Plating bath and method for depositing a metal layer on a substrate

A copper metal plating bath comprising a copper salt, and an additive consumption inhibiting compound having a formula:

• R1—X—R2
• where X is —S(O)n—, —S(O)n—S(O)P—, —S(O)n—S(O)p—S(O)q—, —S(O)n—S(O)p—S(O)q—S(O)u—, —S(O)n—S(O)p—S(O)q—S(O)u—S(O)v—, —S(O)n—S(O)p—S(O)q—S(O)u—S(O)v—S(O)w—, —(S(O)z)m—(CH2)y—(SOz′)m′—, or —SO2—S—(CH2)y—S—SO2—, where n, p, q, u, v, w, z and z′ are each independently an integer from 0 to 2, and m and m′ are independently an integer from 1 to 6 and y is an integer of from 2 to 4;
• R1 and R2 are independently halogen, —OH, (C1-C20) linear, branched, or cyclic alkyl, (C2-C20) linear, branched, or cyclic alkenyl, (C2-C20) linear or branched alkynyl;
• or (C1-C20) alkyl-O(C2-C3O)1R5, (C1-C12) alkylphenyl-O(C2-C3O)1R5, or -phenyl-O(C2-C3O)1R5, where t is an integer of from 1-500 and R5 is hydrogen, (C1-C4) alkyl or phenyl;
• the alkyl, alkenyl, and alkynyl groups are unsubstituted or substituted;
• or
• X is a heteroatom selected from S, O, N, or N substituted with (C1-C6) alkyl or a tosyl group, and R1 and R2 may be taken together along with the atoms to which they are attached to form a 5 to 18 membered heterocyclic ring, unsubstituted or substituted, saturated or unsaturated comprising 1 to 8 heteroatoms, the heterocyclic ring optionally contains one or more carbonyls.

A method of plating a metal on a substrate comprising:

• contacting the substrate with a metal plating bath;
• and applying sufficient current density to the plating bath to deposit the metal on the substrate;
• the plating bath comprises a metal salt from a metal selected from the group consisting of copper, gold, silver, palladium, platinum, cobalt, cadmium, chromium, bismuth, indium, lead, tin, rhodium, iridium, ruthenium, zinc, and mixtures thereof;
• and an additive consumption inhibiting compound having the formula:
• R1—X—R2
• where X is —S(O)n—, —S(O)n—S(O)p—, —S(O)n—S(O)p—S(O)q—, —S(O)n—S(O)p—S(O)q—S(O)u—, —S(O)n—S(O)p—S(O)q—S(O)u—S(O)v—, —S(O)n—S(O)p—S(O)q—S(O)u—S(O)v—S(O)w—, —(S(O)z)m—(CH2)y—(S(O)z′)m′, or —SO2—S—(CH2)y—S—SO2—, where n, p, q, u, v, w, z and z′ are each independently an integer from 0 to 2, and m and m′ are independently an integer from 1 to 6 and y is an integer of from 2 to 4;
• and R1 and R2 are independently halogen, —OH, (C1-C20) linear, branched, or cyclic alkyl, (C2-C20) linear, branched, or cyclic alkenyl, (C2-C20) linear, or branched alkynyl;
• (C1-C20) alkyl-O(C2-C3O)1R5, (C1-C12)alkylphenyl-O(C2-C3O)1R5, or -phenyl-O(C2-C3O)1R5, where t is an integer of from 1-500 and R5 is hydrogen, (C1-C4)alkyl, or phenyl;
• the alky, alkenyl and alkynyl groups may be unsubstituted or substituted;
• or
• X is a heteroatom selected from S, O, N, or N substituted with (C1-C6) alkyl or a tosyl group, and R1 and R2 may be taken together along with the atoms to which they are attached to form a 5 to 18 membered heterocyclic ring unsubstituted or substituted, saturated or unsaturated comprising 1 to 8 heteroatoms, the heterocyclic ring optionally contains one or more carbonyls.

A method for plating copper metal on a substrate comprising:

• contacting the substrate with a metal plating bath;
• and applying sufficient current density to the plating bath to deposit the metal on the substrate;
• the copper metal plating bath comprises a copper salt and an additive inhibiting compound having the formula:
• R1—X—R2
• where X is —S(O)n—, —S(O)n—S(O)p—, —S(O)n—S(O)p—S(O)q—, —S(O)n—S(O)p—S(O)q—S(O)u—, —S(O)n—S(O)p—S(O)q—S(O)uS(O)v—, —S(O)n—S(O)p—S(O)u—S(O)v—S(O)w—, —(S(O)z)m—(CH2)y—(S(O)z′)m′—, or —SO2—S—(CH2)y—S—SO2—, where n, p, q, u, v, w, z and z′ are each independently an integer from 0 to 2, and m and m′ are independently an integer of from 1 to 6, and y is an integer of from 2 to 4;
• R1 and R2 are each independently halogen, —OH, (C1-C20) linear, branched or cyclic alkyl, (C2-C20) linear, branched or cyclic alkenyl, (C2-C20) linear, or branched alkynyl;
• or (C1-C20) alkyl-O(C2-C3O)1R5, (C1-C12) alkylphenyl-O(C2-C3O)1R5, or -phenyl-O(C2-C3O)1R5, where t is an integer of from 1-500 and R5 is hydrogen, (C1-C4) alkyl or phenyl;
• the alkyl, alkenyl, alkynyl may be unsubstituted or substituted;
• or
• X is a heteroatom selected from S, O, N, or N substituted with (C1-C6) alkyl or a tosyl group, and
• R1 and R2 may be taken together along with the atoms to which they are attached to form a 5 to 18 membered heterocyclic ring unsubstituted or substituted, saturated or unsaturated comprising 1 to 8 heteroatoms, the heterocyclic ring optionally contains one or more carbonyls.

An apparatus for electroplating a substrate comprising an electrical power source electrically connected with an insoluble anode and a cathode such that an electrical current can pass through the insoluble anode and the cathode, the insoluble anode and the cathode are in contact with a metal plating bath comprising a salt of a metal selected from the group consisting of copper, gold, silver, palladium, platinum, cobalt, cadmium, chromium, bismuth, indium, rhodium, iridium, ruthenium, zinc or mixtures thereof, and an additive consumption inhibiting compound, the additive consumption inhibiting compound having a formula:

• R1—X—R2
• where X is —S(O)n—, —S(O)n—S(O)p—, —S(O)nS(O)p—S(O)q—, —S(O)n—S(O)p—S(O)q—S(O)u, —S(O)n—S(O)p—S(O)q—S(O)u—S(O)v—, —(S(O)z)m—(CH2)y—(S(O)z′)m′—, or —SO2—S—(CH2)y—S—SO2—, where n, p, q, u, v, w, z and z′ are each independently an integer from 0 to 2, and m and m′ are each independently an integer from 1 to 6 and y is an integer of from 2 to 4;
• R1 and R2 each are independently —OH, halogen, (C1-C20) linear, branched, cyclic alkyl, (C2-C20) linear, branched, or cyclic alkenyl, (C2-C20) linear, or branched alkynyl;
• (C1-C20) alkyl-O(C2-C3O)1R5, (C1-C12) alkylphenyl-O(C2-C3O)1R5, or -phenyl-O(C2-C3O)1R5, where t is an integer of from 1-500 and R5 is hydrogen, (C1-C4)alkyl or phenyl;
• the alkyl, alkenyl and alkynyl groups may be unsubstituted or substituted;
• or
• X is a heteroatom selected from S, O, N, or N substituted with (C1-C6) alkyl or tosyl group, and R1 and R2 may be taken together along with the atoms to which they are attached to form a 5 to 18 membered heterocyclic ring unsubstituted or substituted, saturated or unsaturated comprising 1 to 8 heteroatoms, the heterocyclic ring optionally contains one or more carbonyls.