Metal-passivating CMP compositions and methods
View Patent ↗The present invention provides chemical-mechanical polishing (CMP) compositions and methods for polishing copper- and/or silver-containing substrates. The compositions of the present invention comprise a particulate abrasive, a primary film-forming metal-complexing agent, and a secondary film-forming metal-passivating agent in an aqueous carrier. Methods of polishing a substrate with the compositions of the invention are also disclosed.
1. A chemical-mechanical polishing (CMP) composition suitable for polishing a substrate comprising copper and/or silver, the composition comprising:
(a) about 0.01 to about 10 percent by weight of a particulate abrasive;
(b) about 0.001 to about 1 percent by weight of a primary film-forming metal-complexing agent that comprises an o-hydroxyaryl hydroxamic acid, a salt thereof, or a partially neutralized form thereof;
(c) about 0.005 to about 0.5 percent by weight of a secondary film-forming metal-passivating agent comprising a compound of formula (II): Z—X2(Y2R5)(Y3R6), a salt thereof, or a partially neutralized form thereof; wherein Z is NH2 or OH; X2 is P═O or C; Y2 and Y3 are each independently N, NH, or O; and R5 and R6 can each independently can be R7-(OCH2CH2)n-, or when Y2 and Y3 each independently are N or NH, then R5 and R6 each independently can be N, NH, or CH, and together Y2 and Y3 form a five-membered ring heterocycle with X2, Y2 and Y3; each R7 independently is H, C1-C20-alkyl, phenyl, or C1-C20-alkyl-substituted phenyl; and “n” has an average value in the range of about 2 to about 1000; and
(d) an aqueous carrier therefor.
2. The composition of claim 1 wherein the secondary film-forming metal-passivating agent comprises an amine-substituted nitrogen heteroaromatic compound.
3. The composition of claim 2 wherein the amine-substituted nitrogen heteroaromatic compound comprises 5-aminotetrazole.
4. The composition of claim 3 wherein the at least one secondary film-forming metal-passivating agent comprises 5-aminotetrazole.
5. The composition of claim 3 wherein the at least one secondary film-forming metal-passivating agent comprises a bis-(nonylphenylpoly(oxyethylene)) phosphate ester.
6. The composition of claim 1 wherein the secondary film-forming metal-passivating agent comprises a bis-(poly(oxyethylene)) phosphate ester.
7. The composition of claim 6 wherein the bis-(poly(oxyethylene)) phosphate ester comprises a bis-(nonylphenylpoly(oxyethylene)) phosphate ester.
8. The composition of claim 1 further comprising about 0.01 to about 20 percent by weight of an auxiliary metal-chelating agent selected from the group consisting of oxalic acid, an amino-substituted carboxylic acid, a hydroxyl-substituted carboxylic acid, a salt thereof, a partially neutralized form thereof, and a combination of two or more of the foregoing.
9. The composition of claim 1 wherein the auxiliary metal-chelating agent comprises glycine.
10. The composition of claim 1 wherein the particulate abrasive comprises silica.
11. A chemical-mechanical polishing (CMP) composition suitable for polishing a substrate comprising copper and/or silver, the composition comprising:
(a) about 0.01 to about 10 percent by weight of a particulate abrasive;
(b) about 0.001 to about 1 percent by weight of salicylhydroxamic acid, a salt thereof or a partially neutralized form thereof;
(c) about 0.005 to about 0.5 percent by weight of at least one secondary film-forming metal-passivating agent selected from the group consisting of an amine-substituted nitrogen heteroaromatic compound and a bis-(poly(oxyethylene)) phosphate ester; and
(d) an aqueous carrier therefor.