Copper electroplating baths containing compounds of reaction products of amines and quinones
A polymer composed of a reaction product of an amine and a quinone. The quinone is a Michael addition receptor. The polymer may be an additive for a copper electroplating bath. The polymer may function as a leveler and enable the copper electroplating bath to have high throwing power and provide copper deposits with reduced nodules.
1. An electroplating bath comprising one or more sources of copper ions, one or more accelerators, one or more suppressors, one or more electrolytes and one or more compounds comprising a reaction product of an amine and a quinone wherein the amine has a formula:
where R′ is hydrogen; and R comprises H 2 N(CH 2 ) m —, HO—(CH 2 ) m —, Q-(CH 2 ) m —, a moiety having a structure:
a moiety having a structure:
or
a moiety having a structure:
where R 1 -R 14 are independently chosen from hydrogen and (C 1 -C 3 )alkyl; m is an integer from 2-12, n is an integer from 2-10, p is an integer from 1-10, q is an integer from 2-10 and r, s and t are numbers from 1 to 10; and Q is a 5-6 membered heterocyclic ring having one or two nitrogen atoms in the ring or Q is a benzene sulfonamide moiety.
2. The electroplating bath of claim 1 , wherein the amine has the formula:
wherein R′ is hydrogen and R is the moiety:
wherein R 1 -R 6 are hydrogen, n is an integer from 2-5 and p is an integer from 1-5.
3. The electroplating bath of claim 1 , wherein the amine has a formula:
4. The electroplating bath of claim 1 , wherein the quinone has a formula:
where R 15 , R 16 , R 17 and R 18 are independently chosen from hydrogen, hydroxyl, linear or branched hydroxy(C 1 -C 10 )alkyl halogen, linear or branched (C 1 -C 10 )alkyl and linear or branched amino(C 1 -C 10 )alkyl.
5. The electroplating bath of claim 1 , wherein the quinone has a formula:
where R 19 and R 20 are independently chosen from hydrogen, hydroxyl, linear or branched hydroxy(C 1 -C 10 )alkyl halogen, linear or branched (C 1 -C 10 )alkyl and linear or branched amino(C 1 -C 10 )alkyl, and R 21 , R 22 , R 23 and R 24 are independently chosen from hydrogen, hydroxyl, linear or branched hydroxy(C 1 -C 10 )alkyl halogen, linear or branched (C 1 -C 10 )alkyl and linear or branched amino(C 1 -C 10 )alkyl.
6. The electroplating bath of claim 1 , further comprising one or more sources of tin ions.
7. A method of electroplating comprising:
a) providing a substrate;
b) immersing the substrate in the electroplating bath of claim 1 ;
c) applying a current to the substrate and the electroplating bath; and
d) electroplating copper on the substrate.
8. The method of claim 7 , wherein the electroplating bath of claim 1 further comprises one or more sources of tin ions.
9. The method of claim 7 , wherein the substrate comprises a plurality of one or more of through-holes and blind vias.