Aqueous electrolyte composition having a reduced airborne emission, method and use of this composition
View Patent ↗An aqueous electrolyte for the deposition of a metal layer on a substrate surface as well as a method for the deposition of a metal layer on a substrate surface by which electrolyte and in which method the formation of airborne emissions above the surface of the electrolyte in a plating tank is significantly reduced or more preferably omitted. The aqueous electrolyte composition according to the invention comprises at least one surfactant in a concentration affecting a dynamic surface tension of the composition of ≤35 mN/m.
1. An aqueous electrolyte composition for the deposition of a metal layer on a substrate surface, wherein the composition comprises at least ions of the metal to be deposited and at least one surfactant which is partially fluorinated and is not perfluorinated, wherein the surfactant is comprised in a concentration effecting a dynamic surface tension of the composition of ≤35 mN/m at 20° C.,
wherein the surfactant is at least one surfactant of the general formula C N F M H Z SO 2 X, wherein N is an integer between ≥6 and ≤22, M≤2N, Z=2N+1−M, and X is one of F, Cl, or Br; and
wherein the surfactant is comprised in a concentration range between ≥0.0000001% by weight and ≤0.000002% by weight.
2. The electrolyte composition according to claim 1 , wherein the composition comprises an anti-foaming agent.
3. The electrolyte composition according to claim 2 , wherein the anti-foaming agent is a water based composition comprising at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, alkanesulfonic acid, phosphoric acid, phosphonic acid, malonic acid, malic acid, and lactic acid, and at least one ester of a halogenated alcohol according to the general formula C N X M H Z OH, wherein N is an integer between ≥6 and ≤22, X is F, Cl, or Br, M≤2N, and Z=2N+1−M.
4. The electrolyte composition according to claim 3 , wherein the anti-foaming agent is comprised in a concentration range of between ≥0.0001% by weight and 0.005% by weight.
5. The electrolyte according to claim 1 , wherein the composition comprises a sulfonic acid according to the general formula C N F M H Z SO 2 OH, wherein N is an integer between ≥6 and ≤22, M≤2N, and Z=2N+1−M.
6. The electrolyte composition according to claim 5 , wherein the sulfonic acid is comprised in a concentration range of between ≥0.0008% by weight and ≤0.005% by weight.
7. The electrolyte composition according to claim 1 , wherein the metal to be deposited and of which ions are comprised in the electrolyte composition is at least one metal selected from the group consisting of Cu, Ni, Cr, Ag, Au, Pt, Zn, Fe, In, Ga, W, Se, Te, Mn, Bi, Co, Sn, and Cd.
8. The electrolyte composition according to claim 7 , wherein the metal ions are Cr ions.
9. The electrolyte composition according to claim 1 , wherein the composition is free of perfluorinated compounds.
10. The electrolyte composition of claim 1 , comprising the following:
a compound of the general formula C N F M H Z SO 2 X as the partially fluorinated surfactant,
wherein N is an integer between ≥6 and ≤22, M≤2N, Z=2N+1−M, and X is one of F, Cl, or Br,
wherein the compound is present in a concentration between ≥0.0000004% by weight and ≤0.0000015% by weight;
Zn ions or Cr ions as the metal ions;
wherein the electrolyte composition is free of perfluorinated compounds.
11. The electrolyte composition according to claim 10 wherein the partially fluorinated surfactant is 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluoroctansulphonyl chloride.
12. The electrolyte composition according to claim 1 , wherein the surfactant is comprised in a concentration effecting a dynamic surface tension of the composition of ≤33 mN/m at 20° C.
13. The electrolyte composition according to claim 12 , wherein the surfactant is comprised in a concentration effecting a dynamic surface tension of the composition of ≤30 mN/m at 20° C.
14. The electrolyte composition according to claim 2 , wherein N is an integer between ≥7 and ≤20.
15. The electrolyte composition according to claim 3 , wherein the surfactant is comprised in a concentration range between ≥0.0000004% by weight and ≤0.0000015% by weight.
16. The electrolyte composition according to claim 3 , wherein N is an integer between ≥6 and ≤18.
17. The electrolyte composition according to claim 4 , wherein the anti-foaming agent is comprised in a concentration range of between ≥0.0002% by weight and ≤0.002% by weight.
18. The electrolyte composition according to claim 17 , wherein the anti-foaming agent is comprised in a concentration range of between ≥0.0002% by weight and ≤0.001% by weight.
19. The electrolyte composition according to claim 5 , wherein N is an integer between ≥7 and ≤20.
20. The electrolyte composition according to claim 6 , wherein the sulfonic acid is comprised in a concentration range of between ≥0.001% by weight and ≤0.0025% by weight.
21. A method for the deposition of a metal layer on a substrate surface, said method comprising the steps of:
a) providing a substrate on which the metal layer should be deposited;
b) providing an aqueous electrolyte composition for the deposition of the metal layer on the substrate surface, wherein the composition comprises
i) at least ions of the metal to be deposited, and
ii) an aqueous surfactant composition, wherein the aqueous surfactant composition comprises:
(a) at least one surfactant of the general formula C N F M H Z SO 2 X, wherein N is an integer between ≥6 and ≤22, M≤2N, Z=2N+1−M, and X is one of F, Cl, or Br, wherein the at least one surfactant is partially fluorinated and is not perfluorinated;
(b) at least one anti-foaming agent being a water based composition comprising at least one acid selected from the group consisting of hydrochloric acid, sulfuric acid, alkanesulfonic acid, phosphoric acid, phosphonic acid, malonic acid, malic acid, and lactic acid; and
(c) at least one ester of a halogenated alcohol according to the general formula C N X M H Z OH, wherein N is an integer between ≥6 and ≤22, X is F, Cl, or Br, M≤2N, and Z=2N+1−M; and
(d) at least one sulfonic acid according to the general formula C N F M H Z SO 2 OH, wherein N is an integer between ≥6 and ≤22, M≤2N, and Z=2N+1−M,
wherein the aqueous surfactant composition is added to the aqueous electrolyte composition to provide a dynamic surface tension of ≤35 mN/m at 20° C.; and
c) bringing into contact the aqueous electrolyte composition with the surface of the substrate on which the metal layer should be deposited.
22. The method according to claim 21 , wherein said method comprises the step of maintaining the dynamic surface tension of the aqueous electrolyte composition at ≤35 mN/m at 20° C. by addition of the aqueous surfactant composition.
23. The method according to claim 21 , wherein the metal to be deposited is at least one metal selected from the group consisting of Cu, Ni, Cr, Ag, Au, Pt, Zn, Fe, In, Ga, W, Se, Te, Mn, Bi, Co, Sn, and Cd.
24. The method according to claim 21 , wherein the deposition is performed autocatalytically by addition of at least one reduction agent to the aqueous electrolyte composition.
25. The method according to claim 21 , wherein the deposition is performed galvanically by applying a current between the substrate and an anode.