JP5667927B2 - Treatment liquid for forming migration suppression layer, and method for producing laminate having migration suppression layer - Google Patents

Description

  The present invention relates to a treatment liquid for forming a migration suppression layer and a method for producing a laminate having a migration suppression layer obtained using the treatment liquid.

  In recent years, along with demands for higher functionality of electronic devices, electronic components have been densely integrated and mounted with high density, and printed wiring boards and the like used for these components have also been reduced in size and density. It is out. Under such circumstances, the interval between the wirings in the printed wiring board is becoming narrower, and in order to prevent a short circuit between the wirings, further improvement in insulation reliability between the wirings is required.

  As one of the factors that hinder the insulation between copper or copper alloy wiring, so-called migration of copper ions is known. This is a phenomenon in which when a potential difference occurs between wiring circuits, copper constituting the wiring is ionized due to the presence of moisture, and the eluted copper ions move to the adjacent wiring. Due to such a phenomenon, the eluted copper ions are reduced with time to become a copper compound and grow into a dendrite (dendritic crystal) shape, resulting in a short circuit between the wirings.

  As a method for preventing such migration, techniques for forming a migration suppression layer using benzotriazole have been proposed (Patent Documents 1 and 2). More specifically, in these documents, a layer for suppressing migration of copper ions is formed on a wiring substrate, and the insulation reliability between wirings is improved.

JP 2001-257451 A JP-A-10-321994

On the other hand, as described above, in recent years, the miniaturization of wiring has rapidly progressed, and further improvement in insulation reliability between wirings is required.
The present inventors have studied the migration suppression layer using benzotriazole described in Patent Documents 1 and 2, and as a result, the connection of copper dendrite between wirings has been confirmed, and the migration suppression effect has recently been required. This level was not met and further improvements were needed.

In view of the above circumstances, an object of the present invention is to provide a treatment liquid for forming a migration layer for forming a migration suppression layer that suppresses migration of copper ions between wirings and improves insulation reliability between wirings. And
Another object of the present invention is to provide a method for producing a laminate having a migration suppression layer obtained using the treatment liquid.

  As a result of intensive studies, the present inventors have found that the above problem can be solved by the following configuration.

(1) A treatment liquid for forming a migration suppression layer for forming a migration suppression layer containing an azole compound and water and having a dissolved oxygen content of 8 ppm or less and suppressing ion migration in copper wiring or copper alloy wiring.

(2) The treatment liquid for forming a migration suppression layer according to (1), wherein the amount of dissolved oxygen is less than 4 ppm.

(3) The treatment liquid for forming a migration suppression layer according to (1) or (2), wherein the azole compound contains 1,2,3-triazole and / or 1,2,4-triazole.

(4) The substrate and the substrate with wiring having the copper wiring or the copper alloy wiring arranged on the substrate are brought into contact with the treatment liquid for forming the migration suppression layer according to any one of (1) to (3), Thereafter, the substrate with wiring is washed with a solvent, and a layer forming step of forming a migration suppressing layer containing an azole compound on the surface of the copper wiring or the copper alloy wiring,
The manufacturing method of the laminated body which has a migration suppression layer provided with the insulating layer formation process of forming an insulating layer on the board | substrate with wiring in which the said migration suppression layer was provided.

(5) The copper wiring and the copper alloy wiring are disposed so as to expose a part of the substrate, the copper wiring or the copper alloy wiring disposed on the substrate, and the copper wiring or the copper alloy wiring disposed on the substrate. An exposed wiring-containing laminate having an insulating layer to be covered is brought into contact with the migration suppressing layer forming treatment liquid according to any one of (1) to (3), and then the exposed wiring-containing laminate is washed with a solvent. And the manufacturing method of the laminated body which has a layer formation process of forming a migration suppression layer on the exposed said copper wiring or copper alloy wiring surface.

ADVANTAGE OF THE INVENTION According to this invention, the processing liquid for migration layer formation for suppressing the migration of the copper ion between wiring and forming the migration suppression layer which improves the insulation reliability between wiring can be provided.
Moreover, according to this invention, the manufacturing method of the laminated body which has a migration suppression layer obtained using this processing liquid can also be provided.

It is typical sectional drawing which shows each process in the 1st embodiment of the manufacturing method of the laminated body which has a migration suppression layer of this invention in order. It is a perspective sectional view of a part of an exposed wiring content layered product used by the present invention. It is typical sectional drawing which shows each process in the 2nd embodiment of the manufacturing method of the laminated body which has a migration suppression layer of this invention in order. (A) is the sectional view on the AA line of FIG. It is a partial perspective sectional view of the 2nd embodiment of the layered product which has a migration inhibition layer of the present invention.

Below, the manufacturing method of the laminated body which has the migration suppression layer obtained by using the processing liquid for migration suppression layer formation of this invention and this processing liquid is demonstrated.
First, problems of the prior art and features of the present invention will be described in detail.
The present inventors examined the problems of the prior art (the invention described in Patent Document 1). First, the function of the migration suppression layer formed when the amount of dissolved oxygen in the treatment liquid is large is not sufficient. I found out. When the amount of dissolved oxygen in the treatment liquid is large, corrosion of the surface of the copper wiring or copper alloy wiring is promoted. Therefore, the generation of copper ions is accelerated particularly in a high humidity and applied voltage atmosphere, and the ion trapping ability of the migration suppression layer is used, resulting in a sufficient migration suppression function. become unable.

  In addition, the present inventors have found that when a conventional migration inhibitor such as benzotriazole remains on a substrate between copper wirings or copper alloy wirings (hereinafter also simply referred to as wirings), a substrate with wiring between the wirings It has been found that poor adhesion occurs between the insulating layer provided on the substrate and the substrate, causing a short circuit. On the other hand, when the substrate is washed to remove the migration inhibitor existing between such wirings, the migration inhibitor on the copper wiring or copper alloy wiring is also removed at the same time, and the desired effect is not exhibited. .

Based on the above findings, the present inventors have found that the above-mentioned problems of the prior art can be solved by using a treatment liquid for forming a migration suppression layer containing an azole compound and exhibiting a predetermined dissolved oxygen content. Yes.
That is, by using a treatment liquid having a dissolved oxygen amount of a predetermined value or less, corrosion of copper wiring or copper alloy wiring is further suppressed, and the ability of the azole compound to coordinate to copper ions is maintained. As a result, migration of copper ions is suppressed.
Furthermore, by using an azole compound that is a hetero 5-membered ring compound, the azole compound on the wiring remains even after washing with a solvent. While removing, a migration suppression layer can be formed on the wiring.

  First, the treatment liquid for forming a migration suppression layer used in the present invention will be described in detail, and then a method for producing a laminate having a migration suppression layer obtained using the treatment liquid will be described in detail.

[Treatment solution for forming migration suppression layer]
The treatment liquid for forming a migration suppression layer (treatment liquid for forming a copper ion diffusion suppression layer) of the present invention is a treatment liquid for forming a migration suppression layer for suppressing ion migration in copper wiring or copper alloy wiring. The treatment liquid contains an azole compound and water, and the dissolved oxygen content is 8 ppm or less.
The components (azole compound, water, etc.) contained in the treatment liquid will be described in detail below.

(Azole compound)
The azole compound contained in this treatment liquid is a monocyclic hetero 5-membered ring compound containing one or more nitrogen atoms in the ring. Examples thereof include diazole having 2 nitrogen atoms, triazole having 3 nitrogen atoms, and tetrazole having 4 nitrogen atoms. More specifically, 1,2,3-triazole, 1,2,4-triazole, 1,2,4-triazole-3-carboxamide, tetrazole and the like can be mentioned. Among these, 1,2,3-triazole and 1,2,4-triazole are preferable in that the migration suppression effect of copper ions is more excellent.
The treatment liquid may contain two or more azole compounds.
Moreover, this azole compound may have substituents, such as an alkyl group, a carboxyl group, a hydroxyl group, and an amino group, unless the effect of this invention is impaired.

  The total content of the azole compound in the treatment liquid is not particularly limited, but from the viewpoint of ease of formation of the migration suppression layer and control of the adhesion amount of the migration suppression layer, 0.01 to 10 mass% is preferable, 0.1-5 mass% is more preferable, 0.25-5 mass% is especially preferable. When there is too much total content of an azole compound, control of the deposition amount of a migration suppression layer will become difficult. If the total content of the azole compound is too small, it takes time until the desired amount of migration suppression layer is deposited, resulting in poor productivity.

  On the other hand, when benzotriazole or the like generally used for anticorrosives is used instead, most of the benzotriazole is washed away from the copper wiring or copper alloy wiring by washing with a solvent described later, and the desired effect is obtained. Cannot be obtained. In addition, in a benzotriazole-containing treatment liquid containing an excessive etching agent or a treatment liquid containing an imidazole compound having etching ability, an excessive amount of copper ions is contained in the organic film formed on the copper wiring or copper alloy wiring. In other words, the coating does not have a migration suppressing ability and a desired effect cannot be obtained.

The treatment liquid usually contains water as a solvent. The kind in particular of water used is not restrict | limited, For example, distilled water, ion-exchange water, tap water, and well water are mentioned. Of these, distilled water is preferred because it contains few impurities such as ions.
The content of water is not particularly limited, but is preferably 90 to 99.9% by mass, more preferably 95 to 99.9% by mass, and more preferably 95 to 99.9% by mass with respect to the total amount of the processing solution from the viewpoint of handleability of the processing solution. 97.5% by mass is more preferable.

Note that the treatment liquid may contain a solvent other than water as long as the effects of the present invention are not impaired.
For example, alcohol solvents (eg, methanol, ethanol, isopropanol), ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone), amide solvents (eg, formamide, dimethylacetamide, N-methylpyrrolidone), nitrile solvents (eg, , Acetonitrile, propionitrile), ester solvents (eg, methyl acetate, ethyl acetate), carbonate solvents (eg, dimethyl carbonate, diethyl carbonate), ether solvents, halogen solvents, and the like. Two or more of these solvents may be mixed and used.

The amount of dissolved oxygen in this treatment liquid is 8 ppm or less. By being within this range, copper corrosion or the like in the copper wiring or copper alloy wiring can be suppressed, the adsorption of the azole compound further proceeds, and a migration suppression layer having a high copper ion trapping capability can be formed. Furthermore, it is preferable that the amount of dissolved oxygen is less than 4 ppm in that a migration suppression layer having a higher migration suppression function can be formed.
On the other hand, if the amount of dissolved oxygen exceeds 8 ppm, corrosion occurs on the surface of the copper wiring or copper alloy wiring when the substrate with wiring and the processing liquid come into contact with each other, and the generation of copper ions is accelerated under a high humidity and applied voltage atmosphere. For this reason, the ion trap ability of the migration suppression layer is used, and a sufficient migration suppression function cannot be exhibited.

A method for reducing the amount of dissolved oxygen in the treatment liquid to a predetermined value or less is not particularly limited, and a known method can be used. For example, it is preferable to reduce oxygen in the treatment liquid by degassing. More specifically, bubbling with an inert gas, removal with a film such as a polymer film or an inorganic film, removal of gas components by vacuum, or a combination thereof Method.
As the inert gas, it is preferable to use nitrogen, argon, helium, or a combination thereof. Moreover, in order to eliminate the influence by contamination, it is better to use those inert gases with the highest possible purity.
A known method can be used as a method for measuring the dissolved oxygen concentration. For example, a commercially available solution such as a dissolved oxygen meter DO-31P (manufactured by Toa DKK Co.) or a fluorescent dissolved oxygen meter LDO-HQ10 (manufactured by Hack Company). It can be measured with a dissolved oxygen meter.

On the other hand, it is preferable that copper ions are not substantially contained in the treatment liquid in terms of enhancing the insulation reliability between the wirings in the laminate. If an excessive amount of copper ions is included, copper ions will be included in the migration suppression layer, reducing the effect of suppressing copper ion migration, and insulation reliability between wirings. May be damaged.
The phrase “copper ions are not substantially contained” means that the content of copper ions in the treatment liquid is 1 μmol / l or less, and more preferably 0.1 μmol / l or less. Most preferably, it is 0 mol / l.

Moreover, it is preferable that the processing liquid does not substantially contain an etching agent of copper or a copper alloy from the viewpoint of improving the insulation reliability between the wirings in the laminate. When an etching agent is contained in the processing liquid, copper ions may be eluted in the processing liquid when the substrate with wiring and the processing liquid are brought into contact with each other. Therefore, as a result, copper ions are contained in the migration suppression layer, the effect of suppressing migration of copper ions is reduced, and insulation reliability between wirings may be impaired.
Etching agents include, for example, organic acids (eg, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, formic acid, hydrofluoric acid), oxidizing agents (eg, hydrogen peroxide, concentrated sulfuric acid), chelating agents (eg, iminodiacetic acid, nitrilotriacetic acid, Ethylenediaminetetraacetic acid, ethylenediamine, ethanolamine, aminopropanol), thiol compounds and the like. Etching agents include those having an etching action of copper such as imidazole and imidazole derivative compounds.
Note that the term “substantially free of an etchant” means that the content of the etchant in the treatment liquid is 0.01% by mass or less with respect to the total amount of the treatment liquid. Is more preferably 0.001% by mass or less. Most preferably, it is 0 mass%.

The pH of the treatment liquid is not particularly defined, but is preferably 5 to 12 from the viewpoint of the formation of the migration suppression layer. Especially, from the point which the insulation reliability between wiring in a laminated body is more excellent, it is more preferable that pH is 5-9, and it is further more preferable that it is 6-8.
When the pH of the treatment liquid is less than 5, elution of copper ions from the copper wiring or copper alloy wiring is promoted, and a large amount of copper ions are contained in the migration suppression layer, and as a result, copper ion migration is suppressed. The effect may be reduced. When the pH of the treatment liquid is more than 12, copper hydroxide is precipitated and is easily oxidized and dissolved. As a result, the effect of suppressing migration of copper ions may be reduced.
The pH can be adjusted using a known acid (for example, hydrochloric acid or sulfuric acid) or a base (for example, sodium hydroxide). The pH can be measured using a known measurement means (for example, a pH meter (in the case of an aqueous solvent)).

  In addition, the said process liquid may contain other additives (for example, pH adjuster, surfactant, preservative, precipitation inhibitor, etc.).

[Method for Producing Laminate Having Migration Suppression Layer (First Embodiment)]
One preferred embodiment of the method for producing a laminate having a migration suppressing layer of the present invention is a production method in which the layer forming step, the drying step, and the insulating layer forming step are carried out in this order.
Below, with reference to drawings, the material used at each process and the procedure of a process are demonstrated.

[Layer formation process]
In this step, first, a substrate with wiring having a copper wiring or a copper alloy wiring (hereinafter also simply referred to as wiring) disposed on the substrate is brought into contact with the above-described treatment liquid for forming a migration suppression layer (contact). Process). Then, the board | substrate with wiring after the said contact is wash | cleaned with a solvent (cleaning solvent), and the migration suppression layer containing an azole compound is formed on a copper wiring or copper alloy wiring surface (cleaning process). By this step, a migration suppression layer is formed so as to cover the surface of the copper wiring or the copper alloy wiring, and copper migration is suppressed.
First, materials (such as a substrate with wiring) used in the layer forming step will be described, and then the procedure of the layer forming step will be described.

(Substrate with wiring)
The board | substrate with wiring (inner layer board | substrate) used at this process has a board | substrate and the copper wiring or copper alloy wiring arrange | positioned on a board | substrate. In other words, the substrate with wiring may have a laminated structure including at least a substrate and copper wiring or copper alloy wiring, and the copper wiring or copper alloy wiring may be disposed in the outermost layer. FIG. 1A shows an embodiment of a substrate with wiring. The substrate with wiring 10 includes a substrate 12 and copper wiring or copper alloy wiring 14 (hereinafter simply referred to as wiring 14) disposed on the substrate 12. Also called). In FIG. 1A, the wiring 14 is provided on only one side of the substrate, but may be provided on both sides. That is, the board with wiring 10 may be a single-sided board or a double-sided board.

The substrate is not particularly limited as long as it can support wiring, but is usually an insulating substrate. As the insulating substrate, for example, an organic substrate, a ceramic substrate, a silicon substrate, a glass substrate, or the like can be used.
Resin is mentioned as a material of an organic substrate, For example, it is preferable to use a thermosetting resin, a thermoplastic resin, or resin which mixed them. Thermosetting resins include phenolic resin, urea resin, melamine resin, alkyd resin, acrylic resin, unsaturated polyester resin, diallyl phthalate resin, epoxy resin, silicone resin, furan resin, ketone resin, xylene resin, benzocyclobutene resin Etc. can be used. Examples of the thermoplastic resin include polyimide resin, polyphenylene oxide resin, polyphenylene sulfide resin, aramid resin, and liquid crystal polymer.
In addition, as a material of the organic substrate, a glass woven fabric, a glass nonwoven fabric, an aramid woven fabric, an aramid nonwoven fabric, an aromatic polyamide woven fabric, a material impregnated with the above resin, or the like can be used.

The wiring is made of copper or a copper alloy. When the wiring is composed of a copper alloy, examples of the metal contained other than copper include silver, tin, palladium, gold, nickel, and chromium.
The method for forming the wiring on the substrate is not particularly limited, and a known method can be adopted. Typically, a subtractive method using an etching process and a semi-additive method using electrolytic plating can be given.

The width of the wiring is not particularly limited, but is preferably 1 to 1000 μm and more preferably 3 to 25 μm from the viewpoint of high integration when the formed laminate is applied to a printed wiring board.
The spacing between the wirings is not particularly limited, but is preferably 1 to 1000 μm, and more preferably 3 to 25 μm, from the viewpoint of high integration when the formed laminate is applied to a printed wiring board.
Also, the pattern shape of the wiring is not particularly limited, and may be an arbitrary pattern. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, and the like can be given.

The thickness of the wiring is not particularly limited, but is preferably 1 to 1000 μm, more preferably 3 to 25 μm, from the viewpoint of high integration when the formed laminate is applied to a printed wiring board.
The surface roughness Rz of the wiring is not particularly limited, but is preferably 0.001 to 15 μm and more preferably 0.3 to 3 μm from the viewpoint of adhesion with an insulating layer described later.
As a method for adjusting the surface roughness Rz of the wiring, a known method can be used, and examples thereof include chemical roughening treatment and buffing treatment.
Rz is measured according to JIS B 0601 (1994).

The substrate with wiring used in this step may have wiring in the outermost layer, and may have other metal wiring (wiring pattern) and an interlayer insulating layer in this order between the substrate and wiring. Good. In addition, the other metal wiring and the interlayer insulating layer may include two or more layers alternately in this order between the substrate and the wiring. That is, the substrate with wiring may be a so-called multilayer wiring substrate or build-up substrate.
As the interlayer insulating layer, a known insulating material can be used, and examples thereof include phenol resin, naphthalene resin, urea resin, amino resin, alkyd resin, epoxy resin, and acrylate resin.
The substrate with wiring may be a so-called rigid substrate, flexible substrate, or rigid flexible substrate.

  Further, a through hole may be formed in the substrate. When wiring is provided on both surfaces of the substrate, for example, the wiring on both surfaces may be conducted by filling the via hole with metal (for example, copper or copper alloy).

(Solvent (cleaning solvent))
The solvent (cleaning solvent) used in the cleaning process for cleaning the substrate with wiring is not particularly limited as long as an excess azole compound deposited between the wirings on the substrate can be removed.
Examples of the solvent include water, alcohol solvents (eg, methanol, ethanol, propanol), ketone solvents (eg, acetone, methyl ethyl ketone, cyclohexanone), amide solvents (eg, formamide, dimethylacetamide, N-methylpyrrolidone). Nitrile solvents (eg, acetonitrile, propionitrile), ester solvents (eg, methyl acetate, ethyl acetate), carbonate solvents (eg, dimethyl carbonate, diethyl carbonate), ether solvents, halogen solvents, etc. It is done. Two or more of these solvents may be mixed and used.
Among these, from the viewpoint of liquid permeability between fine wirings, it is preferably a solvent containing at least one selected from the group consisting of water, alcohol solvents, and methyl ethyl ketone, and water or a mixture of alcohol solvents and water. More preferably, it is a liquid.

  Although the boiling point (25 degreeC, 1 atmosphere) of the solvent used is not restrict | limited in particular, 75-100 degreeC is preferable from a safety viewpoint, and 80-100 degreeC is more preferable.

  The surface tension (25 ° C.) of the solvent used is not particularly limited, but it is preferably 10 to 80 mN / m from the viewpoint of better cleaning properties between wirings and further improving insulation reliability between wirings, More preferably, it is 15-60 mN / m.

(Procedure of layer formation process)
The layer forming process will be described by dividing it into two processes, a contact process and a cleaning process.

(Contact process)
First, a substrate with wiring having copper wiring or copper alloy wiring disposed on the substrate and the substrate is brought into contact with the above-described treatment liquid for forming a migration suppression layer. By contacting the substrate with wiring and the treatment liquid, a layer 16 containing an azole compound is formed on the substrate with wiring 10 as shown in FIG. The layer 16 is formed on the substrate 12 and the wiring 14.
The layer 16 containing an azole compound contains an azole compound. The content etc. are substantially synonymous with the content in the migration suppression layer mentioned later. Further, the amount of adhesion is not particularly limited, and it is preferable that the amount of adhesion is such that a migration suppressing layer having a desired amount of adhesion can be obtained through a cleaning step described later.

  A method for contacting the substrate with wiring and the treatment liquid is not particularly limited, and a known method can be employed. For example, dip dipping, shower spraying, spray coating, spin coating and the like can be mentioned, and dip dipping, shower spraying and spray coating are preferred from the standpoint of easy processing and easy adjustment of processing time.

Moreover, as a liquid temperature of the process liquid in the case of contact, the range of 5-60 degreeC is preferable at the point of adhesion amount control of a migration suppression layer, The range of 15-50 degreeC is more preferable, The range of 20-40 degreeC Is more preferable.
The contact time is preferably in the range of 10 seconds to 30 minutes, more preferably in the range of 15 seconds to 10 minutes, and in the range of 30 seconds to 5 minutes in terms of productivity and control of the amount of adhesion of the migration suppression layer. Further preferred.

(Washing process)
Next, the substrate with wiring is washed with a solvent to form a migration suppression layer containing an azole compound on the surface of the copper wiring or copper alloy wiring. Specifically, the wiring board 10 provided with the layer 16 containing the azole compound obtained in FIG. 1B is washed with the above-described cleaning solvent, whereby as shown in FIG. The layer 16 containing the azole compound therebetween is removed and the excess azole compound on the wiring 14 is removed, and the migration suppressing layer 18 containing the azole compound is formed on the wiring 14.

The cleaning method is not particularly limited, and a known method can be employed. For example, a method of applying a cleaning solvent on the substrate with wiring, a method of immersing the substrate with wiring in the cleaning solvent, and the like can be mentioned.
Moreover, as a liquid temperature of a washing | cleaning solvent, the range of 5-60 degreeC is preferable at the point of the adhesion amount control of a migration suppression layer, and the range of 15-30 degreeC is more preferable.
The contact time between the substrate with wiring and the cleaning solvent is preferably in the range of 10 seconds to 10 minutes, more preferably in the range of 15 seconds to 5 minutes, in terms of productivity and adhesion amount control of the migration suppression layer. .

(Migration suppression layer (copper ion diffusion suppression layer))
By passing through the said process, as shown in FIG.1 (C), the migration suppression layer 18 containing an azole compound can be formed on the copper wiring or the copper alloy wiring 14 surface. That is, the migration suppression layer 18 covers the surface of the copper wiring or the copper alloy wiring 14.
As shown in FIG. 1C, it is preferable that the layer containing the azole compound between the wirings 14 is substantially removed. That is, it is preferable that the migration suppression layer 18 is substantially formed only on the surface of the copper wiring or the copper alloy wiring 14.
In the present invention, it is possible to obtain a migration suppressing layer having a sufficient adhesion amount capable of suppressing migration of copper ions even after the solvent is washed.

  The content of the azole compound in the migration-suppressing layer is preferably 0.1 to 100% by mass, more preferably 20 to 100% by mass, from the viewpoint that migration of copper ions can be further suppressed. More preferably, it is 90 mass%. In particular, the migration suppression layer is preferably substantially composed of an azole compound. When there is too little content of an azole compound, the migration inhibitory effect of a copper ion will become low.

  It is preferable that copper ions or metallic copper is not substantially contained in the migration suppression layer. When the migration suppression layer contains a predetermined amount or more of copper ions or metallic copper, the effect of the present invention may be inferior.

The adhesion amount of the azole compound on the surface of the copper wiring or the copper alloy wiring is 5 × 10 ⁻⁹ to 1 × 10 ^{− with} respect to the total surface area of the copper wiring or the copper alloy wiring because the migration of copper ions can be further suppressed. It is preferably ⁶ g / mm ² , more preferably 5 × 10 ⁻⁹ to 2 × 10 ⁻⁷ g / mm ² , and 5 × 10 ^{−9 to} 6 × 10 ⁻⁸ g / mm ² . More preferably.
The amount of adhesion can be measured by a known method (for example, an absorbance method). Specifically, in the absorbance method, first, the migration suppression layer existing between the wirings is washed with water (extraction method using water). Thereafter, the migration suppression layer on the copper wiring or copper alloy wiring is extracted with an organic acid (for example, sulfuric acid), the absorbance is measured, and the adhesion amount is calculated from the liquid amount and the coating area.

  As described above, it is preferable that the layer containing the azole compound is substantially removed between the wirings, but the layer containing the azole compound partially remains within a range not impairing the effects of the present invention. Also good.

[Drying process]
In this step, the substrate with wiring provided with the migration suppressing layer is heated and dried. If moisture remains on the substrate with wiring, migration of copper ions may be promoted. Therefore, it is preferable to remove the moisture by providing this step.

Heat drying conditions are 70 to 120 ° C. (preferably 80 ° C. to 110 ° C.) for 15 seconds to 10 minutes (preferably 30 seconds to 5 minutes) in terms of suppressing oxidation of copper wiring or copper alloy wiring. ) It is preferable to implement. If the drying temperature is too low or the drying time is too short, moisture may not be sufficiently removed. If the drying temperature is too high or the drying time is too long, copper oxide may be formed.
The apparatus used for drying is not particularly limited, and a known heating apparatus such as a constant temperature layer or a heater can be used.

  In addition, this process is arbitrary processes, and when the solvent used at a layer formation process is a solvent excellent in volatility etc., this process does not need to be implemented.

[Insulating layer forming step]
In this step, an insulating layer is formed on a substrate with wiring provided with a migration suppression layer. As shown in FIG. 1D, the insulating layer 20 is provided on the substrate with wiring 10 so as to be in contact with the wiring 14 provided with the migration suppression layer 18 on the surface. By providing the insulating layer 20, the insulation reliability between the wirings 14 is further ensured. Moreover, since the board | substrate 12 and the insulating layer 20 can contact directly, the adhesiveness of the insulating layer 20 is excellent.
First, an insulating layer to be used will be described, and then a method for forming the insulating layer will be described.

As the insulating layer, a known insulating material can be used. For example, a material used as a so-called interlayer insulating layer can be used. Specifically, an epoxy resin, an aramid resin, a crystalline polyolefin resin, an amorphous polyolefin resin, a fluorine-containing resin (polytetrafluoroethylene, Perfluorinated polyimide, perfluorinated amorphous resin, etc.), polyimide resin, polyether sulfone resin, polyphenylene sulfide resin, polyether ether ketone resin, acrylate resin and the like. As an interlayer insulation layer, Ajinomoto Fine Techno Co., Ltd. product, ABF GX-13, etc. are mentioned, for example.
Moreover, you may use what is called a soldering resist layer as an insulating layer. A commercially available solder resist may be used, and specific examples include PFR800 manufactured by Taiyo Ink Manufacturing Co., Ltd., PSR4000 (trade name), SR7200G manufactured by Hitachi Chemical Co., Ltd., and the like.

The method for forming the insulating layer on the substrate with wiring is not particularly limited, and a known method can be adopted. For example, a method of laminating a film of an insulating layer directly on a substrate with a wiring, a method of applying a composition for forming an insulating layer containing a component constituting the insulating layer on a substrate with a wiring, Examples include a method of immersing in a forming composition.
In addition, the said composition for insulating layer formation may contain the solvent as needed. When using the composition for insulating layer formation containing a solvent, after arrange | positioning this composition on a board | substrate, you may heat-process in order to remove a solvent as needed.
Moreover, after providing an insulating layer on a board | substrate with wiring, you may give energy provision (for example, exposure or heat processing) with respect to an insulating layer as needed.

The thickness of the insulating layer to be formed is not particularly limited, and is preferably 5 to 50 μm and more preferably 15 to 40 μm from the viewpoint of insulation reliability between wirings.
In FIG. 1D, the insulating layer is described as a single layer, but may have a multilayer structure.

(Laminated body having migration suppression layer)
Through the above steps, as shown in FIG. 1D, the substrate 12, the wiring 14 disposed on the substrate 12, and the insulating layer 20 disposed on the wiring 14 are provided. A stacked body 30 (a first embodiment of a stacked body having a migration suppressing layer) in which the migration suppressing layer 18 is interposed between the layers 20 can be obtained. The obtained laminated body 30 is excellent in insulation reliability between the wirings 14 and is also excellent in adhesion between the insulating layer 20 and the substrate with wiring 10.
Note that, as shown in FIG. 1D, in the above, a laminated body having a single-layer wiring structure is taken as an example, but the present invention is not limited to this. For example, by using a substrate with multilayer wiring, in which another metal wiring (metal wiring layer) and an interlayer insulating layer are alternately stacked in this order between the substrate and the metal wiring, a multilayer structure with a multilayer wiring structure is manufactured. can do.

  The laminate obtained by the production method of the present invention can be used for various applications and structures, such as a printed wiring board, a motherboard board, a semiconductor package board, and a MID (Molded Interconnect Device) board. And can be used for rigid boards, flexible boards, flex-rigid boards, molded circuit boards, and the like.

Further, a part of the insulating layer in the obtained laminate may be removed and a semiconductor chip may be mounted and used as a printed circuit board.
For example, when a solder resist is used as the insulating layer, a mask with a predetermined pattern is placed on the insulating layer, and energy is applied and cured, and the insulating layer in the non-energy-applied region is removed to expose the wiring. . Next, the exposed wiring surface is cleaned by a known method (for example, using sulfuric acid or a surfactant), and then the semiconductor chip is mounted on the wiring surface.
When a known interlayer insulating layer is used as the insulating layer, the insulating layer can be removed by drilling or laser processing.

Further, a metal wiring (wiring pattern) may be further provided on the insulating layer of the obtained laminate. The method for forming the metal wiring is not particularly limited, and a known method (plating treatment, sputtering treatment, etc.) can be used.
In the present invention, a substrate in which metal wiring (wiring pattern) is further provided on the insulating layer of the obtained laminate is used as a new substrate with wiring (inner layer substrate), and a new insulating layer and metal wiring are newly added. Layers can also be stacked.

[Method for Producing Laminate Having Migration Suppression Layer (Second Embodiment)]
As another preferred embodiment of the method for producing a laminate having a migration suppressing layer of the present invention, a substrate, a copper wiring or a copper alloy wiring disposed on the substrate, and a copper wiring or a copper alloy wiring disposed on the substrate. A laminated body having an exposed wiring having an exposed wiring having an insulating layer covering the copper wiring and the copper alloy wiring so that a part thereof is exposed (hereinafter, also simply referred to as an exposed wiring containing laminated body) is used instead of the above-mentioned substrate with wiring. The manufacturing method which implements the layer formation process to be used and the drying process in this order is mentioned.
Below, with reference to drawings, the material used at each process and the procedure of a process are demonstrated.

[Layer formation process]
In this step, first, the exposed wiring-containing laminate is brought into contact with the above-described treatment liquid for forming a migration suppression layer (contact step). Thereafter, the exposed wiring-containing laminate is washed with a solvent (cleaning solvent) to form a migration suppression layer containing an azole compound on the exposed copper wiring or copper alloy wiring surface (cleaning step).
By this step, a migration layer is formed so as to cover the surface of the exposed copper wiring or copper alloy wiring, and copper migration is suppressed.
First, the material (exposed wiring containing laminated body) used at a layer formation process is demonstrated, and the procedure of a layer formation process is demonstrated after that.

(Laminated body containing exposed wiring)
The laminate containing exposed wiring used in this step is composed of a substrate, a copper wiring or copper alloy wiring (hereinafter, also simply referred to as wiring) disposed on the substrate, and a copper wiring or copper alloy wiring disposed on the substrate. And an insulating layer covering the copper wiring and the copper alloy wiring so that a part thereof is exposed. In FIG. 2, the exposed wiring containing laminate 40 includes a substrate 12, a copper wiring or a copper alloy wiring 14 (hereinafter also simply referred to as a wiring 14), and an insulating layer 20. The wiring 14 includes an exposed copper wiring or copper alloy wiring (hereinafter also simply referred to as wiring 14a) and a copper wiring or copper alloy wiring (hereinafter also simply referred to as wiring 14b) covered with the insulating layer 20. .
In FIG. 2, the exposed wiring 14 a is supported on the substrate 12, but a part thereof may extend outside the substrate 12.

The mode (type, etc.) of the substrate in the exposed wiring-containing laminate used in this step is the same as the mode of the substrate in the substrate with wiring (inner layer substrate) used in the first embodiment described above.
Especially, as a board | substrate (especially insulating board | substrate), it is preferable to use an organic substrate, a thin glass epoxy board | substrate, etc., for example. By using a substrate such as an organic substrate, a so-called flexible printed wiring board can be obtained. Moreover, what is called a rigid printed wiring board can also be obtained by using the rigid board | substrate which consists of a glass epoxy board | substrate.
Resin is mentioned as a material of an organic substrate, For example, a polyimide resin, a polyester resin, a liquid crystal polymer etc. are mentioned.

  The copper wiring or copper alloy wiring in the exposed wiring-containing laminate used in this step (material type, width, spacing, thickness, etc.) includes wiring used in the above-described first embodiment. This is the same as the copper wiring or copper alloy wiring of the substrate (inner layer substrate).

The insulating layer is a layer that covers the copper wiring or the copper alloy wiring so that a part of the copper wiring or the copper alloy wiring is exposed. The ratio of covering the copper wiring or the copper alloy wiring is not particularly limited as long as the copper wiring or the copper alloy wiring portion that can be electrically connected to an electronic component (for example, a semiconductor element) mounted on the substrate remains. .
The mode (type, etc.) of the insulating layer in the exposed wiring-containing laminate used in this step is the same as the mode of the insulating layer in the substrate with wiring (inner layer substrate) used in the first embodiment described above. is there. More specifically, examples of the insulating material constituting the insulating layer include a polyimide resin and a polyester resin.
Moreover, you may use screen printing ink and a photosensitive coverlay as an insulating layer.

  In addition, the manufacturing method in particular of an exposed wiring containing laminated body is not restrict | limited, A well-known method is employable. For example, first, a substrate having copper wiring is manufactured by applying a subtractive method or a semi-additive method to a substrate with copper foil. Next, an insulating film is laminated on the substrate to form an insulating layer covering a part of the copper wiring.

(Solvent (cleaning solvent))
The solvent (cleaning solvent) used in the cleaning process for cleaning the exposed wiring-containing laminate is not particularly limited as long as it can remove excess azole compound deposited on the surface other than the copper wiring or copper alloy surface, The solvent (cleaning solvent) used in the first embodiment described above can be used.

(Process procedure)
The layer forming process will be described by dividing it into two processes, a contact process and a cleaning process.

(Contact process)
The contact step is a step of bringing the exposed wiring-containing laminate into contact with the migration layer forming treatment liquid. Specifically, first, as shown in FIG. 3A, an exposed wiring-containing laminate including a substrate 12 and an exposed copper wiring or copper alloy wiring 14a is prepared. By bringing into contact with the treatment liquid for forming the suppression layer, as shown in FIG. 3B, a layer 16 containing an azole compound is formed on the substrate 12 and the exposed wiring 14a. The layer 16 is formed on the substrate 12, the wiring 14a, and the insulating layer (not shown).
The procedure / conditions of the contact step are the same as the contact steps performed in the first embodiment described above.

(Washing process)
The cleaning step is a step of cleaning the exposed wiring-containing laminate obtained in the contact step with a solvent to form a migration suppression layer containing an azole compound on the surface of the copper wiring or the copper alloy wiring.
Specifically, the exposed wiring-containing laminate provided with the layer 16 containing the azole compound obtained in FIG. 3B is washed with the above-described cleaning solvent, so that the wiring as shown in FIG. While the layer 16 containing the azole compound between 14a is removed, the excess azole compound on the wiring is removed, and the migration suppression layer 18 is formed on the wiring 14a. Note that the layer 16 containing an azole compound between the wirings 14a is removed, and at the same time, the layer 16 containing an azole compound on an insulating layer (not shown) is also removed.
The procedure / conditions of the cleaning process are the same as the cleaning process performed in the first embodiment described above.

(Migration suppression layer)
By passing through the said process, the migration suppression layer containing an azole compound can be formed on the exposed copper wiring or copper alloy wiring surface. As shown in FIG. 3C, the layer containing the azole compound is preferably substantially removed on the surface other than the exposed surface of the wiring 14a. That is, it is preferable that the migration suppression layer 18 is substantially formed only on the exposed surface of the wiring 14a. Note that the surface of the wiring 14a means an upper surface and a side surface other than the lower surface in contact with the substrate 12, as shown in FIG.
The mode of the migration suppression layer to be formed (the content of azole compound, the amount of adhesion, etc.) is the same mode as the migration suppression layer obtained in the first embodiment described above.

[Drying process]
In this step, the laminate provided with the migration suppressing layer is heated and dried. If moisture remains on the laminated body, migration of copper ions may be promoted. Therefore, it is preferable to remove the moisture by providing this step.
In addition, this process is arbitrary processes, and when the solvent used at a layer formation process is a solvent excellent in volatility etc., this process does not need to be implemented.
The procedure / conditions of the drying process are the same as the procedures / conditions of the drying process performed in the first embodiment described above.

(Laminated body having migration suppression layer)
Through the above manufacturing method, a substrate, a copper wiring or copper alloy wiring disposed on the substrate, and a migration suppression layer containing an azole compound formed on a part of the surface of the copper wiring or copper alloy wiring, A laminated body (second embodiment of the laminated body having a migration suppressing layer) having an insulating layer disposed on the substrate and covering the remaining surface of the copper wiring or the copper alloy wiring is obtained. In other words, a part of the copper wiring or copper alloy wiring is covered with an insulating layer, and the surface of the copper wiring or copper alloy wiring not covered with the insulating layer is covered with a migration suppression layer containing an azole compound. A laminate having wiring.
More specifically, as shown in FIG. 4, the substrate 12, the wiring 14 disposed on the substrate 12, the insulating layer 20 disposed on the substrate 12 and covering a part of the wiring 14, and the insulating layer 20 A laminate 100 having a surface-covered wiring having a migration suppressing layer 18 that covers the surface of the wiring 14a on which no wiring is provided is obtained.

  The obtained laminate can be used for various applications, for example, a printed wiring board, a COF (Chip on Film) board, or a TAB (Tape Automated Bonding) board.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

Example 1
Using a polyimide film (Kapton film manufactured by Toray DuPont Co., Ltd.), an exposed wiring-containing laminate (corresponding to a printed wiring board) provided with a comb-shaped copper wiring of L / S = 100 μm / 100 μm and an insulating layer was formed. The exposed wire-containing laminate was produced by the following method.

A 20 μm thick copper foil (F3-WS foil manufactured by Furukawa Electric Co., Ltd.) was pasted on a 25 μm thick polyimide film (Toray DuPont Kapton film) via a 25 μm thick adhesive (N4 manufactured by Hitachi Chemical Co., Ltd.). .
Photoresist (Photec H-W425 manufactured by Hitachi Chemical Co., Ltd.) is laminated on copper foil tape at 100 ° C. under the condition of 4 kgf / cm ² , exposed through a photomask at 80 mJ / cm ² and developed. An etching resist pattern was formed.

Thereafter, the copper foil not covered with the etching resist was selectively removed by etching with a ferric chloride etching solution, and the etching resist was peeled off to obtain a copper wiring of L / S = 100 μm / 100 μm.
Further, an insulating layer (FZ2500 manufactured by Hitachi Chemical Co., Ltd.) was laminated on about half of the obtained substrate, and then exposed and baked to obtain an exposed wiring containing laminate. In addition, about half of the copper wiring in the obtained exposed wiring containing laminated body was coat | covered with the insulating layer.

1,2,4-triazole-3-carboxamide is dissolved in pure water subjected to nitrogen bubbling for about 1 hour, and a migration inhibiting layer forming treatment solution (treatment solution of 1,2,4-triazole-3-carboxamide) Content in the medium: 2.5% by mass). When the amount of dissolved oxygen in the treatment liquid was measured with a dissolved oxygen meter DO-31P (Toa DKK), the amount of dissolved oxygen was 2 ppm.
Next, the obtained exposed wiring containing laminated body was immersed in the produced process liquid for 5 minutes. Then, the exposed wiring containing laminated body obtained using ethanol was wash | cleaned (contact time: 2 minutes, liquid temperature: 25 degreeC), and the laminated body (corresponding to a flexible printed wiring board) which has a migration suppression layer was obtained. Further, the laminate was then dried at 100 ° C. for 2 minutes.

  In addition, by measuring the absorbance of the inter-wiring extract with water, it was confirmed that the migration suppression layer could not be confirmed on the substrate surface between the copper wirings and was removed by ethanol cleaning.

(Measurement of substrate life by water drop test)
Using the obtained laminate, it was applied for 5 minutes and 10 minutes in pure water with a conductivity of 0.05 μS / cm ² and 30 mL, respectively, and then covered with an insulating layer. Occurrence of dendrite connecting between the wirings, which occurred from the anode to the cathode between the non-wiring lines, was measured under an optical microscope (BX-51 manufactured by Olympus Corporation). The results obtained in Example 1 are shown in Table 1.
Evaluation was performed according to the following criteria.
“◯”: When dendrite is not generated between the wirings “△”: Dendrite is generated between the wirings, but no dendrite connecting the wirings is observed, and there is no practical problem “×”: If there is a dendrite that connects the wiring and there is a problem in practical use

(Example 2)
A laminate was produced according to the same procedure as in Example 1 except that 1,2,3-triazole was used instead of 1,2,4-triazole-3-carboxamide. Then, the water drop dropping test performed in Example 1 was implemented using the obtained laminated body. Table 1 shows the results.

Example 3
A laminate was produced in the same manner as in Example 1 except that 1,2,4-triazole was used instead of 1,2,4-triazole-3-carboxamide. Then, the water drop dropping test performed in Example 1 was implemented using the obtained laminated body. Table 1 shows the results.

Example 4
A laminated body was manufactured according to the same procedure as in Example 3 except that the nitrogen bubbling time was changed from 1 hour to 5 minutes in Example 3. Then, the water drop dropping test performed in Example 1 was implemented using the obtained laminated body. Table 1 shows the results.

(Example 5)
A laminate was manufactured according to the same procedure as in Example 3 except that the nitrogen bubbling time was changed from 1 hour to 30 minutes in Example 3. Then, the water drop dropping test performed in Example 1 was implemented using the obtained laminated body. Table 1 shows the results.

Example 6
Using a copper-clad laminate (manufactured by Hitachi Chemical Co., Ltd., MCL-E-679F, substrate: glass epoxy substrate), a substrate with wiring comprising copper wiring of L / S = 23 μm / 27 μm was formed by a semi-additive method. The board | substrate with wiring was produced with the following method.
After the copper-clad laminate is acid washed, washed with water, and dried, a dry film resist (DFR, trade name: RY3315, manufactured by Hitachi Chemical Co., Ltd.) is adjusted to 70 ° C. at a pressure of 0.2 MPa using a vacuum laminator And laminated. After lamination, the copper pattern forming portion was subjected to mask exposure with an exposure machine having a central wavelength of 365 nm under the condition of 70 mJ / m ² . Then, it developed with 1% sodium carbonate aqueous solution, washed with water, and obtained the plating resist pattern.
Through plating pretreatment and water washing, electrolytic plating was performed on the copper exposed between the resist patterns. At this time, an acidic solution of copper (II) sulfate was used as an electrolytic solution, a crude copper plate having a purity of about 99% was used as an anode, and a copper clad laminate was used as a cathode. By electrolysis at 50 to 60 ° C. and 0.2 to 0.5 V, copper was deposited on the cathode copper. Then, it washed with water and dried.
In order to remove the resist pattern, the substrate was immersed in a 4% NaOH aqueous solution at 45 ° C. for 60 seconds. Thereafter, the obtained substrate was washed with water and immersed in 1% sulfuric acid for 30 seconds. Thereafter, it was washed again with water.
The conductive copper between the copper patterns was quickly etched with an etching solution mainly composed of hydrogen peroxide and sulfuric acid, washed with water and dried.
Next, after removing stains and the like on the surface of the copper wiring with a pretreatment agent (CA-5330, manufactured by Mec), the surface of the copper wiring was subjected to roughening with a roughening agent (CZ-8110, manufactured by Mec). .

  Next, the obtained board | substrate with wiring was immersed in the processing liquid for migration suppression layer formation used in Example 3 for 30 seconds. Then, the board | substrate with a wiring obtained using ethanol was wash | cleaned (contact time: 2 minutes, liquid temperature: 25 degreeC). Furthermore, after that, the substrate with wiring was dried at 100 ° C. for 2 minutes.

By performing reflectance measurement, it was confirmed that a migration suppression layer containing 1,2,4-triazole was formed on the copper wiring.
In addition, on the substrate surface between the copper wirings, it was confirmed that the migration suppression layer could not be confirmed and was removed by ethanol washing by measuring the absorbance of the inter-wiring extract with water.

  A laminated body (corresponding to a printed wiring board) having a migration suppressing layer by laminating an insulating layer (PFR-800 manufactured by Taiyo Ink Co., Ltd.) on a substrate with wiring subjected to drying treatment, and then exposing and baking The thickness of the insulating layer was 35 μm). The following lifetime measurement was performed on the obtained laminate.

(Measurement of substrate life by HAST test)
Using the obtained laminate, life measurement was performed under the conditions of a humidity of 85%, a temperature of 130 degrees, a pressure of 1.2 atm, and a voltage of 100 V (use apparatus: EHS-221MD, manufactured by espec).
As an evaluation method, a test of 20 rods was performed, and a resistance value between wirings was set to 1 × 10 ⁹ Ω as a reference resistance value. A rod having a resistance value equal to or higher than the reference resistance value when 120 hours passed from the start of the test was regarded as acceptable.
The results obtained in Example 6 are shown in Table 1.

(Comparative Example 1)
A laminated body was manufactured according to the same procedure as in Example 3, except that oxygen bubbling was performed instead of nitrogen bubbling in Example 3 and a migration suppressing layer forming treatment liquid having a dissolved oxygen content of 8.5 ppm was used. Then, the water drop dropping test performed in Example 1 was implemented using the obtained laminated body. Table 1 shows the results.

(Comparative Example 2)
A laminate was produced in the same manner as in Example 1 except that ethylenediaminetetraacetic acid was used instead of 1,2,4-triazole-3-carboxamide used in Example 1. Then, the water drop dropping test performed in Example 1 was implemented using the obtained laminated body. Table 1 shows the results.

(Comparative Example 3)
A laminate was produced in the same manner as in Example 1 except that benzotriazole was used instead of 1,2,4-triazole-3-carboxamide used in Example 1. Then, the water drop dropping test performed in Example 1 was implemented using the obtained laminated body. Table 1 shows the results.

(Comparative Example 4)
In Example 6, oxygen bubbling was performed instead of nitrogen bubbling, and a laminate was produced according to the same procedure as in Example 6 except that a treatment liquid for forming a migration suppression layer having a dissolved oxygen content of 8.5 ppm was used. Then, the HAST test performed in Example 6 was implemented using the obtained laminated body. Table 1 shows the results.

In Table 1 below, the numerical value in the column of life measurement means (number of rods showing 1 × 10 ⁹ Ω or more after 120 hours / number of test rods), and 20/20 is the best result.
In Table 1, “pH” means the pH of the migration inhibitor treatment solution used in each example and comparative example. A pH meter (manufactured by TOA DK Corporation) was used for pH measurement. “Adhesion amount” in Table 1 means the amount of adhesion of a compound (1,2,3-triazole, 1,2,4-triazole, etc.) contained in the treatment liquid onto the copper wiring, and the measurement is described above. The absorbance method was used.

As shown in Table 1, in Examples 1 to 5 using the treatment liquid for forming a migration suppression layer of the present invention, the connection of dendrite between wirings is not observed, and migration of copper ions is suppressed. It was confirmed.
In particular, in Examples 1 to 3 and 5, the amount of dissolved oxygen was not found to be generated between the wires even when the voltage application time of the water drop test was changed from 5 minutes to 10 minutes. That is, when the amount of dissolved oxygen is less than 4 ppm, the insulation reliability between wirings is more excellent.
Furthermore, as shown in Example 6, an excellent lifetime measurement result was shown in the HAST test, and it was confirmed that the insulation reliability between wirings was excellent.

  On the other hand, in Comparative Example 1 using a treatment liquid having a dissolved oxygen amount of a predetermined value or more, Comparative Example 2 using a compound other than an azole compound, and Comparative Example 3 using a benzotriazole compound, the wirings are connected. The generation of dendrite was confirmed, and the effect of suppressing migration between wirings was inferior. Furthermore, as shown in Comparative Example 4, also in the HAST test, the insulation reliability between the wirings was inferior.

10: Substrate with wiring 12: Substrate 14: Copper wiring or copper alloy wiring 14a: Exposed copper wiring or copper alloy wiring 14b: Copper wiring or copper alloy wiring covered with an insulating layer 16: Layer containing azole compound 18: Migration Suppression layer 20: Insulating film 30, 100: Laminate 40 having migration suppression layer: Exposed wiring containing laminate

Claims (5)

  A treatment liquid for forming a migration suppression layer for forming a migration suppression layer containing azole compound and water and having a dissolved oxygen content of 8 ppm or less and suppressing ion migration in copper wiring or copper alloy wiring.   The treatment liquid for forming a migration suppression layer according to claim 1, wherein the amount of dissolved oxygen is less than 4 ppm.   The treatment liquid for forming a migration suppression layer according to claim 1 or 2, wherein the azole compound contains 1,2,3-triazole and / or 1,2,4-triazole. A substrate with wiring having a substrate and a copper wiring or copper alloy wiring disposed on the substrate, and the treatment liquid for forming a migration suppression layer according to any one of claims 1 to 3, and then the substrate with wiring A layer forming step of forming a migration suppression layer containing an azole compound on the surface of the copper wiring or the copper alloy wiring by washing with a solvent;
The manufacturing method of the laminated body which has a migration suppression layer provided with the insulating layer formation process of forming an insulating layer on the board | substrate with wiring in which the said migration suppression layer was provided. A substrate, a copper wiring or a copper alloy wiring disposed on the substrate, and an insulating layer disposed on the substrate and covering the copper wiring or the copper alloy wiring such that a part of the copper wiring or the copper alloy wiring is exposed And the exposed wiring-containing laminate is contacted with the treatment solution for forming a migration suppression layer according to any one of claims 1 to 3, and then the exposed wiring-containing laminate is washed with a solvent to expose the laminate. The manufacturing method of the laminated body which has a layer formation process which forms a migration suppression layer on a copper wiring or copper alloy wiring surface, and has a migration suppression layer.

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