# Patent

## Title
Composition and method for preparing chemically-resistant roughened copper surfaces for bonding to substrates

## Abstract

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.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of and claims priority benefits from U.S. patent application Ser. No. 11/165,097 filed Jun. 23, 2005, now U.S. Pat. No. 7,108,795, patented Sep. 19, 2006 which is a continuation of U.S. patent application Ser. No. 10/782,177 filed Feb. 17, 2004, now U.S. Pat. No. 6,946,027, which is in turn a divisional of and claims priority benefits from U.S. patent application Ser. No. 10/143,389 filed May 10, 2002, now U.S. Pat. No. 6,716,281. The '389, '027 and '097 patent applications are incorporated herein by reference in their entireties.


FIELD OF THE INVENTION
The present invention relates to preparing copper surfaces for bonding to substrates used in the manufacture of printed circuit boards (PCB's). More particularly, the invention relates to the manufacture of multilayer PCB's.
BACKGROUND OF THE INVENTION
Multilayer PCB's are constructed by interleaving imaged conductive layers of copper with dielectric layers to make a multilayer sandwich. The dielectric layers are organic resin layers that bond the copper layers together. Typically, the layers of copper and dielectric are bonded together by the application of heat and pressure. The surface of the copper is smooth, however, and does not bond easily to the dielectric layer.
Improved bonding can be achieved by etching or otherwise roughening the surface of the copper to provide microscopic crevices and ridges in the surface of the copper. For example, mechanical means may be used to roughen the copper surface. Unfortunately, delicate circuit patterns are susceptible to damage if mechanically roughened. Thus, there is a need for a copper surface roughening process that does not require mechanical roughening of the copper surface.
Oxide processes are also known in which an oxide having a rough surface is formed on the copper surface. The oxide may be formed by chemical treatment of the copper. One such oxide process is described in U.S. Pat. No. 4,512,818, which provides a treatment solution for the formation of black oxide layers on copper surfaces of multi-layered printed circuits. The treatment solution comprises an oxidant and a hydroxide and is characterized by the addition of a water soluble or dispersible polymer to regulate the properties of the black oxide solution.
Another oxide process is described in U.S. Pat. No. 5,861,076. The '076 patent describes a bond enhancement process for promoting strong, stable adhesive bonds between surfaces of copper foil and adjacent resin impregnated substrates or superimposed metallic sublayers. According to the process of the invention, a black oxide-coated copper surface is treated with an aqueous reducing solution containing sodium metabisulfite and sodium sulfide to convert the black oxide coating to a roughened metallic copper coating. The roughened metallic copper-coated surface is then passivated and laminated to a resin impregnated substrate.
U.S. Pat. No. 5,492,595 also pertains to an oxide roughening process. The '595 patent describes a method for treating an oxidized surface of a copper film for bonding to a resinous layer. According to the method of the invention, an oxidized surface of a copper film having cupric oxide whiskers protruding therefrom is contacted with an acidic reducing solution containing thiosulfate to produce a reduced copper surface. The reduced copper surface is then rinsed with an acidic solution, and preferably treated with a passivating agent to minimize any reoxidation prior to laminate formation. A preferred passivating agent is 2-mercaptobenzothiazole.
Oxide processes, while well known, have many shortcomings. A typical oxide process is run at such high temperatures that the substrate is often distorted, leading to quality control problems and additional production costs. The oxidation process is also associated with uniformity problems in which portions of the copper surface are not oxidized or coated by the oxidizing solution. Uniformity problems lead to partial delamination in the multilayer PCB's. To avoid this problem the PCB is often run through multiple passes to obtain a more uniform oxide coating. Performing multiple passes adds considerably to production cost. Thus, there is a need for a copper roughening process that does not require multiple passes or high temperature, and that does not suffer from the uniformity problems of conventional oxide processes.
Another shortcoming of the typical chemical oxide modification process is that a strong reducing agent, such as dimethylamine borane, is applied to the oxide coating to obtain an even oxide coating. This type of adhesion promotion process produces an oxide coating that is fragile and prone to scratching during handling. Inspection of the circuitry prior to lamination is difficult because of the fragility of the oxide coating. Therefore, there is a need for an adhesion promotion process that permits a less problematic inspection after the adhesion promotion process and prior to the lamination step.
In response to the various problems associated with traditional oxide processes, and in particular their time consuming nature and high processing temperatures, alternative oxide coating processes have been developed. These alternative processes combine the oxidation function of the traditional processes with a controlled etch that actually roughens the underlying copper surface while oxidizing it at the same time. These alternative oxide coating processes tend to be much faster than traditional oxide processes because they form bonds with increased strength and therefore do not require multiple passes. In addition, the alternative methods do not require high temperature processing.
One alternative oxide coating process is described in U.S. Pat. No. 5,800,859. The process includes a treating step in which a metal surface is contacted with an adhesion promotion material. The adhesion promotion material includes 0.1 to 20% by weight hydrogen peroxide, an inorganic acid, an organic corrosion inhibitor and a surfactant. The surfactant is preferably a cationic surfactant, usually an amine surfactant and most preferably a quaternary ammonium surfactant.
Another alternative oxide coating process is described in U.S. patent application Ser. No. 09/479,089, which is incorporated herein by reference in its entirety. The '089 application describes a method and composition for providing roughened copper surfaces suitable for subsequent multilayer lamination. The method involves contacting a smooth copper surface with an adhesion promoting composition which includes an oxidizer, a pH adjuster, a topography modifier, and either a coating promoter or a uniformity enhancer.
While alternative oxide processes such as that described the '089 application are advantageous over conventional oxide coating processes for a variety of reasons, the roughened copper surfaces formed by such processes exhibit chemical sensitivity and thus tend to be susceptible to chemical attack. Chemical attack typically occurs during post lamination processing steps. After a multilayer copper and dielectric sandwich is formed through the lamination process, certain post lamination processing steps are performed to prepare the multilayer PCB.
For example, “through-holes” are drilled through the multilayer sandwich in order to connect the inner layers of the circuit board. The act of drilling these holes typically leaves traces of resin smear on the through-hole interconnections that must be removed by a desmear process. One desmear process involves the application of a solvent sweller and a permanganate etch which can chemically attack the bond between the copper surface and dielectric resin at the site of the through holes. The permanganate etch is typically followed by an acid neutralizer which can also chemically attack the bond and cause delamination. While other through-hole cleaning techniques are known, such as plasma etch or laser ablation, these processes generate intense heat which can also attack the copper/resin interface.
Once the desmear process is completed, the drilled holes are made conductive through direct metallization or similar processes. These processes involve numerous alkaline and acid processing steps, all of which can chemically attack the copper/resin interface. Further, the conductive through-hole is usually sealed with a layer of electrolytic copper. The electrolytic process involves alkaline and acidic baths which can also lead to chemical attack of the through-hole interconnects. The result of these chemical attacks is the delamination of the sandwich layers in the area of the through holes.
The chemically attacked area is termed “pink ring” or “wedge void” in the circuit board industry. The formation of pink rings or wedge voids represents serious defects in the PCB's, especially in an era when increasingly high quality and reliability are demanded in the PCB industry. Thus, there is a need for an improved alternative oxide coating process that provides a surface that is less susceptible to chemical attack during post-lamination processing steps.
BRIEF SUMMARY OF THE INVENTION
Accordingly, an object of this invention is to provide a copper surface roughening process that does not require mechanical roughening of the copper surface.
Another object is to provide a copper surface roughening process that does not suffer from the uniformity problems of conventional oxide processes.
A further object is to provide a copper surface roughening process that does not require multiple passes or high temperature.
Yet another object is to provide a copper surface roughening process that provides a surface that is less susceptible to chemical attack during post-lamination processing steps.
A further object is to provide an improved alternative oxide coating process and composition that provides a surface that is less susceptible to chemical attack during post-lamination processing steps than at least some other alternative oxide coating processes and compositions.
A yet further object is to provide a copper surface roughening process that provides a surface that is more acid resistant during post-lamination processing steps.
Another object is to provide an improved alternative oxide coating process and composition that provides a surface that is more acid resistant during post-lamination processing steps than at least some other alternative oxide coating processes and compositions.
At least one of these objects is addressed, in whole or in part, by the present invention. In one embodiment, the invention is a composition and method for roughening a copper surface in order to provide higher bond strengths between the copper and dielectric resin layers in a multilayer PCB, where such bonds are also resistant to chemical attack. The composition comprises an oxidizer, a pH adjuster, a topography modifier, and a coating stabilizer. In another embodiment, the invention is a process for preparing roughened copper surfaces suitable for subsequent multilayer lamination. The process involves contacting a copper surface with an adhesion promoting composition under conditions effective to provide a roughened copper surface, and then contacting the roughened copper surface with an acid resistance promoting composition.


DETAILED DESCRIPTION OF THE INVENTION
While the invention will be described in connection with several embodiments, it will be understood that the invention is not limited to those embodiments. On the contrary, the invention includes all alternatives, modifications, and equivalents as may be included within the spirit and scope of the appended claims.
As noted above, one aspect of the present invention is an adhesion promoting composition which provides a roughened copper surface, comprising an oxidizer, a pH adjuster, a topography modifier, and a coating stabilizer.
Any suitable oxidizer known in the art may be used in the inventive composition. Suitable oxidizers include hydrogen peroxide. The oxidizer may be present in the range between about 0.05 wt % and about 5 wt %, alternatively in the range between about 0.1 wt % and about 4 wt %. As yet another alternative, the oxidizer may be present in the range between about 0.5 wt % and about 3 wt %, alternatively in the range between about 0.5 wt % and about 2 wt %. Proportions of oxidizer in this specification are based on undiluted quantities, although it will be recognized that, in practice, the oxidizers are typically part of an aqueous solution when added to the composition.
If hydrogen peroxide is used as the oxidizer, a hydrogen peroxide stabilizer may be used (although the use of a stabilizer is not required to practice this invention). Non-limiting examples of optional hydrogen peroxide stabilizers include: alkyl monoamines having 2 to 10 carbon atoms, and their salts; polymethylenediamines having 4 to 12 carbon atoms and their salts; alkoxyamines formed by substituting at least one hydrogen atom of ammonia by an alkoxy radical having 2 to 6 carbon atoms and alkoxyamines formed by substituting at least one hydrogen atom connected with the nitrogen atom of an alkyl monoamine having 2 to 10 carbon atoms by an alkoxy radical having 2 to 6 carbon atoms; alkyl acyl radical formed by substituting at least one hydrogen atom of ammonia by an alkyl acyl radical having 3 to 6 carbon atoms, and at least one alkyl acid amide formed by substituting at least one alkyl monoamine having 2 to 10 carbon atoms by an alkyl acyl radical having 3 to 6 carbon atoms; alicyclic imines having a 5 to 8 membered ring; mono-n-propylamine, di-n-propylamine, tri-n-propylamine and hexamethylenediamine; octylamine; and propionylamide. In addition, U.S. Pat. Nos. 3,756,957, and 5,800,859 describe a range of suitable hydrogen peroxide stabilizers; U.S. Pat. Nos. 3,756,957 and 5,800,859 are hereby incorporated by reference in their entirety. An example of a suitable hydrogen peroxide stabilizer from the categories in these patents is sodium phenolsulfonate.
If a hydrogen peroxide stabilizer is used, it may be present in the composition in an amount of from about 0.001 wt % to about 5 wt %, alternatively in an amount of from about 0.005 wt % to about 1 wt %. Alternatively, the hydrogen peroxide stabilizer may be present in the composition in an amount effective to achieve the purpose of stabilizing the hydrogen peroxide to the desired degree.
The choice of pH adjuster is not critical. Any suitable organic or inorganic acid may be used, although nitric acid is not preferred. Non-limiting examples of suitable acids include sulfuric, phosphoric, acetic, formic, sulfamic, hydroxy-acetic acid, and mixtures thereof. Alternatively, sulfuric acid may be selected as the pH adjuster. The pH adjuster may be present in the composition in the range between about 0.01% and about 20% by weight and alternatively in the range between about 0.5% and about 10% by weight.
Suitable topography modifiers are five membered aromatic fused N-heterocyclic ring compounds (hereinafter “N-heterocyclic compounds”) with at least one nitrogen atom in the N-heterocyclic ring:




In the above formula, X may be N or C, and Y may be N or C. The R substituents on the aromatic ring may be H, halogen, hydroxy, alkyl, hydroxyalkyl, amino, aminoalkyl, nitro, nitroalkyl, mercapto, mercaptoalkyl, or alkoxy groups containing from 1 to about 10 or more carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, etc. At least one of the nitrogen atoms in the heterocyclic ring depicted above is bonded directly to a hydrogen atom. The nitrogen atom at the #1 position in the heterocyclic ring is preferably, but not necessarily, bonded to a hydrogen atom. Non-limiting examples of suitable topography modifiers include 1H-benzotriazole (CAS registration number, “CAS”: 95-14-7), 1H-indole (CAS 120-72-9), 1H-indazole (CAS 271-44-3), and 1H-benzimidazole (CAS 51-17-2). Derivatives of N-heterocyclic compounds suitable as topography modifiers include N-heterocyclic compounds with a hydrogen atom bonded to the nitrogen atom at the #1 position in the heterocyclic ring.

Non-limiting examples of suitable derivatives of 1H-benzotriazole (CAS 95-14-7) suitable for use as topography modifiers include: 5-methyl-1H-benzotriazole (CAS 136-85-6), 6-Nitro-1H-benzotriazole (CAS 2338-12-7), 1H-naphtho(1,2-d)triazole (CAS 233-59-0), and 1H-Naphtho[2,3-d]triazole (CAS 269-12-5).
Non-limiting examples of suitable derivatives of indole (1H-Indole; CAS 120-72-9) suitable for use as topography modifiers include: 5-Aminoindole (1H-Indol-5-amine; CAS 5192-03-0), 6-methylindole (1H-Indole, 6-methyl-; CAS 3420-02-8), 1H-indole-5-methyl (CAS 614-96-0), 7-methylindol (1H-Indole, 7-methyl-; CAS 933-67-5), 3-methylindole (1H-Indole, 3-methyl-; CAS 83-34-1), 2-Methylindole (2-Methyl-1H-indole; CAS 95-20-5), 1H-Indole, 3,5-dimethyl-(CAS 3189-12-6), 2,3-Dimethylindole (1H-Indole, 2,3-dimethyl-; CAS 91-55-4), and 2,6-dimethylindole (1H-Indole, 2,6-dimethyl-; CAS 5649-36-5).
Non-limiting examples of suitable derivatives of 1H-indazole (CAS 271-44-3) suitable for use as topography modifiers include: 1H-Indazol-5-amine (CAS 19335-11-6) and 3-Chloro-1H-indazole (CAS 29110-74-5).
Non-limiting examples of suitable derivatives of 1H-benzimidazole (CAS 51-17-2) suitable for use as topography modifiers include: 2-Hydroxy-1H-benzimidazole (CAS 615-16-7), 2-Methyl-1H-benzimidazole (CAS 615-15-6), and 2-(methylthio)-1H-Benzimidazole (CAS 7152-24-1).
The topography modifier may be present in the range between about 0.1 g/l (grams per liter) and about 20 g/l, alternatively in the range between about 0.5 g/l and about 7 g/l. For example, 1H-benzotriazole can be present in the range between about 0.1g/l and about 20 g/l, alternatively in the range between about 0.5 g/l and about 7 g/l.
The topography modifier is thought to vary the surface characteristics of the copper during treatment of the copper surface with the adhesion promoting solution of the invention. During treatment with the adhesion promoting composition of the invention, the copper surface is believed to comprise a complex of copper together with the topography modifier to produce a greater surface area than would be possible without the topography modifier. As a result, the topography modifier has a beneficial effect on peel strength—indeed, peel strength is dramatically reduced if the topography modifier is not used in the adhesion promoting solution. The inventors do not intend the foregoing theory to limit the invention to processes or products that operate as specified by this theory. Any inaccuracy in this theory does not limit the scope of the present invention.
The coating stabilizer is a sulfur compound that renders the roughened copper surface more chemically resistant to subsequent chemical processing. A suitable coating stabilizer may have the following formula:




wherein Z1 is H, Li, Na, K, NH4,





wherein X1 is S or N—R9, and wherein X2 is S or N—R10. The R groups are independently selected from H, halogen, S, epoxide, glycol, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, a C1up to C18 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 C1 up to C18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 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. In addition, any two or more of R1-10 may form a linkage or linkages comprising any of the groups identified above suitable for forming such linkages. Depending on the linkage, some of R1-10 may drop out. For example, if R2 and R3 form an aromatic linkage such as a benzene ring, then R1 and R4 will be nothing. The same holds true for the remainder of R1-8: one substituent of each pair R1 and R2, R3 and R4, R5 and R6, and R7 and R8 will be nothing if the other substituent in the pair is part of an aromatic linkage.

Suitable coating stabilizers falling within formula (I) include the following: 2-mercapto benzothiazole; 2,2′-dithiobis(benzothiazole); 6-ethoxy-2-mercaptobenzothiazole; 2-mercaptothiazoline; and 3,4,5,6-tetrahydro-2-pyrimidinethiol. Alternatively, 2-mercaptothiazoline may be used as the coating stabilizer.
The coating stabilizer may, in the alternative, have the following formula:




wherein Z1 is Li, Na, K, NH4, R3,





wherein Z2 is Li, Na, K or NH4, wherein X1 is S or N—R6, and wherein X2 is S or N—R7. The R groups are independently selected from H, halogen, S, epoxide, glycol, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, a C1 up to C18 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 C1 up to C18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 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 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. In addition, any two or more of R1-7 may form a linkage or linkages comprising any of the groups identified above suitable for forming such linkages.

Suitable coating stabilizers falling within formula (II) include the following: 2-imidazolidinethione; potassium 3-(thiocarbamoyl)-dithiocarbazate; sodium diethyldithiocarbamate; sodium dimethyldithiocarbamate; tetraethylthiuram disulfide; tetramethylthiuram disulfide; and 2,5-dithiobiurea. Alternatively, sodium diethyldithiocarbamate may be used as the coating stabilizer.
The coating stabilizer may be present in the composition in the range between about 1 to about 1000 ppm, alternatively in the range between about 2 to about 200 ppm, alternatively in the range between about 50 to about 150 ppm, alternatively about 100 ppm. For example, 2-mercaptothiazoline can be present at about 100 ppm.
The inventive composition for roughening a copper surface may also optionally include a uniformity enhancer and/or a coating promoter. The optional uniformity enhancer may be a tetrazole such as 1H-tetrazole (CAS 288-94-8) and its derivatives:




The R1 and R2 substituents on the tetrazole ring may be hydroxyl, amino, alkyl, hydroxyalkyl, aminoalkyl, nitroalkyl, mercaptoalkyl, or alkoxy groups containing from 1 to about 10 or more carbon atoms. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, etc. Non-limiting examples of suitable tetrazole derivatives that can be used in the present invention as a uniformity enhancer include: 5-aminotetrazole (CAS 5378-49-4), 5-methyltetrazole (CAS 4076-36-2), 5-methylaminotetrazole (CAS 53010-03-0), 1H-tetrazol-5-amine (CAS 4418-61-5), 1H-tetrazol-5-amine, N,N-dimethyl- (CAS 5422-45-7), 1-methyltetrazole (CAS 16681-77-9), 1-methyl-5-mercaptotetrazole, 1,5-dimethyltetrazole (CAS 5144-11-6), 1-methyl-5-aminotetrazole (CAS 5422-44-6), and 1-methyl-5-methylamino-tetrazole (CAS 17267-51-5).

The optional uniformity enhancer may be present in an amount effective to enhance the uniformity of the roughened copper surface. Alternatively, the uniformity enhancer may be present in the range between about 0.01 to about 10 g/l, alternatively in the range between about 0.1 to about 5 g/l, alternatively in the range between about 0.3 to about 1 g/l, alternatively at about 0.5 g/l. For example, 5-aminotetrazole can be present at about 0.5 g/l.
The optional coating promoter is a five membered aromatic fused N-heterocyclic ring compound with 1 to 3 nitrogen atoms in the fused ring, wherein none of the 1 to 3 nitrogen atoms in the fused ring are bonded to a hydrogen atom:




In the above formula, X may be N or C, and Y may be N or C. The R substituents on the aromatic ring may be H, halogen, hydroxy, alkyl, hydroxyalkyl, amino, aminoalkyl, nitro, nitroalkyl, mercapto, mercaptoalkyl, or alkoxy groups containing from 1 to about 10 or more carbon atoms. The R1 substituents on the heterocyclic ring bonded to the nitrogen atom at the #1 position may be hydroxyl, amino, alkyl, hydroxyalkyl, aminoalkyl, nitroalkyl, mercaptoalkyl, or alkoxy groups. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, etc. Non-limiting examples of optional coating promoters suitable for use in the present invention include: 1-hydroxybenzotriazole (CAS 2592-95-2), 1-methylindole (CAS 603-76-9), 1-methylbenzotriazole (CAS 13351-73-0), 1-methylbenzimidazole (CAS 1632-83-3), 1-methylindazole (CAS 13436-48-1), 1-ethyl-indazole (CAS 43120-22-5), 1H-Indole, 1,5-dimethyl-indole (CAS 27816-53-1), 1,3-dimethyl-indole (CAS 875-30-9), methyl 1-(butylcarbamoyl)-2-benzimidazolecarbonate, 1-(chloromethyl)-1H-benzotriazole, and 1-aminobenzotriazole.

The optional coating promoting may be present in an amount effective to enhance the coating characteristics of the composition. Alternatively, the coating promoter may be present in the range between about 0.01 to about 10 g/l, alternatively in the range between about 0.1 to about 5 g/l, alternatively in the range between about 0.3 to about 3 g/l, alternatively at about 2 g/l. For example, 1-hydroxybenzotriazole can be present at about 2 g/l.
The formulation of the inventive composition for roughening a copper surface may be made up with de-ionized water.
The inventive composition for roughening a copper surface does not require halogen ions and can be free of halogen ions, if desired. The inventors define “halogen ions” as fluoride, chloride, bromide or iodide ions or any combination or equivalent of these ions in aqueous solution. In addition, the composition of the present invention does not require a surfactant to achieve an excellent roughened copper surface.
Halogens can, however, be employed in the formulation if desired. For example, a small amount of chloride ion or other halide ions can be used in the formulation. If employed, halide ions may be present in the range between about 0.1 ppm to about 1000 ppm, alternatively in the range between about 1 ppm to about 100 ppm.
The adhesion promoting composition may optionally comprise a copper salt such as copper sulfate. The aqueous copper ions protect virgin stainless steel surfaces, such as those of a process tank, from chemical attack. Hence it is advantageous to include a quantity of copper salt in the adhesion promoting composition if the copper surface to be treated is dipped into a new or previously unused steel tank. However, there is no requirement to include a copper salt to obtain a highly satisfactory roughened copper surface.
The adhesion promoting composition may also optionally contain a water soluble polymer. Any water soluble polymer known in the art may be used in the present adhesion promoting composition. Suitable water soluble polymers include polymers of ethylene oxide and propylene oxide, polyethylene glycols, polypropylene glycols, and polyvinyl alcohols. The water soluble polymer may be present in the range of between about 0.01 wt % and about 5 wt %, alternatively in the range of between about 0.05 wt % and about 3 wt %, alternatively in the range of between about 0.1 wt % and about 1 wt %, alternatively at about 0.5 wt %. Polyethylene glycol may be selected as the optional water soluble polymer. One suitable source of polyethylene glycol is the product Pluracol® E2000 sold by the BASF Corporation.
A copper surface can be treated with the adhesion promoting composition in a variety of ways, including (but not limited to) immersion in a bath, dipping in a bath, or spraying. The treatment may take place at any temperature and for any duration suitable to obtain the desired uniformed roughened copper surface. For example, suitable roughened copper surfaces may be obtained where the temperature during treatment is in the range from about 40° F. to about 180° F. (about 4° C. to about 82° C.), alternatively from about 70° F. to about 150° F. (about 21° C. to about 66° C.), alternatively from about 80° F. to about 120° F. (about 27° C. to about 49° C.), alternatively about 100° F. (about 38° C.). Suitable roughened copper surfaces may also be obtained with temperatures outside of these ranges, however. With respect to duration, the adhesion promoting composition may, for example, be contacted with the copper surface for about 1 second to about 1 hour, alternatively from about 10 seconds to about 10 minutes, alternatively from about 30 seconds to about 5 minutes, alternatively for about 1 minute. Suitable roughened copper surfaces may also be obtained with contact durations outside of these ranges, however.
In keeping with another aspect of the present invention, the process of preparing roughened copper surfaces suitable for subsequent multilayer lamination includes the following steps, some of which are optional:

    
    
        (i) Providing a substantially clean copper surface, optionally by applying a highly built alkaline cleaning solution to a copper surface. The highly built alkaline cleaning solution comprises a surfactant and a phosphate or a phosphate ester.
        (ii) Optionally dipping the substantially clean copper surface into a pre-dip to condition the surface and/or to remove surplus cleaning solution from the copper surface providing a clean copper surface. One suitable optional pre-dip may comprise an oxidizer, a pH adjuster and a topography modifier, as those components are described above. The oxidizer and topography modifier may be in the pre-dip in the ranges described above. The pH adjuster may be in the pre-dip in the range between about 0.005% and about 10% by weight and alternatively in the range between about 0.01% and about 5% by weight. A hydrogen peroxide stabilizer may be used if hydrogen peroxide is used as the oxidizer. The hydrogen peroxide stabilizer may be selected from the various stabilizers described above and may be in the pre-dip in the ranges described above. Other suitable pre-dips that will be known to those of skill in the art may also be used. The pre-dip treatment may take place at any temperature and for any duration suitable to obtain the desired conditioning and/or cleaning, including the temperatures and durations discussed above for application of the adhesion promoting composition.
        (iii) Applying to the clean copper surface an adhesion promoting composition comprising an oxidizer, a pH adjuster, a topography modifier, a coating stabilizer, and optionally, other optional components as described above.
        (iv) Optionally dipping the uniformly roughened copper surface into a post-dip to provide a roughened copper surface suitable for subsequent multilayer lamination. The optional post-dip is used to coat the roughened copper surface with a coating of organic molecules to enable enhanced bonding between the roughened copper surface and a suitable dielectric resin. The post-dip solution comprises an azole or silane compound. The post-dip may further comprise a titanate, zirconate, or aluminate.

Step (i) may further include draining excess cleaning solution from the copper surface.

    
    


Non-limiting examples of silanes for enhancing the bond strength between the copper surface and the dielectric include any trichloro or trimethoxy silane, especially those derivatives with at least one nitrogen atom such as trimethoxysilylpropyldiethylenetriamine. Other examples of silanes suitable for use in the present invention include:

    
    
        3-methylacryloyloxypropyltrimethoxysilane,
        3-(N-styrylmethyl-2aminoethylamino) propyltrimethoxysilane hydrochloride,
        3-(N-allyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride,
        N-(styrylmethyl)-3-aminopropyltrimethoxysilane hydrochloride,
        N-2-aminoethyl-3-aminopropyltrimethoxysilane,
        3-(N-Benzyl-2-aminoethylamino)-propyltrimethoxy silane hydrochloride,
        beta-(3,4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-aminopropyl-triethoxy silane,
        gamma-glycidoxypropyltrimethoxysilane, and
        vinyltrimethoxysilane.
    
    


Non-limiting examples of titanates that can be used in the present invention include:

    
    
        titanate amine,
        tetraocytl di(ditridecyl)phosphito titanate,
        tetra(2,2-diallyloxymethyl) butyl-di(ditridecyl)phosphito titanate,
        neopentyl(diallyl)oxytri(diocytl)pryo-phosphato titante, and
        neopentyl(diallyl)oxy tri(m-amino)phenyl titanate.
    
    


Non-limiting examples of suitable zirconates (available, for example, from Kenrich Petrochemicals, Inc., Bayonne, N.J.) include:

    
    
        KZ 55-tetra (2,2 diallyloxymethyl)butyl,
        di(ditridecyl)phosphito zirconate,
        NZ-01-neopentyl(diallyl)oxy,
        trineodecanoyl zirconate, and
        NZ-09-neopentyl(diallyl)oxy, tri(dodecyl)benzene-sulfonyl zirconate.
    
    


Further non-limiting examples of suitable zirconates include: tetra (2,2 diallyloxymethyl)butyl-di(ditridecyl)phosphito zirconate, and zirconium IV 2,2-dimethyl 1,3-propanediol.
Non-limiting examples of aluminates that can be used in the present invention include: Kenrich® diisobutyl(oleyl)acetoacetylaluminate (KA 301), and diisopropyl(oleyl)acetoacetyl aluminate (KA 322).
The inventors have found that the use of a coating stabilizer in the inventive adhesion promoting composition, as described above, renders the coating on the copper surface more chemically resistant to subsequent processing than alternative oxide coating processes known in the art which do not use such stabilizer. Another aspect of the present invention is a process in which a copper surface is treated with an adhesion promoting composition in which a coating stabilizer is optional, and then subsequently contacted with a composition that promotes acid resistance. In other words, the roughened copper surface is made resistant to chemical attack by a separate application of an acid resistance promoting composition after the adhesion promoting composition has been applied.
The inventors discovered that this two-step approach is particularly advantageous from a manufacturing standpoint. In particular, it was discovered that some of the coating stabilizers described above are themselves susceptible to chemical attack. When such coating stabilizers are added directly to an adhesion promoting bath which contains a pH adjuster, such as sulfuric acid, they tend to decompose over time into their synthetic components. After such decomposition, the baths no longer produce an acid resistant coating on the copper surface. Typically, decomposition of the coating stabilizer occurs within 30 minutes to 4 hours of addition. The cost associated with continually refreshing the baths to avoid the effects of this decomposition render this process less desirable for commercial manufacturing purposes.
The inventive process which avoids these decomposition issues comprises the steps of (1) contacting with a clean copper surface an adhesion promoting composition under conditions effective to provide a roughened copper surface, and (2) contacting the roughened copper surface with an acid resistance promoting composition.
The adhesion promoting composition is the same as that described above, with the exception that the coating stabilizer is an optional component, and is preferably absent. Thus, the adhesion promoting composition comprises an oxidizer, a pH adjuster, a topography modifier, and, optionally, a coating stabilizer as well as any of the other optional components described above. The adhesion promoting composition may be applied to the copper surface in any of the various manners and under any of the various conditions described above.
Suitable acid resistance promoting compositions include thio compounds, particularly thiocarbamates, thiocarbonates, xanthates, and sulfides. Alternatively, the acid resistance promoting composition is a sulfur-containing compound which may have the following formula:

(S)A−X1   (III)

wherein A is 1-20 (alternatively A may be 1-10 or 1-5) and X1 is Mg, Ca, Li2, Na2, K2, or (NH4)2. As yet another alternative, the acid resistance promoting composition may have the following formula:





wherein A is 1-20 (alternatively A may be 1-10 or 1-5) and X1 is Mg, Ca, Li2, Na2, K2, or (NH4)2.

As yet another alternative, the acid resistance promoting composition may have the following formula:




wherein





O—R3, or S—R3, wherein A is 1-20, wherein X2 is Li, Na, K, NH4,





wherein W2 is





O—R6, or S—R6, and wherein B is 1-20. A may also be 1-10 or 1-5. The R groups are independently selected from H, halogen, S, epoxide, glycol, hydroxy, aryloxy, benzyloxy, alkoxy, haloalkoxy, amino, monoalkylamino, dialkylamino, heteroalkylamino, acyloxy, acyl, ketone, quinone, aldehyde, carbohydrate, organometallic, a C1 up to C18 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 C1 up to C18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 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. In addition, any two adjacent of R1-6 may form a linkage or linkages comprising any of the groups identified above suitable for forming such linkages.

Suitable acid resistance promoting compositions falling with formulas (III), (IV) and (V) above include: sodium dialkyl dithio carbamates, sodium dialkyl polythiocarbamates, sodium dialkyl trithio carbonates, sodium dialkyl polythiocarbonates, sodium diaryl dithio carbamates, sodium diaryl polythiocarbamates, sodium diaryl trithio carbonates, sodium diaryl polythiocarbonates, sodium alkylaryl dithio carbamates, sodium alkylaryl polythiocarbamates, sodium alkylaryl trithio carbonates, sodium alkylaryl polythiocarbonates, potassium dialkyl dithio carbamates, potassium dialkyl polythiocarbamates, potassium dialkyl trithio carbonates, potassium dialkyl polythiocarbonates, potassium diaryl dithio carbamates, potassium diaryl polythiocarbamates, potassium diaryl trithio carbonates, potassium diaryl polythiocarbonates, potassium alkylaryl dithio carbamates, potassium alkylaryl polythiocarbamates, potassium alkylaryl trithio carbonates, potassium alkylaryl polythiocarbonates, ammonium dialkyl dithio carbamates, ammonium dialkyl polythiocarbamates, ammonium dialkyl trithio carbonates, ammonium dialkyl polythiocarbonates, ammonium diaryl dithio carbamates, ammonium diaryl polythiocarbamates, ammonium diaryl trithio carbonates, ammonium diaryl polythiocarbonates, ammonium alkylaryl dithio carbamates, ammonium alkylaryl polythiocarbamates, ammonium alkylaryl trithio carbonates, ammonium alkylaryl polythiocarbonates, dialkyl xanthates, diaryl xanthates, alkylaryl xanthates, sulfide, disulfide, trisulfide, tetrasulfide, polysulfide, and combinations thereof, wherein the alkyl component is a C1 up to C18 alkyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, wherein the aryl component is an aryl or a heteroaryl which may be singly or multiply substituted in singular or multiply bonded fashion, and wherein the substituents are selected from the group consisting of halogen, halide, 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. Several nonlimiting examples of suitable acid resistance promoting compositions are sodium dioctyldithiocarbamate, disodium trithiocarbonate, sodium sulfide, sodium N,N-dibutyldithiocarbamate, and sodium hydroquinone monomethyl ether xanthate (“HQMME-xanthate”).
The acid resistance promoting composition may be contacted with the roughened copper surface in a variety of ways, including (but not limited to) immersion in a bath, dipping in a bath, or spraying. The acid resistance promoting composition may be contacted with the roughened copper surface as an aqueous solution. When applied in this fashion, the composition may be present in the aqueous solution between about 0.1 g/l and about 5 g/l. Alternatively, the composition may be present in the aqueous solution between about 1 g/l and about 3 g/l. As yet another alternative, the composition may be present in the aqueous solution at about 1 g/l.
The acid resistance promoting composition may be contacted with the roughened copper surface for at least about 1 second. Alternatively, the composition may be contacted with the roughened copper surface for between about 1 second to about 5 minutes. As yet another alternative, the composition may be contacted with the roughened copper surface for between about 5 seconds to about 2 minutes.
The acid resistance promoting composition may be contacted with the roughened copper surface at any temperature suitable to obtain the desired acid-resistant roughened copper surface. For example, suitable roughened copper surfaces may be obtained where the temperature during treatment is in the range from about 20° F. to about 180° F. (about −7° C. to about 82° C.), alternatively from about 40° F. to about 150° F. (about 4° C. to about 66° C.), alternatively from about 60° F. to about 120° F. (about 16° C. to about 49° C.), alternatively about 70° F. (about 21° C.), alternatively about room temperature. Suitable acid-resistant roughened copper surfaces may also be obtained with temperatures outside of these ranges, however.
The process of preparing roughened copper surfaces and subsequently post treating the surfaces with an acid resistance promoting composition may also include other optional steps. For instance, the process may comprise the following steps, some of which are optional:

    
    
        (i) Providing a substantially clean copper surface, optionally by applying a highly built alkaline cleaning solution to a copper surface. The highly built alkaline cleaning solution comprises a surfactant and a phosphate or a phosphate ester.
        (ii) Optionally dipping the substantially clean copper surface into a pre-dip to condition the surface and/or to remove surplus cleaning solution from the copper surface providing a clean copper surface. One suitable optional pre-dip may comprise an oxidizer, a pH adjuster and a topography modifier, as those components are described above. The oxidizer and topography modifier may be in the pre-dip in the ranges described above. The pH adjuster may be in the pre-dip in the range between about 0.005% and about 10% by weight and alternatively in the range between about 0.01% and about 5% by weight. A hydrogen peroxide stabilizer may be used if hydrogen peroxide is used as the oxidizer. The hydrogen peroxide stabilizer may be selected from the various stabilizers described above and may be in the pre-dip in the ranges described above. Other suitable pre-dips that will be known to those of skill in the art may also be used. The pre-dip treatment may take place at any temperature and for any duration suitable to obtain the desired conditioning and/or cleaning, including the temperatures and durations discussed above for application of the adhesion promoting composition.
        (iii) Applying to the clean copper surface an adhesion promoting composition comprising an oxidizer, a pH adjuster, a topography modifier, optionally a coating stabilizer, and optionally, other optional components as described above, in order to form a roughened copper surface.
        (iv) Optionally rinsing the roughened copper surface with water.
        (v) Dipping the roughened copper surface in an aqueous solution containing an acid resistance promoting composition, as described above.
        (vi) Optionally dipping the uniformly roughened copper surface into a post-dip to provide a roughened copper surface suitable for subsequent multilayer lamination. The optional post-dip is used to coat the roughened copper surface with a coating of organic molecules to enable enhanced bonding between the roughened copper surface and a suitable dielectric resin. The post-dip solution comprises an azole or silane compound. The post-dip may further comprise a titanate, zirconate, or aluminate.

Step (i) may further include draining excess cleaning solution from the copper surface.

    
    


The inventors have found that the use of an adhesion promoting composition on a copper surface, followed by subsequent treatment with an acid resistance promoting composition, renders the coating on the copper surface more chemically resistant to subsequent processing than other alternative oxide coating processes known in the art. At the same time, inefficiencies in the manufacturing process are avoided because the acid resistance promoting composition is applied in a separate step and thus is not subject to untimely decomposition due to the acidic nature of the adhesion promoting composition bath.
One practical test that can be used to indicate the better adhesion of resins to the present copper surface is a “peel strength” test. Self-adhesive tape is adhered to a treated copper surface which has been laminated to a polymeric substrate. The surface is placed into a nitric acid bath to remove the copper from the non-taped regions of the substrate. The tape is removed and the remaining copper is then mechanically peeled away from the substrate while measuring the force needed to accomplish the peel in pounds per inch. Higher peel strengths are typically indicative of a desirable, tightly-adhering coating.
One practical test that can be used to indicate the better resistance to chemical attack of the present copper surfaces is the simple application of an acid solution to the copper surfaces, followed by observation. Such test is described in further detail below in conjunction with the examples.
The following examples represent specific but nonlimiting embodiments of the present invention:
EXAMPLE 1
A clean copper surface was prepared by treating a substantially clean copper surface in a pre-dip bath at 70° F. (21° C.). The pre-dip bath comprised 1.15 wt % H2O2, 0.05 wt % sodium phenolsulfonate, 0.13 wt % H2SO4, 0.18 wt % benzotriazole (1.8 g/l), balance deionized water. The clean copper surface was removed from the pre-dip bath after one minute.
The clean copper surface was then treated in a bath comprising 1.42 wt % H2O2 (oxidizer), 0.06 wt % sodium phenolsulfonate (H2O2 stabilizer), 8.61 wt % H2SO4 (pH adjuster), 0.57 wt % benzotriazole (“BTA”) (topography modifier), 0.0017 wt % NaCl (chloride ion), 0.38 wt % polyethylene glycol, balance deionized water (see Table 1). The bath temperature was maintained at 100° F. (38° C.). The copper surface was removed from the bath after one minute, rinsed with deionized water, and dried with an air hose. A roughened texture was observed on the copper surface, as is consistent with an alternative oxide coating process. Using an eye-dropper, a solution containing 15% by volume hydrochloric acid was applied to the roughened surface. The roughened surface immediately dissolved, revealing bare copper beneath.
EXAMPLE 2
A clean copper surface was treated in a bath comprising 1.42 wt % H2O2, 0.06 wt % sodium phenolsulfonate, 8.61 wt % H2SO4, 0.57 wt % BTA, 0.0017 wt % (17 ppm) NaCl, 0.38 wt % polyethylene glycol, 1 ppm sodium diethyl-dithiocarbamate (“SDDC”) (a coating stabilizer), balance deionized water (see Table 1). The bath temperature was maintained at 100° F. (38° C.). The copper surface was removed from the bath after one minute, rinsed with deionized water, and dried with an air hose. A roughened texture was observed on the copper surface, as is consistent with an alternative oxide coating process. Using an eye-dropper, a solution containing 15% by volume hydrochloric acid was applied to the roughened surface. The roughened surface dissolved over the course of 10-20 seconds, revealing bare copper beneath. The fact that the surface did not dissolve immediately demonstrates that the roughened surface was more chemically resistant than the roughened surface of Example 1, which was not prepared with a coating stabilizer.
EXAMPLE 3
A roughened copper surface was prepared in the same manner as Example 2, with the exception that the bath contained 5 ppm SDDC (see Table 1). Upon applying a 15% hydrochloric acid solution, the roughened surface dissolved over the course of 20-30 seconds, revealing bare copper beneath. The increased time for the roughened surface to dissolve demonstrates the improved chemical resistance of the surface.
EXAMPLE 4
A roughened copper surface was prepared in the same manner as Example 2, with the exception that the bath contained 20 ppm SDDC (see Table 1). Upon applying a 15% hydrochloric acid solution, the roughened surface dissolved over the course of 50-70 seconds, revealing bare copper beneath. Again, the increased time for the roughened surface to dissolve demonstrates the improved chemical resistance of the surface.
EXAMPLE 5
A roughened copper surface was prepared in the same manner as Example 2, with the exception that the bath contained 100 ppm SDDC (see Table 1). A 15% hydrochloric acid solution was applied to the roughened surface. After three to five minutes, the roughened surface was intact and no bare copper was visible. This demonstrates exceptional acid resistance compared to the surface of Example 1, which was prepared without a coating stabilizer.
See Table 1 for a summary of examples 1 to 5.
EXAMPLES 6 THROUGH 11
Adhesion promoting compositions similar to those tested in Examples 1-5 were used to prepare roughened copper surfaces, which were then tested for peel strength. Specifically, for each of Examples 6-11, a clean copper surface was treated in a bath comprising 1.42 wt % H2O2, 0.06 wt % sodium phenolsulfonate, 8.61 wt % H2SO4, 0.57 wt % BTA, 0.0017 wt % (17 ppm) NaCl, 0.38 wt % polyethylene glycol, and deionized water. In Example 6, no coating stabilizer was used. The bath of Example 7 contained 1 ppm SDDC, the bath of Example 8 contained 5 ppm SDDC, the bath of Example 9 contained 10 ppm SDDC, the bath of Example 10 contained 50 ppm SDDC, and the bath of Example 11 contained 100 ppm SDDC. Peel strength testing demonstrated that the copper surfaces prepared in each of Examples 6-11 exhibited a desirable, tightly-adhering coating. While the data did not show a trend towards improved peel strength with increasing concentrations of coating stabilizer, the data did demonstrate that the use of a coating stabilizer does not negatively impact the peel strength of the roughened copper surface.
Following peel strength testing, the roughened copper surfaces of Examples 6-11 were laminated to an FR4 substrate using a pressure of 292 psi for 60 minutes at 350° F. (177° C.). Subsequent testing on hand-drilled holes through the laminated sandwiches demonstrated significant interconnect etch back for Examples 7 and 11, but none of the sandwiches exhibited any pink ring or wedge attack.
EXAMPLE 12
A clean copper surface was treated in a bath comprising 1.42 wt % H2O2, 0.06 wt % sodium phenolsulfonate, 8.61 wt % H2SO4, 0.57 wt % BTA, 0.0017 wt % (17 ppm) NaCl, 0.38 wt % polyethylene glycol, 1 ppm 2-mercaptothiazoline (“MTZ”) (a coating stabilizer), balance deionized water (see Table 2). The bath temperature was maintained at 1003° F. (38° C.). The copper surface was removed from the bath after one minute, rinsed with deionized water, and dried with an air hose. A roughened texture was observed on the copper surface, as is consistent with an alternative oxide coating process. Using an eye-dropper, a solution containing 15% by volume hydrochloric acid was applied to the roughened surface. The roughened surface dissolved over the course of 10-20 seconds, revealing bare copper beneath. The fact that the surface did not dissolve immediately demonstrates that the roughened surface was more chemically resistant than the roughened surface of Example 1, which was not prepared with a coating stabilizer.
EXAMPLE 13
A roughened copper surface was prepared in the same manner as Example 12, with the exception that the bath contained 5 ppm MTZ (see Table 2). Upon applying a 15% hydrochloric acid solution, the roughened surface dissolved over the course of 40-60 seconds, revealing bare copper beneath. The increased time for the roughened surface to dissolve demonstrates the improved chemical resistance of the surface.
EXAMPLE 14
A roughened copper surface was prepared in the same manner as Example 12, with the exception that the bath contained 20 ppm MTZ (see Table 2). Upon applying a 15% hydrochloric acid solution, the roughened surface dissolved over the course of 70-90 seconds, revealing bare copper beneath. Again, the increased time for the roughened surface to dissolve demonstrates the improved chemical resistance of the surface.
EXAMPLE 15
A roughened copper surface was prepared in the same manner as Example 12, with the exception that the bath contained 100 ppm MTZ (see Table 2). A 15% hydrochloric acid solution was applied to the roughened surface. After three to five minutes, the roughened surface was intact and no bare copper was visible. This demonstrates exceptional acid resistance compared to the surface of Example 1, which was prepared without a coating stabilizer.
See Table 2 for a summary of examples 12 to 15.
EXAMPLES 16 THROUGH 25
For examples 16 through 25, a clean copper surface is treated in a bath comprising 1.42 wt % H2O2, 0.06 wt % sodium phenolsulfonate, 8.61 wt % H2SO4, 0.57 wt % BTA, 0.0017 wt % (17 ppm) NaCl, 0.38 wt % polyethylene glycol, 100 ppm of a coating stabilizer, balance deionized water. The coating stabilizer used for each example is listed in Table 3. The copper surface is removed from the bath after one minute, rinsed with deionized water, and dried with an air hose. A roughened texture is observed on the copper surface, as is consistent with an alternative oxide coating process. Using an eye-dropper, a solution containing 15% by volume hydrochloric acid is applied to the roughened surface. The roughened copper surface of each of Examples 16 through 25 exhibits improved acid resistance compared to the surface of Example 1, which was prepared without a coating stabilizer.
EXAMPLES 26 THROUGH 31
In Examples 26 through 31, a clean copper surface is treated in a bath comprising 1.42 wt % H2O2, 0.06 wt % sodium phenolsulfonate, 8.61 wt % H2SO4, 0.0017 wt % (17 ppm) NaCl, 0.38 wt % polyethylene glycol, 100 ppm MTZ, a topography modifier, optionally a uniformity enhancer and/or coating promoter, balance deionized water. Table 4 lists the topography modifier and optional uniformity and/or coating promoter used in each of Examples 26 through 31.
The copper surface is removed from the bath after one minute, rinsed with deionized water, and dried with an air hose. A roughened texture is observed on the copper surface, as is consistent with an alternative oxide coating process. Using an eye-dropper, a solution containing 15% by volume hydrochloric acid is applied to the roughened surface. The roughened copper surface of each of Examples 26 through 31 is desirably uniformly etched and coated, and exhibits improved acid resistance compared to the surface of Example 1, which was prepared without a coating stabilizer.
EXAMPLE 32
A clean copper surface is treated in a bath comprising 1.42 wt % H2O2, 8.61 wt % H2SO4, 0.57 wt % BTA, 0.5 g/l 5-aminotetrazole (uniformity enhancer), 100 ppm MTZ, balance deionized water. The copper surface is removed from the bath after one minute, rinsed with deionized water, and dried with an air hose. A roughened texture is observed on the copper surface, as is consistent with an alternative oxide coating process. Using an eye-dropper, a solution containing 15% by volume hydrochloric acid is applied to the roughened surface. The roughened copper surface is desirably uniformly etched, and exhibits improved acid resistance compared to the surface of Example 1, which was prepared without a coating stabilizer.
EXAMPLE 33
A roughened copper surface was prepared in the same manner as Example 32, with the exception that 0.5 g/l 1-hydroxybenzotriazole (coating promoter) is used in the bath instead of 0.5 g/l 5-aminotetrazole (uniformity enhancer). The roughened copper surface is desirably coated, and exhibits improved acid resistance compared to the surface of Example 1, which was prepared without a coating stabilizer.
EXAMPLE 34
A clean copper surface was prepared by treating a substantially clean copper surface in a pre-dip bath at 70° F. (21° C.). The pre-dip bath comprised 1.15 wt % H2O2, 0.05 wt % sodium phenolsulfonate, 0.13 wt % H2SO4, 0.18 wt % BTA (1.8 g/l), balance deionized water. The clean copper surface was removed from the pre-dip bath after one minute.
The clean copper surface was then treated in a bath comprising 1.42 wt % H2O2, 0.06 wt % sodium phenolsulfonate, 8.61 wt % H2SO4, 0.57 wt % benzotriazole BTA, 0.0017 wt % NaCl, 0.38 wt % polyethylene glycol, balance deionized water. The bath temperature was maintained at 100° F. (38° C.). The copper surface was removed from the bath after one minute, rinsed with deionized water, and dried with an air hose. A roughened texture was observed on the copper surface, as is consistent with an alternative oxide coating process.
The roughened copper surface was then dipped into a post-treatment bath comprising 1 g/l disodium trithiocarbonate (an acid resistance promoting composition) and the balance deionized water. The bath temperature was maintained at room temperature. The roughened copper surface was removed from the bath after 15 seconds, rinsed with deionized water for 1 minute, and dried with an air hose.
Using an eye-dropper, a solution containing 15% by volume hydrochloric acid was applied to the roughened surface and left there for 15 seconds. On a scale of 1 to 10, where a rating of 1 indicates that the roughened copper surface has dissolved to reveal bare copper beneath, and where a rating of 10 indicates no difference between the surface before and after the acid test, this surface rated a 5. This demonstrates exceptional acid resistance compared to the roughened surface of Example 1, which dissolved immediately upon application of the acid solution (thus rating 1 on the scale of 1 to 10). Subsequent peel strength tests on a laminated portion of the roughened copper surface resulted in a peel strength value of 5.8 lbs/in.
EXAMPLES 35 THROUGH 43
For Examples 35 through 43, a roughened copper surface was prepared in the same manner as Example 34, with the exception that the composition and duration of the post-treatment bath was varied. Table 5 lists the particular acid resistance promoting composition used in the post-treatment bath in each example, along with the concentration, treatment time, peel strength test results and acid resistance test results. The test results for each of Examples 35 through 43 demonstrate exceptional acid resistance compared to the roughened surface of Example 1, which dissolved immediately upon application of the acid solution.
While the invention is described above in connection with preferred or illustrative embodiments and examples, they are not intended to be exhaustive or limiting of the invention. Rather, the invention is intended to cover all alternatives, modifications and equivalents included within its spirit and scope of the invention, as defined by the appended claims.













TABLE 1







Example 1
Example 2
Example 3
Example 4
Example 5





















Oxidizer
1.42 wt %
1.42 wt %
1.42 wt %
1.42 wt %
1.42 wt %



H2O2
H2O2
H2O2
H2O2
H2O2


H2O2
0.06 wt %
0.06 wt %
0.06 wt %
0.06 wt %
0.06 wt %


stabilizer
Sodium
Sodium
Sodium
Sodium
Sodium



Phenol-
Phenol-
Phenol-
Phenol-
Phenol-



sulfonate
sulfonate
sulfonate
sulfonate
sulfonate


pH adjuster
8.61 wt %
8.61 wt %
8.61 wt %
8.61 wt %
8.61 wt %



sulfuric acid
sulfuric acid
sulfuric acid
sulfuric acid
sulfuric acid


Topography
0.57 wt %
0.57 wt %
0.57 wt %
0.57 wt %
0.57 wt %


modifier
BTA (6 g/l)
BTA (6 g/l)
BTA (6 g/l)
BTA (6 g/l)
BTA (6 g/l)


Chloride ion
0.0017 wt %
0.0017 wt %
0.0017 wt %
0.0017 wt %
0.0017 wt %



(17 ppm)
(17 ppm)
(17 ppm)
(17 ppm)
(17 ppm)



NaCl
NaCl
NaCl
NaCl
NaCl


Polyethylene
0.38 wt %
0.38 wt %
0.38 wt %
0.38 wt %
0.38 wt %


Glycol


Coating
None
1 ppm
5 ppm
20 ppm
100 ppm


Stabilizer

SDDC
SDDC
SDDC
SDDC


D.I. water
Balance
Balance
Balance
Balance
Balance


Acid
Immediate
Bare copper
Bare copper
Bare copper
No bare


Resistance
appearance
visible in
visible in
visible in
copper after


(Application
of bare copper
10-20
20-30
50-70
3-5 minutes


of HCl

seconds
seconds
seconds


solution)






















TABLE 2







Example 1
Example 12
Example 13
Example 14
Example 15





















Oxidizer
1.42 wt %
1.42 wt %
1.42 wt %
1.42 wt %
1.42 wt %



H2O2
H2O2
H2O2
H2O2
H2O2


H2O2
0.06 wt %
0.06 wt %
0.06 wt %
0.06 wt %
0.06 wt %


stabilizer
Sodium
Sodium
Sodium
Sodium
Sodium



Phenol-
Phenol-
Phenol-
Phenol-
Phenol-



sulfonate
sulfonate
sulfonate
sulfonate
sulfonate


pH adjuster
8.61 wt %
8.61 wt %
8.61 wt %
8.61 wt %
8.61 wt %



sulfuric acid
sulfuric acid
sulfuric acid
sulfuric acid
sulfuric acid


Topography
0.57 wt %
0.57 wt %
0.57 wt %
0.57 wt %
0.57 wt %


Modifier
BTA (6 g/l)
BTA (6 g/l)
BTA (6 g/l)
BTA (6 g/l)
BTA (6 g/l)


Chloride ion
0.0017 wt %
0.0017 wt %
0.0017 wt %
0.0017 wt %
0.0017 wt %



(17 ppm)
(17 ppm)
(17 ppm)
(17 ppm)
(17 ppm)



NaCl
NaCl
NaCl
NaCl
NaCl


Polyethylene
0.38 wt %
0.38 wt %
0.38 wt %
0.38 wt %
0.38 wt %


Glycol


Coating
None
1 ppm MTZ
5 ppm MTZ
20 ppm MTZ
100 ppm MTZ


Stabilizer


D.I. water
Balance
Balance
Balance
Balance
Balance


Acid
Immediate
Bare copper
Bare copper
Bare copper
No bare


Resistance
appearance
visible in
visible in
visible in
copper after


(Application
of bare
10-20
40-60
70-90
3-5 minutes


of HCl
copper
seconds
seconds
seconds


solution)



















TABLE 3







Example Number
Coating Stabilizer









Example 16
2-mercapto benzothiazole



Example 17
2,2′-dithiobis(benzothiazole)



Example 18
6-ethoxy-2-mercaptobenzothiazole



Example 19
3,4,5,6-tetrahydro-2-pyrimidinethiol



Example 20
2-imidazolidinethione



Example 21
potassium 3-(thiocarbamoyl)-dithiocarbazate



Example 22
sodium dimethyldithiocarbamate



Example 23
tetraethylthiuram disulfide



Example 24
tetramethylthiuram disulfide



Example 25
2,5-dithiobiurea




















TABLE 4






Topography




Example Number
Modifier
Uniformity Enhancer
Coating Promoter







Example 26
5 g/l 1H-indole
None
None


Example 27
4 g/l 6-nitro-1H-
None
None



benzotriazole


Example 28
6 g/l 2-hydroxy-1H-
None
None



benzimidazole


Example 29
0.57 wt % BTA
0.5 g/l 5-aminotetrazole
None


Example 30
0.57 wt % BTA
None
0.5 g/l 1-





hydroxybenzotriazole


Example 31
0.57 wt %
0.05 g/l 5-
2 g/l 1-



tolytriazole
mercaptomethyltetrazole
hydroxybenzotriazole




















TABLE 5









Acid



Post-Treatment
Treatment
Peel
Resistance



Bath
Time
Strength
Rating*







Example
None
n/a
—
1


1


Example
1 g/l disodium
15 seconds
5.8 lbs/in
5


34
trithiocarbonate


Example
1 g/l disodium
30 seconds
5.7 lbs/in
7


35
trithiocarbonate


Example
1 g/l sodium sulfide
15 seconds
5.0 lbs/in
9


36


Example
1 g/l sodium sulfide
30 seconds
4.6 lbs/in
9


37


Example
1 g/l sodium N,N-
30 seconds
5.5 lbs/in
5


38
dibutyldithiocarbamate


Example
1 g/l sodium
30 seconds
6.0 lbs/in
6


39
dioctyldithiocarbamate


Example
0.5 g/l HQMME-
15 seconds
6.2 lbs/in
5


40
xanthate and 0.5 g/l



Na2 trithiocarbonate


Example
0.5 g/l HQMME-
30 seconds
6.3 lbs/in
5


41
xanthate and 0.5 g/l



Na2 trithiocarbonate


Example
0.5 g/l sodium N,N-
15 seconds
6.7 lbs/in
5


42
dibutyldithiocarbamate



and 0.5 g/l



Na2 trithiocarbonate


Example
1 g/l sodium N,N-
30 seconds
6.6 lbs/in
4


43
dibutyldithiocarbamate





*Acid resistance is rated on a scale of 1-10, where a rating of 1 indicates that the roughened copper surface has dissolved to reveal bare copper beneath, and where a rating of 10 indicates no difference between the surface before and after the acid test

## Claims

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—X1 


wherein A is 1-20 and wherein X1 is Mg, Ca, Li2, Na2, K2, or (NH4)2;




wherein A is 1-20 and wherein X1 is Mg, Ca, Li2, Na2, K2, or (NH4)2; and




wherein




O—R3, or S—R3, wherein A is 1-20, wherein X2 is Li, Na, K, NH4,




wherein W2 is




O—R6, or S—R6, wherein B is 1-20, and wherein R1-6 are independently selected from H and halogen, or wherein R1-6 are independently selected from, or any two adjacent R1-6 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 C1 up to C18 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 C1 up to C18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 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 Z1 is H, Li, Na, K, NH4,




wherein X1 is S or N—R9, wherein X2 is S or N—R10 and wherein R1-10 are independently selected from H and halogen, or wherein R1-10 are independently selected from, or any two or more of R1-10 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 C1 up to C18 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 C1 up to C18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 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 R1 and R2, R3 and R4, R5 and R6, and R7 and R8 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 Z1 is Li, Na, K, NH4, R3,




wherein Z2 is Li, Na, K or NH4, wherein X1 is S or N—R6, wherein X2 is S or N—R7, and wherein R1-7 are independently selected from H and halogen, or wherein R1-7 are independently selected from, or any two or more of R1-7 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 C1 up to C18 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 C1 up to C18 alkenyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 alkadienyl which is linear or branched and may be singly or multiply substituted in singular or multiply bonded fashion, a C1 up to C18 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.