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US 4,376,685 AGranted
Acid copper electroplating baths containing brightening and leveling additives
AssigneeM&T Chemicals Inc.
InventorAngus Watson
Life of this patent
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Abstract
The invention is concerned with the electrodeposition of copper from an aqueous acidic bath containing the following additives: a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula : H.sub.2 N--(CH.sub.2).sub.n NH--R wherein R is H or (CH.sub.2).sub.n NH.sub.2 and n=1 to 6 with an epihalohydrin and an alkylating agent; an organic sulfo sulfonate; a polyether; and optionally a thioorganic compound.
Claims45
An aqueous acid copper electroplating bath containing an alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula:
- H.sub.2 N--(CH.sub.2).sub.n NH--R
- wherein R is H or (CH.sub.2).sub.n NH.sub.2 and n=1 to 6, with an epihalohydrin and an alkylating agent.
An aqueous acid copper electroplating bath containing
- a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula:
- H.sub.2 N--(CH.sub.2).sub.n NH--R
- wherein R is H or (CH.sub.2).sub.n NH.sub.2 and n=1 to 6 with an epihalohydrin and an alkylating agent;
- b. An organic sulfo sulfonate represented by the formula:
- R.sub.1 --(S).sub.n --RSO.sub.3 M
- wherein M is an alkali metal or ammonium ion;
- n is from 1 to 6;
- R is selected from the group consisting of 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.sub.1 is selected from the group consisting of MO.sub.3 SR, wherein M & R are as described above, ##STR35## wherein R.sub.2 & R.sub.3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR36## wherein r is from 2 to 6;
- and c. a polyether represented by the formula:
- R(OZ).sub.m
- wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl;
- m is 5 to 100;
- and
- Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T
- 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 the group consisting of hydrogen, alkyl and benzyl.
16 more elements
An aqueous acid copper electroplating bath containing:
- a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula:
- H.sub.2 N(CH.sub.2).sub.n NH R
- wherein R is H or (CH.sub.2).sub.n NH.sub.2 and n=1 to 6 with an epihalohydrin and an alkylating agent;
- b. An organic sulfo sulfonate represented by the formula:
- R.sub.1 --(S).sub.n --RSO.sub.3 M
- wherein M is an alkali metal or ammonium ion;
- n is from 1 to 6;
- R is selected from the group consisting of an alkylene group of from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms;
- R.sub.1 is selected from the group consisting of MO.sub.3 SR, wherein M & R are as described above, ##STR42## wherein R.sub.2 & R.sub.3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR43## wherein r is from 2 to 6;
- c. a polyether represented by the formula:
- R(OZ).sub.m
- wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl;
- m is 5 to 100;
- and
- Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T
- 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 the group consisting of hydrogen, alkyl and benzyl and
- d. A thioorganic compound represented by the formula:
- ##STR44## wherein the bond between C and S and N and C is a single or a double bond, R.sub.1 or R.sub.2 may be hydrogen or R.sub.1 taken together with R.sub.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 the group consisting of S, N and N-substituted atom, R.sub.3 is selected from the group consisting of hydrogen alkyl and aralkyl, and R.sub.4 is ##STR45## wherein R.sub.5 and R.sub.6 are each selected from the group consisting of hydrogen, alkyl and aralkyl groups.
18 more elements
An aqueous acid copper electroplating bath containing:
- a. An alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula:
- H.sub.2 N--(CH.sub.2).sub.n NH--R
- wherein R is H or (CH.sub.2).sub.n NH.sub.2 and n=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:
- MO.sub.3 S(CH.sub.2).sub.a S--S(CH.sub.2).sub.a SO.sub.3 M
- wherein a is from 2 to 6;
- c. a polyether represented by the formula:
- R(OZ).sub.m
- wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkynyl, alkylaryl and arylalkyl;
- m is 5 to 100;
- and
- Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T
- 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 the group consisting of hydrogen, alkyl and benzyl;
- and
- d. an equimolar combination of 2-thiazolidinethione and 1-(2-hydroxyethyl)-2-imidazolidinethione.
15 more elements
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:
- H.sub.2 N--(CH.sub.2).sub.n NH--R
- wherein R is H or (CH.sub.2).sub.n NH.sub.2 and n=1 to 6 with an epihalohydrin and an alkylating agent.
A process for producing bright and leveled copper deposits which comprises electrodepositing copper from an aqueous acidic copper bath containing:
- a. an alkylated polyalkyleneimine obtained as the reaction product of a polyalkyleneimine represented by the formula:
- H.sub.2 N--(CH.sub.2).sub.n NH--R
- wherein R is H or (CH.sub.2).sub.n NH.sub.2 and n=1 to 6 with an epihalohydrin and an alkylating agent;
- b. an organic sulfo sulfonate represented by the formula:
- R.sub.1 --(S).sub.n --RSO.sub.3 M
- wherein M is an alkali metal or ammonium ion;
- n is from 1 to 6;
- R is selected from the group consisting of an alkylene group of from 1 to 8 carbon atoms, a divalent aromatic hydrocarbon and an aliphatic-aromatic hydrocarbon containing 6 to 12 carbon atoms;
- R.sub.1 is selected from the group consisting of MO.sub.3 SR, wherein M & R are as described above, ##STR53## wherein R.sub.2 & R.sub.3 are each hydrogen or an alkyl group having from 1 to 4 carbon atoms, ##STR54## wherein r is from 2 to 6;
- and c. a polyether represented by the formula:
- R(OZ).sub.m
- wherein R is selected from the group consisting of hydrogen, alkyl, alkenyl, alkyryl, alkylaryl and arylalkyl;
- m is 5 to 100;
- and
- Z=(C.sub.u H.sub.2u O).sub.r (C.sub.v H.sub.2v O).sub.s T
- 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 the group consisting of hydrogen, alkyl or benzyl.
16 more elements
Dependencies are inferred from the claim text.