Activation method for silicon substrates comprising at least two aromatic acids
View Patent ↗The present invention relates to an activation composition for activation of silicon substrates, which is an aqueous solution comprising a source of palladium ions, a source of fluoride ions and at least two aromatic acids. The present invention further relates to a method for its use and optionally for subsequent metallization of such treated substrates. The method can be employed in semiconductor and solar cell manufacturing.
1. An activation composition for the activation of silicon substrates, wherein the activation composition is an aqueous solution comprising:
a) source of palladium ions;
b) a source of fluoride ions; and
c) at least two aromatic acids selected from the group consisting of aromatic carboxylic acids, aromatic sulphonic acids, aromatic sulphinic acids, aromatic phosphonic acids and aromatic phosphinic acids.
2. The activation composition of claim 1 wherein the at least two aromatic acids are selected from the group consisting of aromatic carboxylic acids, aromatic sulphonic acids and aromatic phosphonic acids.
3. The activation composition of claim 1 wherein the at least two aromatic acids are selected from aromatic acids according to formulae (I) and (II):
wherein R 1 to R 14 are independently from each other selected from the group consisting of hydrogen, alkyl, aryl, halides, amino, sulphonic acid moiety, carboxylic acid moiety, phosphonic acid moiety, nitro and hydroxyl with the proviso that at least one of R 1 to R 14 is a sulphonic acid moiety, a carboxylic acid moiety or a phosphonic acid moiety.
4. The activation composition according to claim 3 , wherein at least one of the two aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a sulphonic acid moiety.
5. The activation composition according to claim 3 , wherein at least one of the two aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a carboxylic acid moiety.
6. The activation composition according to claim 3 , wherein one of the two aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a sulphonic acid moiety, and one of the two aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a carboxylic acid moiety.
7. The activation composition according to claim 1 wherein the at least two aromatic acids are selected from the group consisting of benzoic acid, 1,2-benzene dicarboxylic acid (phthalic acid), 1,3-benzenedicarboxylic acid (isophthalic acid), 1,4-benzene dicarboxylic acid (terephthalic acid), 1,2,3-benzene tricarboxylic acid (hemimellitic acid), 1,2,4-benzene tricarboxylic acid (trimellitic acid), 1,3,5-benzene tricarboxylic acid (trimesic acid), 1,2,4,5-benzene tetracarboxylic acid (pyromellitic acid), 1,2,3,4,5-benzene pentacarboxylic acid, 1,2,3,4,5,6-benzene hexacarboxylic acid (mellitic acid), 2-nitrobenzoic acid, 3-nitrobenzoic acid, 4-nitrobenzoic acid, 2,5-dinitrobenzoic acid, 2,6-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 3,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,3-aminobenzoic acid, 2,4-diaminobenzoic acid, salicylic acid, p-toluenesulphonic acid, 1-naphthoic acid, 2-naphthoic acid, 2,6-naphthalenedicarboxylic acid, 2-naphthalenesulphonic acid, 5-amino-1-naphtalenesulphonic acid, 5-amino-2-naphtalenesulphonic acid, 7-amino-4-hydroxy-2-naphthalenesulphonic acid and phenyl phosphonic acid.
8. The activation composition according to claim 1 wherein the concentration of the at least two aromatic acids in the activation composition ranges from 0.1 to 1000 mg/L.
9. The activation composition according to claim 1 wherein the concentration of the at least two aromatic acids in the activation composition ranges from 1 to 750 mg/L.
10. The activation composition according to claim 1 wherein the activation composition further comprises d) methane sulphonic acid and/or a mineral acid selected from the group consisting of sulphuric acid, hydrochloric acid, nitric acid, phosphoric acid, methane sulphonic acid, hydrobromic acid, hydrogen iodide, perchloric acid, aqua regia, hydrochlorous acid, iodic acid and nitrous acid.
11. A method for activating at least one silicon substrate which comprises the following steps in the given order:
providing the at least one silicon substrate;
(ii) activating at least a part of the surface of said at least one silicon substrate with the activation composition according to claim 1 .
12. The method of claim 11 characterized in that the silicon substrates comprise surfaces made of silicon oxide, polysilicon, p-doped polysilicon, n-doped polysilicon, silicon nitride and silicon oxynitride.
13. The method according to claim 11 characterized in that the method comprises a further step after step (ii):
(iii) electroless plating of a metal or a metal alloy on the activated silicon substrate.
14. The method of claim 13 wherein the metal to be deposited is selected from the group consisting of copper, cobalt, nickel, copper alloy, cobalt alloy and nickel alloy.
15. The method of claim 13 characterized in that the method further comprises after step (iii):
(iv) heat treatment of the silicon substrate
and thereby forming a metal silicide.
16. The method of claim 14 characterized in that the method further comprises after step (iii):
(iv) heat treatment of the silicon substrate
and thereby forming a metal silicide.
17. The activation composition according to claim 4 , wherein the at least one other aromatic acid according to formulae I and II has the proviso that at least one of R 1 to R 14 is a carboxylic acid moiety.
18. The activation composition of claim 2 wherein the at least two aromatic acids are selected from aromatic acids according to formulae (I) and (II):
wherein R 1 to R 14 are independently from each other selected from the group consisting of hydrogen, alkyl, aryl, halides, amino, sulphonic acid moiety, carboxylic acid moiety, phosphonic acid moiety, nitro and hydroxyl with the proviso that at least one of R 1 to R 14 is a sulphonic acid moiety, a carboxylic acid moiety or a phosphonic acid moiety.
19. The activation composition according to claim 18 , wherein at least one of the aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a sulphonic acid moiety.
20. The activation composition according to claim 18 , wherein at least one of the aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a carboxylic acid moiety.
21. The activation composition according to claim 18 , wherein one of the two aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a sulphonic acid moiety, and one of the two aromatic acids according to formulae I and II has the proviso that at least one of R 1 to R 14 is a carboxylic acid moiety.