Composition for tin-silver alloy electroplating comprising a complexing agent

Patent metadata

Field	Value
Publication number	US-12559852-B2
Application number	US-202017753653-A
Country	US
Kind code	B2
Filing date	Sep 8, 2020
Priority date	Sep 16, 2019
Publication date	Feb 24, 2026
Grant date	Feb 24, 2026

Abstract

An aqueous composition including (a) metal ions including tin ions and silver ions and (b) at least one complexing agent of formula C11

R C12 -X C11 -R C11   (C11)

and their salts,
where X C11 is selected from
(a) a divalent 5 or 6 membered aromatic N-heterocyclic group; (b) a divalent 6 membered aromatic carbocyclic group; and (c) a divalent 5 or 6 membered aliphatic N-heterocyclic group including one N atom and optionally a second heteroatom selected from N and O;
 all of which may be unsubstituted or substituted by one or more OH or one or more R C14 ; R C11 is selected from

 ; and
R C12 is selected from R C11 , X C11 -R C11 , H, OH, NR C14 2 , C 1 to C 10 alkyl, and C 1 to C 10 alkoxy

First claim

The invention claimed is:

1 . An aqueous composition comprising (a) metal ions comprising tin ions and silver ions and (b) at least one complexing agent of formula C11
R C12 -X C11 - R C11   (C11)
and their salts, wherein X C11 is selected from the group consisting of
(a) a divalent 5 or 6 membered aromatic N-heterocyclic group comprising
(i) a single N atom; or
(ii) a first N atom and a second heteroatom selected from N and S, wherein the first N atom and the second heteroatom are separated by at least one C atom; or
(iii) a triazole or a thiadiazole;

(b) a divalent 6 membered aromatic carbocyclic group; and
(c) a divalent 5 or 6 membered aliphatic N-heterocyclic group comprising one N atom and optionally a second heteroatom selected from the group consisting of N and O;
all of which may be unsubstituted or substituted by one or more OH or one or more R C14 ;
R C11 is selected from the group consisting of (a) -X C12 -S[-X C13 -D C11 ] n -R C13 ,

R C12 is selected from the group consisting of R C11 , X C11 -R C11 , H, OH, C 1 to C 10 alkyl, and C 1 to C 10 alkoxy, with the proviso that if X C11 is a divalent 6 membered aromatic carbocyclic group, then R C12 is selected from the group consisting of R C11 , X C11 -R C11 , C 1 to C 10 alkyl, and C 1 to C 10 alkoxy;
X C12 is a chemical bond or a linear, branched or cyclic C 1 -C 6 alkanediyl, which may be unsubstituted or substituted by OH, with the proviso that if (a) X C11 is a divalent 5 or 6 membered aromatic N-heterocyclic group and (b) R C13 is substituted by one OH and (c) R C12 is not R C11 , then X C12 is a chemical bond;
X C13 is a linear, branched or cyclic C 1 -C 6 alkanediyl, which may be unsubstituted or substituted by OH;
X C14 is a chemical bond or a linear or branched C 1 -C 4 alkanediyl;
D C11 is selected from the group consisting of S and O;
R C13 is selected from the group consisting of (a) a linear, branched or cyclic C 1 -C 6 alkyl, which may be unsubstituted or substituted by one or more OH, (b) Ph or X C14 -Ph, which may be substituted by OH or R C14 , with Ph=phenyl, when X C11 is not the aromatic carbocyclic group, and (c) a C 2 to C 4 polyoxyalkylene group;
with the proviso that if X C11 is a divalent 5 or 6 membered aromatic N- heterocyclic group, then R C13 is unsubstituted or substituted by one OH with the exception that if X C11 is a divalent 5 or 6 membered aromatic N-heterocyclic group comprising a first N atom and a second heteroatom that is N, then R C13 is unsubstituted;

R C14 is selected from the group consisting of H and a linear, branched or cyclic C 1 -C 6 alkyl; and

n is 0 or an integer of from 1 to 5;
wherein the composition is free of copper ions.

2 . The aqueous composition according to claim 1 , wherein R C11 is -X C12 —S[X C13 -D C11 ] n -R C13 .

3 . The aqueous composition according to claim 2 , wherein X C12 is a linear or branched C 1 -C 4 alkanediyl, which may be unsubstituted or substituted by OH, with the proviso that if (a) X C11 is a divalent 5 or 6 membered aromatic N-heterocyclic group and (b) R C13 is substituted by one OH and (c) R C12 is not R C12 , then X C12 is a chemical bond.

4 . The aqueous composition according to claim 2 , wherein n is 1 or 2; D C11 is S; and X C13 is a linear or branched C 1 -C 4 alkanediyl, which may be unsubstituted or substituted by one or more OH.

5 . The aqueous composition according to claim 2 , wherein R C13 is selected from the group consisting of (a) a linear or branched C 1 -C 4 alkyl, which may be unsubstituted or substituted by one or more OH, (b) phenyl or benzyl, which may be substituted by OH, methyl or ethyl, where X C11 is not the aromatic carbocyclic group, and (c) a polyoxyethylene or a poly(oxyethylene-co-oxypropylene), with the proviso that if X C11 is a divalent 5 or 6 membered aromatic N-heterocyclic group, then R C13 is unsubstituted or substituted by one OH with the exception that if X C11 is a divalent 5 or 6 membered aromatic N-heterocyclic group comprising a first N atom and a second heteroatom selected from the group consisting of N, then R C13 is unsubstituted.

6 . The aqueous composition according to claim 2 , wherein n is 0 or 1.

7 . The aqueous composition according to claim 2 , wherein n is 1; D C11 is S; and X C13 is a linear or branched C 1 -C 4 alkanediyl, which may be unsubstituted or substituted by one or more OH.

8 . The aqueous composition according to claim 1 , wherein R C11 is

wherein X C14 is a chemical bond, methanediyl, ethanediyl, or propanediyl; and R C14 is H, methyl, ethyl or propyl.

9 . The aqueous composition according to claim 1 , wherein X C11 is selected from the group consisting of a pyrrole, a pyridine, an imidazole, a pyrimidine, and a thiazole, which may be unsubstituted or substituted by one or more methyl, ethyl or propyl.

10 . The aqueous composition according to claim 1 , wherein X C11 is selected from the group consisting of phenyl, which may be unsubstituted or substituted by one or more methyl, ethyl or propyl.

11 . The aqueous composition according to claim 1 , wherein X C11 is selected from the group consisting of piperidine, piperazine, pyrrolidinone and morpholine, which may be unsubstituted or substituted by one or more methyl, ethyl or propyl.

12 . The aqueous composition according to claim 1 , wherein R C12 is selected from the group consisting of R C11 and X C11 -R C11 .

13 . A process for electrodepositing tin or a tin silver alloy onto a substrate by
a) contacting the composition according to claim 1 with the substrate, and b) applying a current to the substrate for a time sufficient to electrodeposit the tin silver alloy layer onto the substrate,
wherein the substrate comprises features having an aperture size from 500 nm to 500 μm and the electrodeposition is performed to fill these features.

14 . The process according to claim 13 , wherein the aperture size is from 1 μm to 200 μm.

Assignees

• Basf Se

Inventors

• Arnold Marco
• Fluegel Alexander
• Kuttner Elisabeth
• Kremzow-Graw Doris
• Engelhardt Nadine
• KASCHEL Johannes

Classifications

• C25D3/64

  containing more than 50% by weight of silver · CPC title

• C07D277/26

  Radicals substituted by sulfur atoms · CPC title

• C07D233/60

  with hydrocarbon radicals, substituted by oxygen or sulfur atoms, attached to ring nitrogen atoms · CPC title

• C07D213/32

  Sulfur atoms · CPC title

• C07C335/18

  being further substituted by singly-bound oxygen atoms · CPC title