Microelectronic substrate cleaning compositions having copper/azole polymer inhibition
View Patent ↗Semi-aqueous, alkaline microelectronic cleaning composition of pH ≥8 containing: (A) at least one secondary alkanolamine that generates hydroxides when in contact with water; (B) at least one organic alcohol ether solvent having an evaporation rate of 0.3 or less when n-butyl acetate's evaporation rate is taken as the baseline rate of 1.0; (C) at least one corrosion inhibiting cyclic amide compound; (D) at least one pH balancing azole metal corrosion inhibitor in an amount of 0.08% or less by weight of the composition; and (E) water; and optionally (F) at least one polyhydroxylated phenol compound corrosion inhibitor; and (G) at least one polyalcohol or polythiol surface modification agent containing vicinal hydroxyl or vicinal sulfhydryl groups to pair with the polyhydroxylated phenol compound corrosion inhibitor.
1. A semi-aqueous, alkaline microelectronic cleaning composition for cleaning a microelectronic substrate, said composition having a pH >8 comprising:
(A) at least one secondary alkanolamine that generates hydroxides when in contact with water;
(B) at least one organic alcohol ether solvent having an evaporation rate of 0.3 or less when n-butyl acetate's evaporation rate is taken as the baseline rate of 1.0;
(C) at least one corrosion inhibiting cyclic amide compound;
(D) at least one pH balancing azole metal corrosion inhibitor in an amount of 0.07% or less by weight of the composition; and
(E) water; and optionally
(F) at least one polyhydroxylated phenol compound corrosion inhibitor; and
(G) at least one polyalcohol or polythiol surface modification agent containing vicinal hydroxyl or vicinal sulfhydryl groups to pair with the at least one polyhydroxylated phenol compound corrosion inhibitor with the proviso that if component (F) is present in the compositions then component (G) is also present but, the compositions may contain component (G) without having component (F) present; wherein said composition is used to clean said microelectronic substrate alone or prior to a rinsing step.
2. A semi-aqueous, alkaline microelectronic cleaning composition according to claim 1 wherein the composition wherein the optional components (F) and (G) are both present in the composition.
3. A composition according to claim 1 wherein the composition has a pH of >9.5.
4. A composition according to claim 1 wherein the secondary alkanolamine component:
(A) is present in the composition in an amount of from about 0.1% to about 50% by weight, the organic alcohol ether solvent;
(B) is present in the composition in an amount of from 5% to about 95% by weight, the cyclic amide corrosion inhibitor component;
(C) is present in the composition in an amount of from about 5% to about 70% by weight, and the water component;
(E) is present in the composition in an amount of from 5% to about 75% by weight, wherein the percentages by weight are based on the weight of the composition.
5. A composition according to claim 1 wherein the secondary alkanolamine component (A) is selected from the group consisting of diethanolamine, diisopropanolamine, N-ethylethanolamine, N-methylethanolamine, and mixtures thereof.
6. A composition according to claim 1 wherein the organic alcohol ether solvent component (B) is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol monomethyl ether, carbitol, butyl glycol, tetraethylene glycol dipropylene glycol methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monophenyl ether, ethylene glycol monobenzyl ether, triethylene glycol methyl ether, triethylene glycol ethyl ether, triethylene glycol butyl ether and mixtures thereof.
7. A composition according to claim 6 wherein the organic alcohol ether solvent component (B) is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol monomethyl ether, carbitol, butyl glycol, tetraethylene glycol dipropylene glycol methyl ether and mixtures thereof.
8. A composition according to claim 1 wherein the cyclic amide component (C) is selected from the group consisting of N-methylpyrrolidinone, N-ethylpyrrolidinone, dimethyl-2-piperidone, 1-(2-hydroxyethyl)-2-pyrrolidinone, 13-lactam, 7-lactam, 5-lactam, s-lactam, 4-aminopetanoic acid lactam (7-valerolactam), and mixtures thereof.
9. A composition according to claim 8 wherein the cyclic amide component (C) is selected from the group consisting of N-methylpyrrolidinone, N-ethylpyrrolidinone, dimethyl-2-piperidone, 1-(2-hydroxyethyl)-2-pyrrolidinone, and mixtures thereof.
10. A composition according to claim 1 wherein the azole component (D) is selected from the group consisting of benzotriazole, an alkylbenzotriazole, benzimidazole, tetrazoles, hydroxybenzotriazole, carboxybenzotriazole, 2-mercaptobenzotriazole, 2-mercaptobenzimidazole, tolyltriazole, mercaptomethyl benzimidazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 1-phenyl-1H-tetrazole-5-thiol and mixtures thereof.
11. A composition according to claim 10 wherein the azole component (D) is selected from the group consisting of benzotriazole, methylbenzotriazole, benzimidazole, tetrazoles, hydroxybenzotriazole, carboxybenzotriazole, 2-mercaptobenzotriazole, 2-mercaptobenzimidazole, and mixtures thereof.
12. A composition according to claim 1 wherein the polyhydroxylated phenol component (F) is selected from the group consisting of catechol, pyrogallol, gallic acid, a gallic acid alkyl ester, an alkylcatechol and mixtures thereof and the polyalcohol or polythiol component (G) is selected from the group consisting of alkanediols, alkanetriols, alkanedithiols, phenyl substituted alkanediols, phenyl substituted alkanetriols, phenyl substituted alkanedithiols and mixtures hereof.
13. A composition according to claim 12 wherein the polyhydroxylated phenol component (F) is selected from the group consisting of catechol, pyrogallol, gallic acid, and mixtures thereof and the polyalcohol or polythiol component (G) is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, butanediol, cyclohexanediol, 1,2-ethylene dithiol and mixtures hereof.
14. A composition according to claim 1 wherein the secondary alkanolamine component (A) is selected from the group consisting of diethanolamine, diisopropanolamine, N-ethylethanolamine, N-methylethanolamine, and mixtures thereof, the organic alcohol ether solvent component (B) is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol monomethyl ether, carbitol, butyl glycol, tetraethylene glycol dipropylene glycol methyl ether and mixtures thereof, the cyclic amide component (C) is selected from the group consisting of N-methylpyrrolidinone, N-ethylpyrrolidinone, dimethyl-2-piperidone, 1-(2-hydroxyethyl)-2-pyrrolidinone and mixtures thereof, the azole component (D) is selected from the group consisting of benzotriazole, methylbenzotriazole, carboxybenzotriazole, benzimidazole, tetrazoles, hydroxybenzotriazole, 2-mercaptobenzotriazole, 2-mercaptobenzimidazole and mixtures thereof, and the polyhydroxylated phenol component (F) is selected from the group consisting of catechol, pyrogallol, gallic acid and mixtures thereof and the polyalcohol or polythiol component (G) is selected from the group consisting of ethylene glycol, propylene glycol, glycerol, butanediol, 1,2-ethylene dithiol and mixtures hereof.
15. A composition according to claim 14 wherein the secondary alkanolamine component
(A) is diethanolamine, the organic alcohol ether solvent component (II) is selected from the group consisting of ethylene glycol butyl ether, diethylene glycol monomethyl ether, carbitol, butyl glycol, tetraethylene glycol dipropylene glycol methyl ether, the cyclic amide component (C) is N-methylpyrrolidinone, the azole component (D) is selected from the group consisting of benzotriazole and, methylbenzotriazole, and the polyhydroxylated phenol component (F) is catechol, and the polyalcohol or polythiol component (G) is selected from the group consisting of ethylene glycol and propylene glycol.
16. A composition according to claim 1 additionally comprising at least one of the following additional components:
(H) at least one polar organic solvent/co-solvent selected from the group consisting of sulfoxides, sulfones, amides, lactones, ethers, alcohols, tertiary alkanolamines, and alcohol ethers other than those employed as component (B); and
(I) at least one surfactant; and
(J) at least one metal chelating or complexing agent.
17. A process for cleaning a microelectronic substrate by removing one or more of photoresist, UV/plasma hardened photoresist, post plasma etch or post etch/ash residue from the substrate comprising contacting the microelectronic substrate with a cleaning composition for a time and at a temperature effective for such removal to occur, said cleaning composition comprising
(A) at least one secondary alkanolamine that generates hydroxides when in contact with water;
(B) at least one organic alcohol ether solvent having an evaporation rate of 0.3 or less when n-butyl acetate's evaporation rate is taken as the baseline rate of 1.0;
(C) at least one corrosion inhibiting cyclic amide compound;
(D) at least one pH balancing azole metal corrosion inhibitor in an amount of 0.07% or less by weight of the composition; and
(E) water; and optionally
(F) at least one polyhydroxylated phenol compound corrosion inhibitor; and
(G) at least one polyalcohol or polythiol surface modification agent containing vicinal hydroxyl or vicinal sulfhydryl groups to pair with the at least one polyhydroxylated phenol compound corrosion inhibitor with the proviso that if component (F) is present in the compositions then component (G) is also present but, the compositions may contain component (G) without having component (F) present, and having a pH >8, wherein said composition is used to clean said microelectronic substrate alone or prior to a rinsing step.
18. A process according to claim 17 wherein the microelectronic substrate is a silicon wafer or glass substrate and the cleaning composition inhibits or minimizes formation of Cu(1)/azole polymer formation during the cleaning process.