TWI830743B - Manufacturing method of plated shaped article and circuit substrate - Google Patents

Abstract

An object of the present invention is to provide a method for manufacturing a plated molded article that can produce a plated molded article with a good shape without penetration of a plating liquid. The manufacturing method of the plated shaped article of the present invention is characterized by including: step (1), exposing a surface treatment agent to a substrate having a copper-containing film on the surface to form a surface treatment substrate, and the surface treatment agent contains 0.001 mass % ~2 mass% of at least one triazole compound (A) selected from triazole (A1) and benzotriazole compound (A2) and 90 mass% to 99.999 mass% of organic solvent (B); step (2) ), forming a coating film of a resist composition on the surface treated substrate; step (3), exposing and developing the coating film to form a resist pattern; and step (4), applying the resist The etch pattern serves as a mask for plating solution processing.

Description

Manufacturing method of plated shaped article and circuit substrate

The invention relates to a manufacturing method of a plated shaped object, a circuit substrate, a surface treatment agent and a surface treatment agent set.

Plating formed objects such as wiring and bumps are formed by forming a resist pattern on a substrate having a metal foil such as copper, and performing a plating solution treatment using the resist pattern as a mask.

In recent years, the demand for high-density mounting of connection terminals such as wiring and bumps on circuit boards of semiconductor devices or display devices such as liquid crystal displays and touch panels has been increasing, and the miniaturization of the connection terminals has been promoted. Along with this, there is also a demand for miniaturization of resist patterns used for forming connection terminals such as wiring and bumps.

However, it is known that when a resist pattern is used as a mask and a plated molded object is formed by treatment with a plating liquid, the plating liquid penetrates between the resist pattern and the substrate (Patent Document 1 to Patent Document 1). Document 2).

[Prior art documents]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2005-274920

[Patent Document 2] Japanese Patent Application Publication No. 2007-065642

If the resist pattern is made finer, there is a greater risk that adjacent wirings or bumps will be connected to each other due to penetration of the plating liquid.

The object of the present invention is to provide a method for manufacturing a plated molded article, which can produce a plated molded article with good shape without the plating liquid penetrating between the resist pattern and the substrate during the plating liquid treatment; to provide a circuit substrate , having a plated shaped article manufactured by the method for manufacturing a plated shaped article; providing a surface treatment agent that can be preferably used in the method of manufacturing a plated shaped article; and providing a surface treatment agent Set.

The inventors of the present invention have conducted diligent research in order to solve the above-mentioned problems. As a result, they found that the above-mentioned problems can be solved by a manufacturing method of a plated molded article having the following structure, and completed the present invention. That is, the present invention relates to, for example, the following [1] to [11].

[1] A method of manufacturing a plated shaped article, characterized by including: exposing a surface treatment agent to a substrate having a copper-containing film on the surface (hereinafter also referred to as a "copper-containing substrate"), and forming a surface-treated substrate Step (1) (hereinafter, also referred to as "step (1)"), the surface treatment agent contains 0.001 mass% to 2 mass% selected from triazole (A1) and benzotriazole compound (A2) At least one triazole compound (A) and 90 mass % to 99.999 mass % of an organic solvent (B); the step (2) of forming a coating film of a resist composition on the surface treatment substrate (hereinafter also referred to as for "steps" (2)"); the step (3) of exposing and developing the coating film to form a resist pattern (hereinafter also referred to as "step (3)"); and using the resist pattern as a mask The step (4) of plating solution treatment is performed under the cover (hereinafter also referred to as "step (4)").

[2] The method for producing a plated shaped article according to [1], wherein the resist composition contains an alkali-soluble resin, an acrylic compound, and a photoradical polymerization initiator.

[3] The method for producing a plated shaped article according to [1], wherein the resist composition contains an acid-dissociating alkali-insoluble resin and a photoacid generator.

[4] The method for manufacturing a plated shaped article according to any one of [1] to [3], wherein the resist pattern has a film thickness of 0.8 μm to 300 μm.

[5] The method for manufacturing a plated shaped article according to any one of [1] to [4], further comprising the step of removing the resist pattern after the step (4) ( 5) (hereinafter also referred to as "step (5)").

[6] The method for manufacturing a plated shaped article according to any one of [1] to [5], wherein the surface treatment agent contains 0.001 to 2 mass % of a triazole compound (A) and 98% by mass to 99.999% by mass of organic solvent (B).

[7] The method for producing a plated shaped article according to any one of [1] to [6], wherein the organic solvent (B) is alkylene glycol monoalkyl ether acetate or alcohol. .

[8] The method for manufacturing a plated shaped article according to any one of [1] to [7], wherein the organic solvent (B) has a standard boiling point of 80°C to 200°C.

[9] A circuit board including a plated molded article manufactured by the method of manufacturing a plated molded article according to any one of [1] to [8].

[10] A surface treatment agent characterized by containing 0.001 mass % to 2 mass % of at least one triazole compound (A) selected from the group consisting of triazole (A1) and benzotriazole-based compounds (A2) and 90 mass % %~99.999% by mass of organic solvent (B).

[11] A surface treatment agent set for producing the surface treatment agent as described in [10]. The surface treatment agent set is characterized in that it has at least a first solution and a second solution, and the third solution A solution containing more than 2 mass % and less than 100 mass % of at least one triazole compound (A) selected from the group consisting of triazole (A1) and benzotriazole-based compounds (A2), and containing more than 0 mass % and 98 Mass % or less of the organic solvent (B); the second solution contains the organic solvent (B).

The method for manufacturing a plated shaped article of the present invention can produce a plated shaped article with good shape without the plating liquid penetrating between the resist pattern and the substrate during the plating liquid treatment. The circuit board of the present invention has high reliability since it has a plated molded article produced by the method of producing a plated molded article of the present invention.

The surface treatment agent of the present invention can be preferably used in the method of manufacturing a plated shaped article of the present invention.

The surface treatment agent kit of the present invention can be preferably used to manufacture the surface treatment agent.

FIG. 1 is a schematic diagram of a method for manufacturing a plated shaped article of the present invention.

FIG. 2 is an electron micrograph of the resist pattern formed in Example 1B.

FIG. 3 is an electron micrograph of the resist pattern formed in Comparative Example 4B.

Hereinafter, after describing the surface treatment agent of the present invention, the manufacturing method of the plated shaped article of the present invention, the circuit board, and the surface treatment agent set will be described.

Unless otherwise mentioned, each component illustrated in this specification, for example, each component in a surface treatment agent may be used individually by 1 type, or may be used in combination of 2 or more types.

<1>Surface treatment agent

The surface treatment agent of the present invention contains 0.001 mass % to 2 mass % of at least one triazole compound (A) selected from triazole (A1) and benzotriazole compound (A2) and 90 mass % to 99.999 mass %. organic solvent (B). In addition, other components (C) may be contained as necessary within the range that the performance of the surface treatment agent of the present invention is not lost.

The surface treatment agent of the present invention can uniformly expose the triazole compound (A) to the entire surface of the copper-containing substrate. The triazole compound (A) exposed on the surface of the copper-containing substrate can form a complex with copper or its derivatives. It is inferred that the triazole compound (A) formed on the surface of the copper-containing substrate contains copper or its derivatives. An extremely thin film of complex (hereinafter also referred to as "surface treatment layer").

<1-1>Triazole compound (A)

In the manufacturing method of a plated shaped article of the present invention, the triazole compound (A) forms a complex with the copper of the copper-containing film, thereby making the surface of the substrate hydrophobic and making the substrate hydrophobic. It has the effect of improving the adhesion with the resist pattern.

The triazole compound (A) is at least one selected from the group consisting of triazole (A1) and benzotriazole-based compound (A2), and the triazole (A1) is 1,2,3-triazole or 1,2,4 -Triazole, the benzotriazole-based compound (A2) includes benzotriazole and a compound in which 1 to 4 hydrogen atoms of the benzene ring of the benzotriazole are substituted with a hydrophobic group.

Examples of the hydrophobic group include alkyl groups such as methyl, ethyl, n-butyl, tert-butyl, isobutyl, n-hexyl, 2-ethylhexyl, and n-dodecyl; and ring Cycloalkyl groups such as butyl, cyclopentyl, cyclohexyl, cyclopentenyl, and isobornyl; alkyl-substituted cycloalkyl groups such as cyclopentylmethyl and cyclohexylmethyl; phenyl, 1-naphthyl Aryl groups such as benzyl and 2-naphthyl; aralkyl groups such as benzyl and 2-phenylethyl; fluorine atom, perfluoromethyl, 1-fluorophenyl and 2,2',2"-trifluoroethyl, etc. Halogen-containing hydrocarbon groups.

The heterocyclic ring of the benzotriazole compound (A2) may be an isomer, and for example, in the case of a benzotriazole containing no hydrophobic group, it includes 1H-benzotriazole and 2H-benzotriazole. Examples of the benzotriazole-based compound (A2) include benzotriazole, tolyzotriazole, and the like.

The content ratio of the triazole compound (A) contained in the surface treatment agent of the present invention is 0.001 mass% to 2 mass%, preferably 0.01 mass% to 1.5 mass%, and more preferably 0.05 mass% to 1 mass%. If the content ratio of the triazole compound (A) is within the above range, when the surface treatment agent of the present invention is spin-coated on the substrate, the triazole compound (A) can be uniformly formed on the entire surface of the copper-containing substrate. As a result of the surface treatment layer, it is possible to manufacture a plated molded article without the penetration of plating liquid on the entire surface of the copper-containing substrate.

<1-2>Organic solvent (B)

The organic solvent (B) is a component for uniformly dissolving the triazole compound (A). By containing the organic solvent (B), the triazole compound (A) can be uniformly exposed to the entire surface of the copper-containing substrate.

The organic solvent (B) can be any organic solvent as long as it can uniformly dissolve the triazole compound (A) and wet the copper-containing film well. Examples include: ethylene glycol monomethyl ether, ethylene glycol Alcohols such as monoethyl ether, diethylene glycol, diethylene glycol monoethyl ether, ethyl lactate, and propylene glycol monomethyl ether; ethyl acetate, ethyl 2-hydroxypropionate, 2-hydroxy-2-methylpropionic acid Esters such as ethyl ester, methyl acetate, and ethoxyethyl acetate; ketones such as methyl amyl ketone and cyclohexanone; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, etc. Alkylene glycol dialkyl ethers such as ethylene glycol di-n-propyl ether and dipropylene glycol dimethyl ether; and ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. esters, propylene glycol monoethyl ether acetate, and propylene glycol mono-n-propyl ether acetate and other alkylene glycol monoalkyl ether acetates.

Among these, alkylene glycol monoalkyl ether acetate and alcohol are preferred in terms of high solubility to the triazole compound (A) and good penetration of the surface treatment agent into the copper-containing film. By well infiltrating the copper-containing film with the surface treatment agent, the triazole compound (A) can be evenly exposed to the entire surface of the copper-containing substrate.

The standard boiling point of the organic solvent (B) is usually 80°C to 200°C, preferably 100°C to 180°C, and more preferably 120°C to 160°C. The organic solvent (B) volatilizes during the period when the surface treatment agent is exposed to the substrate. Therefore, the evaporation rate is too fast or too slow to evenly expose the triazole compound (A) contained in the surface treatment agent to the copper-containing substrate. of the entire surface. If the standard boiling point of the organic solvent (B) is within the above range, the organic solvent (B) has an appropriate volatilization speed, and as a result, the triazole compound (A) can be uniformly exposed to the entire surface of the copper-containing substrate.

In addition, the so-called standard boiling point in this specification refers to the boiling point under one atmosphere.

As the organic solvent (B), propylene glycol monomethyl ether acetate (standard boiling point 146°C), propylene glycol monomethyl ether (standard boiling point 121°C), and ethyl lactate (standard boiling point 154°C) are preferred.

The content ratio of the organic solvent (B) contained in the surface treatment agent of the present invention is 90 mass% to 99.999 mass%, preferably 95 mass% to 99.999 mass%, more preferably 98 mass% to 99.999 mass%. If it is within the above range, the triazole compound (A) can be uniformly and thinly exposed to the entire surface of the copper-containing substrate, and therefore the surface treatment layer of the triazole compound (A) can be uniformly formed on the entire surface of the copper-containing substrate. , as a result, a plated molded article without penetration of plating liquid can be produced.

<1-3>Other ingredients (C)

The surface treatment agent of the present invention may contain other components (C) such as a surfactant and a reducing agent as necessary, within the range that the effect of the surface treatment agent of the present invention is not lost. The surfactant is a component used to uniformly form a surface treatment layer on the surface of a copper-containing substrate by improving the wettability of the surface treatment agent of the present invention to the substrate.

Examples of the surfactant include polyoxyalkylene phenyl ether, polyoxyalkylene methyl phenyl ether, polyoxyalkylene octyl phenyl ether, and polyoxyalkylene nonylbenzene. nonionic surfactants such as ethers; anionic surfactants such as alkyl aryl sulfonates such as sodium dodecylbenzene sulfonate.

The content ratio of other components (C) contained in the surface treatment agent of the present invention is 8 mass% or less, preferably 4 mass% or less, more preferably 1.999 mass% or less, and still more preferably 0 mass%. That is, the surface treatment agent of the present invention further preferably contains only the triazole compound (A) and the organic solvent (B).

<1-4> Manufacturing method of surface treatment agent

The surface treatment agent of the present invention can be produced by uniformly dissolving the triazole compound (A) and optional other components (C) in the organic solvent (B).

The dissolved mixed liquid can be filtered using a filter such as a fine-pore membrane filter to remove impurities.

<2>Surface treatment agent set

The surface treatment agent set of the present invention is a surface treatment agent set for producing the surface treatment agent of the present invention, and includes at least a first solution and a second solution described below.

The first solution contains more than 2 mass % and less than 100 mass % of at least one triazole compound (A) selected from the group consisting of triazole (A1) and benzotriazole-based compounds (A2), and more than 0 mass % and 98 mass %. % or less of organic solvent (B). The first solution may contain said other component (C).

The details of the triazole compound (A) and the organic solvent (B) and other components (C) contained in the first solution are the same as the triazole compound (A) and the organic solvent described in the description of the surface treatment agent of the present invention. (B) and other ingredients (C) are synonymous.

The second solution contains organic solvent (B). The content ratio of the organic solvent (B) contained in the second solution is usually 95 mass% or more, preferably 99 mass% or more. Examples of components other than the organic solvent (B) contained in the second solution include The other ingredients (C).

The details of the organic solvent (B) and other components (C) contained in the second solution are synonymous with the organic solvent (B) and other components (C) described in the description of the surface treatment agent of the present invention. The organic solvent (B) contained in the second solution may be of the same type as the organic solvent (B) contained in the first solution, or may be of a different type. Preferably, it may be the same type as the organic solvent (B) contained in the first solution. ) are of the same species.

The surface treatment agent of the present invention can be produced using the surface treatment agent set of the present invention. Specifically, it can be obtained by using at least one triazole compound (A) selected from the group consisting of triazole (A1) and a benzotriazole compound (A2) in an amount of 0.001% to 2% by mass and an organic solvent (B). It is manufactured by mixing 90 mass% to 99.999 mass%.

<3>Manufacturing method of plated molded article

The manufacturing method of plated shaped objects of the present invention includes: step (1), exposing a surface treatment agent to a substrate with a copper-containing film on the surface to form a surface treatment substrate; the surface treatment agent contains 0.001 mass % to 2 mass % of at least one triazole compound (A) selected from triazole (A1) and benzotriazole compound (A2) and 90 mass% to 99.999 mass% of an organic solvent (B); step (2), in A coating film of a resist composition is formed on the surface treatment substrate; step (3), exposing and developing the coating film to form a resist pattern; and step (4), forming the resist pattern Perform plating solution treatment as a mask.

The method for manufacturing a plated shaped object of the present invention may further include a step (5) of peeling off the resist after the step (4). The plating of the present invention is The outline of the steps of the manufacturing method of the shaped object is shown in FIG. 1 .

When the surface treatment agent of the present invention is exposed to a copper-containing substrate, it is inferred that an extremely thin film of a complex of the triazole compound (A) and copper or its derivative is formed. The complex is a complex of a hydrophobic triazole compound (A), so it is hydrophobic and has no affinity with the hydrophilic plating solution. In the method of manufacturing a plated molded article of the present invention, since such a hydrophobic surface treatment layer is formed on the contact surface between the resist pattern and the copper-containing substrate, it can be inferred that the penetration of the plating liquid occurs between the resist pattern and the copper-containing substrate. The contact surface of the copper-containing substrate can prevent the penetration of plating liquid.

Furthermore, since the triazole compound (A) can improve the adhesion between the resist pattern and the copper-containing film, it is inferred that the contact surface between the resist pattern and the copper-containing substrate where the plating liquid penetrates occurs, that is, particularly This prevents the penetration of plating liquid in areas with weak adhesion.

<3-1>Step (1)

Step (1) is to form a surface-treated substrate having a surface treatment layer on the surface of the copper-containing substrate by exposing the surface treatment agent of the present invention to the copper-containing substrate. The surface treatment layer is a layer that cannot be measured by a common film thickness measuring device such as a stylus type film thickness measuring device or a spectroscopic ellipsometer.

Examples of the copper-containing substrate include a substrate in which a copper-containing film is provided on the surface of a substrate such as a silicon wafer or a glass substrate. Examples of the planar shape of the substrate include a quadrangular shape and a circular shape. Examples of the shape of the substrate surface include a flat surface and an uneven shape like a through silicon via (TSV) structure.

Examples of the copper-containing film include copper compounds such as copper or copper oxide. membrane. The thickness of copper-containing films is usually 10Å~100,000Å.

Examples of methods for exposing the surface treatment agent include methods of forming a coating film by dip coating, spin coating, screen coating, gravure coating, wire bar coating, slit coating, inkjet coating, and the like. Among these, the triazole compound (A) can be uniformly exposed to the entire surface of the copper-containing substrate, and a good surface treatment layer can be formed. As a result, the plating liquid does not penetrate into the resist pattern and the resist pattern during the plating liquid treatment. From the viewpoint of producing a plated molded article with good shape between substrates, exposure by spin coating or screen coating is particularly preferred.

Exposure by spin coating is a method in which a surface treatment agent is placed on the copper-containing substrate while the copper-containing substrate is rotating, whereby the surface treatment agent is spread over the entire copper-containing substrate by the centrifugal force generated by the rotation. The surface spreads evenly, and volatile components such as organic solvents in the surface treatment agent are volatilized while rotating, thereby exposing the surface treatment agent to the copper-containing substrate.

The loading amount of the surface treatment agent in spin coating can be appropriately selected according to the surface area of the copper-containing substrate, and is usually 1cc~20cc, preferably 2cc~10cc. The maximum rotation speed in spin coating is usually 400rpm~4000rpm, preferably 800rpm~3000rpm. The maximum rotation speed during spin coating is usually 10 seconds to 3000 seconds, preferably 30 seconds to 2000 seconds.

The exposure by slit coating is as follows: while pressing a slit nozzle with a slit-like hole in the part where the surface treatment agent is sprayed against the copper-containing substrate, volatile components such as organic solvents in the surface treatment agent are volatilized. The surface treatment agent is thereby exposed to the surface of the copper-containing substrate.

The spray speed of the surface treatment agent in slot coating can be adjusted according to the copper-containing substrate. The surface area is appropriately selected, usually 0.01cc/second ~ 1.0cc/second. The moving speed of the slit nozzle in slot coating is usually 1cm/second to 50cm/second.

After the surface treatment agent of the present invention is exposed to the copper-containing substrate, the copper-containing substrate can be heated. By heating, the organic solvent (B) can be volatilized and a good surface treatment layer can be formed on the surface of the copper-containing substrate. In addition, it is inferred that the formation of a complex of the triazole compound (A) and the copper-containing film can be accelerated by heating, and as a result, it is inferred that a good surface treatment layer can be formed. The heating temperature is usually below 200°C, preferably 70°C to 150°C, and the heating time is usually 0.5 minutes to 20 minutes, preferably 1 minute to 10 minutes.

<3-2>Step (2)

Step (2) is to form a coating film of the resist composition on the surface-treated substrate formed in step (1).

Examples of the resist composition include known resist compositions used in the production of plated molded articles. Examples include Japanese Patent Application Laid-Open No. 2004-309775 and Japanese Patent Application Laid-Open No. 2007-248727. The positive resist composition containing an acid-dissociating alkali-insoluble resin and a photoacid generator described in Japanese Patent Application Publication No. 2015-194715 and Japanese Patent Application Publication No. 2009-169085; and Japan Negative type resistors containing an alkali-soluble resin, an acrylic compound and a photoradical polymerization initiator are described in Japanese Patent Application Laid-Open No. 2000-039709, Japanese Patent Application Laid-Open No. 2007-293306, WO2018/114635, and WO2013/084886. Corrosion composition.

When the negative resist composition is developed after exposure, the exposed The photoresist coating shrinks after swelling. If the adhesiveness between the resist coating film and the substrate is weak during shrinkage, the resist pattern after development may have an undercut shape. If the resist pattern has an undercut shape, the plating liquid will invade into the space created by the undercut shape, so the plating liquid will more easily infiltrate. Therefore, it is preferable to use the negative resist composition as the resist composition because the effect of the manufacturing method of the plated molded article of the present application is clearly apparent.

The resist pattern formed after exposure and development of the positive resist composition is an uncrosslinked resin film, and therefore has weak adhesion to the copper-containing substrate and is prone to infiltration of the plating solution. Accordingly, even if the positive resist composition is used as the resist composition, the effect of the method for manufacturing a plated molded article of the present invention is clearly apparent, so it is preferable.

The coating film of the resist composition can be formed, for example, by spin coating, transfer using a dry film, or slit coating. The detailed conditions for forming the coating film can be appropriately determined according to the type of the resist composition. select. For example, when the negative resist composition is used as the resist composition and a coating film is formed by spin coating, the maximum rotation speed of the spin coating is usually 800 rpm to 4000 rpm, and the time is 10 seconds to 3000 seconds. After spin coating, it is usually heated at 50°C to 200°C for 0.5 to 20 minutes to form a coating film.

The film thickness of the coating film is usually the same as or slightly thicker than the film thickness of the resist pattern formed in step (3), and is usually 0% to 10% thicker than the film thickness of the resist pattern.

<3-3>Step (3)

In step (3), the coating film formed in step (2) is exposed and developed, A resist pattern is formed.

The exposure is usually performed by equal-magnification projection exposure or reduced projection exposure through a mask (such as a reticle) having a light-shielding pattern consistent with the resist pattern to be formed. The exposure light usually uses laser with a wavelength of 190nm~500nm. The exposure amount is appropriately selected depending on the type of resist composition and the film thickness of the coating film. For example, when the resist composition is the negative resist composition, the exposure light is an i-ray (365 nm) laser, and the film thickness of the coating film is 50 μm, the exposure dose is usually 100 mJ/ cm ² ~10,000mJ/cm ² .

After exposure, heat treatment can also be performed before development. Especially when the resist composition is the positive resist composition, heat treatment is usually performed, and the conditions are usually 1 minute to 10 minutes at 70°C to 180°C.

The development is usually performed with a developer. Through selective exposure, the solubility of each part of the coating film with respect to the developer is different. Therefore, when the developer comes into contact with the coating film, the part of the coating film with high solubility is dissolved, and the undissolved part of the coating film forms a resist. pattern.

As the developer, alkaline developers such as potassium hydroxide aqueous solution and tetramethylammonium hydroxide aqueous solution are usually used.

Examples of the development method include a liquid coating method, a dipping method, a stirring method, a spray method, and a shower method. The development time is usually 30 seconds to 600 seconds at 23°C.

After development, the resist pattern can be cleaned with water or the like. Thereafter, drying can be carried out using an air gun or a heating plate.

The film thickness of the resist pattern is usually 0.8μm~300μm. When plating and shaping When the object is a wiring, it is usually 0.8μm~50μm, and when the plated molded object is an electrode, it is 1μm~300μm.

The shape of the resist pattern is selected in accordance with the type of application part of the plating molded article in the circuit board.

For example, when the applied part is a wiring, the shape of the resist pattern is a line and space pattern, and when the applied part is a bump, the shape of the resist pattern is a cube-shaped hole pattern. ).

<3-4>Step (4)

In step (4), the resist pattern formed in step (3) is used as a mask and a plating liquid treatment is performed to produce a plated shaped object.

That is, the resist pattern is used as a mold, and the opening formed by the resist pattern is treated with a plating solution to form a plated molded object.

The plating solution treatment is usually an electrolytic plating solution treatment. As the seed layer for electrolytic plating solution treatment, a copper-containing film located on the surface of the substrate is usually used. A plating film formed on the inner wall of the resist pattern by electroless plating solution treatment may also be used. As a seed layer. The barrier layer may also be formed before forming the seed layer, and the seed layer may be used as a barrier layer.

Before performing the plating solution treatment, in order to improve the affinity between the inner wall of the resist pattern and the plating solution, to remove the oxide film of the copper-containing film, and to remove dirt from the opening of the resist pattern, for example It can perform ashing treatment, flux treatment, and desmear treatment.

There is a surface formed by the present invention at the bottom of the opening of the resist pattern The surface treatment layer of the triazole compound (A) formed by using a treatment agent can be removed or not removed before treatment with the plating solution, either way is acceptable. The surface treatment layer is extremely thin and does not interfere with the plating solution treatment. Therefore, the plating solution treatment can be performed without removing the surface treatment layer.

Examples of the plating solution treatment include copper plating solution treatment, tin plating solution treatment, tin-silver plating solution treatment, solder plating solution treatment, gold plating solution treatment, nickel plating solution treatment, nickel- Gold plating solution treatment and chromium plating solution treatment.

Examples of the copper plating solution treatment include a plating solution treatment using a plating bath containing copper sulfate, copper pyrophosphate, etc.; examples of the gold plating solution treatment include a plating solution treatment using a plating bath containing gold cyanide. Plating solution treatment using a potassium plating bath; Examples of the nickel plating solution treatment include plating solution treatment using a plating bath containing nickel sulfate or nickel carbonate.

The conditions for the electrolytic plating solution treatment can be appropriately selected according to the composition of the plating solution. For example, when it is a plating solution containing copper sulfate, the conditions are usually a temperature of 10°C to 90°C and a current density of 0.1A/ dm ² ~100A/dm ² .

Plating solution treatment Different plating solution treatments can be performed sequentially. For example, by first performing a copper plating solution treatment and then performing a nickel plating solution treatment, the copper pillars of the solder copper pillar bumps can be formed.

<3-5>Step (5)

In step (5), after performing the plating solution treatment in step (4), the resist pattern is further removed.

Examples of the removal of the resist pattern include removing the substrate after step (4) Method of immersing in resist stripper. As the resist stripping liquid, for example, an organic solution containing an alkaline substance such as tetramethylammonium can be used.

After the resist pattern is removed, the copper-containing film other than the area where the plated molding is formed can be removed by wet etching or the like.

As shown above, by at least steps (1) to (4), it is possible to produce a plated molded object suitable for purposes such as wiring or bumping, and it is possible to make a plated product without the plating liquid penetrating between the resist pattern and the substrate. The resulting shape is a plated molded article with good shape.

<4>Circuit substrate

The circuit board of the present invention has a plated molded article produced by the method of producing a plated molded article of the present invention.

The plated molded article manufactured by the method of manufacturing a plated molded article of the present invention has no shape defects caused by the penetration of the plating liquid between the resist pattern and the substrate on the entire surface of the circuit substrate, and has a good shape. Since there is no short circuit between adjacent wirings or bumps, it is a highly reliable circuit board.

The circuit board is a circuit board including wiring or bumps, and specific examples thereof include semiconductor devices, display devices, industrial devices, and the like.

[Example]

Hereinafter, the present invention will be further described in detail based on examples, but the present invention is not limited to these examples.

[Example 1A to Example 4A, Comparative Example 1A to Comparative Example 3A] Production of Surface Treatment Agent 1A to Surface Treatment Agent 7A

Surface treatment agents 1A to 7A were manufactured by uniformly mixing the components shown in Table 1 below at the content ratios shown in Table 1 below.

[Experimental Example 1A] Formation of surface-treated substrate 1A and measurement of contact angle

Spin-coat surface treatment agent 1A (loading amount of surface treatment agent 1A: 5cc, maximum rotation speed: 1,000rpm, time: 0.5 minutes) on a 12-inch silicon wafer with copper foil (thickness: 3000Å) on the surface. The surface-treated substrate 1A was formed by heating at 90° C. for 1 minute using a hot plate.

According to the "Japanese Industrial Standards (JIS) R 3257, 1999" specification, the center (position 1) of the 12-inch silicon wafer of the surface-treated substrate 1A and the position on the peripheral side 4 inches from the center (position 2) The contact angles of water at these three points are measured: , and the position of the periphery 8 inches from the center (position 3). The evaluation results are shown in Table 2 below.

[Experimental Examples 2A to 7A] Formation of surface-treated substrates 2A to 7A and measurement of contact angles

In Experimental Example 1A, except for using the surface treatment agent shown in the following Table 2, surface-treated substrates 2A to 7A were manufactured by the same operation as Experimental Example 1A, and their contact angles were measured. The evaluation results are shown in Table 2 below.

[Experimental Example 8A] Formation of surface-treated substrate 1A and measurement of contact angle

Surface treatment agent 1A is slit-coated (slit nozzle: 70 μm gap (GAP), ejection speed of surface treatment agent 1A: 0.1cc/second, moving speed: 2cm/second) on a surface with copper foil (thickness: 3000Å) ) on a glass epoxy substrate (size: 50 cm in length, 40 cm in width), and heated at 90° C. for 1 minute using a hot plate to form surface-treated substrate 8A.

According to the "JISR 3257, 1999" standard, the surface treatment substrate 8A Water contact at three points: the center of the glass epoxy substrate (position 1), the position on the peripheral edge 10 cm from the center in the longitudinal direction (position 2), and the position on the peripheral edge 10 cm from the center in the transverse direction (position 3) Angle is measured. The evaluation results are shown in Table 2 below.

[Example 1B] Formation of resist pattern and production of plated molded article

A negative resist composition (trade name "THB-151N", manufactured by JSR Co., Ltd., a resist composition containing an alkali-soluble resin, an acrylic compound, and a photoradical polymerization initiator) is spin-coated on the surface. The treatment substrate 1A was heated at 120° C. for 300 seconds using a hot plate to form a coating film of the resist composition. Using a stepper (model "NSR-i10D" manufactured by Nikon Corporation), the coating film of the resist composition was exposed through a pattern mask, and oxidized to 2.38 mass% tetramethylhydrogen. It was immersed in an aqueous ammonium solution for 200 seconds and developed to form a resist pattern (a hole pattern of 20 μm in length, 20 μm in width, and 50 μm in depth).

The state of the bottom of the resist pattern at the position 1 was observed with an electron microscope and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3 below.

A: The resist pattern has no undercut.

B: The resist pattern has undercut.

In addition, an electron micrograph of the resist pattern formed in Example 1B is shown in FIG. 2 .

Using the resist pattern as a mask, an electrolytic plating process is performed by the following method to produce a plated molded article. As a pretreatment for plating, ashing treatment was performed by oxygen plasma (output 100W, oxygen flow rate 100 ml, treatment time 60 seconds), and then sulfuric acid treatment was performed (contact with 10 mass% sulfuric acid aqueous solution for 60 seconds). Then wash with water. The pretreated substrate was immersed in 1 L of copper plating solution (product name "MICROFAB SC-40", manufactured by Enthone Co., Ltd.), and the plating bath temperature was set to 40°C. Electrolytic plating was performed at a current density of 2A/dm ² for 15 minutes to produce a plated molded article.

The interface state of the resist pattern and the surface-treated substrate 1A after the production of the plated shaped article (whether the plating liquid penetrated or not) was observed with an optical microscope, and evaluated based on the following evaluation criteria. The evaluation results are shown in Table 3 below.

A: No penetration of plating solution.

B: There is penetration of plating liquid.

[Example 2B to Example 4B, Comparative Example 1B to Comparative Example 4B] Formation of resist pattern and production of plated molded article

In Example 1B, the surface-treated substrate shown in the following Table 3 was used. Except for this, a resist pattern was formed by the same operation as in Example 1B, a plated molded article was produced, and the same process as in Example 1B was performed. Same rating. The evaluation results are shown in Table 3 below.

Furthermore, in Comparative Example 4B, a 12-inch silicon wafer that was not surface-treated with a surface treatment agent and had copper foil (thickness: 3000Å) on the surface was used as the substrate.

An electron micrograph of the resist pattern formed in Comparative Example 4B is shown in FIG. 3 .

[Example 5B] Formation of resist pattern and production of plated molded article

A negative resist composition (trade name "THB-151N", manufactured by JSR Co., Ltd., a resist composition containing an alkali-soluble resin, an acrylic compound, and a photoradical polymerization initiator) is slit-coated On the surface treatment substrate 8A, use a heating plate at 120 Heating for 300 seconds at ℃ to form a coating film of the resist composition. Using an aligner (manufactured by Suss Microtech, model "MA150"), the coating film of the resist composition was exposed through a pattern mask, and exposed to 2.38 mass % tetramethyl It was immersed in an aqueous ammonium hydroxide solution for 200 seconds and developed to form a resist pattern (a hole pattern of 20 μm in length, 20 μm in width, and 50 μm in depth).

The resist pattern was evaluated in the same manner as in Example 1B, a plated molded article was produced, and the same evaluation as in Example 1B was performed. The evaluation results are shown in Table 3 below.

[Example 6B] Formation of resist pattern and production of plated molded article

A positive resist composition (trade name "THB-820P", manufactured by JSR Co., Ltd., a resist composition containing an acid-dissociating alkali-insoluble resin and a photoacid generator) is spin-coated on the surface-treated substrate 1A on a hot plate at 120° C. for 300 seconds to form a coating film of the resist composition. Using a stepper (model "NSR-i10D" manufactured by Nikon Corporation), the coating film of the resist composition was exposed through a pattern mask, and heated at 110° C. for 300 seconds using a hot plate. , and immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution for 300 seconds and developed to form a resist pattern (a hole pattern of 20 μm in length, 20 μm in width, and 50 μm in depth).

The resist pattern was evaluated in the same manner as in Example 1B, a plated molded article was produced, and the same evaluation as in Example 1B was performed. The evaluation results are shown in Table 3 below.

[Comparative Example 5B] Formation of resist pattern and production of plated molded article

In Example 6B, no surface treatment by surface treatment agent was used and the surface A 12-inch silicon wafer with a copper foil (thickness: 3000Å) was used as the substrate. Except for this, a resist pattern was formed by the same operation as in Example 6B, and a plated molded article was produced, and the same process as in Example 1B was performed. Same rating. The evaluation results are shown in Table 3 below.

[Example 7B] Formation of resist pattern and production of plated molded article

In Example 1B, the same evaluation as in Example 1B was performed except that a 1L/1S line and space pattern with a height of 30 μm and a pitch of 20 μm was formed as a resist pattern. The evaluation results are shown in Table 3 below.

The terms representing the resist composition and the characters representing the shape of the resist pattern in Table 3 below have the following meanings.

‧Resist composition

Negative: A resist composition with a trade name of "THB-151N", manufactured by JSP Co., Ltd., containing an alkali-soluble resin, an acrylic compound, and a photoradical polymerization initiator.

Positive: Trade name "THB-820P", manufactured by JSP Co., Ltd., a resist composition containing an acid-dissociating alkali-insoluble resin and a photoacid generator.

‧Resist pattern shape

A: Hole pattern of 20 μm in length, 20 μm in width, and 50 μm in depth.

B: 1L/1S line and space pattern with a height of 30 μm and a pitch of 20 μm.

Claims (9)

A method for manufacturing a plated shaped object, which is characterized by including: step (1), exposing a surface treatment agent to a substrate with a copper-containing film on the surface to form a surface treatment substrate, whereby a hydrophobic surface treatment layer is formed on The contact surface between the resist pattern and the copper-containing substrate, the surface treatment agent contains 0.001 mass% to 2 mass% selected from the group consisting of triazole (A1), unsubstituted benzotriazole and the benzene ring of benzotriazole At least one triazole compound (A) and 90 mass % to 99.999 of compounds in which 1 to 4 hydrogen atoms are substituted with alkyl groups, alkyl-substituted cycloalkyl groups, aryl groups, aralkyl groups or halogen-containing hydrocarbon groups Mass % organic solvent (B); step (2), forming a coating film of the resist composition on the surface treatment substrate; step (3), exposing and developing the coating film to form a resist pattern; and step (4), using the resist pattern as a mask to perform plating solution treatment. The method for manufacturing a plated shaped object according to claim 1, wherein the resist composition contains an alkali-soluble resin, an acrylic compound, and a photoradical polymerization initiator. The method for manufacturing a plated shaped object according to claim 1, wherein the resist composition contains an acid-dissociating alkali-insoluble resin and a photoacid generator. The method for manufacturing a plated shaped object as described in any one of items 1 to 3 of the patent application, wherein the film thickness of the resist pattern is 0.8 μm ~ 300 μm. The method for manufacturing a plated shaped object as described in any one of items 1 to 3 of the patent application further includes step (5) after the step (4). The resist pattern is removed. The method for manufacturing a plated shaped object as described in any one of items 1 to 3 of the patent application, wherein the surface treatment agent contains 0.001 mass% to 2 mass% of triazole compound (A) and 98 mass% %~99.999% by mass of organic solvent (B). The method for manufacturing a plated shaped article as described in any one of items 1 to 3 of the patent application, wherein the organic solvent (B) is alkylene glycol monoalkyl ether acetate or alcohol. The method for manufacturing a plated shaped object as described in any one of items 1 to 3 of the patent application, wherein the standard boiling point of the organic solvent (B) is 80°C to 200°C. A circuit substrate includes a plated molded article manufactured by the method for manufacturing a plated molded article described in any one of items 1 to 8 of the patent application.