Plating bath and method
View Patent ↗Copper plating baths containing a leveling agent that is a reaction product of a certain imidazole with a certain epoxide-containing compound that deposit copper on the surface of a conductive layer are provided. Such plating baths deposit a copper layer that is substantially planar on a substrate surface across a range of electrolyte concentrations. Methods of depositing copper layers using such copper plating baths are also disclosed.
1. A copper electroplating bath comprising: a source of copper ions, an electrolyte, and a reaction product of one or more nitrogen-containing compounds with one or more epoxide-containing compounds of formula (I) or (II)
wherein Y 1 and Y 2 are independently chosen from H and (C 1 -C 4 )alkyl; Z is Ar, R 12 OArOR 12 , (R 13 O) a Ar(OR 13 ) a , Cy, R 12 CyR 12 , or (R 13 O) a Cy(OR 13 ) a ; r=1-4; Ar=(C 6 -C 18 )aryl; Cy=(C 5 -C 12 )cycloalkyl; each R 12 represents (C 1 -C 8 )alkyl; each R 13 represents a (C 2 -C 6 )alkyleneoxy; each a=1-10; and A represents (C 5 -C 12 )cycloalkyl as a leveling agent.
2. The copper electroplating bath of claim 1 further comprising a second leveling agent.
3. A method of depositing copper on a substrate comprising: contacting a substrate to be plated with the copper electroplating bath of claim 1 and applying a current density for a period of time sufficient to deposit a copper layer on the substrate.
4. The method of claim 3 wherein the substrate is a printed circuit board.
5. The method of claim 4 wherein the printed circuit board comprises through-holes.
6. The copper electroplating bath of claim 1 wherein the nitrogen-containing compound is chosen from amines, amides, ureas, guanides, uracils, thiouracils, pyrrolidines, imidazoles, triazoles, tetrazoles, benzimidazoles, benzotriazoles, piperidines, morpholines, piperazines, pyridines, oxazoles, benzoxazoles, pyrimidines, quinolines, and isoquinolines.
7. The copper electroplating bath of claim 1 wherein Z is Ar, R 12 OArOR 12 , R 13 O) a Ar(OR 13 ) a , or R 12 CyR 12 .
8. The copper electroplating bath of claim 1 wherein A represents a (C 8 -C 10 )cycloalkyl.
9. The copper electroplating bath of claim 1 wherein Y 1 and Y 2 are both H.
10. The copper electroplating bath of claim 1 wherein the source of copper ions is selected from copper sulfate, copper halides, copper acetate, copper nitrate, copper fluoroborate, copper alkylsulfonates, copper arylsulfonates, copper sulfamate, copper gluconate, and mixtures thereof.
11. The copper electroplating bath of claim 1 wherein the electrolyte is selected from sulfuric acid, acetic acid, fluoroboric acid, alkanesulfonic acids, arylsulfonic acids, sulfamic acid, hydrochloric acid, phosphoric acid and mixtures thereof.