Cyanide free electrolyte composition for the galvanic deposition of a copper layer
View Patent ↗A cyanide-free electrolyte composition for the galvanic deposition of a copper layer on substrate surfaces and a method for the deposition of such layers. The electrolyte composition comprises at least copper(II) ions, a hydantoin and/or hydantoin derivative, a di- and/or tricarboxylic acid or salts thereof, and a metalate of an element of the group consisting of molybdenum, tungsten and vanadium and/or a cerium compound.
1. An electrolyte composition for the galvanic deposition of a copper-containing layer on a substrate surface comprising:
a source of copper(II) ions;
a primary complexing agent comprising hydantoin, a hydantoin derivative, or a combination thereof;
a secondary complexing agent comprising a dicarboxylic acid, a salt of a dicarboxylic acid, a tricarboxylic acid, a salt of a tricarboxylic acid, or any combination thereof; and
a metalate, wherein the metalate comprises an element selected from the group consisting of molybdenum, tungsten, vanadium, and combinations thereof and the concentration of the metalate is between 5 mmol/L and 21 mmol/L, and wherein the pH of the composition is between 8 and 13.
2. The electrolyte composition of claim 1 wherein the composition contains no cyanide.
3. The electrolyte composition according to claim 1 comprising a further complexing agent selected from the group consisting of potassium pyrophosphate, sodium pyrophosphate, polyphosphates, pyridinesulfonic acid, tetrapotassium pyrophosphate, disodium dihydrogen pyrophosphate, tetrasodium pyrophosphate, methylglycinediacetic acid, a salt of methylglycinediacetic acid, nitrilotriacetic acid, a salt of nitrilotriacetic acid, and combinations thereof.
4. The electrolyte composition according to claim 1 , wherein the secondary complexing agent is selected from the group consisting of citric acid, succinic acid, malic acid, aspartic acid, tartaric acid, salts thereof and combinations thereof.
5. The electrolyte composition according to claim 1 , wherein said source of copper(II) ions is present in a concentration such that the concentration of the copper(II) ions is between 5 g/L and the solubility limit.
6. The electrolyte composition according to claim 1 , wherein said primary complexing agent comprising hydantoin, a hydantoin derivative, or a combination thereof is present in a concentration between 0.15 mol/L and 2 mol/L.
7. The electrolyte composition according to claim 1 , further comprising a complexing agent selected from the group consisting of potassium pyrophosphate, sodium pyrophosphate, polyphosphates, pyridinesulfonic acid, tetrapotassium pyrophosphate, disodium dihydrogen pyrophosphate, tetrasodium pyrophosphate, methylglycinediacetic acid, a salt of methylglycinediacetic acid, nitrilotriacetic acid, a salt of nitrilotriacetic acid, and combinations thereof in a concentration between 0.1 mol/L and 1.0 mol/L.
8. The electrolyte composition according to claim 1 , further comprising a conducting salt selected from the group consisting of potassium methanesulfonate, sodium methanesulfonate, and a combination thereof.
9. The electrolyte composition according to claim 8 , wherein said conducting salt is present in a concentration between 0.5 mol/L and 1.0 mol/L.
10. The electrolyte composition according to claim 1 , wherein said secondary complexing agent comprising a dicarboxylic acid, a salt of a dicarboxylic acid, a tricarboxylic acid, a salt of a tricarboxylic acid, or any combination thereof is present in a concentration between 0.05 mol/L and 1 mol/L.
11. The electrolyte composition according to claim 1 wherein:
the secondary complexing agent is selected from the group consisting of citric acid, succinic acid, malic acid, aspartic acid, tartaric acid, salts, and combinations thereof;
and
the concentration of the copper(II) ions is between 5 g/L and the solubility limit.
12. The electrolyte composition according to claim 11 , further comprising a complexing agent selected from the group consisting of potassium pyrophosphate, sodium pyrophosphate, polyphosphates, pyridinesulfonic acid, tetrapotassium pyrophosphate, disodium dihydrogen pyrophosphate, tetrasodium pyrophosphate, methylglycinediacetic acid, a salt of methylglycinediacetic acid, nitrilotriacetic acid, a salt of nitrilotriacetic acid, and combinations thereof in a concentration between 0.1 mol/L and 1.0 mol/L; and
further comprising a conducting salt selected from the group consisting of potassium methanesulfonate, sodium methanesulfonate, and a combination thereof.
13. The electrolyte composition according to claim 1 wherein the metalate is selected from the group consisting of a molybdenum oxide metalate, a vanadium oxide metalate, a tungsten oxide metalate, and combinations thereof.
14. The electrolyte composition according to claim 1 wherein the metalate is selected from the group consisting of ammonium molybdate, sodium molybdate dihydrate, sodium tungstate dihydrate, sodium monovanadate, and mixtures thereof.
15. A method for depositing a copper-containing layer on a surface of a substrate, the method comprising:
exposing the surface of the substrate to an electrolyte composition comprising:
a source of copper(II) ions,
a primary complexing agent comprising hydantoin, a hydantoin derivative, or a combination thereof,
a secondary complexing agent comprising a dicarboxylic acid, a salt of a dicarboxylic acid, a tricarboxylic acid, a salt of a tricarboxylic acid, or any combination thereof, and
a metalate, wherein the metalate comprises an element selected from the group consisting of molybdenum, tungsten, vanadium and combinations thereof; and
conducting a current between the substrate and an anode to thereby deposit the copper-containing layer on the surface of the substrate.
16. The method according to claim 15 , wherein the electrolyte composition has a pH between pH 8 and pH 13.
17. The method of claim 15 wherein the substrate surface is cathodically contacted and a current density is applied between the cathodically contacted substrate surface and the anode, wherein the anode is between 0.05 A/dm 2 and 4 A/dm 2 .
18. The method according to claim 15 wherein the metalate is selected from the group consisting of a molybdenum oxide metalate, a vanadium oxide metalate, a tungsten oxide metalate, and combinations thereof.
19. The method according to claim 15 wherein the metalate is selected from the group consisting of ammonium molybdate, sodium molybdate dihydrate, sodium tungstate dihydrate, sodium monovanadate, and mixtures thereof.