Acid copper electroplating baths containing brightening and levelling additives

Claim 2

An acid copper electroplating bath containing an alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula : wherein R is H or (CH 2 ) n' NH 2 and n and n' independently = 1 to 6. with an epihalohydrin and an alkylating agent.

Claim 3

The acid copper bath of claim 1 wherein said polyalkyleneimine is selected from ethylene diamine, propylene diamine, diethylene triamine and dipropylene triamine.

Claim 4

The acid copper bath of claim 1 or claim 2 wherein said alkylating agent is selected from an alkyl halide having from 1 to 3 carbon atoms, an alkylene halide having from 3 to 6 carbon atoms, an alkynyl halide having from 3 to 6 carbon atoms, and an aralkyl halide.

Claim 5

The acid copper electroplating bath of any preceding claim which further comprises an organic sulfo sulfonate represented by the formula : wherein M is an alkali metal or ammonium ion; n" is from 1 to 6; R' is selected from an alkylene group having from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from the group MO 3 SR', wherein M and R' are described above, wherein R 2 and R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, and

Claim 6

The acid copper electroplating bath of claim 4 wherein said organic sulfo sulfonate is a disulfo, sulfonate represented by the formula : wherein a is from 2 to 6.

Claim 7

The acid copper electroplating bath of claim 4 wherein said organic sulfo sulfonate is a sulfonated dialkyl dithiocarbamate represented by the formula : wherein R a may be each an alkyl group of from 1 to 3 carbon atoms or a cycloaliphatic hydrocarbon and b is a number from 2 to 6.

Claim 8

The acid copper electroplating bath of claim 4 wherein said organic sulfo sulfonate is

Claim 9

The acid copper electroplating bath of claim 4 wherein said organic sulfo sulfonate is ;

Claim 10

The acid copper electroplating bath of any preceding claim which further comprises a polyether represented by the formula : wherein R" is selected from hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and wherein u and v = 0 to 4 but at least one of u or v must be greater than 0, r + s = 6 to 200,000; r = 0 when u = 0; s = 0 when v = 0; and T is selected from hydrogen, alkyl and benzyl.

Claim 11

The acid copper electroplating bath of any preced- in g claim which further comprises a thioorganic compound represented by the formula : wherein the bond between C and S and N and C is a single or a double bond, R' 1 or R'2 may be hydrogen or R' 1 taken together with R' 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or carbon atoms and at least one heteroatom selected from S, N and N-substituted atom, R' 3 is selected from hydrogen, alkyl and aralkyl, and R' 4 . is wherein R 5 and R 6 are each selected from hydrogen, alkyl and aralkyl groups.

Claim 12

The acid copper electroplating bath of any preceding claim wherein said epihalohydrin is epichlorohydrin.

Claim 13

The acid copper electroplating bath of any preceding claim wherein said alkylated polyalkyleneimine is formed from substantially equimolar amounts of polyalkyleneimine and alkylating agent.

Claim 14

The acid copper electroplating bath of any preceding claim wherein said thioorganic compound is selected from thiourea, N-alkyl and aryl substituted thioureas, 2-thiazolidinethione, 1-(2-hydroxyethyl) - 2-imidazolidine thione, 2-aminothiazole, 2-imidazoline thione,.2 - mercaptopyridine and benzothiazolethione.

Claim 15

The acid copper electroplating bath of any preceding claim wherein said thioorganic compound consists of an equimolar mixture of 2-thiazolidinethione and 1-(2-hydroxyethyl) -2-imidazolidine thione.

Claim 16

An acid copper electroplating bath containing : (a) An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula : wherein R is H or (CH2)ntNH2 and n and n' independently = 1 to 6. with epichlorohydrin and benzyl chloride, the molar amounts of polyalkyleneimine, epichlorohydrin and benzyl chloride being substantially equal; (b) an organic sulfo sulfonate represented by the formula: wherein a is from 2 to 6; (c) a polyether represented by the formula : wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and wherein u and v = 0 to 4 but at least one of u or v must be greater than 0, r+s = 6 to 200,000; r = 0 when u = 0; s = 0 when v = 0; and T is selected from hydrogen, alkyl and benzyl; (d) an equimolar combination of 2-thiazolidinethione and 1-(2-hydroxyethyl) -2- imidazolidinethione.

Claim 17

An acid copper electroplating bath containing : (a) An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula : wherein R is H or (CH2)ntNH2 and n and n' independently = 1 to 6. with epichlorohydrin and benzyl chloride, the molar amounts of polyalkyleneimine, epichlorohydrin and benzyl chloride being substantially equal; (b) an organic sulfo sulfonate represented by the formula: wherein a is from 2 to 6; (c) a polyether represented by the formula : wherein R is selected from hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and wherein u and v = 0 to 4 but at least one of u or v must be greater than 0, r+s = 6 to 200,000; r = 0 when u = 0; s = 0 when v = 0; and T is selected from hydrogen, alkyl and benzyl; (d) an equimolar combination of 2-thiazolidinethione and 1-(2-hydroxyethyl) -2- imidazolidinethione.

Claim 18

A process for producing copper deposits which comprises electrodepositing copper from an aqueous acidic copper bath containing the reaction product of a polyalkyleneimine represented by the formula : wherein R is H or (CH 2 ) n NH 2 and n and n' independently = 1 to 6 with an epihalohydrin and an alkylating agent.

Claim 19

A process for producing copper deposits which comprises electrodepositing copper from an aqueous acidic copper bath containing the reaction product of a polyalkyleneimine represented by the formula : wherein R is H or (CH 2 ) n NH 2 and n and n' independently = 1 to 6 with an epihalohydrin and an alkylating agent.

Claim 20

The process of claim 1 in which said bath further comprises an organic sulfo sulfonate represented by the formula : wherein M is an alkali metal or ammonium ion; n" is from 1 to 6; R is selected from an alkylene group having from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms; R 1 is selected from MO 3 SR', wherein M and R' are as described above, wherein R 2 and R 3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ; and

Claim 21

The process of claim 2 wherein said organic sulfo sulfonate is a disulfo sulfonate represented by the formula: wherein a is from 2 to 6.

Claim 22

The process of claim 2 wherein said organic sulfo sulfonate is a sulfonated dialkyl dithiocarbamate represented by the formula : wherein R a may be each an alkyl group of from 1 to 3 carbon atoms or a cycloaliphatic hydrocarbon and b is a number from 2 to 6.

Claim 23

The process of claim 2 wherein said organic sulfo sulfonate is

Claim 24

The process cf claim 2 wherein said organic sulfo sulfonate is

Claim 25

The process of any preceding claim in which said bath further comprises a polyether represented by the formula: wherein R" is selected from hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl; m is 5 to 100; and wherein u and v = 0 to 4 but at least one of u or v must be greater than 0, r + s = 6 to 200,000; r = 0 when u = 0; s = 0 when v = 0; and T is selected from hydrogen, alkyl and benzyl.

Claim 26

The process of any preceding claim in which said bath further comprises a thioorganic compound represented by the formula : wherein the bond between C and S and N and C is a single or a double bond. R' 1 or R' 2 may be hydrogen or R I 1 taken together with R' 2 forms a heterocyclic ring structure of 5 to 6 members or a benzo-substituted heterocyclic ring structure of 5 to 6 members wherein said ring members are comprised totally of carbon atoms or of carbon atoms and at least one heteroatom selected from S, N and N-substituted atom, R' 3 is selected from hydrogen, alkyl and aralkyl, and R 4 is wherein R 5 and R 6 are each selected from hydrogen, alkyl° and aralkyl groups.

Claim 27

The process of any preceding claim wherein said thioorganic compound is selected from thiourea, N-alkyl and aryl substituted thioureas, 2-thiazolidinethione, 1-(2-hydroxyethyl) -2-imidazolidinethione, 2-aminothiazole, 2-imidazolinethione, 2-mercaptopyridine, and benzothiazolethione.

Claim 28

The process of any preceding claim wherein said thioorganic compound consists of-an equimolar mixture of 2-thiazolidinethione and 1-(2-hydroxyethyl) -2-imidazolidine thione.