Electrodeposition of copper

Claim 2

A process for electrodepositing copper from an aqueous acidic copper plating bath containing at least one member independently selected from each of the following two groups: A. from 0.005 to 1.0 gram per liter of at least one member of the group consisting of basic diaminotriphenylmethane dyes, basic triaminotriphenylmethane dyes, basic triaminodiphenylnaphthylmethane dyes, and their reduction products; and B. sulfoalkyl sulfide compounds containing the grouping RS n --Alk--SO 3 M where n is an integer 1 to 5, where M is one gram-equivalent of a cation, where --Alk-- is a divalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, and where R is selected from a group consisting of hydrogen, a metal cation, a monovalent hydrocarbon radical including one which carries inert substituents, in which no carbon atom is bound exclusively to heteroatoms, a sulfonic group MO 3 S-- and a sulfoanyl group in an amount of 0.01 milligrams per liter to 1000 milligrams per liter.

Claim 3

The process of claim 1 wherein said basic triaminotriphenylmethane dye is Crystal Violet: ##STR19##

Claim 4

The process of claim 1 wherein said basic triaminotriphenylmethane compound exhibits the formula: ##STR20##

Claim 5

The process of claim 1 wherein said basic diaminotriphenylmethane dye exhibits the formula: ##STR21##

Claim 6

The process of claim 1 wherein said basic triaminotriphenylmethane dye exhibits the formula: ##STR22##

Claim 7

The process of claim 1 wherein said basic triaminotriphenylmethane dye exhibits the formula: ##STR23##

Claim 8

The process of claim 1 wherein said basic triaminotriphenylmethane dye exhibits the formula: ##STR24##

Claim 9

The process of claim 1 wherein said basic triaminotriphenylmethane dye is of the formula: ##STR25## in which 4, 5 or 6 of the substituents R are methyl groups and the remaining 2, 1 or 0 substituents respectively, are benzyl group.

Claim 10

The process of claim 1 wherein said basic triaminodiphenylnaphthylmethane dye exhibits the formula: ##STR26##

Claim 11

The process of claim 1 wherein said basic triaminodiphenylnaphthylmethane dye exhibits the formula: ##STR27##

Claim 12

The process of claim 1 wherein said basic triaminodiphenylnaphthylmethane dye exhibits the formula: ##STR28##

Claim 13

The process of claim 1 wherein said basic triaminodiphenylnaphthylmethane dye exhibits the formula: ##STR29##

Claim 14

A process for electrodepositing copper from an aqueous acidic copper plating bath containing at least one member independently selected from each of the following two groups (A) and (B): A. from 0.005 to 1.0 gram per liter of at least one member of the group consisting of basic diaminotriphenylmethane dyes, basic triaminotriphenylmethane dyes, basic triaminodiphenylnaphthylmethane dyes, and their reduction products; and B. sulfoalkyl sulfide compounds containing the grouping RS n --Alk--SO 3 M where n is an integer 1 to 5, where M is one gram-equivalent of a cation, where --Alk-- is a divalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, and where R is selected from a group consisting of hydrogen, a metal cation, a monovalent hydrocarbon radical including one which carries inert substituents, in which no carbon atom is bound exclusively to heteroatoms, a sulfonic group MO 3 S-- and a sulfolanyl group in an amount of 0.01 milligrams per liter to 1000 milligrams per liter; and at least one member independently selected from at least one of the following three groups (C), (D) and (E) where C. is an organic compound which contains at least ##STR30## in an amount of 0.1 to 50 milligrams per liter; D. is a cationic organic compound of a molecular weight greater than about 500 selected from the group consisting of phenazine azo dyes, polyethyleneimines, alkylated, hydroxyalkylated and sulfoalkylated polyethyleneimines, polyvinylpyridine, polyvinylalkylpyridines, and their quaternization products in an amount of 0.1 to 50 milligrams per liter; and E. is a polyether containing at least five ether atoms per molecule exhibiting molecular weights between 300 and 5,000,000, in an amount of 0.001 to 10 grams per liter.

Claim 15

A process for electrodepositing copper from an aqueous acidic copper plating bath containing at least one member independently selected from each of the following two groups (A) and (B): A. from 0.005 to 1.0 gram per liter of at least one member of the group consisting of basic diaminotriphenylmethane dyes, basic triaminotriphenylmethane dyes, basic triaminodiphenylnaphthylmethane dyes, and their reduction products; and B. sulfoalkyl sulfide compounds containing the grouping RS n --Alk--SO 3 M where n is an integer 1 to 5, where M is one gram-equivalent of a cation, where --Alk-- is a divalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, and where R is selected from a group consisting of hydrogen, a metal cation, a monovalent hydrocarbon radical including one which carries inert substituents, in which no carbon atom is bound exclusively to heteroatoms, a sulfonic group MO 3 S-- and a sulfolanyl group in an amount of 0.01 milligrams per liter to 1000 milligrams per liter; and at least one member independently selected from at least one of the following three groups (C), (D) and (E) where C. is an organic compound which contains at least ##STR30## in an amount of 0.1 to 50 milligrams per liter; D. is a cationic organic compound of a molecular weight greater than about 500 selected from the group consisting of phenazine azo dyes, polyethyleneimines, alkylated, hydroxyalkylated and sulfoalkylated polyethyleneimines, polyvinylpyridine, polyvinylalkylpyridines, and their quaternization products in an amount of 0.1 to 50 milligrams per liter; and E. is a polyether containing at least five ether atoms per molecule exhibiting molecular weights between 300 and 5,000,000, in an amount of 0.001 to 10 grams per liter.

Claim 16

An aqueous acidic copper electroplating bath containing at least one member independently selected from each of the following two groups: A. from 0.005 to 1.0 gram per liter of at least one member of the group consisting of basic diaminotriphenylmethane dyes, basic triaminotriphenylmethane dyes, basic triaminodiphenylnaphthylmethane dyes, and their reduction products; and B. sulfoalkyl sulfide compounds containing the grouping RS n --Alk--SO 3 M where n is an integer 1 to 5, where M is one gram-equivalent of a cation, where --Alk-- is a divalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, and where R is selected from a group consisting of hydrogen, a metal cation, a monovalent hydrocarbon radical including one which carries inert substituents, in which no carbon atom is bound exclusively to heteroatoms, a sulfonic group MO 3 S-- and a sulfolanyl group in an amount of 0.01 milligrams per liter to 1000 milligrams per liter.

Claim 17

An aqueous acidic copper electroplating bath containing at least one member independently selected from each of the following two groups: A. from 0.005 to 1.0 gram per liter of at least one member of the group consisting of basic diaminotriphenylmethane dyes, basic triaminotriphenylmethane dyes, basic triaminodiphenylnaphthylmethane dyes, and their reduction products; and B. sulfoalkyl sulfide compounds containing the grouping RS n --Alk--SO 3 M where n is an integer 1 to 5, where M is one gram-equivalent of a cation, where --Alk-- is a divalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, and where R is selected from a group consisting of hydrogen, a metal cation, a monovalent hydrocarbon radical including one which carries inert substituents, in which no carbon atom is bound exclusively to heteroatoms, a sulfonic group MO 3 S-- and a sulfolanyl group in an amount of 0.01 milligrams per liter to 1000 milligrams per liter.

Claim 18

The bath of claim 14 wherein said basic triaminotriphenylmethane dye is Crystal Violet: ##STR31##

Claim 19

The bath of claim 14 wherein said basic triaminotriphenylmethane compound exhibits the formula: ##STR32##

Claim 20

The bath of claim 14 wherein said basic diaminotriphenylmethane dye exhibits the formula: ##STR33##

Claim 21

The bath of claim 14 wherein said basic triaminotriphenylmethane dye exhibits the formula: ##STR34##

Claim 22

The bath of claim 14 wherein said basic triaminotriphenylmethane dye exhibits the formula: ##STR35##

Claim 23

The bath of claim 14 wherein said basic triaminotriphenylmethane dye exhibits the formula: ##STR36##

Claim 24

The bath of claim 14 wherein said basic triaminotriphenylmethane dye is of the formula: ##STR37## in which 4, 5 or 6 of the substituents R are methyl groups and the remaining 2, 1 or 0 substituents, respectively, are benzyl group.

Claim 25

The bath of claim 14 wherein said basic triaminodiphenylnaphylmethane dye exhibits the formula: ##STR38##

Claim 26

The bath of claim 14 wherein said basic triaminodiphenylnaphthylmethane dye exhibits the formula: ##STR39##

Claim 27

The bath of claim 14 wherein said basic triaminodiphenylnaphthylmethane dye exhibits the formula: ##STR40##

Claim 28

The bath of claim 14 wherein said basic triaminodiphenylnaphthylmethane dye exhibits the formula: ##STR41##

Claim 29

An aqueous acidic copper electroplating bath containing at least one member independently selected from each of the following two groups (A) and (B): A. from 0.005 to 1.0 gram per liter of at least one member of the group consisting of basic diaminotriphenylmethane dyes, basic triaminotriphenylmethane dyes, basic triaminodiphenylnaphthylmethane dyes, and their reduction products; and B. sulfoalkyl sulfide compounds containing the grouping RS n --Alk--SO 3 M where n is an integer 1 to 5, where M is one gram-equivalent of a cation, where --Alk-- is a divalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, and where R is selected from a group consisting of hydrogen, a metal cation, a monovalent hydrocarbon radical including one which carries inert substituents, in which no carbon atom is bound exclusively to heteroatoms, a sulfonic group MO 3 S-- and a sulfolanyl group in an amount of 0.01 milligrams per liter to 1000 milligrams per liter; and at least one member independently selected from at least one of the following three groups (C), (D) and (E) where C. is an organic compound which contains at least ##STR42## in an amount of 0.1 to 50 milligrams per liter; D. is a cationic organic compound of a molecular weight greater than about 500 selected from the group consisting of phenazine azo dyes, polyethyleneimines, alkylated, hydroxyalkylated and sulfoalkylated polyethyleneimines, polyvinylpyridine, polyvinylalkylpyridines, and their quaternization products in an amount of 0.1 to 50 milligrams per liter; and E. is a polyether containing at least five ether atoms per molecule exhibiting molecular weights between 300 and 5,000,000 in an amount of 0.001 to 10 grams per liter.

Claim 30

An aqueous acidic copper electroplating bath containing at least one member independently selected from each of the following two groups (A) and (B): A. from 0.005 to 1.0 gram per liter of at least one member of the group consisting of basic diaminotriphenylmethane dyes, basic triaminotriphenylmethane dyes, basic triaminodiphenylnaphthylmethane dyes, and their reduction products; and B. sulfoalkyl sulfide compounds containing the grouping RS n --Alk--SO 3 M where n is an integer 1 to 5, where M is one gram-equivalent of a cation, where --Alk-- is a divalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, and where R is selected from a group consisting of hydrogen, a metal cation, a monovalent hydrocarbon radical including one which carries inert substituents, in which no carbon atom is bound exclusively to heteroatoms, a sulfonic group MO 3 S-- and a sulfolanyl group in an amount of 0.01 milligrams per liter to 1000 milligrams per liter; and at least one member independently selected from at least one of the following three groups (C), (D) and (E) where C. is an organic compound which contains at least ##STR42## in an amount of 0.1 to 50 milligrams per liter; D. is a cationic organic compound of a molecular weight greater than about 500 selected from the group consisting of phenazine azo dyes, polyethyleneimines, alkylated, hydroxyalkylated and sulfoalkylated polyethyleneimines, polyvinylpyridine, polyvinylalkylpyridines, and their quaternization products in an amount of 0.1 to 50 milligrams per liter; and E. is a polyether containing at least five ether atoms per molecule exhibiting molecular weights between 300 and 5,000,000 in an amount of 0.001 to 10 grams per liter.