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

Abstract

A metal plating bath containing organic compounds that inhibit or retard the consumption of plating bath additives. The additives are chemical compounds that improve the brightness of the plated metal, the physical properties of the plated metal especially with respect to ductility and the micro-throwing power as well as the macro-throwing power of the plating bath. The organic compounds that inhibit or retard the consumption of additives increases the life of the plating bath and improves the efficiency of the plating process. The plating baths containing the organic compounds that inhibit or retard additive consumption can be employed to plate copper, gold, silver, palladium, platinum, cobalt, cadmium, chromium, bismuth, indium, rhodium, ruthenium, and iridium.

1 - 23 . (canceled)  
     
     
         24 . A method for plating a metal on a substrate comprising: contacting the substrate with a metal plating bath; and applying a sufficient current density to the plating bath to deposit the metal on the substrate; the metal plating bath comprises a salt of a metal selected from metals consisting of copper, gold, silver, palladium, platinum, cobalt, cadmium, chromium, bismuth, indium, rhodium, ruthenium, and iridium, and an additive consumption inhibiting compound having the formula:  
       
         
           
           
               
               
           
         
       
       where R, R 1 , R 2 , and R 3  independently comprise hydrogen; halogen; (C 1 -C 20 ) linear, branched, or cyclic alkyl; (C 2 -C 20 ) linear, branched, or cyclic alkenyl; (C 2 -C 20 ) linear, or branched alkynyl; silane; silyl; —Si(OH) 3 ; —CN; —SCN; —C═NS; —SH; —NO 2 ; SO 2 H; —SO 3 M; —PO 3 M; aminyl; aminyl halide; hydroxyaminyl; sulfonyl halide; (C 1 -C 20 ) alkyl-O(C 2 -C 3 O) x R 6 , (C 1 -C 12 ) alkylphenyl-O(C 2 -C 3 O) x R 6 , -phenyl-O(C 2 -C 3 O) x R 6 , where x is an integer of from 1-500 and R 6  is hydrogen, (C 1 -C 4 ) alkyl or phenyl; —P(R 4 ) 2 ; acyl halide; —COR 5 , where R 5  is —OH, or (C 1 -C 20 ) linear, branched, or cyclic alkyl, (C 2 -C 20 ) linear, branched, or cyclic alkenyl, (C 2 -C 20 ) linear or branched alkynyl, or (C 1 -C 20 ) linear, or branched alkoxy; or —OH with the proviso that a carboxyl is present as a substituent on the compound; and M is hydrogen or an alkali metal; or R 1  and R 2  are taken together to form a chemical bond; or R 1  and R 2  are taken together along with the atoms to which they are attached to form a 5 to 7 membered ring, or to form a 5 to 7 membered heterocyclic ring where oxygen or nitrogen are hetero-atoms in the ring the 5 to 7 membered ring or the 5 to 7 membered heterocyclic ring may comprise one or more carbonyl groups; the 5 to 7 membered ring or the 5 to 7 membered heterocyclic ring may be fused with one or more five or six memberd rings, the one or more five or six membered rings may contain one or more oxygen or nitrogen hetero-atoms, the fused rings may contain a carbonyl in the ring; the 5 to 7 membered rings, the fused five or six membered rings and the heterocyclic rings may be unsubstituted or substituted.  
     
     
         25 . (canceled)  
     
     
         26 . The method of  claim 24 , wherein the additive consumption inhibiting compound comprises 2,6-dihydroxybenzoic acid, 4-hydroxybenzoic acid resorcinol, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, methyl-3,4,5-trihydroxybenzoate, methyl-2,4-dihydroxybenzoate, 4-hydroxmandelic acid monohydrate, 3-(phenylthio) acetic acid, gallic acid, 4-vinylkbenzoic acid, 3,4-dihydroxy-cinnamic, 4-methoxy cinnamic acid, 2-hydroxy cinnamic acid, phthalic acid, trans-3-furanacrylic acid, sulfanilic acid, or mixtures thereof.  
     
     
         27 - 28 . (canceled)  
     
     
         29 . The method of  claim 24 , further comprising brighteners, levelers, hardeners, wetting agents, malleability modifiers, ductility modifiers, deposition modifiers, suppressants, or mixtures thereof.  
     
     
         30 - 31 . (canceled)  
     
     
         32 . A method for plating copper metal on a substrate comprising: contacting the substrate with a copper plating bath; and applying sufficient current density to the copper plating bath to deposit copper metal on the substrate; the copper metal plating bath comprises a copper salt and an additive consumption inhibiting compound having the formula:  
       
         
           
           
               
               
           
         
       
       where R, R 1 , R 2 , and R 3  independently comprise hydrogen; halogen; (C 1 -C 20 ) linear, branched, or cyclic alkyl; (C 2 -C 20 ) linear, branched, or cyclic alkenyl; (C 2 -C 20 ) linear or branched alkynyl; sulfonyl halide; —CN; —SCN; —C═NS; —SH; —NO 2 ; SO 2 H; —SO 3 M; —PO 3 M; —P(R 4 ) 2 , where R 4  is hydrogen or halogen; (C 1 -C 20 ) alkyl-O(C 2 -C 3 O) x R 6 , (C 1 -C 12 ) alkylphenyl-O(C 2 -C 3 O) x R 6 , -phenyl-O(C 2 -C 3 O) x R 6 , where x is an integer of from 1-500 and R 6  is hydrogen, (C 1 -C 4 ) alkyl or phenyl; Si(OH) 3 ; silyl; silane; aminyl; aminyl halide; hydroxyaminyl; acyl halide; —COR 5 , where R 5  is OH, or (C 1 -C 20 ) linear, branched, or cyclic alkyl, (C 2 -C 20 ) linear, branched or cyclic alkenyl, (C 2 -C 20 ) linear, or branched alkynyl, or (C 1 -C 20 ) linear or branched alkxoy; or —OH with the proviso that a carboxyl is present as a substituent on the compound when hydroxyl is a substituent on the compound; the (C 1 -C 20 ) alkyl, (C 2 -C 20 ) alkenyl, (C 2 -C 20 ) alkynyl and the (C 1 -C 20 ) alkoxy groups may be unsubstituted or substituted; and M is hydrogen or an alkali metal; or R 1  and R 2  are taken together to form a bond; or R 1  and R 2  may be taken together along with the atoms to which they are attached to form a 5 to 7 membered ring, or to form a 5 to 7 membered heterocyclic ring where oxygen or nitrogen are hetero-atoms in the ring; the 5 to 7 membered ring, or the 5 to 7 membered heterocyclic ring may comprise one or more carbonyl groups; the 5 to 7 membered ring or the 5 to 7 membered heterocyclic ring may be fused with one or more five or six membered rings, the one or more five or six membered rings may contain one or more oxygen or nitrogen atoms, the fused rings may contain a carbonyl in the ring; the 5 to 7 membered rings, the five or six membered fused rings, and the heterocyclic rings may be unsubstituted or substituted.  
     
     
         33 . (canceled)  
     
     
         34 . The method of  claim 32 , wherein the additive consumption inhibiting compound comprises 2,6-dihydroxybenzoic acid, 4-hydroxybenzoic acid resorcinol, 2,3-dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,4,6-trihydroxybenzoic acid, 2,3,4-trihydroxybenzoic acid, methyl-3,4,5-trihydroxsybenzoate, methyl-2,4-dihydroxybenzoate, 4-hydroxymandelic acid monohydrate, 3-(phenylthio) acetic acid, gallic acid, 4-vinylbenzoic acid, 3,4-dihydroxy-cinnamic acid, 4-methoxy cinnamic acid, 2-hydroxy cinnamic acid, pthalic acid, sulfanilic acid, trans-3-furanacrylic acid, or mixtures thereof.  
     
     
         35 - 39 . (canceled)  
     
     
         40 . 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, and ruthenium, and an additive consumption inhibiting compound having a formula:  
       
         
           
           
               
               
           
         
       
       wherein R, R 1 , R 2  and R 3  independently comprise hydrogen; halogen; (C 1 -C 20 ) linear, branched, or cyclic alkyl; (C 2 -C 20 ) linear, branched, or cyclic alkenyl; (C 2 -C 20 ) linear, or branched alkynyl; halogen; sulfonyl halide; —CN; —SCN; —C═NS; —SH; —NO 2 ; —SO 2 H; —SO 3 M; —PO 3 M; (C 1 -C 20 ) alkyl-O(C 2 -C 3 O) x R 6 , (C 1 -C 12 ) alkylphenyl-O(C 2 -C 3 O) x R 6 , -phenyl-O(C 2 -C 3 O) x R 6 , where x is an integer of from 1-500 and R 6  is hydrogen, (C 1 -C 4 ) alkyl or phenyl; —P(R 4 ) 2 , where R 4  is hydrogen or halogen; silyl; silane; —Si(OH) 3 ; aminyl; aminyl halide; hydroxyaminyl; acyl halide; —COR 5 , where R 5  is —OH, or (C 1 -C 20 ) linear, branched or cyclic alkyl, (C 2 -C 20 ) linear, branched, or cyclic alkenyl, (C 2 -C 20 ) linear or branched alkynyl, or (C 1 -C 20 ) linear or branched alkoxy; or —OH with the proviso that when —OH is a substituent a carboxyl group is present on the compound; the (C 1 -C 20 ) alkyl, (C 2 -C 20 ) alkenyl, (C 2 -C 20 ) alkynyl, and the (C 1 -C 20 ) alkoxy groups may be unsubstituted or substituted; and M is hydrogen or an alkali metal; or 
 R 1  and R 2  are taken together to form a chemical bond; or R 1  and R 2  are taken together along with the atoms to which they attached to form a 5 to 7 membered ring, or to form a 5 to 7 membered heterocyclic ring where oxygen or nitrogen are hetero-atoms in the ring, the 5-7 membered ring may comprise one or more carbonyl groups; the 5 to 7 membered ring or the 5 to 7 membered heterocyclic ring may be fused with one or more five or six membered rings, the one or more five or six membered rings may contain one or more oxygen or nitrogen atoms, the fused rings may contain a carbonyl group in the ring; the 5 to 7 membered rings, the five and six membered rings, and the heterocyclic rings may be unsubstituted or substituted.  
 
     
     
         41 - 46 . (canceled)  
     
     
         47 . The apparatus of  claim 40 , wherein the insoluble anode comprises metals of cobalt, nickel, ruthenium, rhodium, palladium, iridium, or platinum.  
     
     
         48 . The apparatus of  claim 47 , wherein the insoluble anode further comprises metals of titanium, zirconium, hafnium, vanadium, niobium, or tantalum.  
     
     
         49 . The apparatus of  claim 48 , wherein the insoluble anode further comprises beryllium, calcium, strontium, barium, scandium, yttrium, lanthanum, or rare earth elements.  
     
     
         50 . (canceled)  
     
     
         51 . The apparatus of  claim 40 , wherein the cathode comprises a wiring board, an integrated circuit, an electrical contact surface, a connector, an electrolyte foil, a silicon wafer, a semi-conductor, a lead frame, an optoelectronic component, a solder bump, a decorative article, a sanitary appliance, and the like.  
     
     
         52 . (canceled)