CN112368643A - Method for producing plated article, circuit board, surface treatment agent, and surface treatment agent set - Google Patents

Method for producing plated article, circuit board, surface treatment agent, and surface treatment agent set Download PDF

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CN112368643A
CN112368643A CN201980044459.2A CN201980044459A CN112368643A CN 112368643 A CN112368643 A CN 112368643A CN 201980044459 A CN201980044459 A CN 201980044459A CN 112368643 A CN112368643 A CN 112368643A
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mass
plating
surface treatment
treatment agent
producing
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CN112368643B (en
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西口直希
桂山真
榊原宏和
松本朋之
远藤彩子
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JSR Corp
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JSR Corp
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

The invention provides a method for manufacturing a plating shaped object, which can manufacture a plating shaped object with a good shape without infiltration of a plating solution. The method for producing a plating formation object of the present invention is characterized by comprising: a step (1) of forming a surface-treated substrate by exposing a surface-treating agent containing 0.001 to 2 mass% of at least one triazole compound (A) selected from the group consisting of triazoles (A1) and benzotriazole compounds (A2) and 90 to 99.999 mass% of an organic solvent (B) to a substrate having a copper-containing film on the surface thereof; a step (2) of forming a coating film of a resist composition on the surface-treated substrate; a step (3) of exposing and developing the coating film to form a resist pattern; and (4) performing a plating solution treatment using the resist pattern as a mask.

Description

Method for producing plated article, circuit board, surface treatment agent, and surface treatment agent set
Technical Field
The present invention relates to a method for producing a plating formation, a circuit board, a surface treatment agent, and a surface treatment agent kit.
Background
Plating formations such as wirings and bumps (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, in connection terminals such as wiring or bumps of circuit boards of display devices such as semiconductor devices, liquid crystal displays, and touch panels, there has been an increasing demand for high-density mounting, and miniaturization of the connection terminals has been advanced. Accordingly, resist patterns used for forming connection terminals such as wirings and bumps are also required to be miniaturized.
However, the following problems are known: when the plating formation is formed by treatment with a plating solution using the resist pattern as a mask, the plating solution penetrates between the resist pattern and the substrate (patent documents 1 to 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 2005-274920
Patent document 2: japanese patent laid-open No. 2007-065642
Disclosure of Invention
Problems to be solved by the invention
If the resist pattern is made finer, the risk of adjacent wires or bumps being connected to each other due to penetration of the plating solution increases.
The invention aims to: to provide a method for producing a plating molded article, which can produce a plating molded article having a good shape without allowing a plating solution to penetrate between a resist pattern and a substrate during a plating solution treatment; providing a circuit board having a plating formation produced by the method for producing a plating formation; providing a surface treatment agent which can be preferably used in the manufacturing method of the plating formation; and a surface treating agent kit.
Means for solving the problems
The present inventors have made diligent studies to solve the above problems. As a result, the present inventors have found that the above problems can be solved by a method for producing a plated shaped article having the following configuration, and have completed the present invention. That is, the present invention relates to, for example, the following [1] to [11 ].
[1] A method for producing a plating formation, comprising: a step (1) (hereinafter, also referred to as "step (1)") of forming a surface-treated substrate by exposing a surface-treating agent containing 0.001 to 2 mass% of at least one triazole compound (a) selected from the group consisting of a triazole (a1) and a benzotriazole compound (a2) and 90 to 99.999 mass% of an organic solvent (B) to a substrate having a copper-containing film on the surface thereof (hereinafter, also referred to as "copper-containing substrate"); a step (2) (hereinafter, also referred to as "step (2)") of forming a coating film of a resist composition on the surface-treated substrate; a step (3) (hereinafter, also referred to as "step (3)") of exposing and developing the coating film to form a resist pattern; and a step (4) of performing a plating solution treatment using the resist pattern as a mask (hereinafter also referred to as "step (4)").
[2] The method for producing a plating formation object according to the above [1], wherein the resist composition contains an alkali-soluble resin, an acrylic compound, and a photo radical polymerization initiator.
[3] The method for producing a plating formation as recited in the above [1], wherein the resist composition contains an acid-dissociable, alkali-insoluble resin and a photoacid generator.
[4] The method for producing a plating formation as recited in any one of the above [1] to [3], wherein the resist pattern has a film thickness of 0.8 μm to 300 μm.
[5] The method for producing a plating formation according to any one of [1] to [4], further comprising a step (5) of removing the resist pattern (hereinafter, also referred to as "step (5)") after the step (4).
[6] The method for producing a plating formation as described in any one of [1] to [5], wherein the surface treatment agent contains 0.001 to 2 mass% of the triazole compound (A) and 98 to 99.999 mass% of the organic solvent (B).
[7] The method for producing a plating formation as described in any one of [1] to [6], wherein the organic solvent (B) is an alkylene glycol monoalkyl ether acetate or an alcohol.
[8] The method for producing a plating formation as recited in any one of the above [1] to [7], wherein the organic solvent (B) has a normal boiling point of 80 ℃ to 200 ℃.
[9] A circuit board comprising the plating formation produced by the method for producing a plating formation according to any one of [1] to [8 ].
[10] A surface treatment agent characterized by containing 0.001-2 mass% of at least one triazole compound (A) selected from the group consisting of triazoles (A1) and benzotriazole compounds (A2) and 90-99.999 mass% of an organic solvent (B).
[11] A surface treatment agent kit for manufacturing the surface treatment agent according to [10], the surface treatment agent kit characterized by:
at least comprises a first solution and a second solution,
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 a triazole (a1) and a benzotriazole compound (a2), and contains more than 0 mass% and 98 mass% or less of an organic solvent (B);
the second solution contains the organic solvent (B).
ADVANTAGEOUS EFFECTS OF INVENTION
The method for producing a plated shaped article according to the present invention can produce a plated shaped article having a good shape without allowing a plating solution to penetrate between a resist pattern and a substrate during a plating solution treatment. The circuit board of the present invention has a plating structure produced by the method for producing a plating structure of the present invention, and therefore has high reliability.
The surface treatment agent of the present invention can be preferably used in the method for producing a plating formation of the present invention.
The surface treatment agent kit of the present invention may be preferably used for manufacturing the surface treatment agent.
Drawings
FIG. 1 is a schematic view of a method for producing a plating formation of the present invention in FIG. 1.
Fig. 2 is an electron micrograph of a resist pattern formed in example 1B.
FIG. 3 is an electron micrograph of a resist pattern formed in comparative example 4B.
Detailed Description
Hereinafter, the method for producing a plated molded article, the circuit board, and the surface treatment agent set according to the present invention will be described.
The components exemplified in the present specification, for example, the components in the surface treatment agent, may be used singly or in combination of two or more unless otherwise mentioned.
<1> surface treating agent
The surface treatment agent of the present invention contains 0.001 to 2 mass% of at least one triazole compound (A) selected from the group consisting of triazoles (A1) and benzotriazole compounds (A2) and 90 to 99.999 mass% of an organic solvent (B). The surface treatment agent of the present invention may contain other component (C) as necessary within a range not to lose the performance of the surface treatment agent.
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 a derivative thereof, and it is inferred that an extremely thin film (hereinafter, also referred to as "surface treatment layer") containing a complex of the triazole compound (a) with copper or a derivative thereof is formed on the surface of the copper-containing substrate.
<1-1> triazole Compound (A)
In the method for producing a plated shaped article of the present invention, the triazole compound (a) forms a complex with copper containing a copper film, thereby rendering the surface of the substrate hydrophobic and imparting an effect of improving adhesion to a resist pattern to the substrate.
The triazole compound (a) is at least one selected from the group consisting of triazole (a1) and benzotriazole compound (a2), the triazole (a1) is 1, 2, 3-triazole or 1, 2, 4-triazole, and the benzotriazole compound (a2) comprises benzotriazole and a compound obtained by substituting 1 to 4 hydrogen atoms of the benzene ring of benzotriazole 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; cycloalkyl groups such as cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, and isobornyl; cycloalkyl groups substituted with alkyl groups such as cyclopentylmethyl and cyclohexylmethyl; aryl groups such as phenyl, 1-naphthyl and 2-naphthyl; aralkyl groups such as benzyl and 2-phenylethyl; a halogen-containing hydrocarbon group such as a fluorine atom, a perfluoromethyl group, a 1-fluorophenyl group, and a2, 2', 2 "-trifluoroethyl group.
The heterocycle of the benzotriazole-based compound (A2) may be an isomer, for example, in the case of benzotriazole free from a hydrophobic group, it includes 1H-benzotriazole and 2H-benzotriazole. Examples of the benzotriazole-based compound (a2) include benzotriazole and tolyltriazole.
The content of the triazole compound (a) in the surface treatment agent of the present invention is 0.001 to 2% by mass, preferably 0.01 to 1.5% by mass, and more preferably 0.05 to 1% by mass. When 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 a substrate, a surface treatment layer of the triazole compound (a) can be uniformly formed on the entire surface of the copper-containing substrate, and as a result, a plated article having no plating solution infiltrated into the entire surface of the copper-containing substrate can be produced.
<1-2> organic solvent (B)
The organic solvent (B) is a component for uniformly dissolving the triazole compound (a), and 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) may be any organic solvent as long as it can uniformly dissolve the triazole compound (a) and can favorably wet the copper-containing film, and examples thereof include: alcohols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, ethyl lactate, and propylene glycol monomethyl ether; esters such as ethyl acetate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl acetoacetate, and ethyl ethoxyacetate; ketones such as methyl amyl ketone and cyclohexanone; alkylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n-propyl ether, and dipropylene glycol dimethyl ether; and alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol mono-n-propyl ether acetate.
Among these, alkylene glycol monoalkyl ether acetates and alcohols are preferable in terms of high solubility in the triazole compound (a) and good wetting of the surface treatment agent to the copper-containing film. The triazole compound (a) can be uniformly exposed to the entire surface of the copper-containing substrate by the surface treatment agent wetting the copper-containing film well.
The organic solvent (B) has a normal boiling point of usually 80 to 200 ℃, preferably 100 to 180 ℃, more preferably 120 to 160 ℃. The organic solvent (B) volatilizes during the exposure of the surface treatment agent to the substrate, and therefore its volatilization rate is too fast or too slow to uniformly expose the triazole compound (a) contained in the surface treatment agent to the entire surface of the copper-containing substrate. If the normal boiling point of the organic solvent (B) is in the range, the organic solvent (B) has an appropriate volatilization rate, and as a result, the triazole compound (a) can be uniformly exposed to the entire surface of the copper-containing substrate.
The normal boiling point in this specification is a boiling point under atmospheric pressure.
As the organic solvent (B), propylene glycol monomethyl ether acetate (normal boiling point: 146 ℃ C.), propylene glycol monomethyl ether (normal boiling point: 121 ℃ C.), and ethyl lactate (normal boiling point: 154 ℃ C.) are preferred.
The content of the organic solvent (B) contained in the surface treatment agent of the present invention is 90 to 99.999% by mass, preferably 95 to 99.999% by mass, and more preferably 98 to 99.999% by mass. Within the above range, the triazole compound (a) can be uniformly and thinly exposed over the entire surface of the copper-containing substrate, and therefore, the surface treatment layer of the triazole compound (a) can be uniformly formed over the entire surface of the copper-containing substrate, and as a result, a plating formation free from permeation of the plating solution can be produced.
<1-3> other Components (C)
The surface-treating agent of the present invention may contain other components (C) such as a surfactant and a reducing agent as necessary within a range not to lose the effects of the surface-treating agent of the present invention. The surfactant is a component for improving the wettability of the surface treatment agent of the present invention to a substrate, thereby enabling a surface treatment layer to be uniformly formed on the surface of a copper-containing substrate.
Examples of the surfactant include: nonionic surfactants such as polyoxyalkylene phenyl ether, polyoxyalkylene methylphenyl ether, polyoxyalkylene octyl phenyl ether and polyoxyalkylene nonyl phenyl ether; and anionic surfactants such as alkyl aryl sulfonates such as sodium dodecylbenzenesulfonate.
The content ratio of the other component (C) contained in the surface treatment agent of the present invention is 8% by mass or less, preferably 4% by mass or less, more preferably 1.999% by mass or less, and still more preferably 0% by mass. That is, the surface treatment agent of the present invention preferably contains only the triazole compound (a) and the organic solvent (B).
<1-4> Process for producing surface-treating agent
The surface treatment agent of the present invention can be produced by uniformly dissolving the triazole compound (a) and, if necessary, the other component (C) in the organic solvent (B).
The dissolved mixture may be filtered by a filter such as a microporous membrane filter to remove impurities.
<2> surface treating agent kit
The surface treatment agent kit of the present invention is a surface treatment agent kit 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 a triazole (a1) and a benzotriazole compound (a2), and more than 0 mass% and 98 mass% or less of an organic solvent (B). The first solution may contain the other component (C).
The details of the triazole compound (a), the organic solvent (B), and the other component (C) contained in the first solution are the same as those of the triazole compound (a), the organic solvent (B), and the other component (C) described in the description of the surface treatment agent of the present invention.
The second solution contains an organic solvent (B). The content of the organic solvent (B) contained in the second solution is usually 95% by mass or more, and preferably 99% by mass or more. The component other than the organic solvent (B) contained in the second solution may be the other component (C).
The details of the organic solvent (B) and the other component (C) contained in the second solution are synonymous with the details of the organic solvent (B) and the other component (C) described in the description of the surface treating agent of the present invention. The organic solvent (B) contained in the second solution may be the same as or different from the organic solvent (B) contained in the first solution, and is preferably the same as the organic solvent (B) contained in the first solution.
The surface treatment agent of the present invention can be produced using the surface treatment agent kit of the present invention. Specifically, the compound can be produced by mixing 0.001 to 2 mass% of at least one triazole compound (a) selected from the group consisting of triazole (a1) and benzotriazole compound (a2) with 90 to 99.999 mass% of an organic solvent (B).
<3> method for producing plated shaped article
The method for producing a plating molded article of the present invention comprises: a step (1) of forming a surface-treated substrate by exposing a surface-treating agent containing 0.001 to 2 mass% of at least one triazole compound (A) selected from the group consisting of triazoles (A1) and benzotriazole compounds (A2) and 90 to 99.999 mass% of an organic solvent (B) to a substrate having a copper-containing film on the surface thereof; a step (2) of 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 (4) performing a plating solution treatment using the resist pattern as a mask.
The method for producing a plating formation of the present invention may further comprise a step (5) of removing the resist pattern after the step (4). Fig. 1 schematically shows the steps of the method for producing a plated shaped article according to the present invention.
The surface treatment agent of the present invention is exposed to a copper-containing substrate, and it is estimated that an extremely thin film of a complex of the triazole compound (a) and copper or a derivative thereof is formed. The complex is a hydrophobic complex of the triazole compound (a), and thus has hydrophobicity and no affinity with a hydrophilic plating solution. In the method for producing a plated shaped article of the present invention, since the hydrophobic surface treatment layer is formed on the contact surface between the resist pattern and the copper-containing substrate, it is estimated that the plating solution can be prevented from penetrating through the contact surface between the resist pattern and the copper-containing substrate where the plating solution penetrates.
Further, since the triazole compound (a) can improve the adhesion between the resist pattern and the copper-containing film, it is presumed that the penetration of the plating solution can be prevented at the contact surface between the resist pattern and the copper-containing substrate where the penetration of the plating solution has occurred, that is, particularly at a place where the adhesion force is weak.
<3-1> step (1)
The step (1) is to form a surface-treated substrate having a surface-treated layer on the surface of a 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 general film thickness measuring apparatus such as a stylus film thickness measuring apparatus or a spectroscopic ellipsometer.
Examples of the copper-containing substrate include a substrate having a copper-containing film provided on a surface of a substrate such as a silicon wafer or a glass substrate. Examples of the planar shape of the substrate include a square shape and a circular shape. The surface of the substrate may have a flat surface or an uneven surface such as a Through Silicon Via (TSV) structure.
The copper-containing film may be a film containing a copper compound such as copper or copper oxide. The thickness of the copper-containing film is usually set to
Figure BDA0002871288770000081
As a method of exposing the surface treatment agent, a method of forming a coating film by dip coating, spin coating, screen coating, gravure coating, wire bar coating, slit coating, inkjet, or the like can be cited. Among these, exposure by spin coating or slit coating is particularly preferable in that 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, so that the plating solution does not penetrate between the resist pattern and the substrate during the plating solution treatment and a good-shaped plated article can be produced.
The exposure by spin coating was as follows: the surface treatment agent is placed on the copper-containing substrate while rotating the copper-containing substrate, whereby the surface treatment agent is uniformly spread over the entire surface of the copper-containing substrate by centrifugal force generated by the rotation, and the surface treatment agent is exposed to the copper-containing substrate by volatilizing volatile components such as an organic solvent in the surface treatment agent while rotating the surface treatment agent.
The amount of the surface treatment agent to be placed in the spin coating can be suitably selected depending on the surface area of the copper-containing substrate, and is usually 1cc to 20cc, preferably 2cc to 10 cc. The maximum rotation speed in the spin coating is usually 400 to 4000rpm, preferably 800 to 3000 rpm. The time for the highest spin speed in the spin coating is usually 10 seconds to 3000 seconds, and preferably 30 seconds to 2000 seconds.
The exposure using slit coating was as follows: while pressing a slit nozzle having slit-shaped holes at a portion where the surface treatment agent is ejected against the copper-containing substrate, a volatile component such as an organic solvent in the surface treatment agent is volatilized, and the surface treatment agent is exposed to the surface of the copper-containing substrate.
The discharge rate of the surface treatment agent in the slit coating can be appropriately selected depending on the surface area of the copper-containing substrate, and is usually 0.01 cc/sec to 1.0 cc/sec. The moving speed of the slit nozzle in the slit coating is usually 1 cm/sec to 50 cm/sec.
The copper-containing substrate may be heated after exposing the surface treatment agent of the present invention to the copper-containing substrate. By heating, the organic solvent (B) can be volatilized, and a favorable surface treatment layer can be formed on the surface of the copper-containing substrate. It is also presumed that the formation of a complex of the triazole compound (a) and the copper-containing film is promoted by heating, and as a result, it is presumed that a favorable surface-treated layer can be formed. The heating temperature is usually 200 ℃ or lower, preferably 70 to 150 ℃, and the heating time is usually 0.5 to 20 minutes, preferably 1 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).
The resist composition may be a known resist composition used for producing a plating formation, and examples thereof include: positive resist compositions containing an acid-dissociable alkali-insoluble resin and a photoacid generator, as described in Japanese patent laid-open Nos. 2004-309775, 2007-248727, 2015-194715, 2009-16901985, and the like; and negative resist compositions containing an alkali-soluble resin, an acrylic compound and a photo-radical polymerization initiator, which are described in Japanese patent laid-open Nos. 2000-039709, 2007-293306, WO2018/114635, WO2013/084886, and the like.
When the negative resist composition is developed after exposure, the exposed resist coating film shrinks after swelling. If the adhesion between the resist coating film and the substrate is weak during shrinkage, the developed resist pattern may have an undercut (undercut) shape. If the resist pattern is formed in an undercut shape, the plating solution enters into the space portion formed by the undercut shape, and thus the plating solution is more likely to penetrate. Therefore, the use of the negative resist composition as the resist composition is preferable because the effect of the method for producing a plating formation according to the present invention is remarkably exhibited.
The resist pattern formed after exposure and development of the positive resist composition is an uncrosslinked resin film, and therefore has poor adhesion to a copper-containing substrate, and thus is likely to be penetrated by a plating solution. Accordingly, the positive resist composition is preferably used because the effect of the method for producing a plating formation of the present invention is remarkably exhibited even when the positive resist composition is used as the resist composition.
The coating film of the resist composition can be formed by, for example, spin coating, transfer with a dry film, or slit coating, and the detailed conditions for forming the coating film can be appropriately selected depending on the kind of the resist composition. For example, in the case of using the negative resist composition as the resist composition and forming a coating film by spin coating, the maximum spin speed of spin coating is usually 800 to 4000rpm for 10 to 3000 seconds, and after spin coating, it is usually heated at 50 to 200 ℃ for 0.5 to 20 minutes, thereby forming a coating film.
The thickness of the coating film is usually the same as or slightly greater than the thickness of the resist pattern formed in step (3), and is usually 0% to 10% greater than the thickness of the resist pattern.
<3-3> step (3)
In step (3), the coating film formed in step (2) is exposed to light and developed to form a resist pattern.
The exposure is usually performed by an equal-magnification projection exposure or a reduction projection exposure through a mask (e.g., reticle) having a light-shielding pattern corresponding to a resist pattern to be formed. The exposure light is generally a laser beam having a wavelength of 190nm to 500 nm. The exposure amount is appropriately selected depending on the kind of the resist composition or 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 (365nm) laser, and the film thickness of the coating film is 50 μm, the exposure amount is usually 100mJ/cm2～10,000mJ/cm2。
After exposure, heat treatment may be performed before development. Particularly, when the resist composition is the positive resist composition, the heat treatment is usually performed under the condition of usually 70 to 180 ℃ for 1 to 10 minutes.
The development is usually carried out by a developer. Since the solubility of each portion of the coating film in the developer varies depending on the selective exposure, the developer comes into contact with the coating film to partially dissolve the coating film having high solubility, and as a result, the undissolved coating film portion forms a resist pattern.
As the developer, an alkaline developer such as an aqueous solution of potassium hydroxide or an aqueous solution of tetramethylammonium hydroxide is generally used.
Examples of the developing method include a liquid coating method, a dipping method, a stirring method, a spraying method, and a shower method. The development time is usually 30 seconds to 600 seconds at 23 ℃.
After development, the resist pattern can be cleaned by water or the like. Thereafter, drying may be performed by an air gun or a hot plate.
The thickness of the resist pattern is usually 0.8 to 300. mu.m, 0.8 to 50 μm when the plating formation is a wiring, and 1 to 300 μm when the plating formation is an electrode.
The shape of the resist pattern is selected in accordance with the type of the component to be applied to the circuit board of the plating formation.
For example, when the application part is a wiring, the shape of the resist pattern is a line and space pattern (line and space pattern), and when the application part is a bump, the shape of the resist pattern is a hole pattern (hole pattern) in a cubic shape.
<3-4> step (4)
In the step (4), the resist pattern formed in the step (3) is used as a mask and is subjected to a plating solution treatment to produce a plating formation.
That is, the openings formed by the resist pattern are treated with a plating solution using the resist pattern as a mold, thereby forming a plated shaped article.
The plating solution treatment is typically an electrolytic plating solution treatment. As the seed (seed) layer to be treated with the electrolytic plating solution, a copper-containing film on the surface of the substrate is generally used, but a plating film formed on the inner wall of the resist pattern by treatment with an electroless plating solution may be used as the seed layer. The barrier layer may also be formed prior to forming the seed layer, which may be used as a barrier layer.
Before the plating solution treatment, for example, ashing (ashing), flux (flux) and desmear (desmear) treatments may be performed 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 in the opening of the resist pattern.
The surface treatment layer of the triazole compound (a) formed by the surface treatment agent of the present invention is present at the bottom of the opening of the resist pattern, and the surface treatment layer may be removed or not removed before the plating solution treatment. Since the surface treatment layer is extremely thin, the plating solution treatment is not hindered, and 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-silver plating solution treatment, solder plating solution treatment, gold 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, or the like; examples of the gold plating solution treatment include a plating solution treatment using a plating bath containing gold potassium cyanide; as the nickel plating solution treatment, for example, a plating solution treatment using a plating bath containing nickel sulfate or nickel carbonate can be cited.
The conditions for the electrolytic plating treatment may be appropriately selected depending on the composition of the plating solution, and in the case of a plating solution containing copper sulfate, the conditions are usually 10 to 90 ℃ and a current density of 0.1A/dm2～100A/dm2。
The plating solution treatment may be performed by sequentially performing different plating solution treatments. For example, a copper pillar of a solder copper pillar bump can be formed by first performing a copper plating solution treatment and then performing a nickel plating solution treatment.
<3-5> step (5)
In step (5), after the plating solution treatment in step (4) is performed, the resist pattern is further removed.
The removal of the resist pattern may be performed, for example, by immersing the substrate after the step (4) in a resist stripping solution. 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 region where the plating formation is formed can be removed by wet etching or the like.
As described above, by performing at least the steps (1) to (4), a plating molded article suitable for the purpose of wiring, bump, or the like can be produced, and a plating molded article having a good shape and free from a shape defect caused by the penetration of a plating solution between the resist pattern and the substrate can be produced.
<4> Circuit Board
The circuit board of the present invention has a plating formation produced by the method for producing a plating formation of the present invention.
The plated shaped article produced by the method for producing a plated shaped article according to the present invention has a good shape without a shape defect caused by a plating solution penetrating between the resist pattern and the substrate on the entire surface of the circuit board, and therefore, there is no short circuit between adjacent wirings or bumps, and thus, a circuit board having high reliability is obtained.
The circuit board includes a circuit board including a wiring or a bump, and specifically includes a semiconductor device, a display device, an industrial device, and the like.
Examples
The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
[ examples 1A to 4A and comparative examples 1A to 3A ] production of surface-treating agents 1A to 7A
The surface-treating agents 1A to 7A were produced by uniformly mixing the components shown in table 1 below at the content ratios shown in table 1 below.
Figure BDA0002871288770000131
[ Experimental example 1A ] formation of surface-treated substrate 1A and measurement of contact Angle
The surface treatment agent 1A was spin-coated (loading amount of the surface treatment agent 1A: 5cc, maximum rotation number: 1,000rpm, time: 0.5 minutes) on a copper foil (thickness:
Figure BDA0002871288770000141
) The surface-treated substrate 1A was formed on the 12-inch silicon wafer by heating at 90 ℃ for 1 minute with a hot plate.
Contact angles of water at three points, that is, the center (position 1) of a 12-inch silicon wafer of the surface-treated substrate 1A, the position on the peripheral edge side 4 inches from the center (position 2), and the position on the peripheral edge 8 inches from the center (position 3), were measured in accordance with the specifications of "Japanese Industrial Standards (JIS) R3257, 1999". 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
Except that the surface treatment agents shown in table 2 below were used in experimental example 1A, surface-treated substrates 2A to 7A were produced by the same procedure as in 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
The surface treatment agent 1A was slit-coated (slit nozzle: 70 μm GAP (GAP), ejection speed of the surface treatment agent 1A: 0.1 cc/sec, moving speed: 2 cm/sec) on a copper foil (thickness:
Figure BDA0002871288770000142
) The glass epoxy substrate (size: 50cm in vertical direction and 40cm in horizontal direction) was heated at 90 ℃ for 1 minute with a hot plate to form a surface-treated substrate 8A.
Contact angles of water at three points, that is, the center (position 1) of the glass epoxy substrate of the surface-treated substrate 8A, the position on the peripheral side in the longitudinal direction (position 2) at a distance of 10cm from the center, and the position on the peripheral side in the lateral direction (position 3) at a distance of 10cm from the center, were measured in accordance with the "JISR 3257, 1999" specifications. The evaluation results are shown in table 2 below.
Figure BDA0002871288770000151
EXAMPLE 1B formation of resist Pattern and production of plating formation
A negative resist composition (a resist composition containing an alkali-soluble resin, an acrylic compound, and a photo radical polymerization initiator, manufactured by JSR corporation) was spin-coated on the surface-treated substrate 1A, and heated at 120 ℃ for 300 seconds by a hot plate to form a coating film of the resist composition. The coating film of the resist composition was exposed to light through a pattern mask using a stepper (model "NSR-i 10D" manufactured by Nikon corporation) and was developed by immersing in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 200 seconds to form a resist pattern (a hole pattern having a longitudinal length of 20 μm, a lateral length of 20 μm, and a depth of 50 μm).
The state of the bottom (bottom) of the resist pattern at the position 1 was observed with an electron microscope, and evaluated with the following evaluation criteria. The evaluation results are shown in table 3 below.
A: the resist pattern is free of undercuts.
B: the resist pattern has an undercut.
Fig. 2 shows an electron micrograph of the resist pattern formed in example 1B.
The resist pattern was used as a mask, and electrolytic plating was performed by the following method to produce a plating formation. 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 (contact with 10 mass% sulfuric acid aqueous solution for 60 seconds) was performed, followed by water washing. The pretreated substrate was immersed in 1L of a copper plating solution (product name "MICROFAB SC-40", manufactured by Lesi (Enthone) Co.) and set at a plating bath temperature of 40 ℃ and a current density of 2A/dm2Then, electrolytic plating was performed for 15 minutes to produce a plated molded article.
The interface state (presence or absence of penetration of the plating solution) between the resist pattern and the surface-treated substrate 1A after the production of the plating formation was observed with an optical microscope, and evaluated according to the following evaluation criteria. The evaluation results are shown in table 3 below.
A: there is no infiltration of plating solution.
B: there is infiltration of the plating solution.
Examples 2B to 4B and comparative examples 1B to 4B formation of resist patterns and production of plating formation
A plating formation was produced by forming a resist pattern in the same manner as in example 1B, except that the surface-treated substrates shown in table 3 below were used in example 1B, and the same evaluation as in example 1B was performed. The evaluation results are shown in table 3 below.
In comparative example 4B, the surface treatment was performed using a copper foil (thickness:
Figure BDA0002871288770000171
) As a substrate, a 12-inch silicon wafer.
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 plating formation
A negative resist composition (a resist composition containing an alkali-soluble resin, an acrylic compound, and a photo radical polymerization initiator, manufactured by JSR corporation) was slit-coated on the surface-treated substrate 8A, and heated at 120 ℃ for 300 seconds by a hot plate to form a coating film of the resist composition. The coating film of the resist composition was exposed to light through a pattern mask using an aligner (aligner) (model "MA 150" manufactured by suss microtech corporation) and was developed by immersing in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 200 seconds to form a resist pattern (a pattern of holes 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 to produce a plating formation, and the evaluation was performed in the same manner as in example 1B. The evaluation results are shown in table 3 below.
EXAMPLE 6B formation of resist Pattern and production of plating formation
A positive resist composition (a resist composition containing an acid-dissociable, alkali-insoluble resin and a photoacid generator, manufactured by JSR corporation, under the trade name "THB-820P") was spin-coated on the surface-treated substrate 1A, and heated at 120 ℃ for 300 seconds with a hot plate to form a coating film of the resist composition. The coating film of the resist composition was exposed to light through a pattern mask using a stepper (product of Nikon corporation, model number "NSR-i 10D"), heated at 110 ℃ for 300 seconds with a hot plate, and developed by immersing in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 300 seconds to form a resist pattern (a hole pattern 20 μm in the vertical direction, 20 μm in the horizontal direction, and 50 μm in depth).
The resist pattern was evaluated in the same manner as in example 1B to produce a plating formation, and the evaluation was performed in the same manner as in example 1B. The evaluation results are shown in table 3 below.
Comparative example 5B formation of resist Pattern and production of plating formation
In example 6B, a copper foil (thickness:
Figure BDA0002871288770000172
) A plating formation product was produced by forming a resist pattern in the same manner as in example 6B, except that the 12-inch silicon wafer of (1) was used as the substrate, and the same evaluation as in example 1B was performed. The evaluation results are shown in table 3 below.
EXAMPLE 7B formation of resist Pattern and production of plating formation
The same evaluation as in example 1B was performed except that in example 1B, a 1L/1S line-and-space pattern having 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 indicating the resist composition and the characters indicating the shape of the resist pattern in table 3 below have the following meanings.
Resist composition
Negative: a resist composition having a trade name of "THB-151N", manufactured by JSP (jet spun), containing an alkali-soluble resin, an acrylic compound, and a photo radical polymerization initiator.
Positive: a resist composition containing an acid-dissociable, alkali-insoluble resin and a photoacid generator, which is manufactured by JSP (jet spinning corporation) under the trade name "THB-820P".
Resist Pattern shape
A: a pattern of holes 20 μm in length, 20 μm in width and 50 μm in depth.
B: a line and space pattern of 1L/1S with a height of 30 μm and a pitch of 20 μm.
Figure BDA0002871288770000191

Claims (11)

1. A method for producing a plating formation, comprising: a step (1) of forming a surface-treated substrate by exposing a surface-treating agent containing 0.001 to 2 mass% of at least one triazole compound (A) selected from the group consisting of triazoles (A1) and benzotriazole compounds (A2) and 90 to 99.999 mass% of an organic solvent (B) to a substrate having a copper-containing film on the surface thereof; a step (2) of forming a coating film of a resist composition on the surface-treated substrate; a step (3) of exposing and developing the coating film to form a resist pattern; and (4) performing a plating solution treatment using the resist pattern as a mask.
2. The method for producing a plating formation according to claim 1, wherein the resist composition contains an alkali-soluble resin, an acrylic compound, and a photo-radical polymerization initiator.
3. The method for producing a plating formation according to claim 1, wherein the resist composition contains an acid-dissociable, poorly-alkali-soluble resin and a photoacid generator.
4. The method for producing a plating formation according to any one of claims 1 to 3, wherein the film thickness of the resist pattern is 0.8 to 300 μm.
5. The manufacturing method of a plating formation according to any one of claims 1 to 4, further comprising a step (5) of removing the resist pattern after the step (4).
6. The method for producing a plating formation according to any one of claims 1 to 5, wherein the surface treatment agent contains 0.001 to 2 mass% of the triazole compound (A) and 98 to 99.999 mass% of the organic solvent (B).
7. The method for producing a plating formation according to any one of claims 1 to 6, wherein the organic solvent (B) is an alkylene glycol monoalkyl ether acetate or an alcohol.
8. The method for producing a plating formation according to any one of claims 1 to 7, wherein the organic solvent (B) has a normal boiling point of 80 ℃ to 200 ℃.
9. A circuit substrate comprising a plating formation produced by the method for producing a plating formation according to any one of claims 1 to 8.
10. A surface treatment agent characterized by containing 0.001-2 mass% of at least one triazole compound (A) selected from the group consisting of triazoles (A1) and benzotriazole compounds (A2) and 90-99.999 mass% of an organic solvent (B).
11. A surface treatment agent kit for manufacturing the surface treatment agent according to claim 10, characterized in that:
at least comprises a first solution and a second solution,
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 a triazole (a1) and a benzotriazole compound (a2), and contains more than 0 mass% and 98 mass% or less of an organic solvent (B);
the second solution contains the organic solvent (B).
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JP2011049468A (en) * 2009-08-28 2011-03-10 Tokyo Ohka Kogyo Co Ltd Surface treatment agent and surface treatment method
JP2016018093A (en) * 2014-07-09 2016-02-01 東レ株式会社 Resin composition for antireflection films, method of producing antireflection film and method of producing pattern using the same, and solid state image sensor
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