Method to remove resist, etch residue, and copper oxide from substrates having copper and low-k dielectric material

1. A method for removing one or more of resist, etching residue, planarization residue, and copper oxide from a substrate comprising copper and a low-k dielectric material, said method comprising the steps of:

A) providing a substrate having a surface comprising copper-containing conductor and a low-k dielectric material and one or more of resist, etching residue, planarization residue, and copper oxide disposed on the surface thereof;

B) contacting the surface of the substrate with a composition comprising:

a) from 0.01% by weight up to 0.12% by weight of a fluoride-providing component selected from HF, NH 4 F, or a mixture thereof;

b) from 1.5% by weight up to 6.0% by weight of a water miscible organic solvent which is a glycol ether;

c) from 0.75% by weight up to 1.25% by weight of an organic acid having from 1 to 3 carbon atoms;

d) from 85% by weight up to 98% by weight water, and

e) optionally from 0% by weight up to 0.15% by weight of a chelator wherein the pH of the composition is less than 3, for a time and at a temperature sufficient to remove the resist, residues, and/or copper oxide.

2. The method of claim 1 , wherein the composition is substantially free of mineral acids and the temperature is between about 20° C. to about 70° C.

3. The method of claim 1 , wherein the glycol ether comprises propylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, or a mixture thereof.

4. The method of claim 1 , wherein the organic acid consists essentially of one or more carboxylic acids.

5. The method of claim 4 , wherein the carboxylic acid comprises an hydroxy substituted carboxylic acid, a carbonyl substituted carboxylic acid, or a mixture thereof.

6. The method of claim 5 , wherein the carboxylic acid is glycolic acid and glyoxylic acid.

7. The method of claim 1 , wherein the composition comprises from about 0.05% by weight to about 1% by weight of a chelator selected from a group of organo-phosphonate compounds having a plurality of phosphonate moieties, or mixtures thereof.

8. The method of claim 7 , wherein the chelator comprises organo-phosphonate compounds which are phosphonic acids.

9. The method of claim 8 , wherein the phosphonic acid is 1-hydroxyethylidene-1,1 diphosphonic acid.

10. The method of claim 1 wherein the time is between about 20 seconds and about 10 minutes, and the temperature is from 15° C. up to 50° C.

11. A method for removing one or more of resist, etching residue, planarization residue, and copper oxide from a substrate comprising copper and a low-k dielectric material, said method comprising the steps of:

A) providing a substrate having a surface comprising copper-containing conductor and a low-k dielectric material and one or more of resist, etching residue, planarization residue, and copper oxide disposed on the surface thereof;

B) contacting the surface of the substrate with a composition comprising:

a. from 0.01% by weight up to 0.12% by weight of ammonium fluoride;

b. from 1.5% by weight up to 3.5% by weight of propylene glycol monomethyl ether (PGME);

c. from 0.75% by weight up to 1.25% by weight of glyoxylic acid;

d. from 85% by weight up to 98% by weight water, and

e. from 0.5% by weight up to 1.0% by weight of 1-hydroxyethylidene-1,1 diphosphonic acid,

wherein the pH of the composition is less than 3 for a time and at a temperature sufficient to remove the resist, residues, and/or copper oxide.