KR20140024906A - Treatment solution for forming migration suppression layer, and production method for laminate having migration suppression layer - Google Patents

Abstract

An object of this invention is to provide the process liquid for migration suppression layer formation for forming the migration suppression layer which suppresses migration of copper ion between wirings, and improves insulation reliability between wirings. The process liquid for migration suppression layer formation of this invention is a process liquid for forming the migration suppression layer which suppresses ion migration in a copper wiring or a copper alloy wiring, contains an azole compound and water, and dissolved oxygen amount is 7.0 ppm It is as follows.

Description

The manufacturing method of the laminated body which has a process liquid for migration suppression layer formation, and a migration suppression layer {TREATMENT SOLUTION FOR FORMING MIGRATION SUPPRESSION LAYER, AND PRODUCTION METHOD FOR LAMINATE HAVING MIGRATION SUPPRESSION LAYER}

This invention relates to the processing liquid for migration suppression layer formation, and the manufacturing method of the laminated body which has a migration suppression layer obtained using this process liquid.

In recent years, with the demand for high functionalization of electronic devices, high density integration of electronic components, high density mounting, and the like have progressed, and miniaturization and high density of printed wiring boards and the like used in them have also advanced. Under such a situation, the spacing of wirings in the printed wiring board is narrower, and further improvement of insulation reliability between wirings is required to prevent short circuits between wirings.

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

As a method of preventing such migration, the technique of forming the migration suppression layer using benzotriazole is proposed (patent document 1 and 2). More specifically, in these documents, a layer for suppressing the migration of copper ions is formed on the wiring board, and the aim is to improve the insulation reliability between the wirings.

Japanese Laid-Open Patent Publication 2001-257451 Japanese Patent Laid-Open No. 10-321994

On the other hand, as mentioned above, in recent years, the refinement | miniaturization of wiring is progressing rapidly, and the further improvement about the insulation reliability between wirings is calculated | required.

MEANS TO SOLVE THE PROBLEM When the present inventors examined the migration suppression layer using the benzotriazole described in patent document 1 and 2, the connection of the copper dendrites was confirmed between wirings, and the migration suppression effect satisfies the level requested | required these days. It was not made, and further improvement was needed.

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

Moreover, this invention also makes it the objective to provide the manufacturing method of the laminated body which has a migration suppression layer obtained using this process liquid.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the said subject could be solved by the following structures.

(1) The process liquid for migration suppression layer formation containing an azole compound and water, and forming a migration suppression layer which suppresses ion migration in copper wiring or copper alloy wiring whose dissolved oxygen amount is 7.0 ppm or less.

(2) The process liquid for migration suppression layer formation as described in (1) whose dissolved oxygen amount is less than 4.0 ppm.

(3) The process liquid for migration suppression layer formation as described in (1) or (2) in which an azole compound contains 1,2,3-triazole and / or 1,2,4-triazole.

(4) The board | substrate with which the wiring which has the copper wiring or copper alloy wiring arrange | positioned on a board | substrate and a board | substrate was formed, and the process liquid for migration suppression layer formation in any one of (1)-(3) is made to contact, and then wiring The layer formation process of wash | cleaning this formed board | substrate with a solvent, and forming the migration suppression layer containing an azole compound on the copper wiring or copper alloy wiring surface,

The manufacturing method of the laminated body which has a migration suppression layer provided with the insulating layer formation process of forming an insulation layer on the board | substrate with wiring in which the migration suppression layer was formed.

(5) Contains exposed wiring having a substrate, a copper wiring or copper alloy wiring disposed on the substrate, and an insulating layer disposed on the substrate and covering the copper wiring or copper alloy wiring so that a portion of the copper wiring or copper alloy wiring is exposed. The laminated body and the process liquid for migration suppression layer formation in any one of (1)-(3) are contacted, and the exposed wiring containing laminated body is wash | cleaned with a solvent after that, on the exposed copper wiring or copper alloy wiring surface. The manufacturing method of the laminated body which has a migration suppression layer provided with the layer formation process which forms a migration suppression layer in the process.

According to this invention, the process liquid for migration suppression layer formation for forming the migration suppression layer which suppresses migration of copper ion between wirings, and improves insulation reliability between wirings can be provided.

Moreover, according to this invention, the manufacturing method of the laminated body which has a migration suppression layer obtained using this process liquid can also be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows each process in order in the 1st Embodiment of the manufacturing method of the laminated body which has a migration suppression layer of this invention in order.
2 is a perspective cross-sectional view of a part of the exposed wiring-containing laminate used in the present invention.
It is typical sectional drawing which shows each process in order 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 sectional drawing along the AA line of FIG.
4 is a perspective cross-sectional view of a portion of a second embodiment of a laminate having a migration suppression layer of the present invention.

EMBODIMENT OF THE INVENTION Below, the suitable aspect of the manufacturing method of the laminated body which has the processing liquid for migration suppression layer formation of this invention, and the migration suppression layer obtained using this processing liquid is demonstrated.

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

MEANS TO SOLVE THE PROBLEM As a result of having examined the problem of the prior art (invention described in patent document 1), when the amount of dissolved oxygen in a process liquid is large, it discovered that the function of the migration suppression layer formed is not enough. If the amount of dissolved oxygen in the treatment liquid is large, corrosion of the copper wiring or the copper alloy wiring surface is promoted. Therefore, in particular, generation of copper ions is accelerated under high humidity and overvoltage atmosphere, and the ion trapping ability of the migration suppression layer is lowered, and as a result, a sufficient migration suppression function cannot be expressed.

In addition, the present inventors, if a conventional migration inhibitor such as benzotriazole remains on the substrate between the copper wiring or copper alloy wiring (hereinafter also referred to simply as wiring), the wiring is formed on the substrate on which the wiring is formed. It was found that adhesion failure and the like occurred between the insulating layer and the substrate, causing short circuits. On the other hand, in order to remove the migration inhibitor existing between such wirings, when the substrate is cleaned, the migration inhibitors on the copper wirings or copper alloy wirings are also removed at the same time, and the desired effect is not expressed.

Based on the above findings, the present inventors have found that the problem of the prior art can be solved by using a treatment solution for forming a migration suppression layer containing an azole compound and exhibiting a predetermined dissolved oxygen amount.

That is, by using the process liquid whose dissolved oxygen amount is below a predetermined value, corrosion of a copper wiring or a copper alloy wiring is suppressed more, and the coordination ability with respect to the copper ion of an azole compound is maintained. As a result, migration of copper ions is suppressed.

In addition, by using the azole compound which is a complex 5-membered ring compound, since the azole compound on the wiring remains even by the washing treatment with a solvent, the wiring is removed while removing the migration inhibitor remaining between the wirings which may cause short circuits between the wirings. The migration suppression layer can be formed on the phase.

First, the process liquid for migration suppression layer formation used by this invention is explained in full detail, and the manufacturing method of the laminated body which has a migration suppression layer obtained using the process liquid after that is explained in full detail.

[Processing liquid for migration suppression layer formation]

The process liquid for migration suppression layer formation (process liquid for copper ion diffusion suppression layer formation) of this invention is a process liquid for forming the migration suppression layer which suppresses 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.

Below, the component (azole compound, water, etc.) contained in a process liquid is explained in full detail.

(Azole compound)

The azole compound contained in this process liquid is a monocyclic hetero 5-membered ring compound containing 1 or more nitrogen atoms in a ring. For example, the diazole of two nitrogen atoms, the triazole of three nitrogen atoms, the tetrazole of four nitrogen atoms, etc. are mentioned. More specifically, 1,2,3-triazole, 1,2,4-triazole, 1,2,4-triazole-3-carboxyamide, tetrazole, etc. are mentioned. Especially, 1,2,3-triazole and 1,2,4-triazole are preferable at the point which the migration inhibitory effect of a copper ion is more excellent.

The treatment liquid may contain two or more kinds of azole compounds.

Moreover, the azole compound may have substituents, such as an alkyl group, a carboxyl group, a hydroxyl group, an amino group, unless the effect of this invention is impaired.

Although the total content of the azole compound in a process liquid is not specifically limited, 0.01-10 mass% is preferable with respect to the process liquid whole quantity from the point of the ease of formation of a migration suppression layer, and control of the adhesion amount of a migration suppression layer, and 0.1- 5 mass% is more preferable, and 0.25-5 mass% is especially preferable. When there is too much total content of an azole compound, it will become difficult to control the amount of deposition of a migration suppression layer. When the total content of the azole compound is too small, it takes time until the deposition amount of the desired migration suppression layer becomes, and the productivity is bad.

On the other hand, when benzotriazole or the like, which is generally used as an anticorrosive, is used instead, most of the benzotriazole is washed away from the copper wiring or the copper alloy wiring by washing with a solvent to be described later. Not obtained. Moreover, in the benzotriazole containing process liquid containing an excess etching agent, and the process liquid containing the imidazole compound which has an etching capability, copper ion is contained excessively in the organic film formed on a copper wiring or a copper alloy wiring. The film has no migration inhibiting ability, and the desired effect is not obtained.

The treatment liquid usually contains water as a solvent. The kind of water used is not specifically limited, For example, distilled water, ion-exchange water, tap water, and purified water are mentioned. Especially, distilled water is preferable at the point that there are few impurities, such as an ion.

Although content of water in particular is not restrict | limited, 90-99.9 mass% is preferable with respect to process liquid whole quantity, 95-99.9 mass% is more preferable with respect to process liquid handleability, etc., 95-97.5 mass% is still more preferable. Do.

Moreover, the process liquid may contain solvents other than water in the range which does not impair the effect of this invention.

For example, alcohol solvents (e.g. methanol, ethanol, isopropanol), ketone solvents (e.g. acetone, methyl ethyl ketone, cyclohexanone), amide solvents (e.g. formamide, dimethyl Acetamide, N-methylpyrrolidone), nitrile solvents (e.g. acetonitrile, propionitrile), ester solvents (e.g. methyl acetate, ethyl acetate), carbonate solvents (e.g., Organic solvents such as dimethyl carbonate, diethyl carbonate), ether solvent, and halogen solvent. You may use these solvent in mixture of 2 or more types.

The dissolved oxygen amount in this treatment liquid is 7.0 ppm or less. By being in the range, corrosion of copper in a copper wiring or a copper alloy wiring is suppressed, adsorption of the said azole compound advances, and the migration suppression layer with high copper ion trapping ability can be formed. In addition, the amount of dissolved oxygen is preferably less than 4.0 ppm in that a migration suppression layer having a higher migration suppression function can be formed.

On the other hand, when the dissolved oxygen amount exceeds 7.0 ppm, corrosion occurs on the surface of the copper wiring or the copper alloy wiring at the time of contact between the substrate on which the wiring is formed and the processing liquid, and the generation of copper ions is accelerated under high humidity and overvoltage atmosphere. We use ion trap ability of and cannot express enough migration restraint function.

The method for making the dissolved oxygen amount of the treatment liquid below a predetermined value is not particularly limited, and a known method can be used. For example, it is preferable to reduce the oxygen in the treatment liquid by degassing, and more specifically, bubbling with an inert gas, removing with a film such as a polymer film or an inorganic film, removing gas components with a vacuum, or a combination thereof. One way is.

As the inert gas, it is preferable to use nitrogen, argon, helium, or a combination thereof. In addition, these inert gases are preferably used as high as possible in order to eliminate the effects of contamination.

Moreover, a well-known method can be used as a measuring method of dissolved oxygen concentration, For example, it is commercially available, such as dissolved oxygen DO-31P (made by Toa DKK) and fluorescent dissolved oxygen type LDO-HQ10 (made by HACH). It can be measured by a dissolved oxygen meter.

On the other hand, from the point of improving the insulation reliability between wirings in a laminated body, it is preferable that a process liquid does not contain copper ion substantially. When an excessive amount of copper ions is contained, copper ions are contained in the layer when the migration suppression layer is formed, the effect of suppressing migration of copper ions is weakened, and insulation reliability between wirings may be impaired.

In addition, the fact that copper ion is not contained substantially shows that content of the copper ion in a process liquid is 1 micromol / L or less, and it is more preferable that it is 0.1 micromol / L or less. Most preferably 0 mol / l.

Moreover, in order to improve the insulation reliability between wirings in a laminated body, it is preferable that the processing liquid does not contain the etching agent of copper or a copper alloy substantially. If an etching agent is contained in the processing liquid, copper ions may elute in the processing liquid when the substrate on which the wiring is formed is brought into contact with the processing liquid. Therefore, as a result, copper ion is contained in a migration suppression layer, the effect which suppresses migration of copper ion becomes weak, and insulation reliability between wirings may be impaired.

Examples of the etchant include organic acids (e.g. sulfuric acid, nitric acid, hydrochloric acid, acetic acid, formic acid, hydrofluoric acid), oxidizing agents (e.g. hydrogen peroxide, concentrated sulfuric acid), chelating agents (e.g. iminodiacetic acid, nitrile) Rotriacetic acid, ethylenediaminetetraacetic acid, ethylenediamine, ethanolamine, aminopropanol), thiol compounds and the like. Moreover, as an etchant, the thing which has an etching action of copper like imidazole, an imidazole derivative compound, etc. is contained.

In addition, the fact that an etchant is not substantially contained means that content of the etchant in a process liquid is 0.01 mass% or less with respect to the process liquid whole quantity, and that it is 0.001 mass% or less from the point which raises the insulation reliability between wirings more. More preferred. Most preferably, it is 0 mass%.

Although the pH of a process liquid is not specifically defined, It is preferable that it is 5-12 from the point of the formation of a migration suppression layer. Especially, it is more preferable that pH is 5-9, and it is further more preferable that it is 6-8 from the point which the insulation reliability between wiring in a laminated body is more excellent.

When the pH of the processing liquid is less than 5, the dissolution of copper ions from the copper wiring or the copper alloy wiring is promoted, and the migration suppression layer contains a large amount of copper ions, and as a result, the effect of suppressing the migration of copper ions is lowered. There is a case. When the pH of the processing liquid is more than 12, copper hydroxide is precipitated and easily oxidized and dissolved, and as a result, the effect of suppressing migration of copper ions may decrease.

In addition, adjustment of pH can be performed using well-known acid (for example, hydrochloric acid, a sulfuric acid), and a base (for example, sodium hydroxide). In addition, the measurement of pH can be performed using a well-known measuring means (for example, pH meter (in the case of a water solvent)).

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

[Method for producing a laminate having a migration suppression layer (first embodiment)]

As a suitable embodiment of the manufacturing method of the laminated body which has a migration suppression layer of this invention, the manufacturing method which performs a layer formation process, a drying process, and an insulation layer formation process in this order is mentioned.

Below, with reference to drawings, the order of the material and process used by each process is demonstrated.

[Layer Formation Step]

In this process, first, the substrate on which the wiring having the copper wiring or the copper alloy wiring (hereinafter, simply referred to as wiring) disposed on the substrate and the substrate is formed is brought into contact with the processing liquid for migration suppression layer formation described above (contacting). fair). Then, the board | substrate with which the said wiring after contact was formed is wash | cleaned with a solvent (cleaning solvent), and the migration suppression layer containing an azole compound is formed on a copper wiring or a copper alloy wiring surface (cleaning process). In other words, the contacting step is to contact the substrate on which the wiring is formed (more specifically, the surface of the substrate on which the wiring is formed with the copper wiring or the copper alloy wiring) and the processing liquid so that the substrate surface of the substrate on which the wiring is formed with an azole compound. And a process for covering the wiring surface. Moreover, a washing process is a process of washing the board | substrate with wiring using a solvent, and removing the azole compound on the surface of a board | substrate. By this process, a migration suppression layer is formed so that the surface of a copper wiring or a copper alloy wiring may be covered, and migration of copper is suppressed.

First, the material (substrate with wiring) etc. used in a layer formation process is demonstrated, and the procedure of a layer formation process is demonstrated after that.

(Substrate with wiring)

The board | substrate (inner layer board | substrate) with which the wiring used in this process was formed has a board | substrate and the copper wiring or copper alloy wiring arrange | positioned on a board | substrate. In other words, the board | substrate with wiring is a laminated structure which has a board | substrate and copper wiring or copper alloy wiring at least, and copper wiring or copper alloy wiring should just be arrange | positioned at the outermost layer. One aspect of the board | substrate with wiring was shown by FIG. 1A, and the board | substrate 10 with wiring is board | substrate 12 and the copper wiring or copper alloy wiring 14 arrange | positioned on the board | substrate 12. FIG. ) (Hereinafter also referred to simply as wiring 14). Although the wiring 14 is formed only in the single side | surface of a board | substrate in FIG. 1A, you may be formed in both surfaces. That is, the board | substrate 10 in which wiring was formed may be a single-sided board | substrate, or a double-sided board | substrate may be sufficient as it.

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

Resin is mentioned as a material of an organic substrate, For example, it is preferable to use thermosetting resin, a thermoplastic resin, or resin which mixed them. As the thermosetting resin, a phenol 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 mentioned. Examples of the thermoplastic resins include polyimide resins, polyphenylene oxide resins, polyphenylene sulfide resins, aramid resins, liquid crystal polymers, and the like.

Moreover, as a material of an organic substrate, a glass woven fabric, a glass nonwoven fabric, an aramid woven fabric, an aramid nonwoven fabric, an aromatic polyamide woven fabric, the material in which these resins were impregnated, etc. can also be used.

The wiring is composed of copper or copper alloy. When wiring is comprised with a copper alloy, as metals other than copper, silver, tin, palladium, gold, nickel, chromium etc. are mentioned, for example.

The formation method of the wiring on a board | substrate is not specifically limited, A well-known method can be employ | adopted. Typically, the subtractive method using an etching process and the semiadditive method using an electrolytic plating are mentioned.

Although the width | variety of wiring is not restrict | limited, 1-1000 micrometers is preferable and 3-25 micrometers is more preferable at the point of high integration when the laminated body formed is applied to a printed wiring board.

Although the space | interval between wirings is not restrict | limited, 1-1000 micrometers is preferable and 3-25 micrometers is preferable at the point of high integration when the laminated body formed is applied to a printed wiring board.

Moreover, the pattern shape of wiring is not specifically limited, Arbitrary patterns may be sufficient. For example, linear form, curve form, square form, circular form etc. are mentioned.

Although the thickness in particular of wiring is not restrict | limited, 1-1000 micrometers is preferable and 3-25 micrometers is more preferable at the point of high integration when the laminated body formed is applied to a printed wiring board.

Although the surface roughness Rz of wiring is not restrict | limited, 0.001-15 micrometers is preferable from a viewpoint of adhesiveness with the insulating layer mentioned later, and 0.3-3 micrometers is more preferable.

As a method of adjusting the surface roughness Rz of wiring, a well-known method can be used, for example, a chemical roughening process, a buff polishing process, etc. are mentioned.

In addition, Rz is measured according to JIS B 0601 (1994).

The board | substrate with wiring used in this process should just have wiring in the outermost layer, and may provide other metal wiring (wiring pattern) and an interlayer insulation layer in this order between a board | substrate and wiring. In addition, the other metal wiring and the interlayer insulating layer may alternately include two or more layers of each layer in this order between the substrate and the wiring. That is, the board | substrate with which wiring was formed may be what is called a multilayer wiring board and a buildup board | substrate.

A well-known insulating material can be used as an interlayer insulation layer, For example, a phenol resin, a naphthalene resin, a urea resin, an amino resin, an alkyd resin, an epoxy resin, an acrylate resin, etc. are mentioned.

Moreover, what is called a rigid board | substrate, a flexible board | substrate, and a rigid flexible board | substrate may be sufficient as the board | substrate with which wiring was formed.

Moreover, the through hole may be formed in the board | substrate. When wiring is formed in both surfaces of a board | substrate, the wiring of both surfaces may be conducted, for example by filling a metal (for example, copper or a copper alloy) in a through hole.

(Solvent (cleaning solvent))

The solvent (cleaning solvent) used in the cleaning process for cleaning the substrate on which the wiring is formed is not particularly limited as long as the excess azole compound or the like deposited between the wirings on the substrate can be removed. Especially, it is preferable that it is a solvent in which an azole compound melt | dissolves. By using this solvent, the excess azole compound deposited on the board | substrate, the excess azole compound on wiring, etc. can be removed more efficiently.

Examples of the solvent include water, alcohol solvents (e.g. methanol, ethanol, propanol), ketone solvents (e.g. acetone, methyl ethyl ketone, cyclohexanone), amide solvents (e.g. For example, formamide, dimethylacetamide, N-methylpyrrolidone), nitrile solvents (e.g. acetonitrile, propionitrile), ester solvents (e.g. methyl acetate, ethyl acetate), carbonate type A solvent (for example, dimethyl carbonate, diethyl carbonate), an ether solvent, a halogen solvent, etc. are mentioned. You may use these solvents in mixture of 2 or more types.

Especially, it is preferable that it is a solvent containing at least 1 chosen from the group which consists of water, an alcoholic solvent, and methyl ethyl ketone from the point of liquid permeability between fine wirings, and it is a mixture of water or an alcoholic solvent, and water. More preferred.

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

Although the surface tension (25 degreeC) of the solvent used is not restrict | limited, It is preferable that it is 10-80 mN / m, and 15-60 mN from the point which the washing | cleaning property between wirings is more excellent and the insulation reliability between wirings improves more. It is more preferable that it is / m.

(Order of Layer Forming Process)

The layer forming step will be described divided into two steps, a contact step and a washing step.

(Contact process)

First, the board | substrate with which the wiring which has the copper wiring or copper alloy wiring arrange | positioned on a board | substrate and a board | substrate is formed, and the process liquid for migration suppression layer formation mentioned above are made to contact. By contacting the substrate on which the wiring is formed and the processing liquid, as shown in FIG. 1B, a layer 16 containing an azole compound is formed on the substrate 10 on which the wiring is formed. In other words, the contact step is a step of covering the surface of the substrate 12 and the wiring 14 of the substrate 10 on which the wiring is formed with the layer 16 containing an azole compound using the treatment liquid. The layer 16 is formed on the substrate 12 and on the wiring 14.

The layer 16 containing an azole compound contains an azole compound. The content is substantially synonymous with content in the migration suppression layer mentioned later. Moreover, the adhesion amount is not specifically limited, It is preferable that it is an adhesion amount which can obtain the migration suppression layer of a desired adhesion amount through the washing | cleaning process mentioned later.

The contact method of the board | substrate with which wiring was formed, and the said processing liquid is not specifically limited, A well-known method can be employ | adopted. For example, dip immersion, shower spray, spray coating, spin coat, etc. are mentioned, Dip immersion, shower spray, spray coating is preferable from the simplicity of processing and the ease of adjustment of a processing time.

Moreover, as liquid temperature of the processing liquid at the time 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 further more desirable.

Moreover, as contact time, the range of 10 second-30 minutes is preferable at the point of productivity and the adhesion amount control of a migration suppression layer, The range of 15 second-10 minutes is more preferable, The range of 30 second-5 minutes is further more desirable.

(Cleaning process)

Next, the board | substrate with which wiring was formed is wash | cleaned with a solvent, and the migration suppression layer containing an azole compound is formed on the copper wiring or copper alloy wiring surface. By carrying out this step, the azole compound on the substrate surface can be washed out. In particular, when a solvent in which an azole compound is dissolved is used as the solvent, azole compounds (particularly, azole compounds on the substrate surface) other than the azole compounds on the copper wiring or copper alloy wiring surface are more easily dissolved and removed. Specifically, as shown in FIG. 1C, the substrate 10 having the wiring on which the layer 16 containing the azole compound obtained in FIG. 14) The layer 16 containing the azole compound of liver is removed, and the excess azole compound on the wiring 14 is removed, and the migration suppression layer 18 containing the azole compound is formed on the wiring 14.

The washing method is not particularly limited, and a known method can be adopted. For example, the method of apply | coating the cleaning solvent on the board | substrate with wiring, the method of immersing the board | substrate with wiring in a cleaning solvent, etc. are mentioned.

Moreover, as liquid temperature of a washing | cleaning solvent, the range of 5-60 degreeC is preferable and the range of 15-30 degreeC is more preferable at the point of adhesion amount control of a migration suppression layer.

Moreover, as contact time of the board | substrate with which the wiring was formed, and the washing | cleaning solvent, the range of 10 second-10 minutes is preferable, and the range of 15 second-5 minutes is more preferable from the point of productivity and the adhesion amount control of a migration suppression layer.

(Migration suppression layer (copper ion diffusion suppression layer))

By passing through the said process, as shown to FIG.1 (C), the migration suppression layer 18 containing an azole compound can be formed on the copper wiring or copper alloy wiring 14 surface. In other words, the migration suppression layer 18 covers the surface of the copper wiring or the copper alloy wiring 14.

In addition, as shown to FIG. 1C, it is preferable that the layer containing the azole compound between the wirings 14 is substantially removed. In short, it is preferable that the migration suppression layer 18 is formed only on the surface of the copper wiring or the copper alloy wiring 14 substantially.

In this invention, even after wash | cleaning the said solvent, the migration suppression layer of sufficient adhesion amount which can suppress migration of copper ion can be obtained.

Since content of the azole compound in a migration suppression layer can suppress migration of a copper ion, it is preferable that it is 0.1-100 mass%, It is more preferable that it is 20-100 mass%, 50-90 mass It is more preferable that it is%. It is preferable that especially a migration suppression layer is comprised substantially from an azole compound. When there is too little content of an azole compound, the migration inhibitory effect of copper ions will become low.

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

Since the adhesion amount of the azole compound on a copper wiring or copper alloy wiring surface can suppress migration of copper ion more, it is 5 * 10 <^-9> -1 * 10 with respect to the total surface area of a copper wiring or copper alloy wiring. ^-6 g / ㎟ of and ^{preferably, 5 × 10 -9 ~ 2 ×} 10 -7 g / ㎟ should preferably more, and, 5 × 10 ^-9 ~ 6 and more preferably from × 10 ^-8 g / ㎟.

In addition, an adhesion amount can be measured by a well-known method (for example, the absorbance method). Specifically, in the absorbance method, first, the migration suppression layer existing between the wirings is washed with water (extraction method by water). Then, the migration suppression layer on a copper wiring or a copper alloy wiring is extracted with an organic acid (for example, sulfuric acid), an absorbance is measured and an adhesion amount is computed from a liquid amount and an application area.

In addition, as mentioned above, although it is preferable that the layer containing an azole compound is substantially removed between wirings, the layer containing some azole compounds may remain in the range which does not impair the effect of this invention.

[Drying process]

In this process, the board | substrate with wiring in which the migration suppression layer was formed is heat-dried. If moisture remains on the substrate on which the wiring is formed, there is a risk of promoting the migration of copper ions. Therefore, it is preferable to remove the moisture by forming the step.

As heat-drying conditions, in the point which suppresses oxidation of a copper wiring or a copper alloy wiring, it is 15 second-10 minutes (preferably 30 second-5 minutes) at 70-120 degreeC (preferably 80 degreeC-110 degreeC). It is preferable to carry out. 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, there is a fear that copper oxide is formed.

The apparatus used for drying is not specifically limited, Well-known heating apparatuses, such as a thermostat and a heater, can be used.

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

[Insulation layer formation process]

In this process, an insulating layer is formed on the board | substrate with which the wiring in which the migration suppression layer was formed was formed. As shown to FIG. 1D, the insulating layer 20 is formed on the board | substrate 10 with which wiring was formed so that the migration suppression layer 18 may contact the wiring 14 formed in the surface. By forming the insulating layer 20, insulation reliability between the wirings 14 is more secured. Moreover, since the board | substrate 12 and the insulating layer 20 can directly contact, the adhesiveness of the insulating layer 20 is excellent.

First, the insulating layer to be used will be described, and next, the method for forming the insulating layer will be described.

As the insulating layer, a known insulating material can be used. For example, the material used as what is called an interlayer insulation layer can be used, Specifically, an epoxy resin, an aramid resin, a crystalline polyolefin resin, an amorphous polyolefin resin, and a fluorine-containing resin (polytetrafluoroethylene, all) Fluorinated polyimide, prefluorinated 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 commercial item may be used for a soldering resist, For example, Taiyo Ink Co., Ltd. make PFR800, PSR4000 (brand name), Hitachi Chemical Co., Ltd. make SR7200G, etc. are mentioned, for example.

The formation method of the insulating layer on the board | substrate with which wiring was formed is not specifically limited, A well-known method can be employ | adopted. For example, the method of laminating the film of an insulating layer on the board | substrate with which wiring was directly formed, the method of apply | coating the composition for insulating layer formation containing the component which comprises an insulating layer on the board | substrate with wiring, or the wiring was formed. The method of immersing a board | substrate in the composition for insulating layer formation, etc. are mentioned.

Moreover, the solvent may be contained in the said composition for insulating layer formation as needed. When using the composition for insulating layer formation containing a solvent, after arrange | positioning the composition on a board | substrate, you may heat-process in order to remove a solvent as needed.

Moreover, after forming an insulating layer on the board | substrate with wiring, you may give energy (for example, exposure or heat processing) to an insulating layer as needed.

The film thickness of the insulating layer formed is not specifically limited, 5-50 micrometers is preferable from a viewpoint of the insulation reliability between wirings, and 15-40 micrometers is more preferable.

In FIG.1 (D), although the insulating layer is described by one layer, a multilayered structure may be sufficient.

(Laminated Body Having Migration Suppression Layer)

By passing through the said process, as shown to FIG. 1D, the board | substrate 12, the wiring 14 arrange | positioned on the board | substrate 12, and the insulating layer 20 arrange | positioned on the wiring 14 are shown. And a laminate 30 (first embodiment of a laminate having a migration suppression layer) having a migration suppression layer 18 interposed between the wiring 14 and the insulating layer 20. The obtained laminated body 30 is excellent in the insulation reliability between the wirings 14, and also excellent in the adhesiveness of the insulating layer 20 and the board | substrate 10 with which the wiring was formed.

In addition, as shown to Fig.1 (D), although the laminated body of the one-layer wiring structure was mentioned above as an example, of course, it is not limited to this. For example, the laminated body of a multilayer wiring structure can be manufactured by using the board | substrate with which the other metal wiring (metal wiring layer) and the interlayer insulation layer were laminated | stacked alternately in this order between the board | substrate and metal wiring. .

The laminated body obtained by the manufacturing method of this invention can be used for various uses and structures, For example, a printed wiring board, the board | substrate for motherboards, the board | substrate for semiconductor packages, a MID (Molded Interconnect Device) board | substrate, etc. are mentioned. And a rigid substrate, a flexible substrate, a flex rigid substrate, a molded circuit board, and the like.

Moreover, you may remove a part of the insulating layer in the obtained laminated body, mount a semiconductor chip, and use it as a printed circuit board.

For example, in the case of using a solder resist as the insulating layer, a mask on a predetermined pattern is disposed on the insulating layer, energized and cured, and the wiring is exposed by removing the insulating layer in the non-energy region. Next, after cleaning the surface of the exposed wiring by a known method (for example, using sulfuric acid or a surfactant), the semiconductor chip is mounted on the wiring surface.

In the case of using a known interlayer insulating layer as the insulating layer, the insulating layer can be removed by drilling or laser processing.

Moreover, you may form a metal wiring (wiring pattern) further on the insulating layer of the obtained laminated body. The method of forming a metal wiring is not specifically limited, A well-known method (plating process, sputtering process, etc.) can be used.

In this invention, the board | substrate with which metal wiring (wiring pattern) was further formed on the insulating layer of the obtained laminated body is used as a board | substrate (inner layer board | substrate) in which the new wiring was formed, and a new insulating layer and metal wiring can also be laminated | stacked in several layers. Can be.

[Method for producing a laminate having a migration suppression layer (second embodiment)]

As another suitable embodiment of the manufacturing method of the laminated body which has a migration suppression layer of this invention, a board | substrate, copper wiring or copper alloy wiring arrange | positioned on a board | substrate, and a part of copper wiring or copper alloy wiring arrange | positioned on a board | substrate A layer forming step and a drying step using a laminate having an exposed wiring (hereinafter simply referred to as an exposed wiring containing laminate) having an insulating layer covering the copper wiring or the copper alloy wiring so as to be exposed instead of the substrate on which the wiring is formed, The manufacturing method performed in this order is mentioned.

Hereinafter, with reference to drawings, the order of the material and process used by each process is demonstrated.

[Layer Formation Step]

In this process, first, the exposed wiring-containing laminate and the above-described processing liquid for migration suppression layer formation are brought into contact with each other (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 process, a migration suppression layer is formed so that the surface of the exposed copper wiring or copper alloy wiring may be covered, and migration of copper is suppressed.

First, the material (exposure wiring containing laminated body) used in a layer formation process is demonstrated, and the procedure of a layer formation process is demonstrated after that.

(Exposed wiring-containing laminate)

The exposed wiring-containing laminate used in this step includes a substrate, a copper wiring or copper alloy wiring (hereinafter simply referred to as wiring) disposed on the substrate, and a portion of the copper wiring or copper alloy wiring disposed on the substrate. It has an insulating layer covering copper wiring or copper alloy wiring so that it may be 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 referred to simply as the wiring 14), and an insulating layer 20. . The wiring 14 is also referred to as exposed copper wiring or copper alloy wiring (hereinafter, also simply referred to as wiring 14a), and copper wiring or copper alloy wiring (hereinafter simply referred to as wiring 14b) coated with the insulating layer 20. It is composed of

In addition, although the exposed wiring 14a is supported on the board | substrate 12 in FIG. 2, the one part may extend out of the board | substrate 12. In addition, in FIG.

The aspect (kind, etc.) of the board | substrate in the exposed wiring containing laminated body used by this process is the same as that of the board | substrate in the board | substrate (inner layer board | substrate) with wiring used in 1st Embodiment mentioned above.

Especially, as a board | substrate (especially an insulated substrate), it is preferable to use an organic substrate, a thin glass epoxy board | substrate, etc., for example. By using board | substrates, such as an organic substrate, what is called a 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 aspect (type of material, width, space | interval, thickness, etc.) of the copper wiring or copper alloy wiring in the exposed wiring containing laminated body used by this process is a board | substrate with wiring used in 1st Embodiment mentioned above (inner-layer board | substrate). Is the same as that of the copper wiring or the copper alloy wiring.

The insulating layer is a layer covering 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 which covers a copper wiring or a copper alloy wiring is not specifically limited, The copper wiring or copper alloy wiring part which can be electrically connected with the electronic component (for example, semiconductor element) etc. mounted on a board | substrate should just remain | survive.

The aspect (kind, etc.) of the insulating layer in the exposed wiring containing laminated body used by this process is the same as the aspect of the insulating layer in the board | substrate (inner layer board | substrate) with wiring used by 1st Embodiment mentioned above. More specifically, as an insulating material which comprises an insulating layer, polyimide resin, a polyester resin, etc. are mentioned, for example.

Moreover, you may use screen printing ink and a photosensitive coverlay as an insulating layer.

In addition, the manufacturing method of an exposure wiring containing laminated body is not specifically limited, A well-known method can be employ | adopted. For example, first, the subtractive method or the semiadditive method is applied to the board | substrate with copper foil, and the board | substrate which has copper wiring is manufactured. Next, an insulating film is laminated on the substrate, and an insulating layer covering a part of the copper wiring is formed.

(Solvent (cleaning solvent))

The solvent (cleaning solvent) used in the washing step of cleaning the exposed wiring-containing laminate is not particularly limited as long as the excess azole compound deposited on the surface other than the copper wiring or the copper alloy surface can be removed, and the above-mentioned descriptions are made. The solvent (washing solvent) used in one 1st embodiment can be used.

(Procedure Order)

The layer forming step will be described divided into two steps, a contact step and a washing step.

(Contact process)

A contact process is a process of contacting an exposure wiring containing laminated body and said process liquid for migration suppression layer formation. Specifically, first, as shown to FIG. 3 (A), the exposed wiring containing laminated body provided with the board | substrate 12 and the exposed copper wiring or copper alloy wiring 14a is prepared, and the exposed wiring containing laminated body By contacting with the processing liquid for migration suppression layer formation, 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 board | substrate 12, on the wiring 14a, and on an insulating layer (not shown).

The order and conditions of the contacting step are made by the same order and condition as the contacting step carried out in the first embodiment described above.

(Cleaning process)

A washing process is a process of washing the exposed wiring containing laminated body obtained by the contact process with a solvent, and forming the migration suppression layer containing an azole compound on the copper wiring or copper alloy wiring surface.

Specifically, as shown in FIG. 3C, the exposed wiring-containing laminate in which the layer 16 containing the azole compound obtained in FIG. While the layer 16 containing the azole compound between) is removed, the excess azole compound on the wiring is removed, and the migration suppression layer 18 is formed on the wiring 14a. In addition, while the layer 16 containing the azole compound between the wirings 14a is removed, the layer 16 containing the azole compound on the insulating layer (not shown) is also removed.

The order and conditions of the washing step are made by the same order and conditions as the washing step carried out 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. In addition, as shown to FIG. 3C, it is preferable that the layer containing an azole compound is substantially removed on surfaces other than the exposed wiring 14a surface. In short, it is preferable that the migration suppression layer 18 is formed only on the exposed wiring 14a surface substantially. In addition, the surface of wiring 14a means the upper surface and side surface other than the lower surface which contact | connects the board | substrate 12, as shown to FIG. 3 (C).

The aspect (content, adhesion amount, etc. of an azole compound) of the migration suppression layer formed is an aspect similar to the migration suppression layer obtained by the 1st embodiment mentioned above.

[Drying process]

At this process, the laminated body in which the migration suppression layer was formed is heat-dried. If moisture remains on the laminate, the migration of copper ions may be promoted. Therefore, it is preferable to remove the moisture by providing the step.

In addition, this process is an arbitrary process, and when this solvent used in a layer formation process is a solvent excellent in volatility, this process does not need to be performed.

The order and conditions of a drying process are made by the same procedure and conditions as the drying process implemented in 1st Embodiment mentioned above.

(Laminated Body Having Migration Suppression Layer)

By passing through the said manufacturing method, it arrange | positions on a board | substrate, the migration suppression layer containing the copper wiring or copper alloy wiring arrange | positioned on a board | substrate, the azole compound formed on the surface of a part of copper wiring or a copper alloy wiring, and a board | substrate. And a laminated body (second embodiment of the laminate having a migration suppression layer) having an insulating layer covering the surface of the remainder of the copper wiring or copper alloy wiring. In other words, a laminate having a surface-coated wiring in which 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. It is a sieve.

More specifically, as shown in FIG. 4, the board | substrate 12, the wiring 14 arrange | positioned on the board | substrate 12, and the insulation arrange | positioned on the board | substrate 12 and covering a part of wiring 14 are covered. The laminated body 100 which has the surface coating wiring which has the layer 20 and the migration suppression layer 18 which coat | covers the surface of the wiring 14a in which the insulating layer 20 is not formed is obtained.

The obtained laminated body can be used for various uses, for example, it can be used as a board | substrate for a printed wiring board, a chip on film (COF) board | substrate, or a TAB (Tape Automated Bonding) board | substrate.

Example

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

(Example 1)

Exposed wiring containing laminated body provided with the comb-tooth shaped copper wiring of L / S = 100micrometer / 100micrometer, and an insulating layer using a polyimide film (Cafton film by Toray Dupont) (it corresponds to a printed wiring board) Was formed. The exposed wiring-containing laminate was produced by the following method.

On a 25-micrometer-thick polyimide film (Katon Film manufactured by Toray DuPont), a copper foil (F3-WS foil manufactured by Furukawa Electric Works) having a thickness of 20 μm was interposed with a 25 μm-thick adhesive (Hitachi Chemical Co., Ltd. N4). It bonded together.

A photoresist (Potech H-W425 manufactured by Hitachi Chemical Co., Ltd.) was laminated on a copper foil tape at 100 ° C. under a condition of 4 kgf / cm 2, exposed to a condition of 80 mJ / cm 2 through a photomask, and developed and etched. A resist pattern was formed.

Thereafter, the copper foil not covered with the etching resist was selectively etched away with a ferric chloride etching solution, and the etching resist was peeled off to obtain a copper wiring having L / S = 100 µm / 100 µm.

Furthermore, about half of the obtained substrate was then laminated with an insulating layer (FZ2500 manufactured by Hitachi Chemical Co., Ltd.), 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-carboxyamide is dissolved in pure water subjected to nitrogen bubbling for about 1 hour, and the treatment liquid for migration suppression layer formation (1,2,4-triazole-3-carboxyamide treatment Content in a liquid: 2.5 mass%) was manufactured. The amount of dissolved oxygen in the treatment liquid was measured by the dissolved oxygen system DO-31P (Toa DKK), and the amount of dissolved oxygen was 2.0 ppm.

Next, the obtained exposed wiring containing laminated body was immersed for 5 minutes in the manufactured process liquid. 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. After that, the laminate was dried at 100 ° C. for 2 minutes.

Moreover, by the absorbance measurement of the inter-wire extraction liquid by water, it was confirmed that the migration suppression layer could not be confirmed on the surface of the board | substrate between copper wirings, and was removed by ethanol washing.

(Substrate Life Measurement by Dropping Test)

Using the obtained laminated body, after applying for 5 minutes and 10 minutes respectively in the pure water of 0.05 microS / cm <2> and 30 ml of conductivity, on the condition of 1.2 V of applied voltages, it spreads from the anode to the cathode between wiring which is not coat | covered with an insulating layer. The generation | occurrence | production of the dendrite which connected between wiring was measured under the optical microscope (BX-51 by Olympus company). The results obtained in Example 1 are shown in Table 1.

Moreover, evaluation was performed according to the following criteria.

"○": When no occurrence of dendrites is observed between wirings

"△": When dendrites are generated between wirings, but no dendrites connecting the wirings are seen, and there is no problem in practical use.

"×": When a dendrites connecting the wirings are generated and there is a problem in practical use

(Example 2)

A laminate was prepared according to the same procedure as in Example 1 except that 1,2,3-triazole was used instead of 1,2,4-triazole-3-carboxyamide. Then, the dropping test performed in Example 1 was performed using the obtained laminated body. Table 1 shows the results.

(Example 3)

A laminate was prepared according to the same procedure as in Example 1 except that 1,2,4-triazole was used instead of 1,2,4-triazole-3-carboxyamide. Then, the dropping test performed in Example 1 was performed using the obtained laminated body. Table 1 shows the results.

(Example 4)

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

(Example 5)

A laminated body was manufactured in the same procedure as in Example 3, except that the time of nitrogen bubbling was changed from 1 hour to 30 minutes in Example 3. Then, the dropping test performed in Example 1 was performed using the obtained laminated body. Table 1 shows the results.

(Example 6)

By using the copper clad laminated board (MCL-E-679F manufactured by Hitachi Chemical Co., Ltd., substrate: glass epoxy substrate), the board | substrate with which the wiring provided with the copper wiring of L / S = 23 micrometer / 27 micrometers was formed by the semiadditive method. It was. The board | substrate with wiring was manufactured by the following method.

After the copper clad laminate was acid washed, washed with water, and dried, a dry film resist (DFR, trade name; RY3315, manufactured by Hitachi Chemical Co., Ltd.) was laminated under a vacuum laminator under a pressure of 0.2 MPa at 70 ° C. After lamination, the copper pattern formation part was mask-exposed on the conditions of 70 mJ / m <2> with the exposure machine of 365 wavelength of center wavelength. Then, it developed with the 1% sodium carbonate aqueous solution, washed with water, and obtained the plating resist pattern.

After plating pretreatment and washing with water, electrolytic plating was performed on the copper exposed between the resist patterns. At this time, the sulfuric acid acid solution of copper (II) sulfate was used for electrolyte solution, the copper plate of the purity about 99% was made into the anode, and the copper clad laminated board was made into the cathode. Copper was deposited on copper of the negative electrode by electrolysis at 50-60 degreeC and 0.2-0.5V. Thereafter, water washing and drying were performed.

In order to peel a resist pattern, the board | substrate was immersed in 45 degreeC 4% NaOH aqueous solution for 60 second. Thereafter, the obtained substrate was washed with water and immersed in 1% sulfuric acid for 30 seconds. Then, it washed with water again.

With the etching liquid containing hydrogen peroxide and sulfuric acid as a main component, the conductive copper between the copper patterns was quickly etched, washed with water, and dried.

Next, after removing contamination etc. of the copper wiring surface with the pretreatment agent (CA-5330 by Mech Corporation), the roughening process of the copper wiring surface was performed with the roughening agent (CZ-8110 by Mech Corporation).

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

By measuring the reflectance, it was confirmed that the migration suppression layer containing 1,2,4-triazole was formed on the copper wiring.

Moreover, on the surface of the board | substrate between copper wirings, the migration suppression layer was not able to confirm by the absorbance measurement of the interwire extraction liquid by water, and it confirmed that it was removed by ethanol washing.

On the board | substrate with which the drying process was performed, the insulating layer (PFR-800 by Taiyo Ink Co., Ltd.) is laminated, it exposes and bakes after that, and has a laminated body which has a migration suppression layer (it corresponds to a printed wiring board) (The film thickness of an insulating layer: 35 micrometers) was manufactured. The following life measurement was performed about the obtained laminated body.

(Substrate Life Measurement by HAST Test)

Using the obtained laminated body, lifetime measurement (usage | use apparatus: EHS-221MD by Epec Co., Ltd.) was performed on condition of 85% of humidity, 130 degree of temperature, 1.2 atm of pressure, and 100V of voltage.

As an evaluation method, 20 lots of tests were done and the resistance value between wiring made 1 * 10 <^{9> (} ohm) the reference resistance value. The resistance value when 120 hours passed from the start of test was made into the pass which shows more than a reference resistance value.

Table 1 shows the results obtained in Example 6.

(Comparative Example 1)

Oxygen bubbling was carried out instead of nitrogen bubbling in Example 3, and a laminated body was manufactured in the same procedure as in Example 3, except that a treatment solution for forming a migration suppression layer having a dissolved oxygen amount of 8.5 ppm was used. Then, the dropping test performed in Example 1 was performed using the obtained laminated body. Table 1 shows the results.

(Comparative Example 2)

A laminate was prepared according to the same procedure as in Example 1 except that instead of 1,2,4-triazole-3-carboxyamide used in Example 1, ethylenediaminetetraacetic acid was used. Then, the dropping test performed in Example 1 was performed using the obtained laminated body. Table 1 shows the results.

(Comparative Example 3)

A laminate was prepared according to the same procedure as in Example 1 except that benzotriazole was used instead of 1,2,4-triazole-3-carboxyamide used in Example 1. Then, the dropping test performed in Example 1 was performed using the obtained laminated body. Table 1 shows the results.

(Comparative Example 4)

Oxygen bubbling was carried out in place of nitrogen bubbling in Example 6, and a laminate was prepared in the same procedure as in Example 6 except that a treatment solution for migration suppression layer formation having a dissolved oxygen amount of 8.5 ppm was used. Then, the HAST test performed in Example 6 was performed using the obtained laminated body. Table 1 shows the results.

In the following Table 1, the numerical value of a lifetime measurement column means (the number of lots / test lots which show 1x10 <^{9> (} ohm) or more after 120 hours), and 20/20 is the best result.

In addition, in Table 1, "pH" means the pH of the migration inhibitor process liquid used by each Example and the comparative example. The pH meter (made by Toa DKK) was used for the measurement of pH. "Amount of adhesion" in Table 1 means the adhesion amount of the compound (1,2,3-triazole, 1,2,4-triazole etc.) contained in a process liquid on the copper wiring, and the measurement mentioned above It carried out by the absorbance method.

As shown in Table 1, in Examples 1-5 using the process liquid for migration suppression layer formation of this invention, connection of the dendrite between wirings was not seen and it was confirmed that migration of copper ion is suppressed. .

In particular, in Examples 1-3 and 5 whose dissolved oxygen amount is less than 4.0 ppm, even if the application time of the voltage of the dropping test was changed from 5 minutes to 10 minutes, generation | occurrence | production of the dendrites between wirings was not seen. In short, when the dissolved oxygen amount is less than 4.0 ppm, insulation reliability between wirings is more excellent.

Moreover, as shown in Example 6, the outstanding 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 the comparative example 1 using the processing liquid whose dissolved oxygen amount is more than predetermined value, the comparative example 2 using the compound other than an azole compound, and the comparative example 3 using the benzotriazole compound, generation | occurrence | production of the dendrite which connects between wirings is confirmed. The effect of suppressing migration between wirings was inferior. Moreover, as shown in the comparative example 4, also in the HAST test, insulation reliability between wiring was inferior.

10: board | substrate with wiring
12: Board
14: copper wiring or copper alloy wiring
14a, 14b: Wiring
16: layer containing an azole compound
18: migration restraint layer
20: insulating layer
30, 100: Laminated body
40: exposed wiring containing laminated body

Claims (5)

The processing liquid for migration suppression layer formation which contains an azole compound and water, and forms the migration suppression layer which suppresses ion migration in copper wiring or copper alloy wiring whose dissolved oxygen amount is 7.0 ppm or less. The method of claim 1,
The processing liquid for migration suppression layer formation whose said dissolved oxygen amount is less than 4.0 ppm. 3. The method according to claim 1 or 2,
The treatment liquid for migration suppression layer formation in which the said azole compound contains 1,2,3-triazole and / or 1,2,4-triazole. The board | substrate with the board | substrate with wiring which has a copper wiring or a copper alloy wiring arrange | positioned on this board | substrate, and the process liquid for migration suppression layer formation as described in any one of Claims 1-3 contacted, and the said wiring after that The layer formation process of wash | cleaning this formed board | substrate with a solvent, and forming the migration suppression layer containing an azole compound on the copper wiring or copper alloy wiring surface,
The manufacturing method of the laminated body which has a migration suppression layer provided with the insulating layer formation process of forming an insulation layer on the board | substrate with wiring in which the said migration suppression layer was formed. An exposed wiring having a substrate, a copper wiring or copper alloy wiring disposed on the substrate, and an insulating layer disposed on the substrate and covering the copper wiring or copper alloy wiring so that a portion of the copper wiring or copper alloy wiring is exposed. The containing laminated body and the process liquid for migration suppression layer formation as described in any one of Claims 1-3 are contacted, The said exposed wiring containing laminated body is wash | cleaned with a solvent after that, and the said exposed copper wiring or copper The manufacturing method of the laminated body which has a migration suppression layer provided with the layer formation process which forms a migration suppression layer on an alloy wiring surface.

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