JP2022098629A - Composition for forming coating film on metal surface comprising maleimide polymer - Google Patents

Abstract

To provide a composition for forming a coating film on a metal surface (a composition for forming an oxidation-preventing film of rewiring for semiconductor to prevent surface oxidation of rewiring metal, a composition for forming an oxidation-preventing film of metal, and a composition for forming an adhesion-enhancing film between rewiring for semiconductor and an interlayer insulating film, in particular useful in a rewiring-forming step in a semiconductor post-process), a wiring substrate and a semiconductor device using them, and a production method thereof.SOLUTION: A composition for forming a coating film on a metal surface includes a polymer comprising a unit structure with a maleimide group and an organic solvent. The polymer preferably comprises a unit structure including a cross-linking site.SELECTED DRAWING: Figure 3

Description

INDUSTRIAL APPLICABILITY The present invention is a metal surface coating film forming composition, particularly a metal surface coating film forming composition (an oxidation-suppressing film-forming composition for semiconductor rewiring, metal oxidation-suppressing), which is useful in a rewiring forming step in a semiconductor post-process. The present invention relates to a film forming composition, a film forming composition for improving adhesion between rewiring for a semiconductor and an interlayer insulating film, and a metal migration suppressing film), a wiring substrate using them, a semiconductor device, and a method for manufacturing them.

With the recent improvement in the characteristics of semiconductor chips, various wiring boards have been used. These wiring boards are often manufactured by forming copper or aluminum wiring, which has high electrical conductivity and is advantageous for speeding up the device, on the base material.

However, although copper or aluminum wiring is easy to form, the surface layer portion thereof may be oxidized during the manufacturing of the wiring board. In that case, the surface layer of the copper or aluminum wiring whose resistance has been increased by oxidation is removed by etching with sulfuric acid or the like, but if the copper or aluminum wiring is fine, most of the copper wiring is removed by etching. Therefore, there is a problem that it becomes difficult to miniaturize copper or aluminum wiring.

Further, after commercialization, copper and aluminum wiring are oxidized depending on the usage environment, which causes a problem that the electrical performance of the device is impaired.

Patent Document 1 describes a wiring containing copper formed on a base material and a polymer film containing a polymer of either titanium oxide or zirconium oxide formed on the surface of the wiring to prevent copper from oxidizing. It has been disclosed. Patent Document 2 contains at least one surfactant selected from a polyoxyalkylene type nonionic surfactant and a phosphoric acid ester type anionic surfactant, and is formed when heat is applied after the surface treatment. A surface treatment agent for a copper-based material having an oxide film having good adhesion is disclosed.

Japanese Unexamined Patent Publication No. 2019-021771 Japanese Unexamined Patent Publication No. 11-310883

INDUSTRIAL APPLICABILITY The present invention is a metal surface coating film forming composition, particularly a metal surface coating film forming composition (an oxidation-suppressing film-forming composition for semiconductor rewiring, metal oxidation-suppressing), which is useful in a rewiring forming step in a semiconductor post-process. A film-forming composition, a film-forming composition for improving adhesion between rewiring for semiconductors and an interlayer insulating film, and a metal migration-suppressing film), a wiring substrate using them, a semiconductor device, and a method for manufacturing them. do.

The present invention includes the following.

[1]
A metal surface coating film forming composition comprising a polymer containing a unit structure having a maleimide group and an organic solvent.

[2]
The metal surface coating film forming composition according to [1], wherein the polymer further comprises a unit structure including a crosslinkable site.

[3]
The metal surface coating film forming composition according to [2], wherein the crosslinkable moiety is an epoxy group.

[4]
The metal surface coating film forming composition according to any one of [1] to [3], further comprising at least one selected from the group consisting of a binder, a cross-linking agent, and an additive.

[5]
The metal surface coating film forming composition according to any one of [1] to [4] for forming a coating film on a metal surface.

[6]
The metal surface coating film forming composition according to [5], wherein the metal surface contains copper or aluminum.

[7]
The metal surface coating film forming composition according to [5], wherein the metal surface contains at least one selected from the group consisting of semiconductor rewiring, printed wiring and solder bumps.

[8]
Use of the metal surface coating film forming composition according to any one of [1] to [4] for forming a coating film on a metal surface.

[9]
Use of the metal surface coating film forming composition according to any one of [1] to [4] for forming a coating film on a metal surface containing copper or aluminum.

[10]
The metal surface coating film forming composition according to any one of [1] to [4] for forming a coating film on a metal surface containing at least one selected from the group consisting of semiconductor rewiring, printed wiring and solder bumps. Use of things.

[11]
A metal surface coating film which is a fired product of a coating film comprising the metal surface coating film forming composition according to any one of [1] to [7].

[12]
The metal surface coating film according to [11], which is an oxidation-suppressing film on a metal surface.

[13]
With the base material
Wiring formed on the base material and having a metal surface,
A wiring board provided with the metal surface coating film according to [11] or [12] on at least a part of the metal surface of the wiring.

[14]
The metal surface of the wiring has a side surface and an upper surface.
The wiring board according to [13], wherein the metal surface coating film is formed on each of the side surface and the upper surface.

[15]
The wiring board according to [13] or [14], wherein the wiring or the metal surface coating film is coated with an insulating film.

[16]
The wiring board according to [15], wherein the metal surface coating film is a film for improving the adhesion between the metal surface of the wiring and the insulating film.

[17]
The wiring board according to any one of [13] to [16], wherein the metal surface coating film is an oxidation inhibitory film on the metal surface of the wiring.

[18]
The step of forming a wiring having a metal surface on a base material, and the metal surface coating film forming composition according to any one of [1] to [7] are applied to the wiring, and the metal of the wiring is applied. A method for manufacturing a wiring substrate, which comprises a step of forming a metal surface coating film on at least a part of a surface.

[19]
[13] A method for manufacturing a wiring board, which comprises a step of heating the wiring board according to any one of [13] to [17] at 100 ° C. to 300 ° C.

[20]
The method for manufacturing a wiring board according to [19], wherein the metal surface of the wiring has a metal oxide layer having a thickness of 100 nm or less after the heating step.

[21]
The method for manufacturing a wiring board according to any one of [18] to [20], wherein the metal surface coating film is an oxidation inhibitory film on the metal surface of the wiring.

[22]
A semiconductor device including a semiconductor element provided with the wiring board according to any one of [13] to [17].

[23]
[18] A method for manufacturing a semiconductor device, which comprises a step of providing a wiring board manufactured by the method according to any one of [18] to [21] on a semiconductor element.

The metal surface coating film forming composition of the present invention is a simple process of simply coating and firing on the surface after rewiring formation, for example, to prevent oxidation of the surface metal, and to re-embed the insulating film for the semiconductor. Since the adhesion between the wiring and the interlayer insulating film can be improved, interface delamination between the semiconductor rewiring and the interlayer insulating film and migration of metal (particularly copper) can be prevented or suppressed. Therefore, the reliability (long-term performance stability) of the electrical characteristics of the semiconductor chip manufactured by using the metal surface coating film forming composition of the present invention can be improved.

It is a schematic diagram which shows the substrate of an Example. It is an FE-SEM photograph (enlarged view) of the side surface part of the substrate of an Example. It is an FE-SEM photograph (enlarged view) of the side surface part of the substrate after high temperature holding made in Example 1. FIG. It is an FE-SEM photograph of the side surface part of the substrate after high temperature holding, which was made in Example 1. FIG. It is an FE-SEM photograph (enlarged view) of the side surface part of the substrate after high temperature holding made in the comparative example 1. FIG. It is an FE-SEM photograph of the side surface part of the substrate after high temperature holding, which was made in the comparative example 1. FIG.

<Metal surface coating film forming composition>
The metal surface coating film forming composition of the present invention contains a polymer containing a unit structure having a maleimide group and an organic solvent. The unit structure having a maleimide group is represented by, for example, the following formula.

上記マレイミド基を有する単位構造が、本発明のポリマーに含まれる単位構造の全体に対し、１０モル％以上含まれることが好ましく、３０～１００モル％含まれることが好ましい。

The unit structure having a maleimide group is preferably contained in an amount of 10 mol% or more, preferably 30 to 100 mol%, based on the total unit structure contained in the polymer of the present invention.

The polymer of the present invention may contain a unit structure other than the unit structure having a maleimide group as long as the effect of the present invention is not impaired. That is, the polymer may be a copolymer with another monomer (for example, having a functional group capable of performing radical polymerization). It is preferable that the unit structure other than the unit structure having a maleimide group includes a unit structure containing a crosslinkable site.

It is considered that having the cross-linking site allows the cross-linking sites to react with each other or the NH group of maleimide, and the polymers having a cross-linking structure can form a metal surface coating film having a more improved effect of the present application. Be done.

Specific examples of the crosslinkable site include a hydroxy group, an epoxy group, an acyl group, an acetyl group, a formyl group, a benzoyl group, a carboxy group, a carbonyl group, an amino group, an imino group, a cyano group, an azo group, an azi group and a thiol group. , Sulf group and allyl group, and among these, an epoxy group is preferable.

When the polymer of the present invention contains a unit structure containing a crosslinkable moiety, the molar ratio of the unit structure including the crosslinkable moiety to the entire unit structure contained in the polymer is, for example, 5 to 50 mol%.

The unit structure including the crosslinkable site is preferably represented by the following formula.

（上記式［Ｉ］中、Ｒ^０は水素原子又は炭素原子数１～１０のアルキル基を表し、Ｌ^１は、単結合、エステル結合、エーテル結合又はアミド結合を表し、Ａ^１は酸素原子又は硫黄原子で中断されていてもよい炭素原子数１～１０のアルキレン基を表し、Ｄ^１は上記架橋性部位を表す。）

(In the above formula [I], R ⁰ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, L ¹ represents a single bond, an ester bond, an ether bond or an amide bond, and A ¹ represents an oxygen atom or an oxygen atom or an amide bond. It represents an alkylene group having 1 to 10 carbon atoms which may be interrupted by a sulfur atom, and D ¹ represents the crosslinkable moiety.)

Examples of the alkyl group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclopropyl group, an n-butyl group, an i-butyl group, an s-butyl group, and t-. Butyl group, cyclobutyl group, 1-methyl-cyclopropyl group, 2-methyl-cyclopropyl group, n-pentyl group, 1-methyl-n-butyl group, 2-methyl-n-butyl group, 3-methyl-n -Butyl group, 1,1-dimethyl-n-propyl group, 1,2-dimethyl-n-propyl group, 2,2-dimethyl-n-propyl group, 1-ethyl-n-propyl group, cyclopentyl group, 1 -Methyl-cyclobutyl group, 2-methyl-cyclobutyl group, 3-methyl-cyclobutyl group, 1,2-dimethyl-cyclopropyl group, 2,3-dimethyl-cyclopropyl group, 1-ethyl-cyclopropyl group, 2- Ethyl-cyclopropyl group, n-hexyl group, 1-methyl-n-pentyl group, 2-methyl-n-pentyl group, 3-methyl-n-pentyl group, 4-methyl-n-pentyl group, 1,1 -Dimethyl-n-butyl group, 1,2-dimethyl-n-butyl group, 1,3-dimethyl-n-butyl group, 2,2-dimethyl-n-butyl group, 2,3-dimethyl-n-butyl Group, 3,3-dimethyl-n-butyl group, 1-ethyl-n-butyl group, 2-ethyl-n-butyl group, 1,1,2-trimethyl-n-propyl group, 1,2,2- Trimethyl-n-propyl group, 1-ethyl-1-methyl-n-propyl group, 1-ethyl-2-methyl-n-propyl group, cyclohexyl group, 1-methyl-cyclopentyl group, 2-methyl-cyclopentyl group, 3-Methyl-cyclopentyl group, 1-ethyl-cyclobutyl group, 2-ethyl-cyclobutyl group, 3-ethyl-cyclobutyl group, 1,2-dimethyl-cyclobutyl group, 1,3-dimethyl-cyclobutyl group, 2,2- Dimethyl-cyclobutyl group, 2,3-dimethyl-cyclobutyl group, 2,4-dimethyl-cyclobutyl group, 3,3-dimethyl-cyclobutyl group, 1-n-propyl-cyclopropyl group, 2-n-propyl-cyclopropyl Group, 1-i-propyl-cyclopropyl group, 2-i-propyl-cyclopropyl group, 1,2,2-trimethyl-cyclopropyl group, 1,2,3-trimethyl-cyclopropyl group, 2,2 3-trimethyl-Cyclopropyl group, 1-ethyl-2-methyl-cyclopropyl group, 2-ethyl-1-methyl-cyclopropyl group, 2-ethyl-2 -Methyl-cyclopropyl group, 2-ethyl-3-methyl-cyclopropyl group, decyl group and the like.

Examples of the alkylene group having 1 to 10 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, cyclopropylene group, n-butylene group, isobutylene group, s-butylene group, and t-butylene group. Cyclobutylene group, 1-methyl-cyclopropylene group, 2-methyl-cyclopropylene group, n-pentylene group, 1-methyl-n-butylene group, 2-methyl-n-butylene group, 3-methyl-n-butylene Group, 1,1-dimethyl-n-propylene group, 1,2-dimethyl-n-propylene group, 2,2-dimethyl-n-propylene, 1-ethyl-n-propylene group, cyclopentylene group, 1- Methyl-cyclobutylene group, 2-methyl-cyclobutylene group, 3-methyl-cyclobutylene group, 1,2-dimethyl-cyclopropylene group, 2,3-dimethyl-cyclopropylene group, 1-ethyl-cyclopropylene group, 2-Ethyl-cyclopropylene group, n-hexylene group, 1-methyl-n-pentylene group, 2-methyl-n-pentylene group, 3-methyl-n-pentylene group, 4-methyl-n-pentylene group, 1 , 1-dimethyl-n-butylene group, 1,2-dimethyl-n-butylene group, 1,3-dimethyl-n-butylene group, 2,2-dimethyl-n-butylene group, 2,3-dimethyl-n -Butylene group, 3,3-dimethyl-n-butylene group, 1-ethyl-n-butylene group, 2-ethyl-n-butylene group, 1,1,2-trimethyl-n-propylene group, 1,2, 2-trimethyl-n-propylene group, 1-ethyl-1-methyl-n-propylene group, 1-ethyl-2-methyl-n-propylene group, cyclohexylene group, 1-methyl-cyclopentylene group, 2- Methyl-cyclopentylene group, 3-methyl-cyclopentylene group, 1-ethyl-cyclobutylene group, 2-ethyl-cyclobutylene group, 3-ethyl-cyclobutylene group, 1,2-dimethyl-cyclobutylene group, 1,3-dimethyl-cyclobutylene group, 2,2-dimethyl-cyclobutylene group, 2,3-dimethyl-cyclobutylene group, 2,4-dimethyl-cyclobutylene group, 3,3-dimethyl-cyclobutylene group, 1-n-propyl-cyclopropylene group, 2-n-propyl-cyclopropylene group, 1-isopropyl-cyclopropylene group, 2-isopropyl-cyclopropylene group, 1,2,2-trimethyl-cyclopropylene group, 1, 2,3-trimethyl-Cyclopropylene group, 2,2,3- Trimethyl-Cyclopropylene group, 1-ethyl-2-methyl-cyclopropylene group, 2-ethyl-1-methyl-cyclopropylene group, 2-ethyl-2-methyl-cyclopropylene group, 2-ethyl-3-methyl- Cyclopropylene group, n-heptylene group, n-octylene group, n-nonylene group or n-decanylen group can be mentioned.

The alkylene group having 1 to 10 carbon atoms which may be interrupted by the oxygen atom or the sulfur atom includes an ether bond or a sulfide bond between one or more carbon-carbon bonds contained in the alkylene group. Say.

It is preferable that L ¹ is an ester bond, and A ¹ is an alkylene group having 1 to 10 carbon atoms interrupted by an oxygen atom.

The weight average molecular weight of the polymer is not particularly limited, but is, for example, 500 to 500,000. If it is less than 500, there is a high possibility that the coated / formed metal surface coating film becomes non-uniform (a portion where the film cannot be formed), and if it exceeds 500,000, the viscosity of the metal surface coating film forming composition is high. May become difficult to apply with a uniform film thickness.

<Organic solvent>
The metal surface coating film forming composition of the present invention contains an organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polymer, but specifically, N, N-dimethylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, diethylene glycol dimethyl ether, cyclopentanone, cyclohexanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, methyllactate, ethyllactate, tetramethylurea, 1,3-dimethyl-2-imidazolinone, Examples thereof include N-cyclohexyl-2-pyrrolidone, N-methyl-2-pyrrolidinone, p-menthan, n-decane and the like, and these can be used alone or in combination of two or more.

Further, the organic solvent of the metal surface coating film forming composition according to the present invention may be an organic solvent generally used in a so-called semiconductor lithography process. Specific examples include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene. Glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethoxyacetate Ethyl, 2-hydroxyethyl acetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, Examples include butyl lactic acid, 2-heptanone, methoxycyclopentane and anisole. These solvents can also be used alone or in combination of two or more.

Further, the metal surface coating film forming composition of the present invention may contain at least one selected from the group consisting of a binder, a cross-linking agent, and an additive.

<Binder>
The metal surface coating film forming composition of the present invention may contain a binder. Specific examples include (meth) acrylic resin, polystyrene derivative, polyhydroxystyrene derivative, phenol novolac, polyester, polyether, polyamic acid ester, polyamic acid, polyimide, bismaleimide, polysulfone, PEEK, amino resin and the like.

The binder of the present invention preferably contains the resin having the following unit structure described in WO2020 / 080207.

［式（１）中、Ｘ^１は、４価の有機基であり、Ｙ^１は、２価の有機基であり、Ｒ^１及びＲ^２は、それぞれ独立に、１価の有機基である。］で表される単位構造を有するポリイミド前駆体。 (A) The following general formula (1):

[In the formula (1), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are independently monovalent organic groups. ] Is a polyimide precursor having a unit structure represented by.

Details of the above X ¹ and Y ¹ will be described later.

Further, it may be a resin having the following unit structure.

<Crosslinking agent>
The metal surface coating film forming composition of the present invention may contain a cross-linking agent. Specific examples include epoxy compounds, epoxy resins, aminoplast cross-linking agents, (blocking) isocyanates, polyfunctional (meth) acrylates and the like.

The following formulas (A-1) to (A-15) can be exemplified as the epoxy compound used in the present invention.

The formula (A-1) is manufactured by Nissan Chemical Industries, Ltd., and the trade names are TEPIC-G, TEPIC-S, TEPIC-SS, TEPIC-HP, and TEPIC-L (all 1,3,5-Tris (2,3-). It can be obtained as (epoxypropyl) isocyanuric acid).

Formula (A-2) is available from Nissan Chemical Industries, Ltd. under the trade name TEPIC-VL.

Formula (A-3) is available from Nissan Chemical Industries, Ltd. under the trade name TEPIC-FL.

Formula (A-4) is available from Nissan Chemical Industries, Ltd. under the trade name TEPIC-UC.

Formula (A-5) is available from Nagase Chemtech Co., Ltd. under the trade name Denacol EX-411.

Formula (A-6) is available from Nagase Chemtech Co., Ltd. under the trade name Denacol EX-521.

Formula (A-7) is available from Mitsubishi Gas Chemical Company, Inc. under the trade name TETRAD-X.

Formula (A-8) is manufactured by Showa Denko KK and can be obtained under the trade name BATG.

Formula (A-9) is available from Nittetsu Chemical & Materials Co., Ltd. under the trade name YH-434L.

Formula (A-10) is available from Asahi Organic Materials Industry Co., Ltd. under the trade name TEP-G.

Formula (A-11) is available from DIC Corporation under the trade name EPICLON HP-4700.

Formula (A-12) is available from Daicel Corporation under the trade name Epolide GT401. Note that a, b, c, and d are 0 or 1, respectively, and a + b + c + d = 1.

In addition, as a compound having an epoxy group, YH-434 (manufactured by Nittetsu Chemical & Materials Co., Ltd., trade name) as an epoxy resin having an amino group, and Eporide GT- as an epoxy resin having a cyclohexene oxide structure. 401, GT-403, GT-301, GT-302, Selokiside 2021, Selokiside 3000 (manufactured by Daicel Chemical Co., Ltd., trade name), as bisphenol A type epoxy resins, Epicoat 1001, 1002, 1003 , 1004, 1007, 1009, 1010, 828 (all manufactured by Yuka Shell Epoxy Co., Ltd., trade name), etc., as the bisphenol F type epoxy resin, Epicoat 807 (Oilized Shell Epoxy Co., Ltd.) ), Etc., as phenol novolac type epoxy resins, Epicoat 152, 154 (above, Yuka Shell Epoxy Co., Ltd., trade name), EPPN201, 202 (above, Nippon Kayaku Co., Ltd.) ), Etc., as cresol novolac type epoxy resins, EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.) , Product name), Epicoat 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd., product name), etc. CY177, CY179 (above, CIBA-GEIGY AG, trade name), Araldite CY-182, CY-192, CY-184 (above, CIBA-GEIGY AG, trade name), Epicron 200, 400 (above, manufactured by Dainippon Ink Industry Co., Ltd., trade name), Epicoat 871, 872 (above, manufactured by Yuka Shell Epoxy Co., Ltd., trade name), ED-5661, ED-5662 (above, Cera) Needs Coating Co., Ltd. (trade name), etc., as the aliphatic polyglycidyl ether, Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512. , EX-522, EX-421, EX-313, EX-314, EX-321 (manufactured by Nagase ChemteX Corporation, trade name) and the like.

The amount of the cross-linking agent added to the polymer is, for example, 5 to 50% by mass.

<Additives>
The metal surface coating film forming composition of the present invention may contain an additive. Specific examples include additives such as lubricants, fillers, plasticizers, antioxidants, UV absorbers, light stabilizers, antistatic agents, flame retardants, colorants, fungicides, and curing accelerators for the purpose. An appropriate amount may be blended accordingly. When the additive is contained, the content of the additive is preferably 0.01% by mass to 20% by mass with respect to 100% by mass of the total amount of the above composition.

<Metal>
The metal referred to in the present invention is not particularly limited. Specific examples include iron, copper, tin and aluminum, but the present invention exhibits excellent properties particularly with respect to copper and aluminum. That is, if it is a metal containing copper or aluminum, the metal surface coating film of the present invention can suppress the formation of copper oxide on the surface of copper and can suppress the formation of aluminum oxide on the surface of aluminum.

As a method for evaluating the oxidation inhibitory ability of a metal by the metal surface coating film of the present invention, after an oxidation treatment test of a metal wiring, for example, a wiring substrate on which a copper wiring is formed, which is described in Examples, visual observation by FE-SEM is performed. It can be confirmed by observing the presence or absence of metal oxide film formation.

The metal may be a material forming at least one selected from the group consisting of semiconductor rewiring, printed wiring and solder bumps.

<Metal surface coating film forming composition>
A metal surface coating film can be formed by applying the metal surface coating film forming composition to a metal surface by a known method and then firing. The coating method is not particularly limited, and ordinary spin coating, dip coating, solvent casting and other coating methods are used. Next, a coating film having a film thickness of 1 nm to 500 nm can be formed through a firing step in a normal atmosphere (firing temperature 100 to 300 ° C., firing time 10 seconds to 1 hour).

<Manufacturing method of wiring board and wiring board>
The "base material" for manufacturing the wiring board referred to in the present invention is a base material for supporting the metal wiring and the insulating film (photosensitive and non-photosensitive) layers described later. The material is not particularly limited, such as metal and resin, and examples thereof include a base material made of silicon and glass. It is preferable that the metal wiring layer and the insulating film layer have strength to maintain the shape, and when the heating step is included, the metal wiring layer and the insulating film layer have heat resistance that does not deform even after the heating step of 100 ° C. to 400 ° C. The shape of the base material is not particularly limited, such as a flat surface, a surface having corners, a curved surface, an uneven surface, and a depression, but is usually a flat plate.

The wiring substrate of the present invention is a wiring substrate including the above-mentioned base material, a wiring including a metal surface formed on the substrate, and the above-mentioned metal surface coating film on at least a part of the surface of the wiring. .. The metal wiring can be manufactured by a known method such as embedding metal in a plating step after making a mold. The metal wiring may have a line-and-space shape having a height and width of, for example, about 1 μm to 20 μm.

By applying and firing the metal surface coating film forming composition on a metal wiring made by a known method by the above method, the above-mentioned metal surface coating film is provided on at least a part of the surface of the wiring. Although a wiring board can be manufactured, it is desirable that the above-mentioned metal surface coating film is formed over the entire exposed portion of the wiring. The wiring formed on the so-called base material usually has a rectangular shape and has a side surface and an upper surface. Since the exposed portion of the wiring on the side surface and the upper surface side is easily oxidized through the next heating step or the like, the metal surface coating film of the present invention is formed on at least a part of each of the side surface and the upper surface. It is preferable that it is formed over the entire surface of each of the side surface and the upper surface. Since the metal surface coating film made from the metal surface coating film forming composition has a thin film thickness as described above, the film has a substantially uniform film thickness (for example, 1 nm to 200 nm and 1 nm to 500 nm) with respect to the metal surface. Despite being such a thin film, the metal surface coating film of the present invention is excellent in the ability to suppress metal oxidation.

The wiring may be further coated with an insulating film (photosensitive, non-photosensitive). The coating method may be a known method, and for example, the insulating film forming composition can be coated by coating and firing on a wiring board provided with the metal surface coating film.

The substrate produced as described above may be subjected to a step of heating at 100 ° C to 300 ° C. The heating step may be applied, for example, in a reliability test as a wiring board used for a semiconductor element. It is usually carried out under the atmosphere at 125 ° C. to 150 ° C. for 1 to 1000 hours, but may be carried out under high humidity conditions such as so-called temperature 85 ° C./humidity 85% (85/85 test).

After the heating test, the thickness of the metal oxide layer on the wiring surface is preferably 1 μm (1000 nm) or less, 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less. , 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 40 nm or less, 30 nm or less, 20 nm or less, 10 nm or less, 10 nm or less, 5 nm or less, 3 nm or less, 2 nm or less, 1 nm or less, 0 nm (oxide film) Is not observed).

<Insulating film, photosensitive insulating film>
As the insulating film and the photosensitive insulating film referred to in the present invention, known ones may be used, but for example, the metal wiring may be formed later in order to electrically insulate between the metal wirings. It is preferable that the insulating film can be manufactured by a coating type or a non-coating type (vapor deposition step (CVD), etc.) that can be embedded without gaps, but from the viewpoint of efficiency of the manufacturing process, a coating type photosensitive insulating film forming composition is preferable. Things are often used. The insulating film is formed to prevent conduction between metal wirings, and is usually used for state-of-the-art semiconductor devices that require a low dielectric constant (for example, 2.0 to 3.5) and finer metal wirings. An insulating film having a low dielectric loss tangent (for example, 0.01 or less) is used. From the viewpoint of ease of shape processing, a photosensitive insulating film that can be shaped by a lithography process is preferable.

As the coating type insulating film, it is manufactured by using an insulating film forming composition (such as an insulating film forming composition for rewiring used for manufacturing a semiconductor device) containing a resin containing a known polyimide, polyarylether, polybenzoxazole or the like. can.

Specific examples thereof include the photosensitive insulating film forming compositions described in WO2019 / 044874, WO2019 / 139028 and WO2020 / 080206.

The photosensitive insulating film referred to in the present invention is preferably a photosensitive insulating film composition containing, for example, the resin having the following structure described in WO2020 / 080207.

［式中、Ｘ^１は、４価の有機基であり、Ｙ^１は、２価の有機基であり、Ｒ^１及びＲ^２は、それぞれ独立に、１価の有機基である。］で表される単位構造を有するポリイミド前駆体、及び
（Ｂ）下記一般式（２０）：

［式中、Ｒ^２３は水素原子又はメチル基を表し、Ｒ^２４は、置換基を有してもよく、酸素原子によって中断されていてもよい炭素原子数１乃至５のアルキレン基を表し、Ｒ^２５は、イソシアネート基又はブロックイソシアネート基を表す。］
で表されるイソシアネート化合物、を含む感光性樹脂組成物、である。 (A) The following general formula (1):

[In the formula, X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and R ¹ and R ² are independently monovalent organic groups. ], And (B) the following general formula (20):

[In the formula, R ²³ represents a hydrogen atom or a methyl group, and R ²⁴ represents an alkylene group having 1 to 5 carbon atoms which may have a substituent and may be interrupted by an oxygen atom. Reference numeral ²⁵ represents an isocyanate group or a blocked isocyanate group. ]
A photosensitive resin composition containing an isocyanate compound represented by.

［式中、Ｚ^１及びＺ^２は、それぞれ独立に、
水素原子、ハロゲン原子、ヒドロキシ基、メルカプト基、カルボキシ基、シアノ基、ホルミル基、ハロホルミル基、スルホ基、ニトロ基、ニトロソ基、オキソ基、チオキシ基、
置換されていてもよい炭素原子数１～１０のアルキル、アルコキシ、もしくはアルキルスルファニル基、
置換されていてもよい炭素原子数２～１０のアルケニル、アルキニル、もしくはアルコキシカルボニル基、又は
置換されていてもよいアミノ、イミノ、もしくはカルバモイル基を表し、
Ｚ^１及びＺ^２は、相互に結合して、ヘテロ原子を含んでもよく、置換基を有していてもよく、縮合していてもよい環を形成してもよく、当該環が芳香族環であるとき、

はＨＯＯＣがＣＯＯＨに対してオルト位にある共役二重結合を示し、当該環が芳香族環であるとき以外の場合、

はＨＯＯＣとＣＯＯＨについてのシス型二重結合を示す。］
で表されるカルボン酸化合物又はその無水物、を含む感光性樹脂組成物であってよい。 Further (C) the following general formula (30):

[In the formula, Z ¹ and Z ² are independent of each other.
Hydrogen atom, halogen atom, hydroxy group, mercapto group, carboxy group, cyano group, formyl group, haloformyl group, sulfo group, nitro group, nitroso group, oxo group, tioxy group,
An alkyl, alkoxy, or alkylsulfanil group having 1 to 10 carbon atoms which may be substituted,
Represents an alkenyl, alkynyl, or alkoxycarbonyl group having 2 to 10 carbon atoms which may be substituted, or an amino, imino, or carbamoyl group which may be substituted.
Z ¹ and Z ² may be bonded to each other to form a ring which may contain a heteroatom, may have a substituent, or may be condensed, and the ring may be an aromatic ring. When

Indicates a conjugated double bond in which the HOOC is in the ortho position with respect to COOH, except when the ring is an aromatic ring.

Shows a cis-type double bond for HOOC and COOH. ]
It may be a photosensitive resin composition containing a carboxylic acid compound represented by (1) or an anhydride thereof.

In the above general formula (1), X ¹ is not particularly limited as long as it is a tetravalent organic group, but is preferably a tetravalent group having 6 to 40 carbon atoms from the viewpoint of achieving both heat resistance and photosensitive characteristics. It is an organic group of, and more preferably an aromatic group or an alicyclic aliphatic group in which ^one -COOR group and ^two -COOR groups and -CONH- group are in ortho positions with each other. Further, the tetravalent organic group represented by X ¹ is more preferably an organic group having an aromatic ring and having 6 to 40 carbon atoms.

More preferably, X ¹ is a tetravalent organic group represented by the following formula (5) or the following formulas (5-1) to (5-7).

Further, the structure of X ¹ may be one kind or a combination of two or more kinds.

In the above general formula (1), Y ¹ is not limited as long as it is a divalent organic group having 6 to 40 carbon atoms, but may be substituted from the viewpoint of achieving both heat resistance and photosensitive characteristics. It is preferably a cyclic organic group having 1 to 4 aromatic rings or an aliphatic ring, or an aliphatic group or a siloxane group having no cyclic structure. More preferably, Y ¹ has a structure represented by the following general formula (6), the following general formula (7), or the following formula (8).

（式中、Ａは、それぞれ独立に、メチル基（－ＣＨ_３）、エチル基（－Ｃ_２Ｈ_５）、プロピル基（－Ｃ_３Ｈ_７）又はブチル基（－Ｃ_４Ｈ_９）を表す。｝

(In the formula, A independently represents a methyl group (-CH ₃ ), an ethyl group (-C ₂ H ₅ ), a propyl group (-C ₃ H ₇ ) or a butyl group (-C ₄ H ₉ ), respectively. .}

Further, the structure of Y ¹ may be one kind or a combination of two or more kinds.

In the above general formula (1), R ¹ and R ² are not particularly limited as long as they are independently monovalent organic groups. For example, R ¹ and R ² each independently have a monovalent aliphatic group, a cyclic aliphatic group, an aromatic group and an aliphatic group having 1 to 30 carbon atoms or 5 to 22 carbon atoms bonded to each other. The group can be a group in which the group is substituted with a halogen atom, a nitro group, an amino group, a cyano group, a methoxy group, an acetoxy group or the like. As the halogen atom, F, Cl, Br, and I are typical.

The entire disclosure described in WO2020 / 080207 publication is incorporated herein by reference.

<Oxidation-suppressing film-forming composition on metal surface>
The metal surface coating film forming composition of the present invention can be used as an oxidation inhibitory film forming composition on a metal surface. The suppression of oxidation of the metal surface is as described above.

<Adhesion-enhancing film-forming composition>
The metal surface coating film forming composition of the present invention can also be used as a film forming composition for improving adhesion between rewiring for semiconductors and an interlayer insulating film.

The metal surface coating film forming composition of the present invention is applied to the metal wiring of the semiconductor rewiring to form the metal surface coating film, whereby the adhesion between the semiconductor rewiring and the interlayer insulating film is improved. The generation of a gap between the wiring and the interlayer insulating film can be suppressed. This gap may be generated through the heating step in the above reliability test. Usually, the interlayer insulating film is an organic substance and the wiring is a metal, so that the adhesion tends to decrease. By applying and firing the adhesion improving film forming composition of the present invention on the metal wiring, the adhesion improving film is formed on at least a part of the surface on the wiring, so that the interlayer insulating film and the metal wiring can be combined. Although it is possible to improve the adhesion between the wiring, it is preferable to form the metal surface coating film on the entire surface from the viewpoint of improving the adhesion between the interlayer insulating film and the metal wiring.

The wiring board of the present invention includes a base material, wiring formed on the base material, and the like.
At least a part of the surface of the wiring is provided with a film for improving the adhesion between the semiconductor rewiring and the interlayer insulating film. The surface of the rewiring has a side surface and an upper surface, and a wiring board having the metal surface coating film formed on at least a part of each of the side surface and the upper surface is preferable. It is more preferable that it is formed over the entire surface of each from the viewpoint of adhesion. The description of the side and top surfaces of the rewiring is as described above.

The rewiring may be a wiring board coated with the insulating film.

The method for manufacturing a wiring substrate of the present invention includes a step of forming wiring on the base material as described above, and a metal surface of the semiconductor rewiring and the interlayer insulating film as described above on the surface of the wiring. The step of applying the coating film forming composition to form a metal surface coating film is included.

The method for manufacturing a wiring board of the present invention includes a step of heating the wiring board at 100 ° C. to 300 ° C., and is a method in which the contact interface peeling between the rewiring surface and the insulating film does not occur. The fact that the contact interface peeling does not occur means that, for example, by observing the cross section of the substrate by the FE-SEM described in the embodiment, there is no visual gap at the contact interface between the metal (rewiring) surface and the insulating film. Say.

<Metal migration suppressing film forming composition>
The metal surface coating film forming composition of the present invention can also be used as a metal migration suppressing film. Metal migration means that the metal used as wiring or electrodes moves on the insulator (migration phenomenon), causing a decrease in the insulation resistance value between the electrodes. Eventually, a short circuit will occur, causing defective electronic components. By applying the metal surface coating film forming composition of the present invention to a metal surface to form a metal surface coating film, the above migration can be prevented or suppressed.

<Semiconductor device, manufacturing method of semiconductor device>
The semiconductor device of the present invention is a semiconductor device including a semiconductor element and the wiring substrate provided above or below the semiconductor element.

In the embodiment, a semiconductor device having a cured relief pattern obtained by a known method for producing a cured relief pattern using the photosensitive insulating film described above is also provided. Therefore, it is possible to provide a semiconductor device having a substrate which is a semiconductor element and a cured relief pattern of an insulating film formed on the substrate by the above-described cured relief pattern manufacturing method. Further, the present invention can also be applied to a method for manufacturing a semiconductor device, which uses a semiconductor element as a substrate and includes the above-mentioned method for manufacturing a cured relief pattern as a part of a process. The semiconductor device of the present invention is a semiconductor device having a surface protective film, an interlayer insulating film, an insulating film for rewiring, a protective film for a flip chip device, or a bump structure of a cured relief pattern formed by the above-mentioned cured relief pattern manufacturing method. It can be manufactured by forming it as a protective film or the like and combining it with a known manufacturing method of a semiconductor device.

Hereinafter, specific examples of the composition according to the present invention will be described with reference to the following examples and the like, but the present invention is not limited thereto.

The weight average molecular weight shown in the following synthetic example of the present specification is a measurement result by gel permeation chromatography (hereinafter, abbreviated as GPC in the present specification). A GPC device (HLC-8320GPC) manufactured by Tosoh Corporation is used for the measurement, and the measurement conditions and the like are as follows.

GPC column: KD-803, KD-805 (manufactured by Shodex)
Column temperature: 50 ° C
Solvent: N, N-dimethylformamide (Kanto Chemical Co., Ltd., special grade), lithium bromide monohydrate (Kanto Chemical Co., Ltd., deer special grade) (30 mM) / phosphoric acid (Aldrich) (30 mM) / tetrahydrofuran (Kanto Chemical Co., Ltd.) Co., Ltd., special grade) (1%)
Flow rate: 1.0 mL / min Standard sample: Polystyrene (manufactured by GL Sciences)

<Production Example 1> Synthesis of dicarboxylic acid diester (1) 4,4'-biphthalic acid dianhydride (Tokyo Kasei Kogyo Co., Ltd.) 200.00 g (0.68 mol) was placed in a 2-liter volumetric flask and 2 -Add 176.92 g (1.366 mol) of hydroxyethyl methacrylate (Aldrich), 0.74 g (0.007 mol) of hydroquinone (Tokyo Kasei Kogyo Co., Ltd.) and 600 g of γ-butyrolactone (Kanto Kagaku, deer special grade) at 23 ° C. After stirring, 108.63 g (1.36 mol) of pyridine (Kanto Kagaku, dehydration) was added, the temperature was raised to 50 ° C., and the mixture was stirred at 50 ° C. for 2 hours to obtain the compound represented by the following formula (1). A solution containing was obtained.

<Production Example 2> Synthesis of polymer (2) as a polyimide precursor 82.46 g of the solution prepared in Production Example 1 and 19.45 g of γ-butyrolactone were placed in a four-necked flask having a capacity of 500 ml, and at about 5 ° C., N , N'-diisopropylcarbodiimide (DIC, Tokyo Kasei Kogyo Co., Ltd.) 13.13 g was dissolved in 30 g of γ-butyrolactone and added dropwise to the reaction solution over 0.5 hours with stirring, and 0.5 hours after the addition. Stirred. Subsequently, 19.68 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane (Tokyo Chemical Industry Co., Ltd.) was dissolved in 30 g of N-methyl-2-pyrrolidinone (Kanto Chemical Co., Inc., special grade deer). It was added dropwise over 2 hours with stirring. Then, the temperature was raised to about 25 ° C., the mixture was stirred for 6 hours, 4.5 g of ethanol (Kanto Chemical Co., Inc., special grade) was added, and the mixture was stirred for 1 hour.

The obtained reaction mixture was added to 1,500 g of methanol (Kanto Chemical Co., Inc., special grade) to form a precipitate composed of a crude polymer. The supernatant was decanted to separate the crude polymer and dissolved in 150.0 g of N-methyl-2-pyrrolidinone to give a crude polymer solution. The obtained crude polymer solution was added dropwise to 2,250 g of water to precipitate the polymer, and the obtained precipitate was filtered off, washed twice with 600 g of methanol, vacuum dried, and powdered polymer (2). ) Was obtained. When the molecular weight of the polymer (2) was measured by GPC (standard polystyrene equivalent), the weight average molecular weight (Mw) was 8,016. The yield was 73.6%. This reaction product has a repeating unit structure represented by the following formula (2).

<Manufacturing example 3>
Polymer 28.5714 g obtained in Production Example 2, IRGACURE [registered trademark] OXE01 (manufactured by BASF, photopolymerization initiator) 1.71 g, AOI-BM (manufactured by Showa Denko KK, 2- (O- [1'). -Methylpropyrideneamino] carboxyamino) ethyl acrylate) 8.57 g, KBM-5103 (3-acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.43 g, IRGANOX [registered trademark] 3114 (manufactured by BASF) , 0.43 g of hindered phenolic oxidation inhibitor) and 0.28 g of phthalic acid (manufactured by Tokyo Kasei Kogyo Co., Ltd.) were dissolved in 48.00 g of cyclohexanone and 12.00 g of ethyl lactate to prepare a composition. Then, it was filtered using a polypropylene microfilter having a pore size of 5 μm to prepare a negative photosensitive resin composition.

<Production Example 4> (Synthesis of maleimide / 4-hydroxybutyl acrylate glycidyl ether copolymer)
10.0 g (103 mmol) of maleimide, 5.2 g (26 mmol) of 4-hydroxybutyl acrylate glycidyl ether, and 0.2 g of 2,2'-azobis (isobutyronitrile) were dissolved in 61.8 g of propylene glycol monomethyl ether. A polymer solution was obtained by heating and polymerizing in nitrogen at 75 ° C. for 24 hours. When the molecular weight of the polymer was measured by GPC (standard polystyrene equivalent), the weight average molecular weight (Mw) was 4,000. This reaction product has a repeating unit structure represented by the following formula.

(Evaluation board)
Titanium (20 nm) and copper (50 nm) were laminated on a silicon substrate by sputtering (FIGS. 1 and 2).

<Example 1>
The maleimide / 4-hydroxybutyl acrylate glycidyl ether copolymer solution obtained in Production Example 4 was diluted with propylene glycol monomethyl ether (PGME) to 6% by mass, and the film was put on an evaluation substrate so as to have a film thickness of 100 nm by a spinner. After coating, the substrate was placed on a hot plate and baked at 230 ° C. for 1 minute to form an oxidation-suppressing film.

Next, the resin composition prepared in Production Example 3 was spin-coated, the substrate was placed on a hot plate, and baked at 115 ° C. for 270 seconds. Then, after exposure (i-line, exposure amount: 500 mJ / cm ² ) using an aligner (PLA-501, manufactured by Canon Inc.), the film is further fired in an oven at 160 ° C. for 1 hour and 230 ° C. for 1 hour under nitrogen to form a film. An insulating film having a thickness of 5 μm was formed. Subsequently, the copper was kept at a high temperature of 150 ° C. for 500 hours in an oven (under the atmosphere), and the reformed state of copper before and after that was confirmed.

The cross-sectional SEM photograph (FIG. 3) after holding at high temperature showed that the copper oxide layer was not formed on the copper surface, but only a thin copper oxide layer of 20 nm was formed on the upper part of the catechol novolak layer.

In addition, a cross-sectional SEM photograph after holding at a high temperature showed that there were few voids in the copper layer and that the diffusion of copper into the insulating film could be suppressed (FIG. 4).

<Comparative Example 1>
The resin composition prepared in Production Example 3 was spin-coated on the evaluation substrate without applying the antioxidant film, and the substrate was placed on a hot plate and baked at 115 ° C. for 270 seconds. Then, after exposure (i-line, exposure amount: 500 mJ / cm ² ) using an aligner (PLA-501, manufactured by Canon Inc.), the film is further fired in an oven at 160 ° C. for 1 hour and 230 ° C. for 1 hour under nitrogen to form a film. An insulating film having a thickness of 5 μm was formed. Subsequently, the copper was kept at a high temperature of 150 ° C. for 500 hours in an oven (under the atmosphere) to confirm the reformed state before and after the high temperature treatment of copper.

In the cross-sectional SEM photograph (Fig. 5) after holding at high temperature, the copper oxide layer is formed as thick as 110 nm on the copper surface, and many voids are seen in the copper layer, so that a large amount of copper is diffused into the insulating film. It was shown that it was (Fig. 6).

In particular, in the rewiring process of semiconductor manufacturing, where demand is expected to increase in the future, by forming the metal surface coating film of the present invention on the wiring, oxidation of the wiring surface does not occur even after the wiring is formed, and the interlayer insulating film is not generated. Since it has excellent adhesion to semiconductors, it can be expected to contribute to improving the long-term reliability of semiconductors.

Claims (23)

A metal surface coating film forming composition comprising a polymer containing a unit structure having a maleimide group and an organic solvent. The metal surface coating film forming composition according to claim 1, wherein the polymer further comprises a unit structure including a crosslinkable moiety. The metal surface coating film forming composition according to claim 2, wherein the crosslinkable moiety is an epoxy group. The metal surface coating film forming composition according to any one of claims 1 to 3, further comprising at least one selected from the group consisting of a binder, a cross-linking agent, and an additive. The metal surface coating film forming composition according to any one of claims 1 to 4, for forming a coating film on a metal surface. The metal surface coating film forming composition according to claim 5, wherein the metal surface contains copper or aluminum. The metal surface coating film forming composition according to claim 5, wherein the metal surface comprises at least one selected from the group consisting of semiconductor rewiring, printed wiring and solder bumps. Use of the metal surface coating film forming composition according to any one of claims 1 to 4 for forming a coating film on a metal surface. Use of the metal surface coating film forming composition according to any one of claims 1 to 4, for forming a coating film on a metal surface containing copper or aluminum. The metal surface coating film forming composition according to any one of claims 1 to 4, for forming a coating film on a metal surface containing at least one selected from the group consisting of semiconductor rewiring, printed wiring and solder bumps. use. A metal surface coating film which is a fired product of a coating film comprising the metal surface coating film forming composition according to any one of claims 1 to 7. The metal surface coating film according to claim 11, which is an oxidation-suppressing film on a metal surface. With the base material
Wiring formed on the base material and having a metal surface,
A wiring board comprising the metal surface coating film according to claim 11 or 12 on at least a part of the metal surface of the wiring. The metal surface of the wiring has a side surface and an upper surface.
The wiring board according to claim 13, wherein the metal surface coating film is formed on each of the side surface and the upper surface. The wiring board according to claim 13 or 14, wherein the wiring or the metal surface coating film is coated with an insulating film. The wiring substrate according to claim 15, wherein the metal surface coating film is a film for improving the adhesion between the metal surface of the wiring and the insulating film. The wiring substrate according to any one of claims 13 to 16, wherein the metal surface coating film is an oxidation-suppressing film on the metal surface of the wiring. The step of forming a wiring having a metal surface on a base material, and the metal surface coating film forming composition according to any one of claims 1 to 7 are applied to the wiring to cover the metal surface of the wiring. A method for manufacturing a wiring substrate, which comprises a step of forming a metal surface coating film on at least a part thereof. A method for manufacturing a wiring board, comprising a step of heating the wiring board according to any one of claims 13 to 17 at 100 ° C. to 300 ° C. The method for manufacturing a wiring board according to claim 19, wherein the metal surface of the wiring has a metal oxide layer having a thickness of 100 nm or less after the heating step. The method for manufacturing a wiring substrate according to any one of claims 18 to 20, wherein the metal surface coating film is an oxidation-suppressing film on the metal surface of the wiring. A semiconductor device including a semiconductor element provided with the wiring board according to any one of claims 13 to 17. A method for manufacturing a semiconductor device, comprising a step of providing a wiring board manufactured by the method according to any one of claims 18 to 21 on a semiconductor element.

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