formamide, dimethyl-2-piperidone (DMPD), tetrahydrofurfuryl alcohol, glycerol, ethylene glycol, an amide, an alcohol, a sulfoxide, a hydroxyamide, an amino alcohols, a (C 2 -C 20 ) alkanediol, a (C 3 -C 20 ) alkanetriol, a cyclic alcohol, propylene glycol, tetrahydrofurfuryl alcohol, diacetone alcohol, 1,4-cyclohexanedimethanol.
19. The method of claim 18 wherein the water-miscible organic solvent is selected from the group consisting of DMSO, NMP, and DMAC.
20. The method of claim 11 wherein the water-miscible organic solvent is present and is a glycol ether selected from the group consisting of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl either, diethylene glycol monobenzyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol ethylene glycol monomethyl ether acetate, ethylene glycol monthly ether acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, propylene glycol, monopropyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene monobutyl ether, dipropylene glycol diisopropyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol, 2-methoxy-2-methylbutanol, 1,1-dimethoxyethane, and 2-(2-butoxyethoxy) ethanol.
21. The method of claim 11 wherein the composition consists of:
from about 0.3 to about 3.5% by weight of EDTA;
from about 20.0 to about 30.0% by weight of an amine compound wherein the amine compound is selected from the group consisting of a secondary amine, a tertiary amine, and mixtures thereof;
from about 0.5 to about 2.0% by weight of a polyfunctional organic acid;
from about 0.025 to about 5.0% by weight of a fluoride ion source selected from the group consisting of ammonium fluoride, a quaternary ammonium fluoride, and a fluoride salt of an aliphatic primary, secondary or tertiary amine having the formula:
R 1 NR 2 R 3 R 4 F
wherein R 1 , R 2 , R 3 and R 4 each individually represent H or a (C 1 -C 4 ) alkyl group;
from about 20 to about 40% by weight of a water-miscible organic solvent; and
from about 0.3 to about 1.5% by weight of a corrosion inhibitor selected from the group consisting of o-tolyltriazole, m-tolyltriazole, p-tolyltriazole, and mixtures thereof.
22. The method of claim 12 where the substrate comprises cobalt metal and aluminum.
23. The method of claim 22 wherein the composition protects the cobalt metal by providing a cobalt metal etch rate of 4 Å/min or less.
24. The method of claim 23 wherein the composition protects the cobalt metal by providing a cobalt metal etch rate of 3 Å/min or less.
25. The method of claim 24 wherein the composition protects the cobalt metal by providing a cobalt metal etch rate of 2 Å/min or less.