TW201309134A - Treatment solution for forming migration suppression layer, and method for manufacturing laminate having migration suppression layer - Google Patents

Abstract

An object of the disclosure is to provide a treatment solution for forming a migration layer for forming a migration suppression layer which inhibits migration of copper ions between wirings and enhances an insulation reliability between the wirings. The treatment solution of the disclosure is a treatment solution for forming the migration suppression layer which inhibits migration of ions in copper wirings or copper alloy wirings. The treatment solution contains azole compounds and water, and has a dissolved oxygen content of 7.0 ppm or less.

Description

Process for forming migration inhibiting layer and method for producing laminated body having migration inhibiting layer

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 by using the treatment liquid.

In recent years, with the demand for higher functionality of electronic devices, high-density integration and high-density mounting of electronic components are progressing, and printed wiring boards and the like used in these electronic components are being miniaturized and high. Densification. In such a situation, the interval between the wirings in the printed wiring board is further narrowed, and in order to prevent short-circuiting between the wirings, the insulation reliability between the wirings is further required to be improved.

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

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

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-257451

[Patent Document 2] Japanese Patent Laid-Open No. Hei 10-321994

On the other hand, as described above, in recent years, the miniaturization of wiring is rapidly progressing, and the insulation reliability between wirings is required to be further improved.

The inventors of the present invention have studied the migration inhibiting layer using benzotriazole described in Patent Document 1 and Patent Document 2, and as a result, it has been confirmed that the copper dendrites are connected between the wirings, and the migration inhibiting effect is not obtained. Meet the latest requirements and need further improvement.

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 inhibiting layer which suppresses migration of copper ions between wirings and improves insulation reliability between wirings.

Further, an object of the present invention is to provide a method for producing a laminate having a migration inhibiting layer obtained by using the treatment liquid.

As a result of intensive studies by the inventors of the present invention, it has been found that the above problems can be solved by the following constitution.

(1) A treatment liquid for forming a migration suppression layer for forming a migration inhibiting layer for suppressing ion migration in a copper wiring or a copper alloy wiring, wherein the treatment liquid for forming a migration inhibiting layer contains an azole compound and water, and the dissolved oxygen amount It is below 7.0 ppm.

(2) The treatment liquid for forming a migration suppression layer according to (1), wherein the dissolved oxygen amount is less than 4.0 ppm.

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

(4) A method for producing a laminate having a migration inhibiting layer, comprising: a layer forming step of causing a wiring-attached substrate having a substrate and a copper wiring or a copper alloy wiring disposed on the substrate, and (1) to (3) The treatment liquid for forming a migration suppression layer according to any one of (3), wherein the substrate having the wiring is washed with a solvent, and a migration inhibiting layer containing an azole compound is formed on the surface of the copper wiring or the copper alloy wiring; The insulating layer forming step forms an insulating layer on the wiring-attached substrate provided with the migration inhibiting layer.

(5) A method for producing a layered body having a migration inhibiting layer, comprising the step of forming a layered body containing the exposed wiring and the migration inhibiting layer according to any one of (1) to (3) After the contact with the treatment liquid, the laminate including the exposed wiring is washed with a solvent, and a migration inhibiting layer is formed on the exposed copper wiring or copper alloy wiring surface. The laminated body including the exposed wiring has a substrate and is disposed on the substrate. In the copper wiring or the copper alloy wiring and the insulating layer, the insulating layer is disposed on the substrate, and the copper wiring and the copper alloy wiring are covered so that a part of the copper wiring or the copper alloy wiring is exposed.

According to the present invention, it is possible to provide a treatment liquid for forming a migration layer for forming a migration inhibiting layer which suppresses migration of copper ions between wirings and improves insulation reliability between wirings.

Further, according to the present invention, it is possible to provide a treatment liquid using the same A method for producing a laminate of the obtained migration inhibiting layer.

In the following, a preferred embodiment of the method for producing a layered body for treating a migration inhibiting layer of the present invention and a layered body having a migration inhibiting layer obtained by using the treating liquid will be described.

First, the problems of the prior art and the features of the present invention will be described in detail.

As a result of examining the problems of the prior art (the invention described in Patent Document 1), the inventors of the present invention first discovered that if the amount of dissolved oxygen present in the treatment liquid is large, the function of the migration inhibiting layer formed is insufficient. When the amount of dissolved oxygen in the treatment liquid is large, corrosion of the surface of the copper wiring or the copper alloy wiring is promoted. Therefore, the generation of copper ions is accelerated particularly in a high-humidity/voltage-increasing environment, and the ion trapping ability of the migration inhibiting layer is lowered, and as a result, a sufficient migration suppressing function cannot be exhibited.

In addition, the inventors of the present invention found that if a previous migration inhibitor such as benzotriazole remains on the substrate between the copper wiring or the copper alloy wiring (hereinafter, simply referred to as wiring), wiring is provided between the wirings. A poor connection or the like is formed between the insulating layer provided on the substrate and the substrate, which causes a short circuit. On the other hand, if the substrate is cleaned in order to remove the migration inhibitor existing in the wiring, the migration inhibitor on the copper wiring or the copper alloy wiring is simultaneously removed, and the desired effect is not exhibited.

Based on the above findings, the inventors of the present invention have found that the above-described problems of the prior art can be solved by using a treatment liquid for forming a migration inhibiting layer which contains an azole compound and exhibits a predetermined amount of dissolved oxygen.

In other words, by using a treatment liquid having a dissolved oxygen amount of a predetermined value or less, The corrosion of the copper wiring or the copper alloy wiring is suppressed in one step, and the coordination ability of the azole compound to the copper ions is maintained. As a result, migration of copper ions is suppressed.

Further, by using an azole compound as a heterocyclic ring compound, the azole compound on the wiring remains even after the cleaning treatment with a solvent, so that it is possible to remove the wiring remaining between the wirings, which may cause a short circuit between wirings. The migration inhibitor is formed and a migration inhibiting layer is 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 thereafter, a method for producing a laminate having a migration suppression layer obtained by using the treatment liquid will be described in detail.

[Treatment liquid for forming migration inhibiting layer]

The treatment liquid for forming a migration suppression layer (the 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 a copper wiring or a copper alloy wiring. The treatment liquid contains an azole compound and water, and the dissolved oxygen amount is 7.0 ppm or less.

Hereinafter, the components (azole compound, water, etc.) contained in the treatment liquid will be described in detail.

(azole compound)

The azole compound contained in the treatment liquid is a monocyclic heterocyclic 5-membered ring compound containing one or more nitrogen atoms in the ring. For example, a diazole having two nitrogen atoms, a triazole having three nitrogen atoms, and a tetrazole having four nitrogen atoms may be mentioned. More specifically, 1,2,3-triazole, 1,2,4-triazole, 1,2,4-triazole-3-carboxydecylamine, tetrazole, etc. are mentioned. Among them, from the viewpoint of further excellent copper ion migration inhibition effect, 1,2,3-triazole and 1,2,4-triazole are preferred.

Two or more kinds of azole compounds may be contained in the treatment liquid.

Further, the azole compound may have a substituent such as an alkyl group, a carboxyl group, a hydroxyl group or an amine group as long as the effects of the present invention are not impaired.

The total content of the azole compound in the treatment liquid is not particularly limited. However, from the viewpoint of easiness of formation of the migration inhibiting layer and control of the amount of adhesion of the migration inhibiting layer, it is preferably 0.01% by mass based on the total amount of the treatment liquid. ~10% by mass, more preferably 0.1% by mass to 5% by mass, particularly preferably 0.25% by mass to 5% by mass. When the total content of the oxazole compound is too large, it is difficult to control the amount of deposition of the migration inhibiting layer. When the total content of the oxazole compound is too small, it takes time until it becomes a desired amount of deposition of the migration inhibiting layer, and productivity is inferior.

On the other hand, when a benzotriazole or the like which is usually used in a corrosion inhibitor or the like is used as a substitute, most of the benzotriazole is washed away from the copper wiring or the copper alloy wiring by cleaning with a solvent described later. , can not get the desired effect. Further, in the case of a treatment liquid containing benzotriazole containing an excessive etchant or a treatment liquid containing an imidazole compound having an etching ability, the organic film formed on the copper wiring or the copper alloy wiring contains excessive copper ions. The film has no migration inhibiting ability and the desired effect cannot be obtained.

In the treatment liquid, water is usually contained as a solvent. The type of water to be used is not particularly limited, and examples thereof include distilled water, ion-exchanged water, tap water, and well water. Among them, distilled water is preferred because of less impurities such as ions.

The content of the water is not particularly limited, but is preferably from 90% by mass to 99.9% by mass, and more preferably from 95% by mass to 99.9% by mass, based on the total amount of the treatment liquid, from the viewpoint of the handleability of the treatment liquid. More preferably, it is 95 mass% - 97.5 mass%.

Further, in the treatment liquid, a solvent other than water may be contained in the range which does not impair the effects of the present invention.

For example, an alcoholic solvent (for example, methanol, ethanol, and isopropyl alcohol), a ketone solvent (for example, acetone, methyl ethyl ketone, and cyclohexanone), a guanamine solvent (for example, formazan, dimethyl Indoleamine, N-methylpyrrolidone), nitrile solvent (eg acetonitrile, propionitrile), ester solvent (eg methyl acetate, ethyl acetate), carbonate solvent (eg dimethyl carbonate, carbonic acid) An organic solvent such as an ethyl ester), an ether solvent or a halogen solvent. Two or more kinds of these solvents may be used in combination.

The amount of dissolved oxygen in the treatment liquid is 7.0 ppm or less. When the amount of dissolved oxygen is within this range, corrosion of copper in the copper wiring or the copper alloy wiring is suppressed, and the adsorption of the azole compound is further progressed, and a migration inhibiting layer having a high copper ion capturing ability can be formed. Further, from the viewpoint of forming a migration inhibiting layer having a higher migration inhibiting function, it is preferred that the dissolved oxygen amount is less than 4.0 ppm.

On the other hand, when the dissolved oxygen amount exceeds 7.0 ppm, when the wiring-attached substrate is brought into contact with the treatment liquid, corrosion occurs on the surface of the copper wiring or the copper alloy wiring, and the generation of copper ions is accelerated in a high-humidity and voltage-increasing environment. Therefore, the ion trapping ability of the migration inhibiting layer is used, and a sufficient migration inhibiting function cannot be exhibited.

The method for setting the dissolved oxygen amount of 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, and more specifically, it is possible to use a foam such as a polymer membrane or an inorganic membrane by foaming with an inert gas, and to use a vacuum. Gas component removal, or a combination of these.

As the inert gas, any one of nitrogen gas, argon gas, and helium gas is preferably used, or a combination thereof. In addition, in order to eliminate the influence of contamination, it is preferred that the inert gas be used as high as possible.

In addition, a well-known method can be used for the method of measuring the dissolved oxygen concentration, and for example, a dissolved oxygen meter DO-31P (manufactured by DKK-TOA Co., Ltd.) or a fluorescent dissolved oxygen meter LDO-HQ10 (manufactured by Hach Co., Ltd.) can be used. A commercially available dissolved oxygen meter is used for measurement.

On the other hand, from the viewpoint of improving the insulation reliability between the wirings in the laminate, it is preferred that the treatment liquid contains substantially no copper ions. When excessive copper ions are contained, when the migration inhibiting layer is formed, copper ions are contained in the layer, and the effect of suppressing migration of copper ions is sometimes weakened, and insulation reliability between wirings is impaired.

Further, the term "substantially free of copper ions" means that the content of copper ions in the treatment liquid is 1 μmol/l or less, more preferably 0.1 μmol/l or less. The best is 0 mol/l.

Further, from the viewpoint of improving the insulation reliability between the wirings in the laminated body, an etchant which does not substantially contain copper or a copper alloy in the treatment liquid is preferable. When an etchant is contained in the treatment liquid, when the substrate with wiring is brought into contact with the treatment liquid, copper ions may be eluted into the treatment liquid. Therefore, copper ions are contained in the migration inhibiting layer, and the effect of suppressing migration of copper ions is sometimes weakened, and insulation reliability between wirings is impaired.

Examples of the etchant include organic acids (for example, sulfuric acid, nitric acid, hydrochloric acid, acetic acid, formic acid, hydrofluoric acid), and oxidizing agents (for example, hydrogen peroxide, rich). Sulfuric acid), a chelating agent (for example, iminodiacetic acid, nitrogen triacetic acid, ethylenediaminetetraacetic acid, ethylenediamine, ethanolamine, aminopropanol), a thiol compound, and the like. Further, as the etchant, an etching action of copper itself, such as an imidazole or an imidazole derivative compound, is also included.

In addition, the content of the etchant in the treatment liquid is 0.01% by mass or less based on the total amount of the treatment liquid, and it is more preferable that the insulation reliability between the wirings is further improved. 0.001% by mass or less. The best is 0% by mass.

The pH of the treatment liquid is not particularly limited, but is preferably 5 to 12 from the viewpoint of the formation of the migration inhibiting layer. Among them, the pH is more preferably from 5 to 9, more preferably from 6 to 8, from the viewpoint of more excellent insulation reliability between wirings in the laminate.

When the pH of the treatment liquid is less than 5, the elution of copper ions from the copper wiring or the copper alloy wiring is promoted, and the migration inhibiting layer contains a large amount of copper ions, and as a result, the effect of suppressing migration of copper ions may be lowered. When the pH of the treatment liquid exceeds 12, the copper hydroxide precipitates and is easily oxidized and dissolved, and as a result, the effect of suppressing migration of copper ions may be lowered.

Further, the pH can be adjusted by using a known acid (for example, hydrochloric acid, sulfuric acid) or a base (for example, sodium hydroxide). Further, the measurement of pH can be carried out by using a known measurement method (for example, a pH meter (in the case of a water solvent)).

Further, other additives (for example, a pH adjuster, a surfactant, a preservative, an anti-precipitation agent, etc.) may be contained in the above treatment liquid.

[Method for Producing Laminated Body Having Migration Relief Layer (First Embodiment)]

As one of preferred embodiments of the method for producing a laminate having a migration inhibiting layer of the present invention, a production method in which a layer forming step, a drying step, and an insulating layer forming step are sequentially performed may be mentioned.

Hereinafter, the materials used in the respective steps and the procedures of the steps will be described with reference to the drawings.

[layer formation step]

In this step, first, a wiring-attached substrate having a substrate and a copper wiring or a copper alloy wiring (hereinafter also referred to as a wiring) disposed on the substrate is brought into contact with the processing liquid for forming a migration suppression layer (contact step). ). Thereafter, the wiring-attached substrate after the contact is washed with a solvent (cleaning solvent) to form a migration inhibiting layer containing an azole compound on the surface of the copper wiring or the copper alloy wiring (cleaning step). In other words, the contacting step is a step of bringing the wiring-attached substrate (more specifically, the surface of the wiring-attached substrate having the side of the copper wiring or the copper alloy wiring) into contact with the treatment liquid, and covering with the azole compound. The surface of the substrate with the wiring and the wiring surface. Further, the washing step is a step of removing the azole compound on the surface of the substrate by washing the substrate with the wiring with a solvent. By this step, the migration inhibiting layer is formed so as to cover the surface of the copper wiring or the copper alloy wiring, thereby suppressing migration of copper.

First, the material used in the layer forming step (substrate with wiring, etc.) will be described, and then the procedure of the layer forming step will be described.

(substrate with wiring)

The wiring-attached substrate (inner substrate) used in this step has a substrate and copper wiring or copper alloy wiring disposed on the substrate. In other words, The substrate with wiring is a laminated structure having at least a substrate and a copper wiring or a copper alloy wiring, and a copper wiring or a copper alloy wiring may be disposed on the outermost layer. 1(a) shows an embodiment of a substrate with wiring, and the substrate 10 with wiring has a substrate 12 and a copper wiring or a copper alloy wiring 14 disposed on the substrate 12 (hereinafter also referred to simply as wiring 14). ). In FIG. 1(a), the wiring 14 is provided only on one side of the substrate, but may be provided on both sides. That is, the substrate 10 with wiring may be a single-sided substrate or a double-sided substrate.

The substrate is not particularly limited as long as it can support the wiring, but is usually an insulating substrate. As the insulating substrate, for example, an organic substrate, a ceramic substrate, a tantalum substrate, a glass substrate, or the like can be used.

The material of the organic substrate is exemplified by a resin, and for example, a thermosetting resin, a thermoplastic resin, or a resin obtained by mixing these is preferably used. Examples of the thermosetting resin include a phenol resin, a urea resin, a melamine resin, an alkyd resin, an acrylic resin, an unsaturated polyester resin, a diallyl phthalate resin, an epoxy resin, an anthrone resin, and furan. Resin, ketone resin, xylene resin, benzocyclobutene resin, and the like. Examples of the thermoplastic resin include a polyimide resin, a polyphenylene ether resin, a polyphenylene sulfide resin, an aromatic polyamide resin, and a liquid crystal polymer.

Further, as a material of the organic substrate, a glass woven fabric, a glass non-woven fabric, an aromatic polyamide woven fabric, an aromatic polyamide woven fabric, an aromatic polyamide woven fabric, or the impregnation of the above resin may be used. Made of materials, etc.

The wiring contains copper or a copper alloy. When the wiring includes a copper alloy, examples of the metal other than copper contained include silver, tin, palladium, gold, nickel, chromium, and the like.

The method of forming the wiring on the substrate is not particularly limited, and a known method can be employed. Representative examples include a subtractive method using an etching treatment or a semi-additive method using electrolytic plating.

The width of the wiring is not particularly limited, but is preferably 1 μm to 1000 μm, and more preferably 3 μm to 25 μm from the viewpoint of high integration of the formed laminate when printed on a printed wiring board.

The interval between the wirings is not particularly limited, but it is preferably 1 μm to 1000 μm, more preferably 3 μm to 25 μm from the viewpoint of high integration of the laminated body formed on the printed wiring board. .

Further, the pattern shape of the wiring is not particularly limited, and may be any pattern. For example, a linear shape, a curved shape, a rectangular shape, a circular shape, etc. are mentioned.

The thickness of the wiring is not particularly limited, but is preferably 1 μm to 1000 μm, and more preferably 3 μm to 25 μm from the viewpoint of high integration of the formed laminate when printed on a printed wiring board.

The surface roughness Rz of the wiring is not particularly limited, but is preferably 0.001 μm to 15 μm, and more preferably 0.3 μm to 3 μm from the viewpoint of adhesion to an insulating layer to be described later.

As a method of adjusting the surface roughness Rz of the wiring, a known method can be used, and examples thereof include a chemical roughening treatment, a buffing treatment, and the like.

Further, Rz is measured in accordance with JIS B 0601 (1994).

The wiring-attached substrate used in this step may have wiring on the outermost layer, and another metal wiring (wiring pattern) and an interlayer insulating layer may be sequentially provided between the substrate and the wiring. Furthermore, it is also possible to alternately include two layers in the order of other metal wirings and interlayer insulating layers between the substrate and the wiring. Each of the above layers. That is, the substrate with wiring may be a so-called multilayer wiring substrate or a build up substrate.

As the interlayer insulating layer, a known insulating material can be used, and examples thereof include a phenol resin, a naphthalene resin, a urea resin, an amine resin, an alkyd resin, an epoxy resin, and an acrylate resin.

Further, the substrate with wiring may be a so-called rigid substrate, a flexible substrate, or a rigid-flex substrate.

In addition, a through hole may be formed in the substrate. When wiring is provided on both surfaces of the substrate, for example, a metal (for example, copper or a copper alloy) may be filled in the via hole to electrically connect the wiring on both sides.

(solvent (cleaning solvent))

The solvent (cleaning solvent) used in the cleaning step of cleaning the substrate with wiring is not particularly limited as long as the excess azole compound or the like deposited between the wirings on the substrate can be removed. Among them, a solvent which dissolves the azole compound is preferred. By using this solvent, excess azole compound deposited on the substrate or excess azole compound on the wiring can be removed more efficiently.

Examples of the solvent include water, an alcohol solvent (for example, methanol, ethanol, or propanol), a ketone solvent (for example, acetone, methyl ethyl ketone, and cyclohexanone), and a guanamine solvent (for example, formamide). Dimethylacetamide, N-methylpyrrolidone), nitrile solvent (eg acetonitrile, propionitrile), ester solvent (eg methyl acetate, ethyl acetate), carbonate solvent (eg dimethyl carbonate) Ester, diethyl carbonate), ether solvent, halogen solvent, and the like. Two or more kinds of these solvents may be used in combination.

Among them, from the viewpoint of the liquid permeability between the fine wiring lines, It is preferably a solvent containing at least one selected from the group consisting of water, an alcohol solvent, and methyl ethyl ketone, and more preferably water or a mixture of an alcohol solvent and water.

The boiling point of the solvent to be used (25 ° C, 1 atm) is not particularly limited, but from the viewpoint of safety, it is preferably from 75 ° C to 100 ° C, more preferably from 80 ° C to 100 ° C.

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

(procedure of layer forming step)

The layer forming step is divided into two steps of a contact step and a washing step.

(contact step)

First, a wiring-attached substrate having a substrate and a copper wiring or a copper alloy wiring disposed on the substrate is brought into contact with the processing liquid for forming a migration suppression layer. By bringing the wiring-attached substrate into contact with the processing liquid, as shown in FIG. 1(b), a layer 16 containing an azole compound is formed on the wiring-attached substrate 10. In other words, the contacting step is a step of covering the surface of the substrate 12 with the wiring 10 and the surface of the wiring 14 by the layer 16 containing the azole compound using the above-described processing liquid. This layer 16 is formed on the substrate 12 and on the wiring 14.

The azole compound is contained in the layer 16 containing the azole compound. The content and the like are substantially the same as those in the migration inhibiting layer described later. In addition, the amount of adhesion There is no particular limitation, and the amount of adhesion is preferably such that a migration inhibiting layer having a desired adhesion amount can be obtained after the washing step described later.

The method of contacting the substrate with wiring and the above treatment liquid is not particularly limited, and a known method can be employed. For example, immersion immersion, spray spray, spray coating, spin coating, and the like are exemplified, and the ease of treatment and the ease of adjustment of the treatment time are preferably soaking, spraying, and spraying.

In addition, the liquid temperature of the treatment liquid at the time of contact is preferably in the range of 5 ° C to 60 ° C, more preferably in the range of 15 ° C to 50 ° C, and more preferably from the viewpoint of controlling the amount of adhesion of the migration inhibiting layer. It is in the range of 20 ° C to 40 ° C.

In addition, 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 more preferably 30 seconds, from the viewpoint of productivity and control of the amount of adhesion of the migration inhibiting layer. ~5 minutes range.

(cleaning step)

Next, the wiring-attached substrate is washed with a solvent, and a migration inhibiting layer containing an azole compound is formed on the surface of the copper wiring or the copper alloy wiring. By carrying out this step, the azole compound on the surface of the substrate can be removed by washing. In particular, when a solvent in which the azole compound is dissolved is used as a solvent, an azole compound other than the azole compound on the surface of the copper wiring or the copper alloy wiring (particularly, an azole compound on the surface of the substrate) is more easily dissolved and removed. Specifically, the wiring-attached substrate 10 provided with the layer 16 containing the azole compound obtained in Fig. 1(b) is washed by the above-mentioned cleaning solvent, whereby the inclusion between the wirings 14 is as shown in Fig. 1(c). The layer 16 of the azole compound is removed, and the excess azole compound on the wiring 14 is removed, and the inclusion of the azole in the wiring 14 is formed. The migration inhibiting layer 18 of the compound.

The washing method is not particularly limited, and a known method can be employed. For example, a method of applying a cleaning solvent onto a substrate having a wiring, a method of immersing a substrate with wiring in a cleaning solvent, and the like can be mentioned.

In addition, the liquid temperature of the cleaning solvent is preferably in the range of 5 ° C to 60 ° C, and more preferably in the range of 15 ° C to 30 ° C from the viewpoint of controlling the amount of adhesion of the migration inhibiting layer.

In addition, 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 15 seconds to 5, from the viewpoint of productivity and control of the amount of adhesion of the migration inhibiting layer. The range of minutes.

(migration suppression layer (copper ion diffusion suppression layer))

By the above steps, as shown in FIG. 1(c), the migration inhibiting layer 18 containing the azole compound can be formed on the surface of the copper wiring or the copper alloy wiring 14. That is, the migration suppressing layer 18 covers the surface of the copper wiring or the copper alloy wiring 14.

Further, as shown in FIG. 1(c), the layer containing the azole compound between the wires 14 is substantially removed. That is, it is preferable that the migration inhibiting layer 18 is formed substantially only on the surface of the copper wiring or the copper alloy wiring 14.

In the present invention, even after the cleaning of the solvent described above, a migration inhibiting layer having a sufficient adhesion amount capable of suppressing migration of copper ions can be obtained.

The content of the azole compound in the migration inhibiting layer is preferably from 0.1% by mass to 100% by mass, more preferably from 20% by mass to 100% by mass, even more preferably 50%, from the viewpoint of further suppressing migration of copper ions. %~90% by mass. In particular, it is preferred that the migration inhibiting layer be substantially composed of an azole compound. When the content of the azole compound is too small, the effect of suppressing migration of copper ions is lowered.

Preferably, the migration inhibiting layer contains substantially no copper ions or metallic copper. When a predetermined amount or more of copper ions or metallic copper is contained in the migration inhibiting layer, the effect of the present invention may be unsatisfactory.

From the viewpoint of further suppressing the migration of copper ions, the adhesion amount of the azole compound on the surface of the copper wiring or the copper alloy wiring is preferably 5 × 10 ^-9 g / mm with respect to the total surface area of the copper wiring or the copper alloy wiring. ² to 1×10 ^-6 g/mm ² , more preferably 5×10 ^-9 g/mm ² to 2×10 ^-7 g/mm ² , and even more preferably 5×10 ^-9 g/mm ² to 6 ×10 ^-8 g/mm ² .

Further, the amount of adhesion can be measured by a known method (for example, an absorbance method). Specifically, in the absorbance method, first, a migration inhibiting layer (extraction method using water) existing between wirings is washed with water. Thereafter, the migration inhibiting layer on the copper wiring or the 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.

Further, as described above, it is preferable that the layer containing the azole compound between the wirings is substantially removed, but a part of the layer containing the azole compound may remain in the range which does not impair the effect of the present invention.

[Drying step]

In this step, the wiring-attached substrate provided with the migration inhibiting layer is dried by heating. If moisture remains on the substrate with the wiring, the migration of copper ions may be promoted. Therefore, it is preferable to remove the moisture by providing this step.

From the viewpoint of suppressing oxidation of the copper wiring or the copper alloy wiring as the heating and drying conditions, it is preferably carried out at 70 ° C to 120 ° C (preferably 80 ° C to 110 ° C) for 15 seconds to 10 minutes (preferably 30 seconds to 5 minutes). If the drying temperature is too low or the drying time is too short, the removal of moisture may not be sufficient. If the drying temperature is too high or the drying time is too long, copper oxide may be formed.

The apparatus for drying is not particularly limited, and a known heating device such as a constant temperature layer or a heater can be used.

In addition, this step is an arbitrary step, and when the solvent used in the layer formation step is a solvent having excellent volatility, the step may not be carried out.

[Insulation layer forming step]

In this step, an insulating layer is formed on the wiring-attached substrate provided with the migration inhibiting layer. As shown in FIG. 1(d), the insulating layer 20 is provided on the substrate 10 with wiring so as to be in contact with the wiring 14 on the surface where the migration suppressing layer 18 is provided. By providing the insulating layer 20, the insulation reliability between the wirings 14 is further ensured. Further, since the substrate 12 and the insulating layer 20 can be in direct contact with each other, the insulating layer 20 is excellent in adhesion.

First, the insulating layer to be used will be described, and next, a method of 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, and specific examples thereof include an epoxy resin, an aromatic polyamide resin, a crystalline polyolefin resin, an amorphous polyolefin resin, and a fluorine-containing resin ( Polytetrafluoroethylene, perfluoropolyimine, perfluorinated amorphous resin, etc.), polyimide resin, polyether oxime resin, polyphenylene sulfide resin, polyether ether ketone resin, acrylate resin, and the like. As the interlayer insulating layer, for example, Ajinomoto Fine-Techno (stock) system can be cited. Made of ABF GX-13 and so on.

Further, as the insulating layer, a so-called solder resist layer can also be used. A commercially available product can be used as the solder resist. Specific examples thereof include PFR800 and PSR4000 (trade name) manufactured by Sun Ink Manufacturing Co., Ltd., and SR7200G manufactured by Hitachi Chemical Co., Ltd.

The method of forming the insulating layer on the substrate with wiring is not particularly limited, and a known method can be employed. For example, a method of directly laminating a film of an insulating layer on a substrate having a wiring, or a method of applying a composition for forming an insulating layer containing a component constituting the insulating layer to a substrate having a wiring, or A method of immersing a wiring-attached substrate in the composition for forming an insulating layer.

Further, the insulating layer forming composition may contain a solvent as needed. When a composition for forming an insulating layer containing a solvent is used, after the composition is placed on the substrate, heat treatment may be performed to remove the solvent as necessary.

Further, after the insulating layer is provided on the wiring-attached substrate, energy may be applied to the insulating layer (for example, exposure or heat treatment).

The film thickness of the insulating layer to be formed is not particularly limited, and is preferably 5 μm to 50 μm, and more preferably 15 μm to 40 μm from the viewpoint of insulation reliability between wirings.

In Fig. 1(d), the insulating layer is described as one layer, but may have a multilayer structure.

(Laminar body with migration suppression layer)

By the above steps, as shown in FIG. 1(d), the following can be obtained. The laminated body 30 (the first embodiment of the laminated body having the migration inhibiting layer) includes the substrate 12, the wiring 14 disposed on the substrate 12, and the insulating layer 20 disposed on the wiring 14, and the migration suppressing layer 18 is interposed 14 is between the insulating layer 20. The insulation reliability between the wirings 14 of the laminated body 30 obtained is excellent, and the adhesion between the insulating layer 20 and the wiring-attached substrate 10 is also excellent.

Further, as shown in FIG. 1(d), the laminated body having one wiring structure is exemplified above, and of course, it is not limited thereto. For example, a laminate having a multilayer wiring structure can be manufactured by using a substrate having a multilayer wiring in which another metal wiring (metal wiring layer) and interlayer insulation are interposed between the substrate and the metal wiring. The layers are alternately laminated in this order.

The laminate obtained by the production method of the present invention can be used for various applications and structures, and examples thereof include a printed wiring board, a mother board substrate, or a semiconductor package substrate, and a molded interconnect device (MID) substrate. For example, it can be used for a rigid substrate, a flexible substrate, a rigid-flex substrate, a molded circuit substrate, or the like.

Further, a part of the insulating layer in the obtained laminated body may be removed, and a semiconductor wafer may be mounted for use as a printed circuit board.

For example, when a solder resist is used as the insulating layer, a predetermined pattern-shaped mask is placed on the insulating layer, energy is applied to be cured, and the insulating layer in the region where no energy is applied is removed to expose the wiring. Then, the surface of the exposed wiring is cleaned (for example, by using sulfuric acid or a surfactant) by a known method, and then the semiconductor wafer is mounted on the wiring surface.

When a well-known interlayer insulating layer is used as the insulating layer, it can be drilled Processing or laser processing to remove the insulation.

Further, a metal wiring (wiring pattern) may be further provided on the insulating layer of the obtained laminated body. The method of forming the metal wiring is not particularly limited, and a known method (plating treatment, sputtering treatment, or the like) can be used.

In the present invention, a substrate in which a metal wiring (wiring pattern) is further provided on the insulating layer of the obtained laminated body can be used as a new wiring-attached substrate (inner substrate), and a plurality of layers of insulation are newly laminated. Layer and metal wiring.

[Method for Producing Laminated Body Having Migration Suppression Layer (Second Embodiment)]

Another preferred embodiment of the method for producing a laminate having a migration inhibiting layer of the present invention includes a layer forming step and a drying step in which the layer forming step uses the following exposed wiring. A laminate having exposed wiring (hereinafter also referred to simply as a laminate including exposed wiring) is provided in place of the wiring-attached substrate having a substrate, a copper wiring or a copper alloy wiring disposed on the substrate, and a substrate disposed on the substrate The insulating layer of the copper wiring and the copper alloy wiring is covered so that a part of the copper wiring or the copper alloy wiring is exposed.

Hereinafter, the materials used in the respective steps and the procedures of the steps will be described with reference to the drawings.

[layer formation step]

In this step, first, the layered body including the exposed wiring is brought into contact with the treatment liquid for forming the migration suppression layer (contact step). Thereafter, the layered body including the exposed wiring is cleaned by a solvent (cleaning solvent) to be exposed A migration inhibiting layer containing an azole compound is formed on the surface of the copper wiring or the copper alloy wiring (cleaning step).

By this step, the migration layer is formed so as to cover the surface of the exposed copper wiring or the copper alloy wiring, thereby suppressing the migration of copper.

First, the material used in the layer forming step (the layered body including the exposed wiring) will be described, and then the procedure of the layer forming step will be described.

(Laminated body with exposed wiring)

The laminate including the exposed wiring used in this step includes a substrate, a copper wiring or a copper alloy wiring (hereinafter also referred to simply as a wiring) disposed on the substrate, and a copper wiring or a copper alloy wiring disposed on the substrate. A portion of the exposed layer covers the insulation of the copper wiring and the copper alloy wiring. In FIG. 2, the laminated body 40 including the exposed wiring includes a substrate 12, a copper wiring or a copper alloy wiring 14 (hereinafter also referred to simply as the wiring 14), and an insulating layer 20. The wiring 14 includes exposed copper wiring or copper alloy wiring (hereinafter also referred to simply as wiring 14a), and copper wiring or copper alloy wiring (hereinafter also simply referred to as wiring 14b) covered with the insulating layer 20.

Further, in FIG. 2, the exposed wiring 14a is supported on the substrate 12, but a part thereof may extend outside the substrate 12.

The form (type, etc.) of the substrate in the laminated body including the exposed wiring used in this step is the same as that of the substrate in the wiring-attached substrate (inner layer substrate) used in the first embodiment.

Among them, as the substrate (particularly, an insulating substrate), for example, an organic substrate, a thin glass epoxy substrate, or the like is preferably used. A so-called flexible printed wiring board can be obtained by using a substrate such as an organic substrate. In addition, by using the package A rigid substrate including a glass epoxy substrate can be obtained as a so-called rigid printed wiring board.

The material of the organic substrate may, for example, be a resin, and examples thereof include a polyimide resin, a polyester resin, and a liquid crystal polymer.

The form of the copper wiring or the copper alloy wiring in the laminated body including the exposed wiring used in this step (the type, width, interval, thickness, and the like of the material) and the wiring-attached substrate used in the first embodiment ( The copper wiring or the copper alloy wiring of the inner layer substrate has the same form.

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, and may be any copper wiring or copper alloy wiring portion that can be electrically connected to an electronic component (for example, a semiconductor element) mounted on the substrate.

The form (type, etc.) of the insulating layer in the laminated body including the exposed wiring used in this step is the same as that of the insulating layer in the wiring-attached substrate (inner layer substrate) used in the first embodiment. More specifically, examples of the insulating material constituting the insulating layer include a polyimide resin, a polyester resin, and the like.

Further, as the insulating layer, a screen printing ink or a photosensitive cover layer may also be used.

Further, the method for producing the laminate including the exposed wiring is not particularly limited, and a known method can be employed. For example, a substrate having copper wiring is first produced by applying a subtractive method or a semi-additive method to a substrate with a copper foil. Next, an insulating film is laminated on the substrate to form an insulation covering a portion of the copper wiring. Floor.

(solvent (cleaning solvent))

The solvent (cleaning solvent) used in the cleaning step of cleaning the laminate including the exposed wiring is not particularly limited as long as the excess azole compound or the like deposited on the surface other than the surface of the copper wiring or the copper alloy can be removed, and the above-mentioned first 1 Solvent (cleaning solvent) used in the embodiment.

(procedure of steps)

The layer forming step is divided into two steps of a contact step and a washing step.

(contact step)

The contacting step is a step of bringing the layered body including the exposed wiring into contact with the processing liquid for forming a migration layer. Specifically, as shown in FIG. 3( a ), a laminate including an exposed wiring including the substrate 12 and the exposed copper wiring or copper alloy wiring 14 a is prepared, and the laminated body including the exposed wiring and the migration inhibiting layer are prepared. The formation treatment liquid is brought into contact, whereby as shown in FIG. 3(b), a layer 16 containing an azole compound is formed on the substrate 12 and the exposed wiring 14a. This layer 16 is formed on the substrate 12, on the wiring 14a, and on an insulating layer (not shown).

The procedure and conditions of the contact step are set according to the same procedures and conditions as those of the contact step carried out in the first embodiment.

(cleaning step)

The washing step is a step of forming a migration inhibiting layer containing an azole compound on the surface of the copper wiring or the copper alloy wiring by using a solvent to clean the laminate including the exposed wiring obtained by the contacting step.

Specifically, the layered body including the exposed wiring provided with the layer 16 containing the azole compound obtained in FIG. 3(b) is washed by the above-described cleaning solvent, whereby the inclusion between the wires 14a is as shown in FIG. 3(c). The layer 16 of the azole compound is removed, and the excess azole compound on the wiring is removed, and the migration inhibiting layer 18 is formed on the wiring 14a. Further, while the layer 16 containing the azole compound between the wiring 14a is removed, the layer 16 containing the azole compound on the insulating layer (not shown) is also removed.

The procedures and conditions of the washing step are set according to the same procedures and conditions as those of the washing step carried out in the first embodiment.

(migration suppression layer)

By the above steps, a migration inhibiting layer containing an azole compound can be formed on the exposed copper wiring or copper alloy wiring surface. Further, as shown in FIG. 3(c), it is preferable that the layer containing the azole compound is substantially removed on the surface other than the surface of the exposed wiring 14a. That is, it is preferable that the migration suppressing layer 18 is formed substantially only on the surface of the exposed wiring 14a. Further, the surface of the wiring 14a is an upper surface and a side surface other than the lower surface in contact with the substrate 12 as shown in FIG. 3(c).

The form of the migration inhibiting layer (the content of the azole compound, the amount of adhesion, and the like) is the same as that of the migration inhibiting layer obtained in the first embodiment.

[Drying step]

In this step, the layered body provided with the migration inhibiting layer is dried by heating. If moisture remains on the laminate, the migration of copper ions may be promoted. Therefore, it is preferred to remove the moisture by providing this step.

In addition, this step is an arbitrary step, and when the solvent used in the layer formation step is a solvent having excellent volatility, the step may not be carried out.

The procedure and conditions of the drying step are set according to the same procedures and conditions as those of the drying step carried out in the first embodiment.

(Laminar body with migration suppression layer)

By the above-described production method, a laminate (a second embodiment having a laminate having a migration suppression layer) having a substrate, a copper wiring or a copper alloy wiring disposed on the substrate, and a copper wiring can be obtained. Or a migration inhibiting layer containing an azole compound on the surface of a part of the copper alloy wiring, and an insulating layer disposed on the substrate and covering the surface of the residual portion of the copper wiring or the copper alloy wiring. In other words, the laminated body is covered with an insulating layer by a part of the copper wiring or the copper alloy wiring, and the surface of the copper wiring or the copper alloy wiring which is not covered by the insulating layer is covered with the migration-inhibiting layer containing the azole compound and has the surface-covered wiring. Laminated body.

More specifically, as shown in FIG. 4 , the laminated body 100 having the surface-covered wiring having the substrate 12 , the wiring 14 disposed on the substrate 12 , and the wiring 12 disposed on the substrate 12 can be obtained. A part of the insulating layer 20 and a migration inhibiting layer 18 on the surface of the wiring 14a on which the insulating layer 20 is not provided.

The obtained laminate can be used for various purposes, for example, as a substrate for a printed wiring board, a chip on film (COF) substrate, or a Tape Automated Bonding (TAB) substrate.

[Example]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples.

(Example 1)

A polyimide film (a Kapton film manufactured by Toray DuPont Co., Ltd.) is used to form a laminate including an exposed wiring having a comb-shaped copper wiring and an insulating layer of L/S = 100 μm/100 μm (corresponding to a printed wiring board) . The laminate including the exposed wiring was produced by the following method.

20 μm thick copper foil (F3-WS foil manufactured by Furukawa Electric Co., Ltd.) was bonded to a 25 μm thick polyimide film (made by Toray DuPont) via a 25 μm thick adhesive (N4 manufactured by Hitachi Chemical Co., Ltd.) Kapton film).

A photoresist (Photec H-W425 manufactured by Hitachi Chemical Co., Ltd.) was laminated on a copper foil tape at 100 ° C under conditions of 4 kgf/cm ² , and exposed through a mask at 80 mJ/cm ² . Development is then carried out to form a resist pattern.

Thereafter, the copper foil not covered by the resist was selectively etched away by using a ferric chloride etching solution, and then the 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 a laminate including exposed wiring. Further, about half of the copper wiring in the obtained laminate including the exposed wiring was covered with an insulating layer.

Dissolving 1,2,4-triazole-3-carboxyguanamine in nitrogen for about 1 hour In the pure water-foamed water, a treatment liquid for forming a migration inhibiting layer (content of 1,2,4-triazole-3-carboxyguanamine in the treatment liquid: 2.5% by mass) was prepared. The amount of dissolved oxygen in the treatment liquid was measured by a dissolved oxygen meter DO-31P (DKK-TOA), and as a result, the dissolved oxygen amount was 2.0 ppm.

Then, the obtained laminate containing the exposed wiring was immersed in the produced treatment liquid for 5 minutes. Thereafter, a laminate including exposed wiring (contact time: 2 minutes, liquid temperature: 25 ° C) obtained by washing with ethanol was used to obtain a laminate having a migration inhibiting layer (corresponding to a flexible printed wiring board). Further, the laminate was dried at 100 ° C for 2 minutes.

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

(Measurement of substrate life by drop drop test)

Using the obtained laminate, under the conditions of an applied voltage of 1.2 V for 5 minutes and 10 minutes in pure water having a conductivity of 0.05 μS/cm ² and 30 mL, under an optical microscope (Olympus) Production BX-51) The production of dendrites was measured, and the dendrites were dendrites between the wirings from the anode to the cathode between the wirings not covered with the insulating layer. The results obtained in Example 1 are shown in Table 1.

Furthermore, evaluation was performed based on the following criteria.

"○": No occurrence of dendrite in the wiring closet

"△": The occurrence of dendrites was observed in the wiring closet, but no dendrite was formed in the wiring closet, and there was no problem in practical use.

"X": The dendrite that connects the wiring closet is generated. Situation

(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-carboxydecylamine. Thereafter, the water drop dropping test carried out in Example 1 was carried out using the obtained laminate. The results are shown in Table 1.

(Example 3)

A laminate was produced according to the same procedure as in Example 1 except that 1,2,4-triazole was used instead of 1,2,4-triazole-3-carboxydecylamine. Thereafter, the water drop dropping test carried out in Example 1 was carried out using the obtained laminate. The results are shown in Table 1.

(Example 4)

In Example 3, a laminate was produced according to the same procedure as in Example 3 except that the time for bubbling nitrogen gas was changed from 1 hour to 5 minutes. Thereafter, the water drop dropping test carried out in Example 1 was carried out using the obtained laminate. The results are shown in Table 1.

(Example 5)

In Example 3, a laminate was produced according to the same procedure as in Example 3 except that the time for bubbling nitrogen gas was changed from 1 hour to 30 minutes. Thereafter, the water drop dropping test carried out in Example 1 was carried out using the obtained laminate. The results are shown in Table 1.

(Example 6)

A copper clad laminate (MCL-E-679F manufactured by Hitachi Chemical Co., Ltd., substrate: glass epoxy substrate) was used, and formed by a semi-additive method with L/S=23 Wiring board with copper wiring of μm/27 μm. The substrate with wiring is fabricated by the following method.

After the copper-clad laminate was subjected to acid cleaning, water washing, and drying, a dry film resist (DFR, trade name: RY3315, Hitachi Chemical Co., Ltd.) was laminated at 70 ° C under a pressure of 0.2 MPa using a vacuum laminator. Made by Ltd.). After lamination, the copper pattern forming portion was mask exposed at 70 mJ/m ² using an exposure machine having a center wavelength of 365 nm. Thereafter, development was carried out using a 1% aqueous sodium carbonate solution, and water washing was carried out to obtain a pattern of the plating resist.

After pre-plating treatment and water washing, electrolytic plating is performed on the copper exposed between the resist patterns. At this time, in the electrolytic solution, a sulfuric acid acidic solution of copper (II) sulfate was used, and a plate of crude copper having a purity of about 99% was made into an anode, and a copper-clad laminate was made into a cathode. Electrolysis is carried out at 50 ° C to 60 ° C and 0.2 V to 0.5 V, whereby copper is deposited on the copper of the cathode. Thereafter, it is washed with water and dried.

In order to peel off 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 then immersed in 1% sulfuric acid for 30 seconds. Thereafter, the water was washed again.

The copper which is turned on between the copper patterns is quickly etched by an etching solution containing hydrogen peroxide or sulfuric acid as a main component, and then washed with water and dried.

Then, the surface of the copper wiring was removed by a pretreatment agent (manufactured by MEC Corporation, CA-5330), and then the surface of the copper wiring was roughened by a roughening treatment agent (CZ-8110 manufactured by MEC Corporation).

Then, the obtained wiring-attached substrate was immersed in the treatment liquid for forming migration suppression layer used in Example 3 for 30 seconds. Thereafter, use ethanol The obtained substrate with wiring was cleaned (contact time: 2 minutes, liquid temperature: 25 ° C). Further, the substrate with wiring was dried at 100 ° C for 2 minutes.

By performing reflectance measurement, it was confirmed that a migration inhibiting layer containing 1,2,4-triazole was formed on the copper wiring.

In addition, in the surface of the substrate between the copper wirings, the migration inhibiting layer could not be confirmed by the absorbance measurement of the inter-wiring extract using water, and it was confirmed that the migration inhibiting layer was removed by ethanol washing.

An insulating layer (PFR-800 manufactured by Sun Ink Co., Ltd.) was laminated on a wiring-attached substrate subjected to a drying process, and then exposed and baked to form a laminate having a migration inhibiting layer (corresponding to a printed wiring) Substrate) (film thickness of insulating layer: 35 μm). The following life measurement was performed on the obtained laminate.

(Measurement of substrate life using Highly Accelerated Stress Test (HAST))

Using the obtained laminate, the life measurement was carried out 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 (using apparatus: manufactured by Espec Corporation, EHS-221MD).

As a method of evaluation, a test of 20 shots was carried out, and the resistance value between the wirings was 1 × 10 ⁹ Ω as a reference resistance value. The rod whose resistance value was greater than or equal to the reference resistance value after 120 hours from the start of the test was set as the pass.

The results obtained in Example 6 are shown in Table 1.

(Comparative Example 1)

In Example 3, oxygen foaming was performed instead of nitrogen foaming and used. A laminate was produced according to the same procedure as in Example 3 except that the treatment liquid for forming a migration suppression layer was dissolved in an amount of 8.5 ppm. Thereafter, the water drop dropping test carried out in Example 1 was carried out using the obtained laminate. The results are shown in Table 1.

(Comparative Example 2)

A laminate was produced according to the same procedure as in Example 1 except that ethylenediaminetetraacetic acid was used instead of the 1,2,4-triazole-3-carboxyoximeamine used in Example 1. Thereafter, the water drop dropping test carried out in Example 1 was carried out using the obtained laminate. The results are shown in Table 1.

(Comparative Example 3)

A laminate was produced according to the same procedure as in Example 1 except that benzotriazole was used instead of the 1,2,4-triazole-3-carboxyguanamine used in Example 1. Thereafter, the water drop dropping test carried out in Example 1 was carried out using the obtained laminate. The results are shown in Table 1.

(Comparative Example 4)

In Example 6, a laminate was produced according to the same procedure as in Example 6 except that oxygen foaming was used instead of nitrogen foaming, and a treatment liquid for forming a migration suppression layer having a dissolved oxygen amount of 8.5 ppm was used. Thereafter, the HAST test carried out in Example 6 was carried out using the obtained laminate. The results are shown in Table 1.

In Table 1 below, the numerical value in the column of the life measurement indicates (the number of rods of 1 × 10 ⁹ Ω or more after 120 hours), and 20/20 is the best result.

In addition, in Table 1, "pH" is used in each example and comparative example. The migration inhibitor treats the pH of the solution. The pH was measured using a pH meter (manufactured by DKK-TOA Co., Ltd.). The "adhesion amount" in Table 1 indicates the amount of the compound (1,2,3-triazole, 1,2,4-triazole, etc.) contained in the treatment liquid on the copper wiring, and the measurement is performed by the above. The absorbance method is used.

As shown in Table 1, in Examples 1 to 5 in which the treatment liquid for forming a migration suppression layer of the present invention was used, the connection of dendrites between the wirings was not observed, and migration of copper ions was suppressed.

In particular, in the case of the dissolved oxygen amount in Examples 1 to 3 and Example 5, even when the application time of the voltage for dropping the water drop test was changed from 5 minutes to 10 minutes, no dendritic crystals between the wirings were observed. produce. That is, when the dissolved oxygen amount is less than 4.0 ppm, the insulation reliability between the wirings is further excellent.

Further, as shown in Example 6, it was confirmed that the endurance measurement result was excellent in the HAST test, and 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 the azole compound, and Comparative Example 3 using a benzotriazole compound, it was confirmed that the connection wiring was confirmed. The generation of dendrites and the effect of suppressing migration between wiring lines are not good. Further, as shown in Comparative Example 4, in the HAST test, the insulation reliability between wirings was also poor.

10‧‧‧Substrate with wiring

12‧‧‧Substrate

14‧‧‧Bronze wiring or copper alloy wiring

14a‧‧‧ exposed copper wiring or copper alloy wiring

14b‧‧‧Copper wiring or copper alloy wiring covered by insulating layer

16‧‧‧layer containing azole compound

18‧‧‧migration suppression layer

20‧‧‧Insulation

30, 100‧‧‧Layer with migration inhibition layer

40‧‧‧Laminated body with exposed wiring

1(a) to 1(d) are schematic cross-sectional views showing, in order, the respective steps in the first embodiment of the method for producing a layered product having a migration inhibiting layer of the present invention.

Fig. 2 is a perspective cross-sectional view showing a part of a laminate including exposed wiring used in the present invention.

3(a) to 3(c) are schematic cross-sectional views showing, in order, the respective steps in the second embodiment of the method for producing a layered product having a migration inhibiting layer of the present invention. Fig. 3 (a) is a cross-sectional view taken along line A-A of Fig. 1.

Fig. 4 is a perspective cross-sectional view showing a part of a second embodiment of a laminate having a migration suppression layer according to the present invention.

12‧‧‧Substrate

14‧‧‧Bronze wiring or copper alloy wiring

14a‧‧‧ exposed copper wiring or copper alloy wiring

14b‧‧‧Copper wiring or copper alloy wiring covered by insulating layer

18‧‧‧migration suppression layer

20‧‧‧Insulation

100‧‧‧Layer with migration inhibition layer

Claims (5)

A treatment liquid for forming a migration suppression layer for forming a migration inhibiting layer for suppressing ion migration in a copper wiring or a copper alloy wiring, wherein the treatment liquid for forming a migration inhibiting layer contains an azole compound and water, and the dissolved oxygen amount is 7.0 ppm. the following. The treatment liquid for forming a migration suppression layer according to Item 1, wherein the amount of dissolved oxygen is less than 4.0 ppm. The treatment liquid for forming a migration inhibiting layer according to the above aspect of the invention, wherein the azole compound comprises 1,2,3-triazole and/or 1,2,4-triazole. A method for producing a laminate having a migration inhibiting layer, comprising: a layer forming step of causing a wiring-attached substrate having a substrate and a copper wiring or a copper alloy wiring disposed on the substrate, and the first item of the patent application scope When the treatment liquid for forming a migration suppression layer according to any one of the items 3 is contacted, the substrate having the wiring is washed with a solvent, and migration inhibition of the azole compound is formed on the surface of the copper wiring or the copper alloy wiring. And an insulating layer forming step of forming an insulating layer on the wiring-equipped substrate on which the migration inhibiting layer is provided. A method for producing a laminate having a migration inhibiting layer, comprising the step of forming a laminate comprising exposed wiring and a migration inhibiting layer according to any one of claims 1 to 3 Contact with the treatment liquid, and then the above-mentioned laminated body containing the exposed wiring is washed with a solvent to be exposed The migration preventing layer is formed on the surface of the copper wiring or the copper alloy wiring, and the laminated body including the exposed wiring includes a substrate, the copper wiring or the copper alloy wiring and the insulating layer disposed on the substrate, and the insulating layer is disposed on the substrate. Further, the copper wiring or the copper alloy wiring is covered so that a part of the copper wiring or the copper alloy wiring is exposed.