Composition and method for preparing chemically-resistant roughened copper surfaces for bonding to substrates
View Patent ↗The invention is directed to a method and composition for providing chemically-resistant roughened copper surfaces suitable for subsequent multilayer lamination. In one embodiment, a smooth copper surface is contacted with an adhesion promoting composition under conditions effective to provide a roughened copper surface, the adhesion promoting composition comprising an oxidizer, a pH adjuster, a topography modifier, and a sulfur-containing coating stabilizer. In another embodiment, a smooth copper surface is contacted with an adhesion promoting composition under conditions effective to provide a roughened copper surface, the adhesion promoting composition comprising an oxidizer, a pH adjuster, and a topography modifier. Then, in a subsequent step, the roughened copper surface is contacted with an acid resistance promoting composition.
1. A process for preparing roughened copper surfaces suitable for subsequent multilayer lamination, said process comprising the steps of:
contacting with a copper surface an adhesion promoting composition under conditions effective to provide a roughened copper surface; and
contacting said roughened copper surface with a sulfur compound.
2. The process according to claim 1 , wherein said sulfur compound has a formula selected from the group consisting of:
(S) A —X 1
wherein A is 1-20 and wherein X 1 is Mg, Ca, Li 2 , Na 2 , K 2 , or (NH 4 ) 2 ;
wherein A is 1-20 and wherein X 1 is Mg, Ca, Li 2 , Na 2 , K 2 , or (NH 4 ) 2 ; and
wherein
O—R 3 , or S—R 3 , wherein A is 1-20, wherein X 2 is Li, Na, K, NH 4 ,
wherein W 2 is
O—R 6 , or S—R 6 , wherein B is 1-20, and wherein R 1-6 are independently selected from H and halogen, or wherein R 1-6 are independently selected from, or any two adjacent R 1-6 can be a linkage comprising S, epoxide, glycol, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, a C 1 up to C 18 alkyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a cycloalkyl which may be singly or multiply substituted in singular or multiply bonded fashion, a heterocyclic which may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkynyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, an aryl which may be singly or multiply substituted in singular or multiply bonded fashion, a heteroaryl which may be singly or multiply substituted in singular or multiply bonded fashion, an alkylaryl which may be singly or multiply substituted in singular or multiply bonded fashion, an arylalkyl which may be singly or multiply substituted in singular or multiply bonded fashion, and combinations thereof, wherein the substituents are selected from the group consisting of halogen, epoxide, glycol, N, O, S, haloalkyl, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, alkyl, aryl, and combinations thereof.
3. The process according to claim 2 , wherein said sulfur compound is selected from the group consisting of sodium dioctyldithiocarbamate, disodium trithiocarbonate, sodium sulfide, sodium N,N-dibutyldithiocarbamate and sodium hydroquinone monomethyl ether xanthate.
4. The process according to claim 3 , wherein said sulfur compound is sodium sulfide.
5. A copper surface adhesion promoting composition comprising:
an oxidizer;
an acid;
a 5-membered aromatic fused N-heterocyclic ring compound, wherein the N-heterocyclic ring has a nitrogen atom at position 1 bonded to a hydrogen atom; and
a sulfur compound.
6. The composition of claim 5 , wherein said sulfur compound has the formula:
wherein Z 1 is H, Li, Na, K, NH 4 ,
wherein X 1 is S or N—R 9 , wherein X 2 is S or N—R 10 and wherein R 1-10 are independently selected from H and halogen, or wherein R 1-10 are independently selected from, or any two or more of R 1-10 can be a linkage comprising S, epoxide, glycol, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, a C 1 up to C 18 alkyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a cycloalkyl which may be singly or multiply substituted in singular or multiply bonded fashion, a heterocyclic which may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkynyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, an aryl which may be singly or multiply substituted in singular or multiply bonded fashion, a heteroaryl which may be singly or multiply substituted in singular or multiply bonded fashion, an alkylaryl which may be singly or multiply substituted in singular or multiply bonded fashion, an arylalkyl which may be singly or multiply substituted in singular or multiply bonded fashion, and combinations thereof, wherein the substituents are selected from the group consisting of halogen, epoxide, glycol, N, O, S haloalkyl, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, alkyl, aryl, and combinations thereof, and wherein one substituent of each pair R 1 and R 2 , R 3 and R 4 , R 5 and R 6 , and R 7 and R 8 may be nothing if the other substituent in the pair is part of an aromatic linkage.
7. A copper surface adhesion promoting composition according to claim 6 , wherein said sulfur compound is selected from the group consisting of 2-mercapto benzothiazole; 2,2′-dithiobis(benzothiazole); 6-ethoxy-2-mercaptobenzothiazole; 2-mercaptothiazoline; and 3,4,5,6-tetrahydro-2-pyrimidinethiol.
8. The composition of claim 5 , wherein said sulfur compound has the formula:
wherein Z 1 is Li, Na, K, NH 4 , R 3 ,
wherein Z 2 is Li, Na, K or NH 4 , wherein X 1 is S or N—R 6 , wherein X 2 is S or N—R 7 , and wherein R 1-7 are independently selected from H and halogen, or wherein R 1-7 are independently selected from, or any two or more of R 1-7 can be a linkage comprising S, epoxide, glycol, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, a C 1 up to C 18 alkyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a cycloalkyl which may be singly or multiply substituted in singular or multiply bonded fashion, a heterocyclic which may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C 1 up to C 18 alkynyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, an aryl which may be singly or multiply substituted in singular or multiply bonded fashion, a heteroaryl which may be singly or multiply substituted in singular or multiply bonded fashion, an alkylaryl which may be singly or multiply substituted in singular or multiply bonded fashion, an arylalkyl which may be singly or multiply substituted in singular or multiply bonded fashion, and combinations thereof, wherein the substituents are selected from the group consisting of halogen, epoxide, glycol, N, O, S haloalkyl, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, alkyl, aryl, and combinations thereof.
9. A copper surface adhesion promoting composition according to claim 8 , wherein said sulfur compound is selected from the group consisting of 2-imidazolidinethione; potassium 3-(thiocarbamoyl)-dithiocarbazate; sodium diethyldithiocarbamate; sodium dimethyldithiocarbamate; tetraethylthiuram disulfide; tetramethylthiuram disulfide; and 2,5-dithiobiurea.