Mixture of oligomeric phenazinium compounds and acid bath for electrolytically depositing a copper deposit

1. A mixture of oligomeric phenazinium compounds, containing at least two phenazinium compounds selected from the group consisting of:

a) compounds containing two monomeric units having the following chemical formula <I>:

and

b) compounds containing three monomeric units having the following chemical formula <II>:

as well as further oligomeric phenazinium compounds, wherein, in the aforementioned chemical formula <I> and <II>, the structure unit N(R 5/5′/5″ )CC(R 4/4′/4″ )C(R 3/3′/3″ ) has one of the chemical formula <IIIa> or <IIIb>:

wherein further

R 1 , R 2 , R 3 , R 4 , R 6 , R 7 , R 8 , R 9 , R 1′ , R 2′ , R 3′ , R 4′ , R 6′ , R 7′ , R 8′ , R 9′ , R 1″ , R 2″ , R 3″ , R 4″ , R 6″ , R 7″ , R 8″ and R 9″ have each independently one of the meanings selected from the group consisting of hydrogen, halogen, NH 2 , amino substituted with lower alkyl, OH, CN, SCN, SH, C 1-8 alkyl and phenyl as well as a single bond that links the individual monomeric units together,

R 5 , R 5′ and R 5″ denote each independently H, C 1-8 alkyl or phenyl, and

at least one of the residues selected from the group consisting of R 2 , R 2′ , R 2″ , R 3 , R 3′ R 3″ , R 7 , R 7′ , R 7″ , R 8 , R 8′ and R 8″ has one of the meanings selected from the group consisting of halogen and hydroxy,

wherein further A − is an acid anion and

wherein further all of the oligomeric phenazinium compounds having the chemical formula <I> and <II> are contained in the mixture in an amount of at least 80 mol-%.

2. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein at least one of the residues selected from the group consisting of R 2 , R 2′ , R 2″ , R 3 , R 3′ R 3″ , R 7 , R 7′ , R 7″ , R 8 , R 8′ and R 8″ in the oligomeric phenazinium compounds according to the chemical formula <II> has one of the meanings selected from the group consisting of halogen and hydroxy.

3. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein at least one of the residues selected from the group consisting of R 2 , R 2′ , R 2″ , R 8 , R 8′ and R 8″ represents lower alkyl.

4. The mixture of oligomeric phenazinium compounds according to claim 3 , wherein lower alkyl is methyl or ethyl.

5. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein at least one of the residues selected from the group consisting of R 3 , R 3′ R 3″ , R 7 , R 7′ , and R 7″ represents a lower alkylated amine.

6. The mixture of oligomeric phenazinium compounds according to claim 5 , wherein the lower alkylated amine is selected from the group consisting of N-methylamine, N-ethylamine, N,N-dimethylamine and N,N-diethylamine.

7. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein at least one of the residues selected from the group consisting of R 5 , R 5′ and R 5″ represents methyl or phenyl.

8. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein the acid anion A − is selected from the group consisting of sulfate, hydrogen sulfate, halide, tetrafluoroborate, hexafluorophosphate, nitrate, acetate, trifluoroacetate and methanesulfonate.

9. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein the monomeric units in the compounds are selected from the group consisting of:

7-N,N-dimethylamino-3-hydroxy-2-methyl-5-phenyl-phenazinium,

3-chloro-7-N,N-dimethylamino-5-phenyl-phenazinium,

8-dimethylamino-10-phenyl-10H-phenazine-2-one,

3-N-ethylamino-7-hydroxy-5-phenyl-phenazinium,

3-chloro-7-N-ethylamino-5-phenyl-phenazinium,

3-methyl-8-N-methylamino-10-phenyl-10H-phenazine-2-one.

10. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein the compounds have chemical formulae selected from the group consisting of:

wherein R 1 , R 2 , R 4 , R 6 , R 8 , R 9 , R 1′ , R 2′ , R 3′ , R 4′ , R 6′ , R 8′ , R 9′ , R 1″ , R 2″ , R 3″ , R 4″ , R 6″ , R 8″ and R 9″ have the above mentioned meanings and wherein R 10 , R 11 , R 11′ , R 10′ and R 11″ represent hydrogen or lower alkyl.

11. The mixture of oligomeric phenazinium compounds according to claim 1 , selected from the group consisting of:

3′-N,N-dimethylamino-3,8′-dimethyl-8-(N-methylamino)-7′-oxo-10,5′-diphenyl-5′,7′-dihydro-[2,2′]biphenazinyl-10-ium chloride;

3,8′,8″-trimethyl-8,3′,3″-tris-(N-methylamino)-7″-oxo-10,5′, 5″-triphenyl-5′, 10′, 5″,7″-tetrahydro-[2,2′;7′,2″]terphenazine-10-ium chloride;

8,3′-bis-(N,N-dimethylamino)-8′-methyl-7′-oxo-10,5′-diphenyl-5′,7′-dihydro-[2,2]biphenazinyl-10-ium hydrogen sulfate; 3,8′-bis-(N,N-dimethylamino)-8,3′-dimethyl-5,10′-diphenyl-7-hydroxy-[2,2]biphenazinyl-5,10′-ium tetrafluoroborate;

3,8′-bis-(N,N-dimethylamino)-8,3′-dimethyl-5,10′-diphenyl-7-hydroxy-[2,2′]biphenazinyl-5,10′-ium chloride;

8′-N,N-diethylamino-3-N,N-dimethylamino-7-hydroxy-8-methyl-5,10′-diphenyl-[2,2′]biphenazinyl-6,10′-ium sulfate;

8,3′,3″-tris-(N,N-dimethylamino)-7″-oxo-10,5′,5″-triphenyl-5′,10′,5″,7″-tetrahydro-[2,2′;7′,2″]terphenazine-10-ium hydrogen sulfate;

3,8′-bis-(N,N-diethylamino)-7-hydroxy-5,10′-diphenyl-[2,2′]biphenazinyl-6,10′-ium sulfate;

7-chloro-3,8′-bis-(N,N-dimethylamino)-5,10′-diphenyl-8-methyl-[2,2]biphenazinyl-5,10′-ium chloride;

7-chloro-3,8′-bis-(N,N-dimethylamino)-8,3′-dimethyl-5,10′-diphenyl-[2,2′]biphenazinyl-5,10′-ium chloride;

7-chloro-3,8′-bis-(N,N-dimethylamino)-5,10′-diphenyl-[2,2′]biphenazinyl-5,10′-ium chloride;

7-chloro-3,8′,8″-tris-(N,N-dimethylamino)-8,3′-dimethyl-5,10′,10″-triphenyl-[2,2′;7′,2″]terphenazinyl-5,10′,10″-ium chloride;

7-chloro-8,1′-dimethyl-8′-N,N-dimethylamino-5,10′-diphenyl-[2,2′]biphenazinyl-5,10′-ium chloride;

8,3′,3″-tris-(N,N-dimethylamino)-7″-oxo-10,5′,5″-triphenyl-5″,7″-dihydro-[2,2′;7′,2″]terphenazine-10,5′-ium hydrogen sulfate;

8,8′-bis-(N-methylamino)-3-chloro-10,10′-diphenyl-[2,2′]biphenazinyl-10,10′-ium chloride; and

3,3′,3″-tris-(N-methylamino)-8″-chloro-5,5′,5″-triphenyl-[8,2′;8,7″]terphenazine-5,5′,5″-ium chloride.

12. The mixture of oligomeric phenazinium compounds according to claim 1 , wherein at least one of the residues selected from the group consisting of R 2 , R 3 , R 7 and R 8 in the oligomeric phenazinium compounds according to the chemical formula <II> has one of the meanings selected from the group consisting of halogen and hydroxy.