US 6,607,653 B1Granted

Plating bath and process for depositing alloy containing tin and copper

AssigneesDaiwa Fine Chemicals Co., Ltd., Ishihara Chemical Co., Ltd.

InventorsKiyotaka Tsuji, Keigo Obata, Takao Takeuchi, Hidemi Nawafune, Tetsuji Nishikawa

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Abstract

The present invention provides a tin-copper alloy plating bath, tin-copper-bismuth alloy plating bath or tin-copper-silver alloy plating bath containing a soluble metal compound and a specific sulfur-containing compound. The plating bath of the present invention is an alloy plating bath containing tin and copper, the bath being capable of preventing deposition of copper on a tin anode by substitution, having low dependence of plated coating composition on current density, high bath stability and resistance to turbidness.

Claims15

Dependent claims

A lead-free tin-copper alloy plating bath comprising:

(A) a soluble tin (II) compound;
(B) a soluble copper compound;
and
(C) at least one sulfur-containing compound selected from the group consisting of the following compounds (i)-(iii):
(i)an aliphatic sulfide compound represented by the following formula (1):
Re—Ra—[(X—Rb)L—(Y—Rc)M—(Z—Rd)N]—Rf (1)
(wherein the symbols represent the following:
M is an integer of 1-100, L and N are each 0 or an integer of 1-100;
Y represents S or S—S, X and Z are the same or different and each represents 0, S or S—S;
Ra represents C1-12 straight-chain or branched-chain alkylene or 2-hydroxypropylene;
Rb, Rc and Rd are the same or different and each represents methylene, ethylene, propylene, 2-hydroxy-propylene, butylene, pentylene or hexylene;
in X—Rb, Y—Rc and Z—Rd, the position of each other is not limited and may be randomly positioned, and when the bond X—Rb's, Y—Rc's or Z—Rd's are repeated, the X—Rb's, Y—Rc's or Z—Rd's may be composed of two or more kinds of bonds;
Re and Rf may be the same or different and each represents carboxyl, hydroxyl, —O-alkyl, —S-alkyl, —O-alkenyl, —O-alkynyl, —O-aralkyl, —O-allyl, —O-polycyclic cycloalkyl, —O-acetyl, —O-aryl or —O-polycyclic aryl;
among Re and Rf, the groups other than carboxyl and hydroxyl may be substituted by at least one group selected from the group consisting of halogen, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxyl.),
(ii) a sulfide compound (excluding dithiodianiline) having a basic nitrogen atom represented by the following formula (2):
Rg—[(S)X—Rh]p-[(S)Y—Ri)]q (2)
(wherein the symbols represent the following:
X and Y are each an integer of 1-4, p is 0 or an integer of 1-100, q is an integer of 1-100;
in which
(a) when p=0, Rg and Ri means (1) and (2) below:
(1) Rg and Ri are the same or different and each represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, at least one of Rg and Ri having one or more basic nitrogen atom, or
(2) Rg and Ri are bonded to each other and form a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg and Ri may be the same or different;
(b) when p is an integer of 1-100, Rg, Rh and Ri mean (1) or (2) below:
(1) Rg and Ri represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, Rh represents alkylene, alkenylene, alkynylene, aralkylene, cycloalkylene, polycyclic cycloalkylene, arylene, polycyclic arylene, heterocyclic group or polycyclic heterocyclic group, at least one of Rg, Rh and Ri having one or more basic nitrogen atom, or
(2) Rg and Rh, Rg and Ri, or Rh and Ri are bonded, or Rg and Rh, and Rh and Ri are simultaneously bonded, forming a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg, Rh and Ri may be the same or different;
in the above (a) and (b), Rg, Rh and Ri may be substituted by at least one group selected from the group consisting of halogen, amino, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxy.), and
(iii) a thiocrown ether compound.

26 more elements

A tin-copper-bismuth alloy plating bath comprising:

(A) a soluble tin (II) compound,
(B) a soluble copper compound,
(C) a soluble bismuth compound, and
(D) at least one sulfur-containing compound selected from the group consisting of the following compounds (i)-(iii):
(i) an aliphatic sulfide compound represented by the following formula (1):
Re—Ra—[(X—Rb)L—(Y—Rc)M—(Z—Rd)N]—Rf (1)
(wherein the symbols represent the following:
M is an integer of 1-100, L and N are each 0 or an integer of 1-100;
Y represents S or S—S, X and Z are the same or different and each represents 0, S or S—S;
Ra represents C1-12 straight-chain or branched-chain alkylene or 2-hydroxypropylene;
Rb, Rc and Rd are the same or different and each represents methylene, ethylene, propylene, 2-hydroxy-propylene, butylene, pentylene or hexylene;
the positions of X—Rb, Y—Rc and Z—Rd are not limited and may be randomly positioned, and when the bond X—Rb's, Y—Rc's or Z—Rd's are repeated, the X—Rb's, Y—Rc's or Z—Rd's may be composed of two or more kinds of bonds;
Re and Rf may be the same or different and each represents hydrogen, carboxyl, hydroxyl, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, allyl, polycyclic cycloalkyl, aryl, polycyclic aryl, —O-alkyl, —S-alkyl, —O-alkenyl, —O-alkynyl, —O-aralkyl, —O-allyl, —O-polycyclic cycloalkyl, —O-acetyl, —O-aryl or —O-polycyclic aryl;
among Re and Rf, the groups other than hydrogen, carboxyl and hydroxyl may be substituted by at least one group selected from the group consisting of halogen, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxyl.),
(ii) a sulfide compound containing a basic nitrogen atom represented by the following formula (2):
Rg—[(S)X—Rh]p-[(S)Y—Ri)]q (2)
(wherein the symbols represent the following:
X and Y are each an integer of 1-4, p is 0 or an integer of 1-100, q is an integer of 1-100;
in which
(a) when p=0, Rg and Ri means (1) and (2) below:
(1) Rg and Ri are the same or different and each represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, at least one of Rg and Ri having one or more basic nitrogen atom, or
(2) Rg and Ri are bonded to each other and form a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg and Ri may be the same or different;
(b) when p is an integer of 1-100, Rg, Rh and Ri mean (1) or (2) below:
(1) Rg and Ri represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, Rh represents alkylene, alkenylene, alkynylene, aralkylene, cycloalkylene, polycyclic cycloalkylene, arylene, polycyclic arylene, heterocyclic group or polycyclic heterocyclic group, at least one of Rg, Rh and Ri having one or more basic nitrogen atom, or
(2) Rg and Rh, Rg and Ri, or Rh and Ri are bonded, or Rg and Rh, and Rh and Ri are simultaneously bonded, forming a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg, Rh and Ri may be the same or different;
in the above (a) and (b), Rg, Rh and Ri may be substituted by at least one group selected from the group consisting of halogen, amino, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxy.), and
(iii) a thiocrown ether compound.

26 more elements

A tin-copper-silver alloy plating bath comprising:

(A) a soluble tin (II) compound;
(B) a soluble copper compound;
(C) a soluble silver compound, and
(D) at least one sulfur-containing compound selected from the group consisting of the following compounds (i)-(iii):
(i) an aliphatic sulfide compound (excluding thiodiglycolic acid and thiodiglycol) represented by the following formula:
Re—Ra—[(X—Rb)L—(Y—Rc)M—(Z—Rd)N]—Rf (1)
(wherein the symbols represent the following:
M is an integer of 1-100, L and N are each 0 or an integer of 1-100;
Y represents S or S—S, X and Z are the same or different and each represents 0, S or S—S;
Ra represents C1-12 straight-chain or branched-chain alkylene or 2-hydroxypropylene;
Rb, Rc and Rd are the same or different and each represents methylene, ethylene, propylene, 2-hydroxy-propylene, butylene, pentylene or hexylene;
the positions of X—Rb, Y—Rc and Z—Rd, are not limited and may be randomly positioned, and when the bond X—Rb's, Y—Rc's or Z—Rd's are repeated, the X—Rb's, Y—Rc's or Z—Rd's may be composed of two or more kinds of bonds;
Re and Rf may be the same or different and each represents hydrogen, carboxyl, hydroxyl, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, allyl, polycyclic cycloalkyl, aryl, polycyclic aryl, —O-alkyl, —S-alkyl, —O-alkenyl, —O-alkynyl, —O-aralkyl, —O-allyl, —O-polycyclic cycloalkyl, —O-acetyl, —O-aryl or —O-polycyclic aryl;
among Re and Rf, the groups other than hydrogen, carboxyl and hydroxy may be substituted by at least one group selected from the group consisting of halogen, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxy.),
(ii) a sulfide compound containing a basic nitrogen atom represented by the following formula (2):
Rg—[(S)X—Rh]p-[(S)Y—Ri)]q (2)
(wherein the symbols represent the following:
X and Y are each an integer of 1-4, p is 0 or an integer of 1-100, q is an integer of 1-100;
in which
(a) when p=0, Rg and Ri means (1) and (2) below:
(1) Rg and Ri are the same or different and each represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, at least one of Rg and Ri having one or more basic nitrogen atom, or
(2) Rg and Ri are bonded to each other and form a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg and Ri may be the same or different;
(b) when p is an integer of 1-100, Rg, Rh and Ri mean (1) or (2) below:
(1) Rg and Ri represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, Rh represents alkylene, alkenylene, alkynylene, aralkylene, cycloalkylene, polycyclic cycloalkylene, arylene, polycyclic arylene, heterocyclic group or polycyclic heterocyclic group, at least one of Rg, Rh and Ri having one or more basic nitrogen atom, or
(2) Rg and Rh, Rg and Ri, or Rh and Ri are bonded, or Rg and Rh, and Rh and Ri are simultaneously bonded, forming a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg, Rh and Ri may be the same or different;
in the above (a) and (b), Rg, Rh and Ri may be substituted by at least one group selected from the group consisting of halogen, amino, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxy), and
(iii) a thiocrown ether compound.

26 more elements

Dependencies are inferred from the claim text.

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Abstract

A lead-free tin-copper alloy plating bath comprising:

(A) a soluble tin (II) compound;
(B) a soluble copper compound;
and
(C) at least one sulfur-containing compound selected from the group consisting of the following compounds (i)-(iii):
(i)an aliphatic sulfide compound represented by the following formula (1):
Re—Ra—[(X—Rb)L—(Y—Rc)M—(Z—Rd)N]—Rf (1)
(wherein the symbols represent the following:
M is an integer of 1-100, L and N are each 0 or an integer of 1-100;
Y represents S or S—S, X and Z are the same or different and each represents 0, S or S—S;
Ra represents C1-12 straight-chain or branched-chain alkylene or 2-hydroxypropylene;
Rb, Rc and Rd are the same or different and each represents methylene, ethylene, propylene, 2-hydroxy-propylene, butylene, pentylene or hexylene;
in X—Rb, Y—Rc and Z—Rd, the position of each other is not limited and may be randomly positioned, and when the bond X—Rb's, Y—Rc's or Z—Rd's are repeated, the X—Rb's, Y—Rc's or Z—Rd's may be composed of two or more kinds of bonds;
Re and Rf may be the same or different and each represents carboxyl, hydroxyl, —O-alkyl, —S-alkyl, —O-alkenyl, —O-alkynyl, —O-aralkyl, —O-allyl, —O-polycyclic cycloalkyl, —O-acetyl, —O-aryl or —O-polycyclic aryl;
among Re and Rf, the groups other than carboxyl and hydroxyl may be substituted by at least one group selected from the group consisting of halogen, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxyl.),
(ii) a sulfide compound (excluding dithiodianiline) having a basic nitrogen atom represented by the following formula (2):
Rg—[(S)X—Rh]p-[(S)Y—Ri)]q (2)
(wherein the symbols represent the following:
X and Y are each an integer of 1-4, p is 0 or an integer of 1-100, q is an integer of 1-100;
in which
(a) when p=0, Rg and Ri means (1) and (2) below:
(1) Rg and Ri are the same or different and each represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, at least one of Rg and Ri having one or more basic nitrogen atom, or
(2) Rg and Ri are bonded to each other and form a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg and Ri may be the same or different;
(b) when p is an integer of 1-100, Rg, Rh and Ri mean (1) or (2) below:
(1) Rg and Ri represents alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl, polycyclic cycloalkyl, aryl, polycyclic aryl, heterocyclic group or polycyclic heterocyclic group, Rh represents alkylene, alkenylene, alkynylene, aralkylene, cycloalkylene, polycyclic cycloalkylene, arylene, polycyclic arylene, heterocyclic group or polycyclic heterocyclic group, at least one of Rg, Rh and Ri having one or more basic nitrogen atom, or
(2) Rg and Rh, Rg and Ri, or Rh and Ri are bonded, or Rg and Rh, and Rh and Ri are simultaneously bonded, forming a monocyclic or polycyclic ring having one or more basic nitrogen atom;
in the above (1) and (2), Rg, Rh and Ri may be the same or different;
in the above (a) and (b), Rg, Rh and Ri may be substituted by at least one group selected from the group consisting of halogen, amino, cyano, formyl, alkoxy, carboxyl, acyl, nitro and hydroxy.), and
(iii) a thiocrown ether compound.

26 more elements