JP2016535453A - Promoting adhesion of printed circuit boards - Google Patents

Abstract

Compositions and methods for enhancing adhesion between a copper conductive layer and a dielectric material during the manufacture of printed circuit boards. The conditioning composition comprises a functional organic compound and preferably a transition metal ion. Functional organic compounds such as purine derivatives can form self-assembled monolayers. The adhesion promoting composition includes an acid, preferably an inorganic acid, and an oxidizing agent. The latter composition also includes a corrosion inhibitor and / or a transition metal ion selected from Zn, Ni, Co, Cu, Ag, Au, Pd, or other Pt group metals. Also good. The corrosion inhibitor may contain a nitrogen-containing aromatic heterocyclic compound. [Selection] Figure 1

Description

  The present invention relates to an improvement in adhesion to an insulating layer on a metal surface such as copper in the production of a printed circuit board.

  A multilayer circuit board (MLB) has, among other things, a number of metal layers defining a circuit pattern and a number of insulating layers therebetween. The metal layer defining today's circuit patterns is typically formed from copper and the insulating layer is generally formed from a resinous fiber-impregnated dielectric material. Each of these layers can have various thicknesses. For example, they can be on the order of microns, or can be much thicker.

  In the production of MLB, it is desirable to enhance the adhesion between the conductive layer and the insulating layer in order to avoid delamination during subsequent manufacturing operations or use. A so-called “black oxide” process has been used for many years to form a strong adherent copper oxide layer to which the insulating layer adheres well. The black oxide process has been replaced in many industries by a process that involves the formation of an organometallic conversion coating (OMCC) as described in US Pat. These organometallic conversion coating processes include exposing the copper circuit layer to an adhesion promoter solution that includes various components such as oxidants, inhibitors, and mineral acids.

  One limitation in the organometallic conversion coating process is that the organometallic conversion coating must be a uniform color, such as dark brown or chocolate color. The industry associates this color with a uniform film with strong adhesion. A dark uniform color is preferred because it provides copper with a color contrast useful for defect inspection. For example, it provides contrast for inspection of so-called “pink ring” defects. Organometallic conversion coating processes that produce significantly lighter coatings are generally unacceptable or at least undesirable in most applications. Light colored films are substantially more difficult to detect “pink ring” defects.

US Pat. No. 5,800,859

Briefly, therefore, the application is a method for enhancing the adhesion between a copper conductive layer and a dielectric material during the manufacture of a printed circuit board comprising:
Contacting the copper conductive layer with a conditioning composition, the conditioning composition comprising a functional organic compound and a transition metal ion, wherein the functional organic compound is on a copper surface. A process capable of forming a self-assembled monolayer on
Thereafter, contacting the copper conductive layer with an adhesion promoting composition comprising an oxidant, an inorganic acid, and a corrosion inhibitor;
It is related with the method characterized by including.

In another aspect, the present invention is a method for enhancing adhesion between a copper conductive layer and a dielectric material during the manufacture of a printed circuit board comprising:
Contacting the copper conductive layer with a conditioning composition comprising an organic N-containing compound capable of forming a self-assembled monolayer on the copper surface;
Thereafter, the copper conductive layer, an oxidizing agent, an inorganic acid, a corrosion inhibitor, and a transition metal ion selected from the group consisting of zinc, nickel, cobalt, copper, silver, gold, palladium, and other platinum group metals A step of contacting with an adhesion promoting composition comprising: the corrosion inhibitor comprising a nitrogen-containing aromatic heterocyclic compound;
Relates to a method comprising:

The present invention further includes a nitrogen-containing aromatic heterocyclic compound and a transition metal ion, wherein the heterocyclic compound has the following ring group:
Or an amine substituent on the ring, wherein R ⁷ is hydrogen, hydrocarbyl group, substituted hydrocarbyl group, hydroxy group, or negative charge, and the heterocyclic compound is self-assembled on the copper surface The present invention relates to an aqueous alkaline composition capable of forming a monomolecular layer.

  The present invention is also an aqueous composition for treating a copper surface to enhance adhesion to a dielectric, comprising zinc, nickel, cobalt, copper, silver, gold, palladium, and other platinum group metals. About 0.02 wt% to about 2 wt% transition metal ions selected from the group consisting of: about 10 wt% to about 50 wt% sulfuric acid, and about 1 wt% to about 10 wt% hydrogen peroxide And a corrosion inhibitor containing a nitrogen-containing aromatic heterocyclic compound.

In another aspect, the present invention relates to a method for enhancing adhesion between a copper conductive layer and a dielectric material during the manufacture of a printed circuit board. The method includes contacting the copper conductive layer with a conditioning composition comprising a nitrogen-containing aromatic heterocyclic compound capable of forming a self-assembled monolayer on the copper surface. The nitrogen-containing aromatic heterocyclic compound is represented by the following formula:
(Formula I)
In the formula, R ² , R ⁶ , and R ⁸ are each independently hydrogen, hydrocarbyl group, substituted hydrocarbyl group, hydroxycarbonyl group, alkoxycarbonyl group, alkoxy group, hydroxy group, sulfhydryl group (sulfhydryl). R ⁷ is selected from the group consisting of hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a hydroxy group, and a negative charge, and R ^{9 is} selected from the group consisting of R ⁹ , a halogen group, a nitro group, a cyano group, and NR ⁹ R ^10. And R ¹⁰ are each independently selected from the group consisting of hydrogen, hydrocarbyl groups, and substituted hydrocarbyl groups. Thereafter, the copper conductive layer is brought into contact with an adhesion promoting composition comprising an oxidant, an inorganic acid, a corrosion inhibitor, and a surfactant.

The invention further relates to a method for producing a copper conductive layer for bonding to a dielectric material during the production of a printed circuit board. The method includes the step of contacting the copper conductive layer with a conditioning composition comprising a nitrogen-containing aromatic heterocyclic compound and an anionic surfactant. Nitrogen-containing aromatic heterocyclic compound is capable of forming a self-assembled monolayer on the copper surface, the following ring group,
Or an amine substituent on the ring, wherein R ⁷ is hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a hydroxy group, or a negative charge. Thereafter, the copper conductive layer is brought into contact with an adhesion promoting composition comprising an acid and an oxidizing agent.

The present invention also relates to a method for producing a copper conductive layer for bonding to a dielectric material during the production of a printed circuit board. The method includes contacting the copper conductive layer with a conditioning composition comprising a nitrogen-containing aromatic heterocyclic compound, an alkali metal iodide, and a glycol ether. Nitrogen-containing aromatic heterocyclic compound is capable of forming a self-assembled monolayer on the copper surface, the following ring group,
Or an amine substituent on the ring, wherein R ⁷ is hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a hydroxy group, or a negative charge.

  Hereinafter, some other aspects and features will be clarified and partially shown.

FIG. 1 is a series of bar graphs showing peel strength as a function of copper content for various laminates made at 15.5 bar after treatment with the inventive modifiers and adhesion promoters described in Example 18. It is. However, each adjusting agent and adhesion promoter composition contained copper ions having a concentration in the range of 0 g / L to 10 g / L. FIG. 2 is a series of bar graphs showing the peel strength as a function of copper content for a laminate made at 24.1 bar after further treatment with the conditioning and adhesion promoter of the present invention as described in Example 18. is there. However, each adjusting agent and adhesion promoter composition contained copper ions having a concentration in the range of 0 g / L to 10 g / L. FIG. 3 further illustrates a series of peel strengths as a function of copper content before reflow for a laminate produced at 15.5 bar after treatment with a modifier and adhesion promoter, as described in Example 19. It is a bar graph. However, each adjusting agent and adhesion promoter composition contained copper ions having a concentration in the range of 0 g / L to 10 g / L. FIG. 4 further illustrates a series of peel strengths as a function of copper content before reflow for a laminate produced at 24.1 bar after treatment with a modifier and adhesion promoter as described in Example 19. It is a bar graph. However, each adjusting agent and adhesion promoter composition contained copper ions having a concentration in the range of 0 g / L to 10 g / L. FIG. 5 further illustrates a series of peel strengths as a function of copper content after reflow of a laminate produced at 15.5 bar after treatment with a modifier and adhesion promoter as described in Example 19. It is a bar graph. However, each adjusting agent and adhesion promoter composition contained copper ions having a concentration in the range of 0 g / L to 10 g / L. FIG. 6 further illustrates a series of peel strengths as a function of copper content after reflow of a laminate produced at 24.1 bar after treatment with a modifier and adhesion promoter as described in Example 19. It is a bar graph. However, each adjusting agent and adhesion promoter composition contained copper ions having a concentration in the range of 0 g / L to 10 g / L. FIG. 7 is a series of bar graphs showing peel strength as a function of copper content for laminates made at 15.5 bar after treatment with the modifier and adhesion promoter described in Example 20. However, each adjusting agent and the adhesion promoting composition contain copper ions in a range of 0 g / L to 10 g / L, and the adhesion promoting composition did not contain the adjusting agent. FIG. 8 is a series of bar graphs showing peel strength as a function of copper content for laminates made at 24.1 bar after treatment with the modifier and adhesion promoter described in Example 20. However, each adjusting agent and the adhesion promoting composition contain copper ions in a range of 0 g / L to 10 g / L, and the adhesion promoting composition did not contain the adjusting agent. FIG. 9 is a series of bar graphs showing peel strength as a function of copper content for laminates made at 15.5 bar after treatment with the modifier and adhesion promoter described in Example 20. However, each adjusting agent and adhesion promoting composition contain copper ions in a content range of 0 g / L to 10 g / L, and the adhesion promoting composition contained ~ 1 g / L adjusting agent # 2. FIG. 10 is a series of bar graphs showing peel strength as a function of copper content for laminates made at 24.1 bar after treatment with the modifier and adhesion promoter described in Example 20. However, each adjusting agent and adhesion promoting composition contain copper ions in a content range of 0 g / L to 10 g / L, and the adhesion promoting composition contained ~ 1 g / L adjusting agent # 2. FIG. 11 is a series of bar graphs showing peel strength as a function of modifier # 2 content in the adhesion promoting composition of the laminate produced according to Example 21. However, each adjusting agent and adhesion promoting composition contained copper ions with a content of about 5 g / L. FIG. 12 is a series of bar graphs showing peel strength as a function of copper content for the laminate produced according to Example 22. However, the copper ion of the density | concentration of the range of 0 g / L-50 g / L was added with respect to the adhesion promotion composition, and adjustment agent # 2 was not added. FIG. 13 is a series of bar graphs showing peel strength as a function of copper content for the laminate produced according to Example 22. However, it was copper ion of the density | concentration of the range of 0 g / L-50 g / L, and the adhesion promotion composition contained ~ 1 g / L of adjustment agent # 2. FIG. 14 is a series of bar graphs showing peel strength as a function of dwell time between the application of the modifier and the application of the adhesion promoting composition for the laminate produced according to Example 23. However, each adjusting agent and adhesion promoter contained 40 g / L of copper ions. FIG. 15 is a series of bar graphs showing peel strength as a function of modifier # 2 content in the adhesion promoting composition of the laminate produced according to Example 24. However, each adjusting agent and adhesion promoting composition contained about 10 g / L of copper ions. FIG. 16 is a series of bar graphs showing peel strength as a function of modifier # 2 content in the adhesion promoting composition of the laminate produced according to Example 24. However, each adjusting agent and adhesion promoting composition contained about 10 g / L of copper ions.

The present invention relates to compositions and methods for enhancing adhesion between copper conductive layers and non-conductive laminates. As a general proposal, the growth of an adhesive organometallic conversion coating on the surface of a copper conductive layer causes the copper conductive layer to oxidize copper to cuprous or cupric ions on the surface of the conductive layer. Occurs by contact with an adhesion promoting composition. Cuprous ions (Cu ⁺ ) formed by the oxidation reaction are generally dominant on the surface, and cupric ions (Cu ²⁺ ) are generally dominant in solution. At the same time that copper is chemically dissolved in the adhesion promoter from the conductive copper layer, the cuprous ions on the surface combine with the corrosion inhibitor in the adhesion promoter composition to form a copper-inhibitor complex. Thereby, the form of the finely roughened surface of the conductive copper layer is obtained. This finely roughened copper surface promotes adhesion with the subsequently applied insulating layer.

  In the method of the present invention, prior to contacting the copper conductive layer with the adhesion promoting composition, the copper conductive layer is preferably nitrogen-containing capable of forming a self-assembled monolayer (SAM) on the copper surface. Contacting with a conditioning composition comprising a heterocycle. It has been found that molecules capable of forming a SAM can be incorporated into an alkaline detergent or used in another pre-soak composition. Self-assembled monolayers consist essentially of high-density organic films formed from nitrogen-containing heterocyclic molecules chemisorbed on the copper surface, or other film-forming organic nitrogen or organic sulfur compound monolayers. Configured. While not being bound by any particular theory, the self-assembled monolayer formed on the copper surface from the conditioning solution passivates the copper surface by interfering with the contact of oxygen contained in the adhesion promoting composition. It is considered to be. Therefore, otherwise, the effect of the subsequently applied adhesion promoting liquid is controlled by preventing the formation of excess copper oxide resulting from the aggressive influence of the peroxide component of the adhesion promoting liquid.

  In addition to the nitrogen-containing heterocycle, the conditioning composition preferably includes a transition metal ion, generally in the form of a transition metal salt. Useful transition metal ions include zinc, nickel, copper, cobalt, silver, gold, palladium, and other platinum group metals. Preferably, the transition metal ion is selected from the group consisting of zinc, nickel, cobalt, silver, gold, palladium, and other platinum group metals, more preferably zinc, nickel, cobalt, or silver, and even more Zinc, nickel or cobalt is preferable. Zinc is preferred. Various salts of transition metals such as sulfates, chlorides, other halides, most mainly iodides, phosphates, phosphites, carbonates and various carboxylates such as oxalates Can be used. Oxides can also be used. The presence of these transition metal ions in the adjustment liquid is believed to contribute to the thermal stability of the chemical conversion film produced in the subsequent treatment with the adhesion promoting liquid. In a preferred embodiment of the invention, zinc is incorporated into the conditioning liquid in the form of an alkaline dispersion of ZnO, an alkali metal zincate solution, or a zinc ammonium halide such as zinc ammonium chloride.

Preferably, the nitrogen-containing heterocycle is a purine compound corresponding to, for example, the following general formula:
(Formula I)
In the formula, R ² , R ⁶ and R ⁸ are each independently hydrogen, hydrocarbyl group, substituted hydrocarbyl group, hydroxycarbonyl group, alkoxycarbonyl group, alkoxy group, hydroxy group, sulfhydryl group, halogen group, nitro group. , Cyano group and NR ⁹ R ¹⁰ , R ⁷ is selected from the group consisting of hydrogen, hydrocarbyl group, substituted hydrocarbyl group, hydroxy group, and negative charge, R ⁹ and R ¹⁰ are each Independently, selected from the group consisting of hydrogen, hydrocarbyl groups, and substituted hydrocarbyl groups. Preferably, R ⁹ and R ¹⁰ are each independently selected from the group consisting of hydrogen, an alkyl group, a substituted alkyl group, an aralkyl group, and an aryl group.

In particularly preferred embodiments, R ⁶ of formula I comprises NR ⁹ R ¹⁰ . When the hydrocarbon substituent is substituted, the substituent of the hydrocarbyl group is preferably an amino group, a cyano group, a nitro group, a halogen group, a hydroxy group, or a sulfhydryl group. Most preferably, R ⁹ is hydrogen and R ¹⁰ is a benzyl group, that is, the compound forming the self-assembled monolayer is most preferably an amino-substituted purine such as 6-benzylaminopurine described below. .
However, it is also advantageous that the compounds of the formula I contain unsubstituted purines. In a preferred alkaline conditioning solution, R ⁷ is preferably hydrogen and the nitrogen-containing aromatic heterocyclic compound can be deprotonated by contact with a copper substrate. Thus, in solution, especially in contact with a copper substrate, R ⁷ contains a hydroxy group or a negative charge.

The following groups in the purine ring allow efficient interaction with the metal surface (copper).
The following ring groups,
And other substituents on the ring (in the case of 6-benzylaminopurine, R ⁷ is a benzyl group)
By the presence of at least one of the above, a coordination bond can be formed at the interface between the metal and the purine compound.

  After treatment of the conditioning surface with the adhesion promoting composition and subsequent lamination, it has been found that the purine derivatives in the conditioning liquid contribute to the bonding strength between the copper conductor and the resin. It was further found that the purine derivatives contribute to the thermal stability of the conversion coating produced by subsequent treatment with an adhesion promoter.

Purines and particularly amine-substituted purines are particularly preferred,
And other nitrogen heterocycles containing at least one of the amino substituents on the ring can effectively function to form a self-assembled monolayer on the copper surface from the conditioning solution. Exemplary heterocycles that function effectively for this purpose include the following benzotriazoles (benzotriazole (BTA)),
And various substituted benzotriazoles, substituted triazoles, unsubstituted triazoles, tetrazoles, and benzimidazoles. In addition to amines, the heterocycle can contain functional ring substituents such as thiols, vinyl ethers, thiamides, amines, carboxylic acids, esters, alcohols, silanes, and alkoxysilanes. Exemplary compounds useful for forming self-assembled monolayers include adenine, 2-mercaptobenzimidazole, mercaptobenzothiazole, and di (sulfhydrylmethyl) benzene.

  In some embodiments of the conditioning liquid of the present invention, various other functional organic compounds can be present as components that form the self-assembled monolayer. In particular, in these embodiments, the conditioning solution comprises a transition metal cation, and the self-assembled monolayer is an arylamine such as aniline, aniline derivatives, toluidine, and toluidine derivatives; benzylamine, tolylamine, benzylamine derivatives And aralkylamines such as tolylamine derivatives; various alkylamines, particularly aliphatic amines; including thiophene, thiophene derivatives, benzothiophene, benzothiophene derivatives, benzothiazoles, and benzothiazole derivatives. Sulfur aromatic heterocyclic compounds; arylthiols such as thiophenol, thiophenol derivatives, tolylthiol, and tolylthiol derivatives; formed from other aralkylthiols such as benzyl mercaptan and di (sulfhydrylmethyl) benzene It is possible.

Among nitrogen-containing heterocycles, suitable components capable of forming a self-assembled monolayer include polyfunctional compounds having the following structural formula (Ia) or the following structural formula (Ib). ,
Where
A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , and A ₇ are carbon atoms or nitrogen atoms, and A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , and the total number of nitrogen atoms derived from a ₇ is located in 0,1,2, or 3;
A ₁₁ , A ₂₂ , A ₃₃ , A ₄₄ , A ₅₅ , A ₆₆ , and A ₇₇ are an electron pair, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted vinyl ether, substituted or Selected from the group consisting of unsubstituted amides, substituted or unsubstituted amines, substituted or unsubstituted carboxylic acids, substituted or unsubstituted esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes;
At least one of A ₁₁ , A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ is a substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted It is selected from the group consisting of esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes.

The following part of the aromatic heterocycle from which the self-assembled monolayer is formed is
May contain a substituted nitrogen, i.e., R ⁷ may be a hydrocarbyl group, but as a result of the deprotonation of the compound, a negatively charged aromatic heterocycle forms copper on the surface of the metal substrate. At least one of the film-forming aromatic heterocycles so that it can be used to interact with copper (I) and copper (II) ions in the form of (I) rich organometallic adhesive films. It is preferable that one nitrogen atom is bonded to an acidic hydrogen atom. In short, an aromatic N-containing heterocycle useful for the formation of a monolayer has the following groups where R ⁷ is hydrogen:
It is particularly preferred that the hydrogen is acidic, eg, exhibits a pKa of about 5 to about 13, such as a pKa of about 3.5 to about 11, such as a pKa of about 4 to about 10. The ring may be fused to an aromatic or cycloalkyl group that may be a monocyclic or heterocyclic ring.

Among the polyfunctional compounds represented by the structural formula (Ia) and the structural formula (Ib), those having the following structural formula (II), the following structural formula (III), or the following structural formula (IV) are preferable.
In the formula, A ₂₂ , A ₄₄ , A ₅₅ , A ₆₆ , and A ₇₇ are defined with respect to the structural formula (Ia) and the structural formula (Ib).

Other specific multifunctional compounds for forming a self-assembled monolayer include those having the following structural formula (V):
Where
A ₂ , A ₃ , A ₄ , and A ₅ are carbon atoms or nitrogen atoms, and the total number of nitrogen atoms derived from A ₂ , A ₃ , A ₄ , and A ₅ is 0, 1, or 2 ;
A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ are hydrogen, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or Selected from the group consisting of unsubstituted carboxylic acids, substituted or unsubstituted esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes;
At least one of A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ is substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted ester, substituted Or selected from the group consisting of unsubstituted alcohol, substituted or unsubstituted silane, and substituted or unsubstituted alkoxysilane.

  In addition, various nitrogen-containing aromatic heterocyclic compounds that form a self-assembled monolayer include one or more ring substitutions selected from the group consisting of a cyano group, a nitro group, a halogen group, a hydroxy group, and a sulfhydryl group. It may contain a group. For example, the monolayer film may be formed of heterocyclic rings such as mercaptobenzimidazoles, mercaptobenzothiazoles, and mercaptobenzotriazoles.

  In addition, when the corrosion inhibitor component of the adhesion promoting liquid contains a component that can be chemically adsorbed on the copper surface, such as benzotriazole or benzotriazole 5-carboxylic acid, the substrate is treated with a conditioning liquid, and the subsequent heterocyclic The process of the present invention, combined with treatment with an adhesion promoter containing a corrosion inhibitor, forms a complex of the self-assembled monolayer from the conditioning solution, the corrosion inhibitor from the adhesion promoter, and copper. This is believed to interact synergistically in some or all cases to enhance the bonding of the copper substrate to the dielectric in the lamination step of the multilayer circuit board manufacturing process.

In general, the process of the present invention is performed according to the following procedure.
1. The surface of the copper conductive layer is etched using the microetching liquid composition.
2. Rinse the etchant composition on the surface of the copper conductive layer.
3. The etched surface is cleaned by contacting the surface with an alkaline cleaner. The alkaline detergent may contain molecules capable of forming a self-assembled monolayer (SAM) on the copper surface, if necessary.
4). Rinse the cleaning composition on the surface of the copper conductive layer.
5. The cleaned and etched surface of the copper conductive layer is contacted with a presoak composition comprising molecules capable of forming a self-assembled monolayer (SAM) on the copper surface. This step is optional if the alkaline detergent contains molecules capable of forming a self-assembled monolayer (SAM) on the copper surface.
6). Rinse the presoak composition on the surface of the copper conductive layer.
7. The cleaned, etched, and presoaked surface of the copper conductive layer is contacted with the adhesion promoting composition.
8). The adhesion promoter composition on the surface of the copper conductive layer is rinsed and an organometallic conversion coating is formed thereon.
9. The surface of the copper conductive layer is dried.
10. The organometallic conversion coating is examined to confirm the presence of a substantially uniform dark reddish brown to chocolate brown color with no significant inhomogeneities or striations. The presence of a uniform brown indicates the presence of a conversion coating that enhances the adhesion of the copper substrate to the dielectric in the subsequent lamination steps of the manufacturing process.
11. The surface of the copper conductive layer having the organometallic conversion coating thereon is attached to the prepreg laminate.

  The method of the present invention is described in more detail below.

Micro-etching In some embodiments, the surface of the copper conductive layer is pre-coated with a discoloration-preventing film, for example, by incorporating a discoloration-preventing agent in the resist removal composition used in the process immediately prior to etching resist removal. It may be. Discoloration inhibitors used in such removers are, for example, triazoles or other films. Accordingly, the conductive copper surface is typically microetched, cleaned, and immersed in the pre-soak composition prior to exposure to the adhesion promoting composition.

  The surface of the copper conductive layer is exposed to the etchant by dipping, spraying, cascading, or any other industrially appropriate method. The etching solution can be, for example, a micro-etching solution containing about 12 wt% to 20 wt% sodium persulfate and 2 wt% to 5 wt% sulfuric acid containing a trace amount of phenol sulfuric acid. For example, Enthone It is prepared by diluting a concentrate available under the trademark PC-7077 (from Enthone Inc.) by 40% to 60%. Generally, the copper conductive layer is exposed to the etchant composition at a solution temperature of typically 20 ° C. to 40 ° C. for a duration of 10 seconds to 120 seconds, such as 20 seconds to 60 seconds. Etching fines and roughens the copper surface to remove excess copper oxide and other oxide contaminants prior to treatment with the conditioning solution of the present invention and subsequent adhesion promoting solution.

  Next, the etched copper conductive layer etchant composition is generally rinsed in warm water (tap water or deionized water) for 10 seconds to 120 seconds. Preferably the rinse water is deionized water to allow good process control. Preferably, the rinse water is drained for 10 to 30 seconds to avoid over-dilution of the composition of subsequent processes.

Cleaning The etched surface of the copper conductive layer is then cleaned in an alkaline cleaner by dipping, spraying, cascading, or any other industrially appropriate method. Useful compositions include Enthone (R) PC-7086 and Enthone (R) PC-7096 (concentration 10% to 15%, available from Enthone Inc.). PC-7086 consists of monoethanolamine (78% by weight), 1-methylbenzotriazole (0.06% by weight), KOH (10% by weight), water (12% by weight), and quaternary ammonium salt (0. PC-7096 contains water (16% by weight), monoethanolamine (72% by weight), 25% tetramethylammonium hydroxide (3.2% by weight), ethylenediamine (0.17% by weight). ), Ethoxylated quaternary ammonium salt (0.032 wt%), 1-methylbenzyltriazole (0.06 wt%), aqueous choline base (2.2 wt%), and KOH (8 wt%). . In general, the copper conductive layer is washed at a solution temperature of generally 30 ° C. to 50 ° C. for a duration of 30 seconds to 240 seconds, such as 45 seconds to 90 seconds. In some embodiments of the present invention, the cleaning composition optionally further comprises molecules capable of forming a self-assembled monolayer on the copper surface. Such molecules are further described below in connection with pre-soaked compositions. Cleaning with an alkaline cleaner is effective in removing oily residues, residual photoresist, and other organic and inorganic contaminants present on the copper substrate as a result of previous steps in the circuit board manufacturing process. Also, the cleaning with an alkaline cleaning agent neutralizes residual acid on the copper surface that is not completely removed in the rinsing step after microetching.

  Next, the alkaline cleaning composition of the copper conductive layer that has been etched and cleaned is typically rinsed in warm water (tap water or deionized water) for 10 seconds to 120 seconds. Preferably the rinse water is deionized water to allow good process control. Preferably, the rinse water is drained for 10 to 30 seconds to avoid over-dilution of the composition of subsequent processes.

Preconditioning with Conditioner The cleaned and etched surface of the copper conductive layer is then contacted with a modifier composition comprising molecules capable of forming a self-assembled monolayer on the copper surface. . In general, the copper conductive layer is contacted with the pre-soaked composition at a solution temperature of generally 30 ° C. to 50 ° C. for a duration of 30 seconds to 240 seconds, such as 45 seconds to 90 seconds.

  In addition to nitrogen-containing heterocycles or other functional organic compounds that form self-assembled monolayers, the conditioning solution can be useful, for example, iodide ions in the form of KI, ethanolamines such as MEA, anions, etc. A surfactant, diethylene glycol butyl ether, and any other compound or combination of any other compound, such as zinc ion in the form of a zinc compound such as zinc iodide or zinc ammonium carbonate. It may be. Iodide ions and zinc ions in the modifier contribute to enhanced bonding of the copper substrate to the dielectric in the lamination step after application of the adhesion promoter. Although synergistic effects are not a requirement of the prepared compositions used in the methods described herein, the alkalinity of the adjusted composition is often synergistic with the iodide ions optionally contained therein. It is understood that the anticorrosive property of the surface after the treatment with the subsequent adhesion promoting liquid can be imparted, and the bond strength between the chemical conversion film and the resin after lamination can be enhanced.

Instead of zinc ions or in combination with zinc ions, the modifier may contain certain other transition metal ions such as, for example, nickel, cobalt, silver, gold, palladium, or other platinum group metals. Good. A further option is the presence of copper ions. Zinc or other transition metals are typically pairs selected from the group consisting of chloride, iodide, phosphate, carbonate, and various carboxylates such as malate and oxalate. It is incorporated into the preparation as a salt containing an anion. Oxides can also be used. Thus, the conditioning composition comprises zinc ions in the form of Zn ²⁺ , Zn ²⁺ / ammonia complex, zinc oxide, ZnO ₂ ²⁻ , or combinations thereof. The composition is one or more selected from the group consisting of chloride, iodide, bromide, phosphate, carbonate, hydroxide, and various carboxylates such as malate and oxalate. In the case of zincate, the counterion is a cation such as Na ⁺ , K ⁺ , and / or NH ₄ ⁺ .

Preferably, since the modifier is alkaline, it functions as an alkaline cleaner on the copper surface, thereby eliminating the need for a separate alkaline cleaning step. Moreover, alkalinity promotes the solubility of oxides or hydroxides of other transition metals as well as zinc sources such as zinc oxide. The pH of the modifier is more preferably in the range of about 10 to about 15, even more preferably in the range of about 10 to about 14, and most preferably in the range of about 13.5 to about 14. Also, these ranges of pH function to maintain a shelf life during storage and extend the regulator bath life during process operation. Alkalinity can be easily provided by the presence of an alkali metal hydroxide such as NaOH or KOH. Potassium hydroxide is preferred because of its good solubility and resistance to carbonation due to CO ₂ absorption from the environment.

A particularly preferred source of zinc ions, particularly in alkaline solutions, is a zinc ammonium complex or a combination of a zinc ammonium complex and an alkaline zincate. A source of very useful commercial zinc, zinc ammonium complex (30 wt% to 60 wt%), ammonium carbonate (10 wt% to 30 wt%), 0.1% by weight of ammonium hydroxide (NH ₃ reference And 10 wt%) and a trace amount of zinc oxide in the form of zincate ions, a composition available under the trade name ZINPLEX 15. In the preferred range of pH 10 to pH 14, zinc is primarily present as Zn ²⁺ or Zn ²⁺ / ammonia complexes, although some zincate ions (ZnO ₂ ²⁻ ) may be present at the upper end of the range, It is thought that it contributes to the thermal stability of the chemical conversion film applied after that from an adhesion promotion liquid.

  We believe that zinc ions or other transition metal ions, and especially the combination of zinc ions and ammonia, promote the formation of more effective protective films, including components that form self-assembled monolayers on copper substrates. It has been. The complexing ability of ammonia further contributes to the cleaning of the copper surface by contact with the cleaning agent / conditioning agent. For example, contact with an alkaline modifier is effective to remove oxidative and oily residues such as fingerprints from the copper surface, thereby enhancing the effectiveness of subsequently applied adhesion promoting compositions.

  For process control purposes, the modifier is preferably substantially free of peroxides, and more preferably substantially free of other oxidizing agents as well. For example, in general, the regulator preferably comprises a solution having an oxidation potential of about 0.8 V to 1.02 V or less, typically as indicated by, for example, purine, guanine and adenine.

  The preferred presence of iodide ions in the conditioning agent promotes the reduction of cupric ions to cuprous ions, which in turn is a corrosion inhibitor composition of cuprous ions and adhesion promoting liquid (eg, It is believed to promote the formation of complexes with (benzotriazole), thereby forming a conversion coating that enhances the bond strength between the copper substrate and the resin in the laminate. Preferably, the concentration of iodide ions in the conditioning solution is from about 0.001% to about 1.00% by weight.

  The adjustment liquid preferably contains an alcohol, and more preferably contains a glycol ether such as diethylene glycol butyl ether. Other alcohols described herein for incorporation into the adhesion promoting liquid can also optionally be present in the conditioning liquid. Alcohols, and particularly preferred glycol ethers, have been found to function as dispersants and further provide solubility and stability. Preferably, the conditioning solution includes an alcohol component at a concentration of about 1.00% to about 20.00% by weight.

  The adjustment composition may further contain an alkanolamine such as methanolamine. Alkanolamines are detergents with good chelating ability. Preferably, the alkanolamine is present at a concentration of about 1.00% to about 20.00% by weight.

  The conditioning liquid wets the copper surface to reduce the interfacial tension and enhances the solubility of the components that form a self-assembled monolayer on the substrate, preferably one or more anionic surfactants. It is more preferable to include. Of the anionic surfactants, both aryl sulfonates and sulfate esters are preferred. Examples of anionic surfactants that can be included in the conditioning solution are sodium 2-ethylhexyl sulfate sold under the trade name Niaprof 08 and dodecylbenzene sulfone sold under the trade name Calsoft Las 99. Sodium acid. When present, the nonionic surfactant is preferably present in the conditioning solution at a concentration of from about 0.0005% to about 1.00% by weight.

The modifier is preferably selected from the group consisting of Zn, Ni, Co, Cu, Ag, Au, Pd, and other platinum group metals, more preferably Zn, Ni, Co, Ag, Au, or Pd. And even more preferably Zn, Ni or Co, most preferably Zn, from about 0.1 wt% to about 3 wt% transition metal, and from about 0.05 wt% to about 2 .5 wt% cyclic = includes combination with nitrogen-containing aromatic heterocycle containing NR ⁷ group. More preferably, the solution further comprises about 0.04 wt% to about 4 wt% iodide ions, preferably in the form of KI.

  Also, preferred embodiments of the modifier generally comprise an anionic surfactant at a concentration of about 0.001% to about 0.03% by weight, and about 0.5% to about 5% by weight. Containing at least one of a concentration of glycol ethers. Preferred embodiments also generally include an alkanolamine such as monoethanolamine at a concentration of about 0.5 wt% to about 5 wt%.

  In each of these various embodiments, the nitrogen-containing aromatic heterocycle preferably comprises purine or purine derivatives at a concentration of from about 0.05% to about 2.5% by weight.

  The etched copper conductive layer modifier composition is then generally rinsed in warm water (tap water or deionized water) for 10 seconds to 120 seconds. Preferably the rinse water is deionized water to allow good process control. Preferably, the rinse water is drained for 10 to 30 seconds to avoid over-dilution of the composition of subsequent processes. Preferably, the copper surface is substantially dry or minimally wet prior to contact with the adhesion promoting composition.

Adhesion promotion The cleaned and etched copper conductive layer surface is then contacted with an adhesion promotion composition. Contact with the adhesion promoting composition can be made by any conventional means, for example, by dipping the adhesion promoting composition in a bath, spraying, or any other contacting means. Contact may be part of a continuous process. As is well understood in the art, the dipping process simply involves dipping the substrate into the bath of the composition for a desired period of time. The spraying process generally involves application using a series of automated squeegee-type mechanisms. The method of application is not critical to the present invention. However, as described above, for example, there are many bath stagnations in the dipping process, and therefore, the allowable range for the copper content is larger in the spray process than in the dipping process.

The adhesion promoting composition may contain an oxidizing agent. Useful oxidizing agents include hydrogen peroxide and persulfates, such as ammonium persulfate, potassium persulfate, and sodium persulfate. In general, hydrogen peroxide is incorporated into the adhesion promoting composition of the present invention as an oxidizing agent that oxidizes copper on the substrate. An oxidizing agent, such as hydrogen peroxide, is present in the adhesion promoting composition at a concentration of at least about 1% by weight. The concentration of the oxidizing agent, such as hydrogen peroxide, is generally about 20% or less, and in certain preferred embodiments is about 10% or less. One preferred concentration of hydrogen peroxide is about 0.5% to about 4% by weight of the adhesion promoting composition. If the concentration of hydrogen peroxide in the adhesion promoting composition is too high, the roughened surface structure of the conductive layer forms a somewhat dendritic structure that is more fragile than the desired roughening effect, so a lower concentration of hydrogen peroxide. It has been found that the bond that forms is weaker than when is used. Furthermore, if there is over-etching due to excessive hydrogen peroxide, the organometallic chemical conversion film becomes turbid. Unless otherwise specified, all percentages herein are by weight. Further, all the densities are standardized so as to represent the density of each element assuming that the density is used at 100%. For example, in one embodiment, the H ₂ O ₂ solution added to the composition is 35% concentrated H ₂ O ₂ instead of 100% concentrated H ₂ O ₂ . However, the above numerical values such as 20%, 10%, and 4% are 100% H ₂ O ₂ % in the final composition, not 35% H ₂ O _{2 in} the final composition.

  In order to increase the stability of the composition, the composition is preferably initially substantially free of copper and any other transition metals that tend to destabilize the oxidant. For example, copper ions are avoided in the initial solution because copper ions tend to destabilize hydrogen peroxide. This requirement is relevant to the initial composition in that copper is avoided in the virgin composition before use to promote adhesion. However, in use, copper is not excluded from the composition because in practice copper tends to accumulate in solution during use.

  Certain other transition metal ions have been found to contribute to the thermal stability of the conversion coating without destabilizing the peroxide. Transition metals beneficially included in the initial bath include nickel, cobalt, silver, gold, palladium, and other platinum group metals.

  In addition to nickel, cobalt, silver, gold, palladium, and other platinum group metals (plus copper that is incorporated into the composition at the time of use), the adhesion promoting composition can decompose the oxidizing agent in the composition. Transition metal is “substantially” free in that it is any low enough trace amount that does not contribute significantly to the transition metal, for example, in a sufficiently low amount that does not increase the degradation rate by more than about 10%. is there.

The adhesion promoting composition contains one or more inorganic acids primarily for the purpose of dissolving copper and maintaining other components of the composition in solution. Various acids such as mineral acids including phosphoric acid, nitric acid, sulfuric acid, and mixtures thereof are practical. In a preferred embodiment, both HNO ₃ and H ₂ SO ₄ are employed. In addition to solubilizing Cu, H ₂ SO ₄ has been found to moderate the etch rate and thus contribute to the prevention of substrate over-etching in isolated regions. HNO ₃ increases the etch rate; increases the solubility of Cu; contributes to the prevention of premature sludge formation; works synergistically with H ₂ O ₂ , H ₂ SO ₄ , and corrosion inhibitors to darken the film Turn into. The total acid concentration in the composition is generally at least 1% of the composition, preferably at least 8% of the composition, and in certain preferred embodiments is at least 14% of the composition. The etch rate is too slow when the concentration of acid except nitric acid is too high, which can result in an organometallic conversion film that is non-uniform and too bright in color. For this reason, the acidity level in the prior composition is generally selected to be about 20%. However, in the present invention, it is possible to increase the acidity to a maximum of about 25% or more, which is expected with an acidity increased to about 25% by the use of other additives described herein. This is because the film does not lighten. The overall acidity is generally maintained below about 50%. In one preferred embodiment, therefore, there is about 20% of _H 2 _SO 4 (50% grade) and about 22% to about 28% of the acid containing about 5% _HNO 3 (95% grade). In one preferred embodiment, the inorganic acid comprises at least about 30% of the composition. Another preferred embodiment employs 28% H ₂ SO ₄ (50% grade) and 5% HNO ₃ (95% grade). In these preferred embodiments, HNO ₃ is used because it has been discovered that it has a unique ability to solubilize inhibitor-Cu complexes better than other mineral acids. This contributes to the etching rate, improves the shape of the chemical conversion film, and increases the copper-containing capacity of the adhesion promoting bath. The above weight fraction is the proportion of acid in the final composition as described above and is based on the use of 100% concentrated acid, the preferred form of acid actually added is 50% concentrated H ₂ SO ₄ , and about 95% concentrated HNO ₃ .

  When a combination of nitric acid and sulfuric acid is included in the adhesion promoting liquid, the total mineral acid content is preferably at least about 20% by weight. More preferably, the nitric acid is present at a concentration that differs at least between the total mineral acid content and 20% by weight.

One preferred composition employs HNO ₃ so that the entire composition is adapted. Specifically, thiourea complexing agents are particularly avoided because of the explosive nature when mixed with HNO ₃ .

In general, triazoles, tetrazoles, imidazoles, and mixtures thereof have been proposed as corrosion inhibitors in adhesion promoting compositions. Useful corrosion inhibitors include benzotriazole, triazole, benzimidazole, and imidazole, for the effectiveness of copper chelating ability, the effectiveness of corrosion prevention, and the effectiveness of promoting darkening of the surface of the organic metal conversion coating. Particularly preferred are benzotriazole (BTA) compounds. The presently most preferred BTA compound is 1,2,3-benzotriazole, also known as adiaminobenzene or benzeneazimide, having the formula C ₆ H ₄ NHN ₂ . Purines and purine derivatives of formula I can also be used and may be multifunctional compounds of formula I (a), formula I (b), formula III, formula IV, and formula V. Particularly desirable results are achieved with a corrosion inhibitor at a concentration of at least 0.1% by weight, more preferably greater than 0.5% by weight, and sometimes greater than 1% by weight. Generally, the corrosion inhibitor is present in the composition at 20 wt% or less, preferably 10 wt% or less, more preferably less than 5 wt%, based on the total weight of the adhesion promoting composition. A high concentration of over 5% may be desirable because it can allow a reduction in processing time. However, in certain preferred embodiments, the concentration is less than 5%, or less than 1%.

  The present invention also includes monomeric alcohols, oligomeric alcohols, polymeric alcohol derivatives, oligomers, including, but not limited to, alcohol sulfates, alcohol sulfonates, and alcohol ethoxylates, as described in further detail below. Various additives to the adhesion promoting composition selected from alcohol derivatives and monomeric alcohol derivatives are employed.

Preferred embodiments of the present invention can use sulfonated anionic surfactants. It has been discovered that this surfactant contributes to H ₂ O ₂ stabilization in addition to surface wetting. Of such surfactants, the most particularly preferred is dodecylbenzenesulfonic acid (DDBSA). DDBSA is available under the trade name Calsoft LAS 99 from the Ashland Distribution Company (Santa Ana, Calif.), Or from the Pilot Chemical Company (Santa Fe Springs, Calif.). Such other surfactants include sodium dodecylbenzenesulfonate available from the Organic Division of Witco Corporation (New York, NY) under the name Witconate 1850, Stepan Company (Northfield, Ill.). An isopropylamine salt of branched alkylbenzene sulfonic acid available under the trade name Polystep A-11 and TEA dodecyl benzene sulfonate available under the trade name Norfox T-60 from Norman, Fox & Company, Vernon, Calif. Can be mentioned. The sulfonated anionic surfactant is used in an amount sufficient to achieve surface wetting and H ₂ O ₂ stabilization, which amount can vary depending on the overall composition of the adhesion promoter. . One preferred embodiment comprises at least about 0.0001% sulfonated anionic surfactant. As a general proposition, the concentration of the sulfonated anionic surfactant is at least about 0.005%, preferably at least about 0.1%, less than about 10%, preferably about 5%. Less than, more preferably less than about 2%. A specific example employs 0.002% of the surfactant, especially DDBSA.

Also, a preferred embodiment of the present invention employs a sulfated anionic surfactant. One preferred example of this compound has the formula _{C 4 H 9 CH (C 2} H 5) CH 2 SO 4 Na, 2-ethylhexyl sodium sulfate, also known as 2-ethylhexanol sodium sulfate. It is available from Niacet Corporation (Niagara Falls, NY) under the trade name Niaprof 08 and contains 38.5% to 40.5% sodium 2-ethylhexyl sulfate and balance water. Alternatives include sodium tetradecyl sulfate available under the trade name Niaprof 4 from Niacet, sodium lauryl sulfate available under the trade name Polystep B-5 from Stepan Company (Northfield, Ill.), And Henkel Corporation / Emery Group. , Cospha / CD (Ambler, Pa.), Sodium n-decyl sulfate available under the trade name Sulfotex 110. The addition of the sulfated anionic surfactant compound surprisingly makes it possible to increase the acidity without the expected detrimental effect of lightening the film. Since the acidity can be increased in this way, the copper content increases. It also contributes to darkening the film. In this embodiment, the compound is present in a concentration sufficient to increase the copper content without substantially lightening the coating. Typical concentrations are at least about 0.001%, preferably at least about 0.1%. The concentration of the sulfated anionic surfactant is about 10% or less, preferably about 5% or less. One preferred range is from about 0.05% to 2%. In one preferred embodiment, the concentration of sulfated anionic surfactant is about 0.5%. The other concentration is 0.15%.

In a preferred embodiment, the composition also includes a nonionic surfactant. Anionic surfactants and nonionic surfactants complement each other in the action of adhesion promoters and produce a conversion coating with the most advantageous properties that enhance the adhesion of the resin to the copper conductor. Anionic surfactants are effective in removing oily / greasy residues on the copper substrate and preventing their redeposition. However, anionic surfactants also include negatively charged heads that can be easily deactivated by water hardness (Ca ²⁺ and Mg ²⁺ ions), which hinders its cleaning efficiency. Optionally, auxiliaries can be used to maintain the effectiveness of the anionic surfactant by sequestering calcium and magnesium ions. However, non-ionic surfactants with no negative charge are not affected by calcium ions or magnesium ions, so the presence of the non-ionic surfactants can prevent oily residues even in hard water adhesion promoting compositions. Ensure removal.

  In any case, it has been discovered that the combination of an anionic surfactant and a nonionic surfactant in the adhesion promoter provides an unexpected additional benefit of improving peel strength. In one preferred embodiment, the surfactant is one or more ethoxylated nonylphenol, such as polyoxyethylene nonylphenol. Polyoxyethylene nonylphenol is available from Dow Chemical Company (Midland, MI) under the trade name Tergitol NP9. Alternatives include ethoxylated nonylphenol available under the trade name Tergitol NP8 from Dow Chemical Company (Midland, MI) and nonylphenoxypolyethoxyethanol available under the tradename Triton N from Union Carbide Corporation (Danbury, CT). And ethoxylated nonylphenol (or nonoxynol-2) available from Rhone-Poulenc's Surfactant & Specialty Division (NJ) under the name Igepal CO-210. The surfactant concentration is chosen to be sufficient to improve peel strength. One preferred embodiment comprises at least about 0.0001% ethoxylated phenol derivative. As a general proposition, the concentration is at least about 0.01%, preferably at least about 0.2%, less than about 10%, preferably less than about 5%. One preferred range is from about 0.0001% to about 2%. One exemplary embodiment includes 0.02%.

  It has been discovered that by incorporating certain alcohols that solubilize the BTA copper complex into the adhesion promoting composition, the copper content of the adhesion promoting composition can be increased. The alcohol may be monovalent or may be multivalent such as, for example, divalent (ie, diol), trivalent (ie, triol), tetravalent, or pentavalent. The alcohol may be at least one of a primary alcohol, a secondary alcohol, and a tertiary alcohol.

  Suitable aliphatic alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, pentanol, neopentanol, hexanol, cyclohexanol, furfuryl alcohol, and tetrahydrofurfuryl alcohol. And other monohydric alcohols. In general, because of the high temperature process conditions, high boiling alcohols, for example, above about 110 ° C., are preferred over low boiling alcohols.

  Suitable aliphatic saturated alcohols include, for example, diols such as ethylene glycol; propylene glycols such as propane-1,2-diol and propane-1,3-diol; butane-1,2-diol, butane-1,3. -Butylene glycols such as diol, butane-2,3-diol, butane-1,4-diol, and 2-methylpropane-1,3-diol; pentane-1,5-diol, pentane-1,4-diol Pentylene glycol such as pentane-1,3-diol and 2,2-dimethyl-1,3-propanediol; hexane-1,2-diol, hexane-1,4-diol, hexane-1,5- Diol, hexane-1,6-diol, 2-methylpentane-2,4-diol, and 1,2-cyclohexanediol Hexylene glycol; heptylene glycol such as 2-methyl-2-propylpropane-1,3-diol; 2-ethylhexane-1,3-diol, and 2,5-dimethylhexane-2,5-diol And dihydric alcohols such as nonanediol, decanediol, and dodecanediol. Derivatives of certain diols such as ethers such as methoxypropanol and methoxybutanol are also suitable.

  Suitable aliphatic saturated alcohols include triols such as glycerol, butanetriol and pentanetriol.

Oligomeric alcohols are those alcohols and alcohol derivatives, for example, ethers containing a plurality of repeating units of the following general formula:
In which R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are hydrogen or generally from 1 to about 6 carbon atoms, more typically 1 carbon atom. May be low molecular weight hydrocarbons having from ˜3, and more generally from 1 to 2 carbon atoms. Generally, the number of repeating units in the oligomer is small, for example from about 2 to about 12, more typically from about 2 to about 6, and more typically 2, 3 or 4. Suitable oligomeric alcohols include diethylene glycol, diethylene glycol methyl ether, diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, and dipropylene glycol.

  Also suitable are unsaturated diols such as acetylene alcohols such as butenediol, hexenediol, and butynediol. An example of a suitable trihydric alcohol is glycerol.

  In this embodiment, the additive is present in a concentration sufficient to increase the copper content of the composition. Generally, this concentration is at least about 0.01%, and in some embodiments at least about 0.5%. The concentration of this additive is about 20% or less, and in some embodiments about 10% or less.

  Preferred alcohols generally have a molecular weight of about 300 g / mol to 4000 g / mol, about 4000 g / mol, preferably about 80 g / mol, and about 76.09 g / mol of at least one of propylene glycol and oligomeric polypropylene glycol. Is mentioned. At least one of propylene glycol and oligomeric polypropylene glycol is at a concentration of about 0.1 wt% to about 5 wt%, more preferably about 0.2 wt% to about 1 wt%, such as about 0.5 wt%. Added. It has been discovered that incorporating at least one of propylene glycol and oligomeric polypropylene glycol into the adhesion promoting composition generally improves the peel strength between the copper conductive layer and the prepreg and improves the appearance of the organometallic conversion coating.

Another preferred alcohol that has proven particularly effective is oligomeric triethylene glycol (TEG). Specifically, the composition comprising this oligomer has a copper content of from about 30 g up to about 35 g, and even about 40 g / L, per liter of solution, in a dipping process application. In spray and immersion process applications, as well as in automated and conveyorized applications, these compositions have a copper content of up to about 45 g / L and even up to 50 g / L. This triethylene glycol is an oligomer in that it is a relatively intermediate molecular weight molecule having a structure containing minority units derived from a relatively low molecular weight molecule. This is in contrast to relatively high molecular weight polymers. This triethylene glycol is also significantly different in properties by removing one of its units, as opposed to polymeric compounds where removal of one or a few units has little effect on molecular properties. It is oligomeric. This triethylene glycol has the molecular formula C ₆ H ₁₄ O ₄ , more specifically has the formula HO (C ₂ H ₄ O) ₃ H, and has a molecular weight of 150.17. In this embodiment, triethylene glycol is present at a concentration of at least about 0.01%, generally at least about 0.5%, and in one embodiment at least about 0.8%. The concentration of TEG is about 20% or less, preferably about 10% or less. In a preferred embodiment, the concentration of TEG is about 1%. TEG also has the added benefit of contributing to the stabilization of H ₂ O ₂ .

The composition also optionally includes additional H ₂ O ₂ stabilizers. Suitable stabilizers include, for example, dipicolinic acid, glycolic acid and thioglycolic acid, ethylenediaminetetraacetic acid and its derivatives, magnesium salt of aminopolycarboxylic acid, sodium silicate, phosphate, phosphonate, and sulfonic acid Salt. Where the composition includes a stabilizer, preferably the stabilizer is present in an amount of 0.001% or more, and even at least 0.005% by weight of the adhesion promoting composition. Generally present in the composition at 1% by weight or less. Preferred compositions contain additional stabilizers but depend primarily on the stabilizing function of the TEG as described above.

The composition further includes a source of halide ions. This source is preferably HCl and provides a chloride ion concentration in the range of about 10 ppm to 100 ppm, preferably about 20 ppm to about 100 ppm, more preferably about 30 ppm to about 100 ppm. The unit “ppm” associated with aqueous compositions is on a mass to volume basis, and 1 ppm generally corresponds to 1 μg / mL or 1 mg / L. In one embodiment, the chloride ion concentration range is about 60 ppm to 65 ppm. In one embodiment, the chloride ion concentration range is about 65 ppm to 75 ppm. In one embodiment, the chloride ion concentration range is about 75 ppm to 85 ppm. In one embodiment, the chloride ion concentration range is about 85 ppm to 95 ppm. The preferred ranges will vary depending on the overall composition and application in other embodiments. It has been discovered that this increased Cl ⁻ level compared to the initial composition contributes to an increased ratio of cuprous to cupric, which increases the peel strength. The Cl ⁻ level gradually decreases and then stabilizes during use of the composition. Thus, an initial Cl ⁻ ion concentration of about 20 ppm to about 100 ppm is preferred in one embodiment to achieve a Cl ⁻ ion content on the order of about 20 ppm to 80 ppm in use.

  The adhesion promoting composition is prepared by mixing the components in an aqueous solution, preferably using deionized water. In accordance with standard safety practices, hydrogen peroxide is added to the composition in diluted form.

  In one form, the adhesion promoting composition is ready-to-use and can be used directly for substrate immersion or other exposure. In another form, the invention is a concentrate that is diluted to form a composition for immersion or other exposure.

Exemplary ready-to-use compositions include:
0.5 wt% to 8 wt.% _H 2 _{O 2}
16% to 25% by weight _H 2 SO ₄
0.1 wt% to 10 wt% of HNO ₃
0.1% to 2% by weight of 1,2,3-benzotriazole 0.01% to 5% by weight of triethylene glycol 0.05% to 2% by weight of 2-ethyloxosulfonate (Niaprof 08)
0.0001% to 2% by weight of dodecylbenzenesulfonic acid (DDBSA)
0.0001% to 2% by weight of polyoxyethylene nonylphenol (Tergitol NP9)
40% to 70% by weight of deionized water

When provided as a concentrate, the range mentioned above for the preferred proportions of the components is in principle doubled since the product is diluted, for example with 50% water, in the preparation of the composition used. In one embodiment, the concentrate has the following components:
32 wt% to 50 _wt.% Of _H 2 SO ₄
0.2 wt% to 20 wt% of HNO ₃
0.2% to 4% by weight of 1,2,3-benzotriazole 0.02% to 10% by weight of triethylene glycol 0.002% to 4% by weight of 2-ethyloxosulfonate (Niaprof 08)
0.0002% to 4% by weight of dodecylbenzenesulfonic acid (DDBSA)
0.0002% to 4% by weight of polyoxyethylene nonylphenol (Tergitol NP9)

H ₂ O ₂ is added later and is not included in the concentrated composition. This concentrate is later incorporated into the overall solution, for example, about 43% by weight of this concentrate, 7% by weight H ₂ O ₂ and about 50% by weight water.

As noted above, various preferred embodiments of adhesion promoting compositions also include transition metal ions, but it has been found that it is important to selectively select the transition metal ions of the composition. Many types of transition metal ions, adversely affect the stability of the peroxide component of the composition, or to facilitate the example H _2, O 2, _NOx and release of significant volumes of harmful gas and SOx, etc., or May be both. However, other transition metal ions do not have a significant adverse effect on the stability of the peroxide and do not generate significant volumes of toxic gases, and the thermal stability of the conversion coating formed in the adhesion promotion step of the process. Can contribute to sex.

  Preferred transition metal ions to be included in the adhesion promoting solution include zinc, nickel, copper, cobalt, silver, gold, palladium, and other platinum group metals. Transition metal ions are preferably incorporated into the adhesion promoting composition in the form of their salts. Thus, suitable adhesion promoters include cation forms of zinc, nickel, copper, cobalt, silver, gold, palladium or other platinum group metals, as well as counter-anions derived from salts, which are used as transition metal ions. Function. More preferably, the transition metal ion comprises Zn, Ni, Co, Ag, Au, Pd or other platinum group metals, more preferably comprises Zn, Ni, Co or Ag, or comprises Zn, Ni or Co. . Preferably, the transition metal is introduced in the form of sulfate, chloride, bromide, iodide, phosphate, or various carboxylates such as malate and oxalate. For example, complex salts such as zinc ammonium halide can also be used. Preferably, the adhesion promoting liquid comprises a transition metal ion at a concentration of about 0.02% to about 2% by weight, a nitrogen-containing corrosion inhibitor at a concentration of about 0.1% to about 5% by weight, and about 10%. Sulfuric acid at a concentration of from wt% to about 50 wt% and hydrogen peroxide at a concentration of from about 1 wt% to about 10 wt%. More preferably, the composition comprises one or more anionic surfactants at a concentration of about 0.01% to 1% by weight and an alcohol at a concentration of about 0.1% to 3% by weight. Including. Even more preferably, the composition further comprises one or more nonionic surfactants at a concentration of about 0.0005% to about 0.2% by weight. In each of these various embodiments, it is preferred that the composition further comprises nitric acid at a concentration of about 0.5 wt% to about 15 wt%.

Most preferably, the transition metal ion component of the adhesion promoting liquid comprises zinc ions. A particularly preferred source of zinc ions is ZnSO ₄ .

In a particularly preferred embodiment, the adhesion promoting composition is
20% to 35% by weight sulfuric acid;
2% to 8% by weight of nitric acid;
4% to 12% by weight of hydrogen peroxide;
0.2% to 3% by weight of benzotriazole (Cobratec 99);
0.05 wt% to 0.5 wt% zinc sulfate;
0.2% to 2% by weight of triethylene glycol;
0.02-wt% to 0.5wt% sodium 2-ethylhexyl sulfate sold under the trade name Niaprof08;
0.0005% to 0.01% by weight of sodium dodecylbenzenesulfonate sold under the name Calsoft Las 99;
0.0005% to 0.01% by weight of polyoxyethylene nonylphenol sold under the trade name Tergitol NP9;
Generally 45% to 70% by weight of balanced deionized water;
including.

  The contact of the copper surface with the adhesion promoting composition is generally at a temperature of about 20 ° C. to about 40 ° C., but can operate at temperatures outside this reasonable range. The contact time is generally 1 second or longer, preferably 5 seconds or longer, often at least 10 seconds, and most preferably at least 30 seconds. The maximum contact time can be up to 10 minutes, but the contact time is preferably 5 minutes or less, and most preferably 2 minutes or less. Contact times of about 1 minute or less than 1 minute are standard. If the contact time of the adhesion promoting composition with the copper surface is too long, the copper surface is etched away by dissolution, or microporous crystalline precipitates that form a fine roughened surface are present on the surface of the conductive material. There is a risk of precipitation or both.

  Next, the adhesion promoting liquid composition of the copper conductive layer having an organometallic conversion coating thereon is generally rinsed in warm water (tap water or deionized water) for 10 seconds to 120 seconds. Preferably the rinse water is deionized water to allow good process control. The rinse water is preferably drained for 10 to 30 seconds and then the surface is dried.

  After the copper surface is contacted with the adhesion promoting composition to form a finely roughened surface, the prepreg layer is generally placed directly adjacent to the copper surface, and the prepreg layer is directly bonded to the copper surface in the bonding process. A multilayer PCB is formed.

  Suitable base material materials for printed circuit boards include, for example, high pressure laminates (ie, layers of fiber material bonded together with a thermosetting resin under heat and pressure). Generally, the laminate layer comprises electrical material grade paper bonded with phenolic resin or epoxy resin, or continuous filament glass cloth bonded with epoxy resin system. As a specific example of the laminate layer, XXXPC which is an electrical insulating paper impregnated with a phenol resin; FR-2 which is similar to XXXPC and has flame retardancy; FR which is a self-extinguishing laminate of an electrical insulating paper and an epoxy resin -3; G-10 which is a laminate of glass cloth sheet and epoxy resin; FR-4 which is a self-extinguishing laminate similar to G-10; G-11 which is a glass cloth and epoxy mixture; and G-11 It is FR-5 which is a flame retardant type. In one embodiment of the present invention, the organic circuit board material is an FR-4 laminate layer that is placed in intimate contact over the passive component pattern and the two are laminated together.

  Generally, in the bonding process, heat and pressure are applied to initiate the bonding reaction. The mechanical bond in the bonding process is due to the penetration of the polymer material of the insulating layer into the micro-roughened surface provided in the adhesion promotion process. Although it may be desirable to perform a specially constructed rinse step following the adhesion promotion step, in many cases it is sufficient to rinse with water.

  The prepreg insulating layer is applied directly to the finely roughened surface, i.e. preferably without any intermediate metal deposits, etc. on the finely roughened surface, but if necessary, U.S. Pat. No. 6,294,220. Applied after treatment of copper oxide removal or reduction operation to further enhance bond strength as disclosed in. Pressure is applied by placing the layers forming the PCB multilayer stack in a press. When pressure is applied, the pressure is generally from 100 psi to 400 psi, preferably from 150 psi to 300 psi. The temperature for this bonding process is generally at least about 100 ° C, preferably from about 120 ° C to about 200 ° C. The bonding process is generally performed at any time from 5 minutes to 3 hours, and most usually from 20 minutes to 1 hour, but good adhesion between the first layer and the second layer is achieved. It is carried out for a time and pressure sufficient to guarantee and at a sufficiently high temperature. During this bonding process, the polymer material of the insulating layer, typically an epoxy resin, tends to flow, ensuring that the conductive pattern in the metal is substantially encapsulated between the insulating layers and avoiding subsequent water and air ingress. To do. The MLB may be formed by arranging a plurality of layers in the bonding step and laminating the plurality of layers in a single step.

  The exemplary arrangement discussed in detail herein is a prepreg layer adhered to a copper surface, but the present invention also applies to other dielectric materials to copper, whether it is permanent or temporary. Includes improved adhesion. For example, the present invention improves the adhesion between copper and a dielectric solder mask. The present invention also improves copper adhesion to inks, polymeric photoresists, and dry films. The present invention also has applications related to photoimageable dielectrics or other dielectrics used in the context of high density interconnect and sequential build-up techniques.

  Having described the invention in detail, it will be apparent that modifications and variations are possible without departing from the scope of the invention as defined in the appended claims.

  The following non-limiting examples are provided to further illustrate the present invention.

Example 1: Control Adhesion Promotion Process A multiple adhesion promotion process was performed on copper specimens using commercially available microetch solutions, cleaning agents, and adhesion promotion compositions. These processes, designated A0S, were control processes and were performed to provide comparative data of peel strength, conversion coating appearance, and number of solder immersion cycles for delamination.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. By immersing or spraying the copper piece with the microetching liquid composition at a solution temperature of 27 ° C. ± 3 ° C. for 30 seconds to 45 seconds, the surface of the copper piece is microetched liquid Enthone (registered trademark) PC-7077 (concentration 40 % To 60%, available from Enthone Inc.). PC-7077 is a conventional microetching solution containing sodium persulfate, sodium phenol sulfate, and sulfuric acid.
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. By immersing or spraying the copper pieces with an alkaline cleaning composition at a solution temperature of 43 ° C. ± 6 ° C. for 60 seconds to 120 seconds, the etching surface of the copper pieces is washed with an alkaline cleaner / conditioner Enthone (registered trademark) PC- 7096 (concentration 10% to 15%, available from Enthone Inc.).
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.
5. The cleaned and etched surfaces of the three copper pieces are dipped or sprayed with the adhesion promoting composition to obtain the adhesion promoting composition AlphaPREP® PC-7030 (100% concentration, available from Enthone Inc.). ). One set of copper pieces was contacted with AlphaPREP® PC-7030 for 45 seconds. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 1 minute. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 2 minutes. The solution temperature was 43 ° C. ± 6 ° C. The components and concentrations contained in the adhesion promoting composition were as follows.
6). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
7. Optionally, the copper pieces are air dried at ambient temperature or up to about 35 ° C to 40 ° C for 30 seconds to 5 minutes.

  The copper pieces treated in this way were examined for film appearance and defects prior to lamination to a standard FR4 prepreg laminate such as Isola FR370HR (high performance FR-4 material).

Example 2: Control Adhesion Promotion Process A multiple adhesion promotion process was performed on copper specimens using commercially available microetch solutions, cleaning agents, and adhesion promotion compositions. These processes, designated A0, were control processes and were performed to provide comparative data of peel strength, conversion coating appearance, and number of solder immersion cycles for delamination. The A0 control process was performed in the same manner as the A0S control process of Example 1 except that the chloride ion concentration of the adhesion promoting composition was increased from about 85 ppm to about 95 ppm.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. By immersing or spraying the copper pieces with the micro-etching liquid composition at a solution temperature of 27 ° C. ± 3 ° C. for 30 seconds to 45 seconds, the surfaces of the three copper pieces were microetched liquid Enthone (registered trademark) PC-7077 ( 40% to 60% concentration, available from Enthone Inc.).
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. By immersing or spraying the copper pieces with an alkaline cleaning composition at a solution temperature of 43 ° C. ± 6 ° C. for 60 seconds, the etching surface of the three copper pieces was made into the alkaline cleaning agent Enthone® PC-7096 (concentration 10). % -15%, available from Enthone Inc.).
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.
5. The cleaned and etched surfaces of the three copper pieces are dipped or sprayed with the adhesion promoting composition to obtain the adhesion promoting composition AlphaPREP® PC-7030 (100% concentration, available from Enthone Inc.). ). One set of copper pieces was contacted with AlphaPREP® PC-7030 for 45 seconds. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 1 minute. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 2 minutes. The solution temperature was 43 ° C. ± 6 ° C. The components and concentrations contained in the adhesion promoting composition were as follows.
PC-7030M (including MPG (monopropylene glycol)):
PC-7030M-1 (without MPG (monopropylene glycol)):
Although not used in this example, the following composition gives equivalent results.
Monopropylene glycol is preferably included to inhibit premature sludge formation in the adhesion promoting composition bath.
6). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
7. Optionally, the copper pieces are air dried at ambient temperature or up to about 35 ° C to 40 ° C for 30 seconds to 5 minutes.

  The copper pieces treated in this manner were examined for film appearance and defects prior to lamination to at least one of a standard phenol-filled prepreg laminate, a halogen-free prepreg laminate, and a polyimide prepreg laminate. Useful phenol-filled dielectrics include those sold under the trade names Isola 370H, Isola FR408HR, and Isola IS410. Useful halogen-free high glass transition temperature dielectrics include DE 156 and DE 155, and useful polyimides include Isola P95 and Isola P96.

Example 3: A novel preparation step followed by an adhesion promotion process A multiple adhesion promotion process was performed on copper specimens using commercially available micro-etch solutions, cleaning agents, and adhesion promotion compositions. These processes, designated A1, were control processes and were performed to provide comparative data for peel strength, conversion coating appearance, and number of solder immersion cycles for delamination. The A1 control process was performed in the same manner as the A0 control process of Example 2, except that the copper pieces were contacted with the pre-soaked composition prior to contact with the adhesion promoting composition.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. By immersing or spraying the copper pieces with the micro-etching liquid composition at a solution temperature of 27 ° C. ± 3 ° C. for 30 seconds to 45 seconds, the surfaces of the three copper pieces were microetched liquid Enthone (registered trademark) PC-7077 ( 40% to 60% concentration, available from Enthone Inc.).
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. By immersing or spraying the copper pieces with an alkaline cleaning composition at a solution temperature of 43 ° C. ± 6 ° C. for 60 seconds, the etched surface of the three copper pieces is made into a novel alkaline cleaning agent / conditioner Enthone® ( SAM8-R1; concentration 10% -15%). SAM8-R-1 has the following composition.
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
5. The cleaned and etched surface of the copper strip is contacted with a pre-soak composition containing sodium bicarbonate (Na ₂ CO ₃ .H ₂ O, 30 g / L) for 60 seconds at a solution temperature of 43 ° C. ± 6 ° C.
6). Rinse the copper pieces with warm deionized water for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.
7. The cleaned and etched surfaces of the three copper pieces are dipped or sprayed with the adhesion promoting composition to obtain the adhesion promoting composition AlphaPREP® PC-7030 (100% concentration, available from Enthone Inc.). ). One set of copper pieces was contacted with AlphaPREP® PC-7030M-1 for 45 seconds. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 1 minute. One set of copper pieces was contacted with AlphaPREP® PC-7030M for 2 minutes. The solution temperature was 43 ° C. ± 6 ° C. The components and concentrations contained in the adhesion promoting composition were as follows.
8). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
9. Optionally, the copper pieces are air dried at ambient temperature or up to about 35 ° C to 40 ° C for 30 seconds to 5 minutes.

  Copper pieces treated in this manner were examined for film appearance and defects prior to lamination to standard epoxy or novolac resins.

Example 4: Adhesion Promotion Process with 6-Benzylaminopurine Preparation Step A multiple adhesion promotion process was performed on copper specimens. These processes, designated A3, were performed according to the method of the present invention. In these processes, copper pieces were pre-soaked in a composition containing molecules capable of forming a self-assembled monolayer on the copper surface. Further, the adhesion promoting composition was further changed with polypropylene glycol.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. By immersing or spraying with the microetching liquid composition at a solution temperature of 27 ° C. ± 3 ° C. for 30 seconds to 45 seconds, or both of the copper pieces, the surfaces of the three copper pieces are microetching liquid Enthone. Contact with PC-7077 (concentration 40% -60%, available from Enthone Inc.).
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. The etched surface of the three copper pieces was immersed in or sprayed with an alkaline cleaning composition at a solution temperature of 43 ° C. ± 6 ° C. for 60 seconds to make the etched surface of the three copper pieces alkaline cleaning agent Enthone® PC-7096 (concentration) 10% to 15%, available from Enthone Inc.).
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
5. The cleaned and etched surface of the copper strip is contacted with a pre-soak composition containing 6-benzylaminopurine (5 g / L, available from KingChem or Aldrich Chemicals) at a solution temperature of 43 ° C. ± 6 ° C. for 60 seconds.
6). Rinse the copper pieces with warm deionized water for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.
7. Adding polypropylene glycol or propylene glycol (0.5 wt% to 1.0 wt%) to the cleaned and etched surface of the three copper pieces by dipping or spraying the copper pieces with an adhesion promoting composition. Contact with the adhesion promoting composition AlphaPREPM® PC-7030M (concentration 100%, available from Enthone Inc.). One set of copper pieces was contacted with AlphaPREP® PC-7030 for 45 seconds. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 1 minute. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 2 minutes. The solution temperature was 43 ° C. ± 6 ° C. The components and concentrations contained in the adhesion promoting composition were as follows.
8). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
9. Optionally, the copper pieces are air dried at ambient temperature or up to about 35 ° C to 40 ° C for 30 seconds to 5 minutes.

  Copper strips treated in this manner were inspected for film appearance and defects prior to lamination to standard FR4 prepreg laminates available under the trade names Isola FR4, Panasonic 155 plus, Nanya 170, or Nanya 175. .

Example 5: Adhesion promotion process using 6-benzylaminopurine preparation A multiple adhesion promotion process was performed on copper specimens. These processes, designated A6, were performed according to the method of the present invention. In these processes, copper pieces were pre-soaked in a composition containing molecules capable of forming a self-assembled monolayer on the copper surface. The adhesion promoting composition was further changed with methanesulfonic acid.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. While maintaining the solution temperature at 27 ° C. ± 3 ° C., the surface of the three copper pieces is immersed in the micro-etching solution Enthone (30 to 45 seconds) by dipping and / or spraying with the micro-etching composition. Contacted with PC-7077 (concentration 40% -60%, available from Enthone Inc.).
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. By dipping and / or spraying with an alkaline detergent / conditioner composition for 60 seconds at a solution temperature of 43 ° C. ± 6 ° C. on a copper piece, the etching surface of the three copper pieces is washed with an alkaline detergent. Contact with Enthone® SAM8-R1 (concentration 10% to 15%, available from Enthone Inc.).
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
5. The cleaned and etched surface of the copper strip is contacted with a pre-soak composition containing 6-benzylaminopurine (5 g / L, available from KingChem or Aldrich Chemical) for 60 seconds at a solution temperature of 43 ° C. ± 6 ° C.
6). Rinse the copper pieces with warm deionized water for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.
7. By dipping or spraying the copper pieces with the adhesion promoting composition, the cleaned and etched surfaces of the three copper pieces are treated with methanesulfonic acid (2 wt%) so that the solution contains nitric acid, sulfuric acid, and methanesulfonic acid. In contact with a modified adhesion promoting composition AlphaPREPM® PC-7030 (100% concentration, available from Enthone Inc.). One set of copper pieces was contacted with AlphaPREP® PC-7030 for 45 seconds. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 1 minute. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 2 minutes. The solution temperature was 43 ° C. ± 6 ° C. The components and concentrations contained in the adhesion promoting composition were as follows.
8). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
9. Optionally, the copper pieces are air dried at ambient temperature or up to about 35 ° C to 40 ° C for 30 seconds to 5 minutes.

  Copper pieces treated in this manner were examined for film appearance and defects prior to lamination to standard FR4 prepreg laminates available under the trade names Isola 370FR, Isola FR408HR, or Isola Is410.

Example 6: Adhesion promotion process A multiple adhesion promotion process was performed on copper specimens. These processes, designated A7, were performed according to the method of the present invention. In these processes, copper pieces were pre-soaked in a composition containing molecules capable of forming a self-assembled monolayer on the copper surface. The adhesion promoting composition was further changed with methanesulfonic acid and polypropylene glycol.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. By immersing or spraying with the microetching liquid composition at a solution temperature of 27 ° C. ± 3 ° C. for 30 seconds to 45 seconds, or both of the copper pieces, the surfaces of the three copper pieces are microetching liquid Enthone. Contact with PC-7077 (concentration 40% -60%, available from Enthone Inc.).
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. By immersing or spraying with an alkaline detergent composition for 60 seconds at a solution temperature of 43 ° C. ± 6 ° C., or both of the copper pieces, the etched surface of the three copper pieces is made into an alkaline detergent Enthone (registered) (Trademark) PC-7096 (concentration 10%-15%, available from Enthone Inc.).
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
5. The cleaned and etched surface of the copper strip is contacted with a presoak composition containing 6-benzylaminopurine (available from 5 g / L, KingChem or Aldrich) for 60 seconds at a solution temperature of 43 ° C. ± 6 ° C.
6). Rinse the copper pieces with warm deionized water for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.
7. Add the cleaned and etched surfaces of the three copper pieces to polypropylene glycol (0.5 wt-1.0 wt%) with an average molecular weight of 76.1 g / mol available from KingChem or Aldrich Chemical. And the adhesion promoting composition AlphaPREPM® PC modified by adding methanesulfonic acid (2% by weight), available from Huntsman Corporation, so that the solution contains sulfuric acid, nitric acid and methanesulfonic acid. Contact with -7030 (100% concentration, available from Enthone Inc.). The copper pieces were then dipped and / or sprayed with the adhesion promoting composition. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 45 seconds. One set of copper pieces was contacted with AlphaPREP® PC-7030M for 1 minute. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 2 minutes. The solution temperature was 43 ° C. ± 6 ° C. The components and concentrations contained in the adhesion promoting composition were as follows.
8). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
9. Optionally, the copper pieces are air dried at ambient temperature or up to about 35 ° C to 40 ° C for 30 seconds to 5 minutes.

  The copper pieces treated in this manner were inspected for appearance and defects in the coating prior to lamination to a standard FR4 prepreg laminate.

Example 7: Adhesion Promotion Process of the Invention A multiple adhesion promotion process was performed on copper specimens. These processes, designated A8, were performed according to the method of the present invention. In these processes, the copper pieces were cleaned in an alkaline cleaner composition further comprising molecules capable of forming a self-assembled monolayer on the copper surface. The adhesion promoting composition was further changed with methanesulfonic acid and polypropylene glycol.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. In either case, the surface of the three copper pieces is microetched by spraying with the microetching liquid composition at a solution temperature of 27 ° C. ± 3 ° C. for 30 seconds to 45 seconds or by immersing the copper pieces in the solution. Contact with liquid Enthone (R) PC-7077 (concentration 40% -60%, available from Enthone Inc.).
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. In any case, at a solution temperature of 43 ° C. ± 6 ° C., the copper piece was immersed in an alkaline detergent composition for 60 seconds, or by spraying the copper piece with the alkaline detergent composition, The etched surface is contacted with an alkaline detergent Enthone® SAM8-R1 (concentration 10% -15%, available from Enthone Inc.) further comprising 6-benzylaminopurine (5 g / L).
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.
5. The cleaned and etched surface of the three copper pieces was modified by adding polypropylene glycol (0.5 wt%) with a molecular weight of 76.1 g / mol and methanesulfonic acid (2 wt%) added The solution is then contacted with an adhesion promoting composition AlphaPREPM® PC-7030 (100% concentration, available from Enthone Inc.) that has been modified to include nitric acid, sulfuric acid, and methanesulfonic acid. Contact was made by dipping or spraying or both. One set of copper pieces was contacted with AlphaPREP® PC-7030M for 45 seconds. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 1 minute. One set of copper pieces was contacted with AlphaPREP® PC-7030 for 2 minutes. The solution temperature was 43 ° C. ± 6 ° C. The components and concentrations contained in the adhesion promoting composition were as follows.
6). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
7. Optionally, the copper pieces are air dried at ambient temperature or up to about 35 ° C to 40 ° C for 30 seconds to 5 minutes.

  The copper pieces treated in this manner were inspected for appearance and defects in the coating prior to lamination to a standard FR4 prepreg laminate.

Examples 8-14: Adhesion Promotion Process A multiple adhesion promotion process named B0S, B0, B1, B3, B6, B7, and B8 was performed on the copper specimens. Adhesion promotion processes B0S, B0, B1, B3, B6, B7 and B8 are used to simulate an operational adhesion promotion process in which the adhesion promotion composition accumulates substantial copper ion concentrations. , B3, B6, B7 and B8, respectively, except that 30 g / L of copper ions were blended in the adhesion promoting composition, the same as processes A0S, A0, A1, A3, A6, A7 and A8.

Example 15: Lamination process Copper strips treated as described in Examples 1-14 according to the following procedure are available under the trade names Isola 370HR, Isola IS410, Nanya 170, Nanya 175, or Panasonic R1551. Laminate at 188 ° C. on various types of standard FR4 prepreg laminates.
1. One side of the copper strip and one side of the prepreg were each coated with DuPont (TM) Tedlar (R) PVF film.
2. The copper strip and the uncoated side of the opposite side of the prepreg were placed in contact with each other.
3. The sides coated with Tedlar® were then brought into contact with the platen and compressed together on a hydraulic press at about 765 kPa (about 111 PSI) for 5 minutes.
4). The pressure was increased to 1436 kPa (about 208.33 PSI) for 10 minutes.
5. The pressure was increased to 1917 kPa (about 211 PSI) for 60 minutes.
6). The pressure was reduced to 1436 kPa (about 208.33 PSI) for 5 minutes.

  Next, a solder pot immersion test and a peel strength test were performed on the prepreg coated with the copper piece.

  The solder pot immersion test is performed by dropping a part of a copper laminated prepreg into molten solder at a temperature of 260 ° C. at a cycle of 10 seconds. The number of cycles until delamination is recorded.

  Peel strength is measured using an Instron 4442 instrument (ASTM standard). Peel strength is performed on five samples.

  Furthermore, the etching rate of copper in the adhesion promoting composition was measured by measuring the copper ion concentration in the adhesion promoting composition.

The experimental results are summarized in Tables 1 to 3 below.
(Table 1: Experimental data of copper pieces treated in adhesion promoting composition for 2 minutes)
(Table 2: Experimental data of copper pieces treated in adhesion promoting composition for 1 minute)
(Table 3: Experimental data of copper pieces treated in adhesion promoting composition for 45 seconds)

  “Appearance” in the above table is a qualitative visual measurement of the appearance of the organometallic conversion coating. A rating of 5 means that the film was an excellent dark brown color that the industry associates with a strong adhesive film. A rating of 4 means that the film was good and uniform dark reddish brown. Rating 3 means that the film was reasonably uniform and inferior to ratings 4 or 5, but was still dark brown. Evaluation 1 or evaluation 2 means that the film was uneven and the dark reddish brown was uneven.

  As shown in Tables 1 to 3, the results of various adhesion promotion processes result in adhesion promotion in addition to pre-soaking in compositions containing molecules capable of forming self-assembled monolayers on the copper surface. It has been shown that the incorporation of propylene glycol or polypropylene glycol into the composition improves the overall performance of the adhesion process. Advantageous results achieved include improved appearance of the organometallic conversion coating, increased peel strength, and increased number of solder immersion cycles prior to delamination. In some respects, the adhesion promotion process was improved when a composition having a significant copper content was employed. Therefore, to conclude that the adhesion promoting composition can be used to extend the duration when copper pieces are pre-soaked in a composition containing molecules capable of forming a self-assembled monolayer. Can do.

Example 16: Adhesion Promotion Process A multiple adhesion promotion process was performed on copper specimens. These processes were performed according to the method of the present invention. In these processes, copper pieces were pre-soaked in a composition containing molecules capable of forming a self-assembled monolayer on the copper surface. Further, the adhesion promoting composition was further changed with polypropylene glycol.

The adhesion promotion process was performed on three sets of 1 inch (25.4 mm) × 2 inch (50.8 mm) copper pieces according to the following procedure.
1. By immersing or spraying with the microetching liquid composition at a solution temperature of 27 ° C. ± 3 ° C. for 30 seconds to 45 seconds, or both of the copper pieces, the surfaces of the three copper pieces are microetching liquid Enthone. Contact with PC-7077 (concentration 40% -60%, available from Enthone Inc.).
2. Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
3. The etched surface of the three copper pieces was immersed in or sprayed with an alkaline cleaning composition at a solution temperature of 43 ° C. ± 6 ° C. for 60 seconds to make the etched surface of the three copper pieces alkaline cleaning agent Enthone® PC-7096 (concentration) 10% to 15%, available from Enthone Inc.).
4). Rinse the copper pieces with warm water (tap water or deionized water) for 30 seconds.
5. The cleaned and etched surface of the copper strip is contacted with a presoak composition having the following composition.
The cleaned and etched copper pieces were brought into contact with this adjusting solution for 60 seconds at a solution temperature of 43 ° C. ± 6 ° C.
6). Rinse the copper pieces with warm deionized water for 30 seconds. Water was drained from the copper strip for 10 to 20 seconds to avoid unnecessary dilution of the adhesion promoting composition.

The cleaned and etched surface of the three copper pieces is contacted with an adhesion promoting composition (specific gravity 1.13) having the following composition:

  The solution temperature at the time of contact with the copper piece of the adhesion promoting liquid was 43 ° C. ± 6 ° C. In repeated operations using this adhesion promoting bath, the copper content exceeded 40 g / L. After lamination in the manner as described herein above, the high Tg phenol cured laminate achieved a peel strength of 690 N / m and withstood 10 IR reflows without peeling. The Panasonic 1551 halogen-free laminate achieved an initial peel strength of 835 N / m, which maintained 755 N / m after 10 IR reflows. The Nanya NPG 170 halogen-free laminate achieved an initial peel strength of 733 N / m, which increased to 784 N / m after 10 IR reflows. The ISOLA 370 laminate achieved an initial peel strength of 835 N / m to 890 N / m, which maintained 770 N / m to 850 N / m after 10 IR reflows.

Example 17: Testing at various copper levels A number of adhesion promotion tests were performed on copper pieces according to the method of the present invention.

  The copper pieces are micro-etched, rinsed, washed and rinsed again as described above, then at 43 ° ± 6 ° C. for 60 seconds or 120 seconds, two different ones of either Conditioner # 1 or Conditioner # 2. It was immersed in one side of the preparation liquid. Conditioner # 1 contains 6-benzylaminopurine and generally corresponds to the composition shown for the conditioner used in Example 3 above. Regulator # 2 contains 6-benzylaminopurine and Zinplex and generally corresponds to the regulator composition used in Example 16. Thereafter, the copper piece was rinsed, drained, and contacted with the adhesion promoting composition.

  A control group (Experiment # 7) was prepared using only the standard alkaline cleaning solution and then performed using the adhesion promoter of Example 16.

  After the treatment with the adhesion promoting liquid, the copper piece was generally laminated on the dielectric material by the above method. In some cases, lamination was done after 10 IR reflows, and in other cases, lamination was done before reflowing.

After the lamination process, the peel strength test was performed on the laminated composite material as described above. The results of the peel strength of the copper pieces laminated before reflow are shown in Table 5, and the results of the copper pieces laminated after reflow are shown in Table 6.
(Table 5: Lamination before 10 reflows—ISOLA 370HR peel strength)
(Table 6: After 10 IR reflows-ISOLA370HR peel strength)

  Due to the presence of polyglycol WL-5000 containing 0.1% by weight of butylated hydroxytoluene in the adhesion promoting solution, the adhesion promoting composition of Experiment # 6 gave poor results both before and after reflow. It was. The presence of these components has been found to have a significant adverse effect on peel strength.

  However, either (1) Preparation Agent # 1 (Experiment # 3, Experiment # 5, Experiment # 8) or (2) Modifier # 2 (Experiment # 1 to Experiment # 5, Experiment # 8, Experiment # 9) All of the remaining experiments using k gave substantially superior results to the control group (experiment # 7). In experiments using both modifier # 2 and the adhesion promoter of Example 16 containing Zn ions, a further increase in peel strength was obtained (experiment # 4).

Example 18
In order to simulate a commercial operation where the conditioning liquid and adhesion promoter are subjected to contact with a series of different copper substrates in repeated cycles of conditioning, adhesion promotion and lamination operations, Experimental operation was performed. Copper was added at a rate that reflects the actual accumulation of copper ions in the adhesion promoter during commercial operation where each of the two treatment compositions is contacted with the copper substrate in repeated cycles. The adjustment process in each operation was performed using an adjustment liquid having a composition of the adjustment agent # 2. The treatment conditions with the adjusting agent and the adhesion promoting liquid were those described in Example 17.

  In the test run of this example, 1 g / L, 5 g / L, or 10 g / L of copper was added to the adhesion promoter. The treated copper pieces were then laminated to a dielectric material at either 15.5 bar or 24.1 bar, and the resulting laminate composite material was tested for peel strength.

  The average peel strength of the composite material containing three different dielectrics is shown in FIG. 1 for the laminate made at 15.5 bar and in FIG. 2 for the laminate made at 24.1 bar.

Example 19
Another series of tests was conducted substantially as described in Example 18.

  In this experiment, three different dielectric materials were used: Isola 370R, Isola 408HR, and Isola IS410. For each combination of modifier and adhesion promoter, individual lamination experiments were conducted at a lamination pressure of either 15.5 bar or 24.1 bar. The peel strength test was performed both before and after reflow.

  The average peel strength of a composite material containing three different dielectrics is shown in FIG. 3 for a laminate made at 15.5 bar and tested before reflow, and for a laminate made at 24.1 bar and tested before reflow The laminate shown in FIG. 4 and produced at 15.5 bar and tested after reflow is shown in FIG. 5, and the laminate produced at 24.1 bar and tested after reflow is shown in FIG.

Example 20
In one series of tests, Example 19 was used except that 1 g / L of Conditioner # 2 was included in the adhesion promotion liquid and the other series of tests used the adhesion promotion liquid of Example 16 without impurities. Another series of tests was performed as described in.

  For the laminate after treatment with the adhesion promoting liquid of Example 16 where the average peel strength of the composite material containing three different dielectrics was made at 15.5 bar and 24.1 bar, respectively, and no modifier # 2 was added 7 and FIG. 8, the laminates prepared at 15.5 bar and 24.1 bar, respectively, and treated with an adhesion promoter containing ˜1 g / L of modifier # 2 are shown in FIGS. 9 and 10. It was shown to.

Example 21
Another series of tests was generally performed as described in Example 17. As five different substrates, 370HR, 408HR, IS410, Pan R-1556, and Nanya NPG 170 LT were used. The adhesion promoting liquid contains copper ions with a concentration of 5 g / L, and contains a regulator # 2 in a proportion in the range of 0 g / L to 10 g / L. Lamination was performed at a pressure of 15.5 bar.

  The average peel strength obtained is shown in FIG.

Example 22
Except for an adhesion promoter containing substantially wide range and high concentrations, ie, 0 g / L, 1 g / L, 10 g / L, 40 g / L, and 50 g / L of copper ions, substantially as described in Example 18. Two further series of tests were conducted in the manner described above. Each operation was performed using the adhesion promoting liquid of Example 16 following the conditioner # 2. The adhesion promoting liquid did not contain any adjusting agent.

  The peel test results of this example are shown as bar graphs in FIGS.

Example 23
Further tests were generally performed as described in Example 18. The adhesion promoting liquid of Example 16 was used following the conditioner # 2. Both the modifier and the adhesion promoting liquid contain copper ions at a concentration of 40 g / L. The dwell time between application of the modifier and application of the adhesion promoter was varied.

  The peel test result of this example is shown in a bar graph in FIG. “Hang time” refers to the time required to remove most of the water film adhering to the copper strip after treatment with the modifier. “Cool dry” refers to the cooling drying time following removal of the water film.

Example 24
Except that the copper ion concentration in the adhesion promoting composition was 10 g / L and only the dielectric substrates 370HR, 408HR, and 410HR were tested, additional experimental experiments were generally performed as described in Example 21. Drove.

  The results of peel strength are shown in FIGS.

  In view of the above, it will be seen that the several objects of the invention are achieved and other advantageous results are obtained.

  When introducing an element of the present invention, or a preferred embodiment thereof, the articles “a”, “an”, “the” and “said” have one or more elements Intended to mean existing. The terms “comprising”, “including”, and “having” are intended to be inclusive and mean that there may be additional elements other than the listed elements. .

  Since various modifications can be made in the above compositions and processes without departing from the scope of the present invention, all contents contained in the above description and shown in the accompanying drawings are exemplary. And should not be construed as limiting.

Claims (37)

A method for enhancing adhesion between a copper conductive layer and a dielectric material during the manufacture of a printed circuit board,
Contacting the copper conductive layer with a conditioning composition, the conditioning composition comprising a functional organic compound and a transition metal ion, wherein the functional organic compound is a self-assembled monomolecule on a copper surface. A step capable of forming a layer;
Thereafter, contacting the copper conductive layer with an adhesion promoting composition comprising an oxidant, an inorganic acid, and a corrosion inhibitor;
A method comprising the steps of:   The method of claim 1, wherein the transition metal ion is selected from the group consisting of zinc, nickel, cobalt, copper, silver, gold, palladium, and other platinum group metals.   The method of claim 2, wherein the transition metal is selected from the group consisting of zinc, nickel, cobalt, silver, gold, palladium, and other platinum group metals.   The method of claim 2, wherein the transition metal ion comprises zinc. The method of claim 4, wherein Zn is present in the conditioning composition in the form of Zn ²⁺ , Zn ²⁺ / ammonia complex, zinc oxide, ZnO ₂ ²⁻ , or combinations thereof.   The method according to any one of claims 1 to 5, further comprising a counter anion selected from the group consisting of chloride, iodide, bromide, phosphate, carbonate, hydroxide, and carboxylate.   The method according to any one of claims 1 to 6, wherein the functional organic compound is selected from the group consisting of arylamines, arylthiols, aralkylthiols, and aromatic sulfur-containing heterocycles.   The functional organic compound is selected from the group consisting of aniline, aniline derivatives, toluidine, toluidine derivatives, benzothiazoles, thiophene, thiophene derivatives, benzothiophene, and benzothiophene derivatives. The method according to any one. The functional organic compound has the following ring group:
Or a nitrogen-containing aromatic heterocyclic compound containing an amine substituent on the ring, wherein R ⁷ is hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a hydroxy group, or a negative charge. The method according to any one of 1 to 6. The heterocyclic compound capable of forming a self-assembled monolayer has the following ring group:
10. The method of claim 9, comprising both an amine substituent on the ring. The functional organic compound includes a nitrogen-containing aromatic heterocyclic compound containing the following ring group,
Wherein R ⁷ is a substituted hydrocarbyl group containing a substituent selected from the group consisting of an amino group, a cyano group, a nitro group, a halogen group, a hydroxy group, and a sulfhydryl group. The method according to any one.   The method according to any one of claims 9 to 11, wherein the nitrogen-containing aromatic heterocyclic compound contains a ring substituent selected from the group consisting of a cyano group, a nitro group, a halogen group, a hydroxy group, and a sulfhydryl group. .   The method according to claim 12, wherein the nitrogen-containing aromatic heterocyclic compound comprises a compound selected from the group consisting of mercaptobenzimidazoles, mercaptobenzothiazoles, and mercaptobenzotriazoles.   The method according to claim 1, wherein the conditioning composition comprises purine or a purine derivative. The method according to claim 14, wherein the purine or purine derivative compound is represented by the following formula.
(Formula I)
(Wherein R ² , R ⁶ , and R ⁸ are each independently hydrogen, hydrocarbyl group, substituted hydrocarbyl group, hydroxycarbonyl group, alkylcarbonyl group, alkoxycarbonyl group, alkoxy group, alkenoxy group, hydroxy group, Selected from the group consisting of a hydroxyalkyl group, a hydroxyalkenyl group, a sulfhydryl group, a halogen group, a nitro group, a cyano group, and NR ⁹ R ¹⁰ , wherein R ⁷ is hydrogen, a hydrocarbyl group, a substituted hydrocarbyl group, a hydroxy group, and a negative group Selected from the group consisting of charges, R ⁹ and R ¹⁰ are each independently selected from the group consisting of hydrogen, hydrocarbyl groups, and substituted hydrocarbyl groups.   The purine derivative is present, and the purine derivative is substituted or unsubstituted vinyloxy group, substituted or unsubstituted amide, substituted or unsubstituted amine, hydroxycarbonyl group, substituted or unsubstituted alkoxycarbonyl group, hydroxyalkyl group, hydroxyalkenyl group 16. The method of claim 15, wherein the method is substituted with a functional group selected from the group consisting of: a substituted or unsubstituted silyl group, and a substituted or unsubstituted alkoxysilyl group. The method according to claim 9, wherein the nitrogen-containing aromatic heterocyclic compound is represented by the following structural formula (Ia) or the following structural formula (Ib).
(Where
A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , and A ₇ are carbon atoms or nitrogen atoms, and A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , and the total number of nitrogen atoms derived from a ₇ is located in 0,1,2, or 3;
A ₁₁ , A ₂₂ , A ₃₃ , A ₄₄ , A ₅₅ , A ₆₆ , and A ₇₇ are an electron pair, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted vinyl ether, substituted or Selected from the group consisting of unsubstituted amides, substituted or unsubstituted amines, substituted or unsubstituted carboxylic acids, substituted or unsubstituted esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes;
At least one of A ₁₁ , A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ is a substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted It is selected from the group consisting of esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes. ) The method according to claim 17, wherein the nitrogen-containing aromatic heterocyclic compound is represented by the following structural formula (II), the following structural formula (III), or the following structural formula (IV).
(In the formula, A ₂₂ , A ₄₄ , A ₅₅ , A ₆₆ , and A ₇₇ are defined with respect to the structural formula (Ia) and the structural formula (Ib).) The method according to any one of claims 9 to 10, wherein the nitrogen-containing aromatic heterocyclic compound is represented by the following structural formula (V).
(Where
A ₂ , A ₃ , A ₄ , and A ₅ are carbon atoms or nitrogen atoms, and the total number of nitrogen atoms derived from A ₂ , A ₃ , A ₄ , and A ₅ is 0, 1, or 2 ;
A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ are hydrogen, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or Selected from the group consisting of unsubstituted carboxylic acids, substituted or unsubstituted esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes;
At least one of A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ is substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted ester, substituted Or selected from the group consisting of unsubstituted alcohol, substituted or unsubstituted silane, and substituted or unsubstituted alkoxysilane. )   20. A method according to any preceding claim, wherein the adhesion promoting composition further comprises a transition metal ion.   21. The method of claim 20, wherein the adhesion promoting liquid comprises a transition metal ion selected from the group consisting of zinc, nickel, cobalt, silver, gold, palladium, and other platinum group metals.   The method according to claim 21, wherein the adhesion promoting liquid contains zinc ions. The corrosion inhibitor is the following ring group,
Or a nitrogen-containing aromatic heterocyclic compound containing an amine substituent on the ring, wherein R ⁷ is hydrogen, a hydrocarbyl group, or a substituted hydrocarbyl group. Method. The heterocyclic compound of the corrosion inhibitor is the following ring group,
24. The method of claim 23 comprising both an amine substituent on the ring.   The aqueous composition according to claim 23, wherein the nitrogen-containing aromatic heterocyclic compound of the corrosion inhibitor comprises a compound selected from the group consisting of mercaptobenzimidazoles, mercaptobenzothiazoles, and mercaptobenzotriazoles. . The method according to claim 23, wherein the corrosion inhibitor is represented by the following structural formula (Ia) or the following structural formula (Ib).
(Where
A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , and A ₇ are carbon atoms or nitrogen atoms, and A ₁ , A ₂ , A ₃ , A ₄ , A ₅ , A ₆ , and the total number of nitrogen atoms derived from a ₇ is located in 0,1,2, or 3;
A ₁₁ , A ₂₂ , A ₃₃ , A ₄₄ , A ₅₅ , A ₆₆ , and A ₇₇ are an electron pair, hydrogen, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted vinyl ether, substituted or Selected from the group consisting of unsubstituted amides, substituted or unsubstituted amines, substituted or unsubstituted carboxylic acids, substituted or unsubstituted esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes;
At least one of A ₁₁ , A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ is a substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted It is selected from the group consisting of esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes. ) 27. The method according to claim 26, wherein the corrosion inhibitor is represented by the following structural formula (II), the following structural formula (III), or the following structural formula (IV).
(In the formula, A ₂₂ , A ₄₄ , A ₅₅ , A ₆₆ , and A ₇₇ are defined with respect to the structural formula (Ia) and the structural formula (Ib).) The method according to claim 23, wherein the corrosion inhibitor is represented by the following structural formula (V).
(Where
A ₂ , A ₃ , A ₄ , and A ₅ are carbon atoms or nitrogen atoms, and the total number of nitrogen atoms derived from A ₂ , A ₃ , A ₄ , and A ₅ is 0, 1, or 2 ;
A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ are hydrogen, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or Selected from the group consisting of unsubstituted carboxylic acids, substituted or unsubstituted esters, substituted or unsubstituted alcohols, substituted or unsubstituted silanes, and substituted or unsubstituted alkoxysilanes;
At least one of A ₂₂ , A ₃₃ , A ₄₄ , and A ₅₅ is substituted or unsubstituted vinyl ether, substituted or unsubstituted amide, substituted or unsubstituted amine, substituted or unsubstituted carboxylic acid, substituted or unsubstituted ester, substituted Or selected from the group consisting of unsubstituted alcohol, substituted or unsubstituted silane, and substituted or unsubstituted alkoxysilane. )   24. The method of claim 23, wherein the corrosion inhibitor comprises purine or a purine derivative.   30. A method according to any preceding claim, wherein the conditioning composition is substantially free of peroxide.   31. A method according to any preceding claim, wherein the conditioning composition is substantially free of oxidizing agents.   32. A method according to any preceding claim, wherein the conditioning composition comprises an aqueous solution having an oxidation potential of about 1.02V, 0.8V, 0.2V, or 0.1V or less.   33. A method according to any preceding claim, wherein the conditioning composition comprises a solution having a pH of about 10 to about 15.   60. The method of claim 59, wherein the pH of the conditioning solution is from about 10 to about 14.   61. The method of claim 60, wherein the pH of the conditioning solution is from about 13.5 to about 14. A nitrogen-containing aromatic heterocyclic compound and a transition metal ion, wherein the heterocyclic compound has the following ring group:
Or an amine substituent on the ring, wherein R ⁷ is hydrogen, hydrocarbyl group, substituted hydrocarbyl group, hydroxy group, or negative charge, and the heterocyclic compound is self-assembled on the copper surface A water-based alkaline composition capable of forming a monomolecular layer. A method for producing a copper conductive layer for bonding to a dielectric material during the production of a printed circuit board,
Including a step of contacting the copper conductive layer with a nitrogen-containing aromatic heterocyclic compound, an adjustment composition containing an alkali metal iodide, and a glycol ether, wherein the nitrogen-containing aromatic heterocyclic compound has the following ring Group,
Or an amine substituent on the ring, wherein R ⁷ is hydrogen, hydrocarbyl group, substituted hydrocarbyl group, hydroxy group, or negative charge, and the heterocyclic compound is self-assembled on the copper surface A method characterized in that a monolayer can be formed.