TW202240780A - Method for manufacturing multilayer wiring board, kit for forming laminated film, and composition in which an organic film having excellent adhesion can be formed on the inner wall surface of a via hole, and the metal can be excellently embedded in the via hole - Google Patents

Abstract

The present invention provides a method for manufacturing a multilayer wiring board, in which an organic film having excellent adhesion to a plating layer can be formed on the inner wall surface of a via hole, and the metal can be excellently embedded in the via hole by a plating treatment. The multilayer wiring board is manufactured by the method including: a first formation step for forming a first organic film 16 on a wiring 13 inside a via hole 11 formed in an insulating layer 14 provided on the wiring 13; a second forming step for forming a second organic film 17 on the inner wall surface of the via hole 11 after forming the first organic film 16; a removing step for removing the first organic film 16 after forming the second organic film 17; and a plating step for forming a plating layer 18 inside the via hole 11 after removing the first organic film 16. The second organic film 17 is formed by using a polymer (I) having a first functional group capable of interacting with a group on the surface of the insulating layer 14, and has a second functional group capable of forming a bond with the metal contained in the plating layer 18.

Description

Manufacturing method of multilayer wiring board, set for forming laminated film, and composition

The present invention relates to a method for manufacturing a multilayer wiring board, a set for forming a laminated film, and a composition.

In the semiconductor manufacturing process, as a method of forming multilayer wiring on a semiconductor wafer, there is known a technique of forming a via hole in an interlayer insulating film and embedding metal in the via hole by plating. In this technique, a barrier film is formed on the inner wall surface of the via hole before embedding the metal in order to prevent the metal filled in the via hole from diffusing into the insulating film (for example, refer to Patent Document 1).

In Patent Document 1, it is disclosed that a monomolecular film is formed on the wiring by using a silane coupling agent or a titanium coupling agent on the bottom surface of the through-hole of the wafer in which the through-hole is formed on the insulating film on the wiring, and then on the through-hole. After forming a barrier film including Co-W-B alloy or the like on the side surface or the upper surface of the insulating film, the monomolecular film is removed, and then the wiring exposed on the bottom surface of the through hole is used as a catalyst to form electroless plating from the bottom surface of the through hole film, whereby the metal is embedded into the interior of the via hole. [Prior art literature] [Patent Document]

[Patent Document 1] International Publication No. 2019/151078

[Problem to be Solved by the Invention] In the semiconductor manufacturing process, further miniaturization is being studied in order to meet the demand for higher capacity and higher speed. In addition, in order to achieve microfabrication, attempts are being made to develop new materials. Also for the barrier film formed inside the via hole in the multilayer wiring forming step, a new material with higher performance is required instead of the previous metal layer. As for the performance as a barrier film, in addition to the adhesiveness with the insulating film, it also has excellent adhesion with the metal embedded in the via hole, and there are few voids or seams in the metal embedded in the via hole. , Excellent metal embedding properties, etc.

The present invention is made in view of the above-mentioned problems, and its main purpose is to provide an organic film having excellent adhesion with the plating layer to be formed on the inner wall surface of the through-hole, and to provide a metal coating for the through-hole that can be treated by plating. A method of manufacturing a multilayer wiring board with excellent embedding properties. [Means to solve the problem]

In order to solve the above-mentioned problems, according to the present invention, the following means can be provided.

[1] A method of manufacturing a multilayer wiring board, which is a method of manufacturing a multilayer wiring board, the method of manufacturing a multilayer wiring board comprising: a first forming step of forming a first organic film on wiring inside a through hole, the A through hole is formed in the insulating layer provided on the wiring to penetrate the insulating layer in the thickness direction; in the second forming step, after forming the first organic film, a second organic film is formed on the inner wall surface of the through hole. Two organic films; a removing step of removing the first organic film after forming the second organic film; and a plating step of removing the inside of the through hole after removing the first organic film by plating processing to form a metal layer, the second organic film is formed using a polymer (I) having a first functional group that can interact with a group that the insulating layer has on the surface layer, and has a polymer (I) that can interact with a group contained in the metal layer The metal forms a bonded second functional group.

[2] A set for forming a laminated film for pretreatment for forming a metal layer inside a through-hole of a multilayer wiring board by plating, the set for forming a laminated film comprising: a polymer (I ), having a functional group and a cross-linking group, the functional group may be bonded to a silicon atom selected from a hydrogen atom, a hydroxyl group, a side oxygen group and -N(R ¹ ) ₂ (wherein, R ¹ is independently is a hydrogen atom or a monovalent organic group with 1 to 20 carbons) to form a bond with at least one group of the group consisting of; and the polymer (II) has a functional group.

[3] A composition for pretreatment for forming a metal layer inside a through-hole of a multilayer wiring board by plating, the composition comprising: a polymer having a functional group, and an acid anhydride At least one crosslinking group in the group consisting of a group and a protected carboxyl group, the functional group can be bonded to a silicon atom selected from a hydrogen atom, a hydroxyl group, a side oxygen group, and -N(R ¹ ) ₂ (wherein, R ¹ are each independently a hydrogen atom or a monovalent organic group with 1 to 20 carbons); group interaction of at least one of the group consisting of; and a solvent. [Effect of the invention]

According to the manufacturing method of this invention, the organic film excellent in the adhesiveness with a plating layer can be formed in the inner wall surface of a through-hole. In addition, the embedding property of the metal treated by plating is excellent in the through hole in which the organic film is formed on the inner wall surface by the manufacturing method of the present invention. According to the production method of the present invention, an organic film exhibiting such excellent characteristics can be obtained by simple operations such as coating.

Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "-" is the meaning which includes the numerical value described before and after "-" as a lower limit and an upper limit.

"Manufacturing method of multilayer wiring board" The manufacturing method of the present disclosure (hereinafter, also referred to as "the present manufacturing method") is a step of forming multilayer wiring on a substrate to obtain a multilayer wiring substrate, including embedding metal into the vias by plating. The pretreatment of the step inside the hole is a step of forming an organic film on the inner wall surface of the via hole provided on the insulating layer on the wiring. The organic membrane is formed using a composition for selective surface modification as an organic material. The organic film formed on the inner wall surface of the through hole has a barrier function of suppressing the diffusion of the metal embedded into the inside of the through hole by the plating process to the insulating layer. The manufacturing method specifically includes the following first forming step, second forming step, removing step and plating step. (First Formation Step) A step of forming a first organic film on the wiring inside the via hole formed on the insulating layer on the wiring. (Second Forming Step) A step of forming a second organic film on the inner wall surface of the through hole after forming the first organic film. (Removing Step) A step of removing the first organic film after forming the second organic film. (Plating step) A step of forming a plating layer inside the through-hole after removing the first organic film. Hereinafter, details of this production method will be described with reference to the drawings as appropriate.

FIG. 1 is a schematic view showing a series of steps in forming an organic film inside a via hole provided on a wiring board 10 . In addition, in FIG. 1, the partial enlarged view of the through-hole 11 and its peripheral part is shown. (a) of FIG. 1 shows a state before an organic film is formed on the inner wall surface 12 using the composition for selective surface modification.

As shown in FIG. 1( a ), the wiring board 10 includes wiring 13 . The wiring 13 is formed of a metal material. The metal constituting the wiring 13 is not particularly limited, and examples thereof include copper, iron, zinc, cobalt, aluminum, titanium, tin, tungsten, zirconium, tantalum, germanium, molybdenum, ruthenium, gold, silver, platinum, palladium, Nickel etc. Furthermore, the metal contained in the wiring 13 may be a simple metal, or may be an alloy, a conductive nitride, a metal oxide, or the like. Among these, the wiring 13 is preferably formed of a conductive material containing copper, cobalt, aluminum, tungsten, germanium, ruthenium, gold, silver, platinum, or palladium, more preferably made of copper (Cu) or cobalt (Co) of conductive material. An insulating layer 14 is provided on the wiring 13 adjacent to the wiring 13 .

The insulating layer 14 is formed of silicon-containing material. The insulating layer 14 preferably has a surface bonded to the silicon atom selected from a hydrogen atom, a hydroxyl group, a side oxygen group and -N(R ¹ ) ₂ (wherein, R ¹ is independently a hydrogen atom or a carbon number 1 ~20 monovalent organic groups. The same applies hereinafter) is at least one group (hereinafter also referred to as "silicon-containing group"). Specific examples of the silicon-containing group include Si-H, Si-OH (silanol group), Si=O, Si-N(R ¹ ) ₂ and the like. Examples of the material constituting the insulating layer 14 include semiconductor materials (SiO ₂ , SiOC, Si ₃ N ₄ , SiNx, SiON, etc.) such as silicon oxide, silicon nitride, and silicon oxynitride.

A through hole 11 is disposed on the insulating layer 14 . The via hole 11 is formed on the insulating layer 14 so as to penetrate the insulating layer 14 in the thickness direction. Accordingly, the wiring 13 is exposed at the bottom 15 inside the via hole. Furthermore, the method of forming the via hole 11 on the insulating layer 14 is not particularly limited, for example, a previously known method such as dry etching can be suitably used.

It is preferable to perform treatment for surface modification of the wiring board 10 (more specifically, surface modification of the insulating layer 14 ) on the wiring board 10 plated and embedded by this manufacturing method (substrate modification step). The substrate modification treatment can be either dry or wet. In the case of dry type, the substrate modifying treatment in this manufacturing method is preferably ashing treatment using N ₂ /H ₂ gas or O ₂ gas. In the case of a wet method, from the viewpoint of improving the coatability and adhesiveness of the composition for selective surface modification, it is preferable to use tetramethyl ammonium hydroxide (tetramethyl ammonium hydroxide, TMAH), hydrogen fluoride (hydrogen fluoride, HF), ammonia (NH ₃ ), tetramethyl ammonium fluoride (tetramethyl ammonium fluoride, TMAF), or citric acid treatment liquid contact treatment.

＜First forming step＞ In this manufacturing method, in the first formation step, first, the first organic film 16 is formed on the wiring 13 exposed at the bottom 15 of the via hole 11 (see FIG. 1( b )). The first organic film 16 is a film covering the wiring 13 , and is formed directly on the wiring 13 using a composition (hereinafter also referred to as “first composition”) containing the compound (A) and a solvent as main components of the film. Specifically, it is preferable to form the first organic film 16 on the bottom 15 by a method including the following steps 1A and 2A. (Step 1A) A step of applying the first composition to the surface of the wiring board 10 . (Step 2A) A step of removing the solvent from the first composition coated on the surface of the substrate.

· Step 1A: Coating step In this step, the present composition is applied to at least the surface of the bottom portion 15 of the wiring board 10 . As a method of applying the composition, for example, a spray method, a roll coater method, a spinner method, a slit die coater method, a bar coater method, an inkjet method, etc. are mentioned. Among these, it is preferable to apply the composition by a spin coating method, a slit die coating method, or a bar coating method.

For the surface of the substrate coated with the composition, for example, plasma treatment using H ₂ , a mixed gas of N ₂ and H ₂ , O ₂ gas, etc., or a wet modification treatment for making the surface of the substrate hydrophilic may be performed. deal with. In terms of improving applicability and sufficiently promoting the surface modification using the composition, it is preferable to perform plasma treatment on the surface of the substrate on which the composition is applied so that the coated surface of the composition is sufficiently At least one of Si-OH, Si-H and Si-N is generated.

· Step 2A: Solvent removal step In this step, heat treatment is preferably performed to remove the solvent from the composition coated on the surface of the substrate. Thereby, the first organic film 16 is formed on the surface of the wiring 13, and the surface of the wiring 13 exposed to the bottom 15 inside the via hole is selectively modified with the compound (A). The heat treatment can be performed, for example, using a heating device such as an oven or a hot plate. In the case of heat treatment, the heating temperature also depends on the type of solvent, but is preferably 50°C or higher, more preferably 80°C or higher, and still more preferably 100°C or higher. In addition, the heating temperature is preferably at most 250°C, more preferably at most 200°C. The heating time is preferably from 0.5 minute to 30 minutes, more preferably from 1 minute to 20 minutes. The thickness of the formed first organic film 16 is, for example, 1 nm˜10 nm, preferably 1 nm˜5 nm, more preferably 1 nm˜3 nm.

In addition, in order to remove unadsorbed compound (A) and the like, the surface of the substrate on which the first organic film 16 is formed may be subjected to rinsing treatment such as washing with an organic solvent or washing with running water. Examples of organic solvents used as eluents include propylene glycol monomethyl ether acetate, isopropanol, acetone, methyl ethyl ketone, methyl n-propyl ketone, and two or more of these mixed solvents, etc.

＜Second forming step＞ In the next second forming step, after the first organic film 16 is formed on the bottom 15 by the first forming step, the second organic film 17 is formed on the inner wall surface 12 (see (c) of FIG. 1 and (c) of FIG. 1 d)). The second organic film 17 is formed using a polymer composition including a polymer and a solvent. Specifically, it is preferable to form the second organic film 17 by a method including the following steps 1B and 2B. (Step 1B) A step of applying a polymer composition to the surface of wiring board 10 . (Step 2B) A step of removing the solvent from the polymer composition coated on the surface of the substrate.

· Step 1B: Coating step In this step, at least the inner surface of the through hole 11 in the wiring substrate 10 is coated with a polymer composition. The method of coating the polymer composition is not particularly limited, for example, the method exemplified in step 1A can be used.

· Step 2B: Solvent removal step In this step, heat treatment is preferably performed to remove the solvent from the polymer composition coated on the surface of the substrate. Thereby, the second organic film 17 is directly formed on the inner wall surface 12, and the surface of the inner wall surface 12 inside the through hole is selectively modified. The heat treatment can be performed, for example, using a heating device such as an oven or a hot plate. In the heat treatment, the heating temperature is preferably at least 80°C, more preferably at least 100°C, and still more preferably at least 120°C. In addition, the heating temperature is preferably at most 300°C, more preferably at most 280°C. The heating time is preferably from 0.5 minute to 30 minutes, more preferably from 1 minute to 20 minutes. The thickness of the formed second organic film 17 is, for example, 1 nm˜50 nm, preferably 1 nm˜5 nm, more preferably 1 nm˜3 nm.

In addition, in order to remove unadsorbed polymers and the like, the surface of the substrate on which the organic film is formed may be rinsed with an organic solvent or rinsed with running water. Examples of organic solvents used as eluents include propylene glycol monomethyl ether acetate, isopropanol, acetone, methyl ethyl ketone, methyl n-propyl ketone, and two or more of these mixed solvents, etc.

The second organic film 17 has a functional group capable of forming a bond with a metal contained in the plating layer 18 (see (f) of FIG. 1 ) formed inside the via hole by a plating step described later (hereinafter also referred to as "functional group FM"). The functional group FM is preferably a functional group capable of forming a coordination bond with a metal element, for example, a carboxyl group, a thioether group, a dithiocarbonyl group (-C(=S)-S-), a thioaminomethyl group Ester group (-NR ²⁰ -C(=O)-S-), thioamide group (-C(=S)-NR ²⁰ -), etc. In addition, the functional group FM corresponds to a "second functional group". R ²⁰ represents a hydrogen atom or a monovalent group. Specific examples of the case where R ²⁰ is a monovalent group include a monovalent hydrocarbon group having 1 to 10 carbon atoms.

One form of the second organic film 17 is a multilayer structure. Specifically, as shown in FIG. 1(c) and FIG. 1(d), the second organic film 17 is a first layer 17a formed on the inner wall surface 12 and a second layer formed on the first layer 17a. Laminated film of 17b. The first layer 17a is selectively formed on the inner wall surface 12 (refer to FIG. The substance (I) has a functional group (hereinafter, also referred to as “functional group F1 ”) capable of interacting with a group on the surface of the insulating layer 14 . In addition, the second layer 17 b is selectively formed on the first layer 17 a using a composition (hereinafter also referred to as “third composition”) containing the polymer (II) and a solvent (see FIG. 1( d )). At this time, the formation of the second organic film 17 (the first layer 17 a and the second layer 17 b ) is hindered on the surface of the first organic film 16 .

Moreover, when forming the laminated film including the first layer 17a and the second layer 17b on the inner wall surface 12, it can be carried out by the following method: First, the first layer is formed by using the second composition through step 1B and step 2B 17a, and then use the third composition to implement step 1B and step 2B again to form the second layer 17b.

In the case where the second organic film 17 has a multilayer structure, as a method of obtaining the second organic film 17 having the functional group FM, it is possible to include: using a functional group having the functional group FM or generating the functional group FM by heat (hereinafter A method of using a polymer having a functional group FM or a functional group FP as the polymer (II) as the polymer (I); when forming a film, by polymerizing A method in which a functional group FM of a substance (I) reacts with a functional group of a polymer (II) to generate a functional group FM, and the like.

Another form of the second organic film 17 is a single-layer structure. When the second organic film 17 is a single-layer film, the second organic film 17 is formed using a polymer (I) that is a functional group F1 capable of interacting with groups (silicon-containing groups) on the surface layer of the insulating layer 14 . In this case, the second organic film 17 is preferably formed by using a composition (hereinafter also referred to as "fourth composition") comprising a polymer (hereinafter also referred to as "polymer (III)") and a solvent, and The step 1B and step 2B are carried out to form on the inner wall surface 12, the polymer (III) has a functional group F1 and a functional group FM capable of forming a bond with the metal contained in the plating layer 18 or by heat Instead, the functional group FP yields the functional group FM.

＜Removal procedure＞ In this step, after the second organic film 17 is formed on the inner wall surface 12 , the first organic film 16 is removed with the second organic film 17 remaining (see FIG. 1( e )). The method of removing the first organic film 16 is not particularly limited, and for example, a method of bringing the first organic film 16 into contact with a treatment agent is mentioned. The treatment agent preferably contains an organic acid. As this organic acid, acetic acid, citric acid, malic acid, 2-ethylhexanoic acid etc. are mentioned, for example.

In the removal step, in the case of dissolving and removing the first organic film 16 by contacting the first organic film 16 with an organic acid, it may further include making the through hole 11 Step in which the surface is brought into contact with alkali (alkali treatment step). Thereby, the residue of the first organic film 16 on the surface of the through-hole can be reduced as much as possible, and when the metal is embedded in the inside of the through-hole by the plating step described later, the embedding of the metal can be carried out satisfactorily. better. Examples of the base to be used include organic bases such as triethylamine, 4-dimethylaminopyridine (DMAP), pyridine, tetramethylammonium hydroxide, ammonia solution, and hydrazine solution; Sodium hydride, K ₂ CO ₃ , Cs ₂ CO ₃ and other inorganic bases, etc. Among them, organic bases are more preferable.

＜Plating procedure＞ In this manufacturing method, after the wiring 13 is exposed to the bottom 15 by removing the first organic film 16, plating is then performed with the organic film 17 remaining, thereby forming a plated layer as a metal layer inside the via hole. The cladding layer 18 (see (f) of FIG. 1 ). The plating method is not particularly limited, and known electrolytic plating, electroless plating, hot-dip plating, vacuum plating, vapor phase plating, and the like can be used. When applying to a semiconductor manufacturing process, it is preferable to use electrolytic plating or electroless plating among these, and it is especially preferable to use electroless plating. Specifically, there may be mentioned a method of forming an electroless plating layer from the bottom 15 upward by using the wiring 13 exposed to the bottom 15 as a catalyst. In addition, after the plating process, you may perform the planarization process of a board|substrate surface etc. as needed.

The metal contained in the plating layer 18 is not particularly limited, and examples thereof include the same metals as those exemplified as the constituent material of the wiring 13 . Among these, the plating layer 18 preferably contains Cu or Co.

Since there are few voids or seams in the plating layer 18 formed in this manner, a highly reliable multilayer wiring board can be produced.

Next, the selective modification compositions (first composition, second composition, third composition, and fourth composition) used in this production method will be described. In addition, as each component which comprises a composition, unless mentioned in particular, it may use individually by 1 type, and may use it in combination of 2 or more types.

＜First composition＞ The first composition is used to form the first organic film 16 disposed on the bottom 15 of the through hole 11 . The first composition is preferably a compound (hereinafter also referred to as "compound (A)") having a functional group (hereinafter also referred to as "functional group FS") capable of forming a bond with a metal contained in wiring 13 . The type of bonding between the functional group FS and the metal is not particularly limited, and examples thereof include covalent bonding, ionic bonding, and coordinate bonding. Among these, coordinate bonding is preferable in that the bonding force between the wiring 13 and the compound (A) is large. Specifically, the functional group FS is preferably a functional group capable of coordinate bonding with the metal contained in the wiring 13, and is particularly preferably selected from the group consisting of cyano, boronic acid, phosphoric acid, phosphonic acid, phosphoric acid ester, and phosphine. At least one of the group consisting of ester groups, thiol groups, disulfide groups and groups containing carbon-carbon unsaturated bonds.

The compound (A) may be a low-molecular compound or a polymer. Here, the "low molecular weight compound" in this specification is a compound which does not show a molecular weight distribution, and differs from a polymer in this point. When the compound (A) is a low-molecular compound, from the viewpoint of improving the hydrophobicity of the self-assembled film and improving the matrix selectivity of the second organic film 17, the compound (A) preferably has 6 or more carbon atoms, More preferably, it has 12 or more carbon atoms. In addition, when the compound (A) is a low molecular weight compound, the carbon number is preferably 50 or less, more preferably 40 or less.

Specific examples when the compound (A) is a low molecular weight compound include: capronitrile, octanonitrile, decanonitrile, dodecanenitrile, tetradecanenitrile, the following formula (a-1) to formula (a- 5) Compounds etc. represented respectively. [chemical 1]

When the compound (A) is a polymer, the main skeleton of the polymer (hereinafter also referred to as "polymer (A)") is not particularly limited. As the monomer constituting the polymer (A), a monomer having a polymer unsaturated carbon-carbon bond can be preferably used. Specific examples of the monomer include, for example, alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, aromatic Vinyl compounds, N-substituted maleimide compounds, vinyl compounds with heterocyclic structures, conjugated diene compounds, nitrogen-containing vinyl compounds, olefins, vinyl cycloalkanes, cycloalkenes, and unsaturated dicarboxylic At least one monomer in the group consisting of acid dialkyl ester compounds. In addition, in this specification, a "(meth)acryl group" means including an acryl group and a methacryl group. "(Meth)acrylic acid" means including acrylic acid and methacrylic acid.

Specific examples of the monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, (meth)acrylate, and alkyl (meth)acrylate. base) isopropyl acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, (meth)acrylate ) n-stearyl acrylate, etc.; Examples of (meth)acrylates having an alicyclic structure include: (meth)cyclohexyl acrylate, (meth)acrylate 2-methylcyclohexyl, (meth) ) tricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate, tricyclo[5.2.1.0 ^2,5 ]decane-8-yloxyethyl (meth)acrylate, (methyl) Isobornyl acrylate, etc.; Examples of (meth)acrylates having an aromatic ring structure include phenyl (meth)acrylate, benzyl (meth)acrylate, etc.; Examples of aromatic vinyl compounds include: styrene , 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-tert-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, tertiary butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl) di Methylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, 4-tert-butylstyrene, diphenylethylene, vinyl naphthalene, etc.; as N-substituted maleic acid Amide compounds, for example: N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4- Methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornyl N-cyclodecanylmaleimide, N-tricyclodecanylmaleimide, N-adamantylmaleimide, N-phenylmaleimide, N-(2-methylphenyl) Maleimide, N-(4-methylphenyl)maleimide, N-(4-ethylphenyl)maleimide, N-(2,6-dimethylphenyl) ) maleimide, N-benzylmaleimide, N-naphthylmaleimide, etc.; Examples of vinyl compounds having a heterocyclic structure include tetrahydrofurfuryl (meth)acrylate , Tetrahydropyranyl (meth)acrylate, 5-ethyl-1,3-dioxan-5-ylmethyl (meth)acrylate, 5-methyl-1,3-(meth)acrylate Dioxan-5-ylmethyl ester, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(methyl) Oxymethyl-acrylate-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl)(meth)acrylate, glycerol (meth)acrylate Carbonate, (meth)acrylic acid (γ- Amide-2-yl) ester, N-(meth)acrylate oxyethylhexahydrophthalimide, N-vinyl-2-pyrrolidone, vinylpyridine, etc.; as conjugated di Olefin compounds include 1,3-butadiene, isoprene, etc.; examples of nitrogen-containing vinyl compounds include 2-(dimethylamino)ethyl (meth)acrylate, etc.; examples of olefins include Enumerate: propylene, butene, pentene, etc.; As vinyl cycloalkane, vinyl cyclopentane, vinyl cyclohexane, etc. can be enumerated; As cycloalkene, cyclopentene, cyclohexene, etc. can be enumerated; As unsaturated Examples of the dialkyl dicarboxylate compound include diethyl itaconate and the like.

As the monomer constituting the polymer (A), among the above, it is preferably selected from alkyl (meth)acrylates, (meth)acrylates with an alicyclic structure, (meth)acrylates with an aromatic ring structure, ) acrylate, aromatic vinyl compound, conjugated diene compound, olefin, vinyl cycloalkane, and cycloalkene at least one of the group consisting of.

The polymer (A) preferably contains a structural unit derived from a monomer having an aromatic ring. In this case, it is preferable in terms of forming an organic film with high heat resistance. As the monomer having an aromatic ring, a monomer having an aromatic ring can be arbitrarily selected from the above-described monomers, and among them, an aromatic vinyl compound can be preferably used. In addition, in the monomer having an aromatic ring, the aromatic ring may have a substituent. Examples of substituents include monovalent hydrocarbon groups having 1 to 5 carbons, halogenated alkyl groups having 1 to 5 carbons, alkoxy groups having 1 to 5 carbons, or halogen atoms.

In the polymer (A), the ratio of the structural unit derived from a monomer having an aromatic ring to all the structural units contained in the polymer (A) is preferably at least 20 mol %, more preferably 30 mol % % or more, and preferably more than 50 mol%.

The polymer (A) may have a functional group FS on any one of the main chain and the side chain. The polymer (A) preferably has a functional group FS at the end of the main chain, more preferably It has a functional group FS at the single end of the polymer chain.

The method for obtaining the polymer (A) having a functional group FS at the end of the main chain is not particularly limited, and may be appropriately selected according to the type of functional group FS to be introduced. For example, a method of reacting an active end of a polymer obtained by anionic polymerization with an end-treating agent having a functional group FS; by reacting an active end of a polymer with an end-treating agent capable of generating a functional group FS , introducing a structure that can generate a functional group FS into the end of the polymer, and then performing a treatment (such as deprotection) for generating a functional group FS, thereby generating a method for a functional group FS; A method in which a functional group FG is reacted with a terminal treatment agent to introduce a functional group FG to the terminal of a polymer, and then a compound having a functional group capable of reacting with the functional group FG and a functional group FS is reacted with the functional group FG introduced into the polymer. Wait.

The method for synthesizing the polymer (A) is not particularly limited. For example, in the case where the polymer (A) is obtained by polymerizing a monomer having a polymer unsaturated carbon-carbon bond, the monomer can be used in a suitable solvent, a polymerization initiator, etc. The polymer (A) is produced according to known methods such as radical polymerization and anionic polymerization. The form of polymerization for obtaining the polymer (A) is not particularly limited, and examples thereof include random polymerization, block (co)polymerization, and the like.

In the case of obtaining a polymer having a functional group FS at the end of the main chain, it is preferable to utilize anionic polymerization. In the case of anionic polymerization, examples of the polymerization initiator include alkali metal compounds such as n-butyllithium, second-butyllithium, and tert-butyllithium. The amount of the polymerization initiator used is, for example, 0.001 mol to 1 mol relative to 1 mol of the total amount of monomers used in the reaction. As a polymerization solvent, aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons etc. are mentioned, for example. The amount of the polymerization solvent used is preferably an amount in which the total amount of monomers used in the reaction is 1% by mass to 60% by mass relative to the entire amount of the reaction solution.

During polymerization, the reaction temperature is, for example, -100°C to 120°C. The reaction time varies depending on the type of the polymerization initiator and monomer, or the reaction temperature, but is usually 0.1 to 10 hours. The polymer obtained by the above reaction may be directly used in the preparation of the composition in the state of being dissolved in the reaction solution, or may be used in the preparation of the composition after being separated from the reaction solution. The polymer can be separated by, for example, a method of injecting the reaction solution into a large amount of poor solvent, drying the precipitate thus obtained under reduced pressure, or a method of removing the reaction solution by distillation under reduced pressure using an evaporator, etc. to proceed.

The polymer (A) preferably has a polystyrene-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) of 1,000 or more. When Mw is 1,000 or more, a sufficiently high organic film such as heat resistance or chemical resistance can be obtained, which is preferable in this point. Mw is more preferably at least 2,000, further preferably at least 3,000. In addition, from the viewpoint of improving film-forming properties, Mw is preferably at most 10,000, more preferably at most 9,000, and still more preferably at most 8,000. The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.

The first composition is preferably a liquid composition obtained by dissolving or dispersing the compound (A) in a solvent. The solvent is preferably an organic solvent capable of dissolving the compound (A) and not reacting with each component. Examples of the solvent used in the preparation of the first composition include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents.

The amount of the compound (A) contained in the first composition is preferably at least 0.1% by mass, more preferably at least 0.2% by mass, and still more preferably at least 0.5% by mass, based on the total amount of the compound (A) and the solvent. When the content of the compound (A) is 0.1% by mass or more, the surface modification of the wiring 13 can be sufficiently performed by the compound (A), and adhesion of the second composition can be suppressed, which is preferable in this point. In addition, the content of the compound (A) is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 10% by mass, based on the total amount of the compound (A) and the solvent. When the content of the compound (A) is 30% by mass or less, the film thickness of the first organic film 16 does not become too large, and the viscosity of the first composition does not become too high, so that good applicability can be ensured.

＜Second composition＞ Next, each component contained in a 2nd composition, and other components mix|blended as needed are demonstrated. The second composition is a polymer composition for forming the first layer 17 a on the inner wall surface 12 of the through hole 11 . This second composition contains a polymer (I) having a functional group (functional group F1 ) capable of interacting with a group that the insulating layer 14 has on the surface layer and a solvent. In addition, the functional group F1 corresponds to "the first functional group". In this specification, the so-called "interaction" refers to the formation of chemical bonds between molecules, or the effect of physical force between molecules, which is also called "adsorption". The interaction includes not only covalent bonding, ionic bonding, and metal bonding, but also coordinate bonding, hydrogen bonding, and van der Waals force.

[Polymer (I)] Functional group F1 The functional group F1 of the polymer (I) is preferably selected from the group consisting of a hydrogen atom, a hydroxyl group, a side oxygen group, and -N(R ¹ ) ₂ A functional group that selectively interacts (adsorbs) at least one group (silicon-containing group) bonded to a silicon atom. More specifically, the functional group F1 is preferably selected from silanol groups, alkoxysilyl groups, -N(Si(R ⁵ ) ₃ ) ₂ , amino groups, hydroxyl groups, and conjugated nitrogen-containing heterocyclic groups. At least one of the group consisting of. Here, R ⁵ are each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbons.

When the functional group F1 is the group "-N(Si(R ⁵ ) ₃ ) ₂ ", examples of the monovalent organic group having 1 to 10 carbons in R ⁵ include monovalent hydrocarbon groups having 1 to 10 carbons . The conjugated nitrogen-containing heterocyclic group is a group having a conjugated nitrogen-containing heterocyclic ring, specifically, a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, an indole ring, a pyrrole ring, A group having a ring structure such as an imidazole ring, a pyridine ring, a triazole ring, and a triazine ring. Furthermore, the conjugated nitrogen-containing heterocyclic group may have a substituent on the heterocyclic part. As this substituent, a C1-C5 alkyl group, a halogen atom, etc. are mentioned, for example.

In terms of high affinity with the silicon-containing group on the surface layer of the insulating layer 14, and the aspect that the storage stability of the second composition can be improved, the functional group F1 is more preferably selected from the group consisting of silanol group, alkoxy At least one of the group consisting of a silyl group and a conjugated nitrogen-containing heterocyclic group exhibits selective adsorption with respect to silicon oxide, which can further improve the adhesion between the first layer 17a and the insulating layer 14 In terms of the improvement effect of , it is further preferable to contain an alkoxysilyl group.

·Crosslinking group The polymer (I) preferably has more crosslinkable groups. Here, the term "crosslinkable group" in this specification refers to a group in which functional groups of the same type or different types react with each other to form a covalent bond by applying heat or the like. Since the polymer (I) has a crosslinkable group, an organic film having high heat resistance and dielectric breakdown resistance can be formed, which is preferable in this point. In addition, the crosslinkability of the polymer (I) can be used to form a crosslinked structure between the first layer 17 a and the second layer 17 b, thereby improving the adhesion of the second organic film 17 . Examples of the crosslinkable group include a group having a carbon-carbon unsaturated bond, a group having a condensed ring structure of an aromatic ring and a cyclobutane ring, a cyclic ether group, a cyclic carbonate group, an acid anhydride group, and a carboxyl group. , protected carboxyl, etc.

Specific examples of the crosslinkable group include, for example, a group having a carbon-carbon unsaturated bond: vinyl, vinyloxy, allyl, (meth)acryl, vinylphenyl, etc.; As the group having a condensed ring structure of an aromatic ring and a cyclobutane ring, for example, a group having a condensed ring structure of a cyclobutane ring and a benzene ring, a group having a condensed ring structure of a cyclobutane ring and a naphthalene ring, etc.; As the cyclic ether group, for example, oxiranyl group, oxetanyl group, etc. are mentioned; as the protected carboxyl group, the group "-COOR ⁹ " (wherein, R ⁹ is a thermally separable group) and the like are mentioned.

（式（X-1）中，R ⁶、R ⁷及R ⁸是以下的（1）或（2）。（1）R ⁶、R ⁷及R ⁸分別獨立地為碳數1～10的烷基或碳數3～20的一價脂環式烴基。（2）R ⁶及R ⁷表示相互結合並與R ⁶及R ⁷所鍵結的碳原子一起構成的碳數4～20的脂環式烴結構或環狀醚結構。R ⁸為碳數1～10的烷基、碳數2～10的烯基或碳數6～20的芳基。「*」表示是結合鍵） Specific examples of the group "-COOR ⁹ " include, for example, a structure represented by the following formula (X-1), an acetal structure of a carboxylic acid, a ketal structure of a carboxylic acid, and the like. [Chem 2]

(In formula (X-1), R ⁶ , R ⁷ and R ⁸ are the following (1) or (2). (1) R ⁶ , R ⁷ and R ⁸ are each independently an alkane with 1 to 10 carbons group or a monovalent alicyclic hydrocarbon group with 3 to 20 carbons. (2) R ⁶ and R ⁷ represent an alicyclic ring with 4 to 20 carbons combined with each other and the carbon atoms to which R ⁶ and R ⁷ are bonded Formula hydrocarbon structure or cyclic ether structure. R ⁸ is an alkyl group with 1 to 10 carbons, an alkenyl group with 2 to 10 carbons, or an aryl group with 6 to 20 carbons. "*" means a bond)

Specific examples of the structure represented by the formula (X-1) include: tert-butoxycarbonyl, 1-cyclopentylethoxycarbonyl, 1-cyclohexylethoxycarbonyl, 1-norbornyl ethoxycarbonyl, 1-phenylethoxycarbonyl, 1-(1-naphthyl)ethoxycarbonyl, 1-benzylethoxycarbonyl, 1-phenethylethoxycarbonyl and the like.

Specific examples of the acetal ester structure of carboxylic acid include: 1-methoxyethoxycarbonyl, 1-ethoxyethoxycarbonyl, 1-propoxyethoxycarbonyl, 1-butoxy ethoxycarbonyl, 1-cyclohexyloxyethoxycarbonyl, 2-tetrahydropyranyloxycarbonyl, 1-phenoxyethoxycarbonyl, 2-tetrahydrofuryloxycarbonyl and the like.

Specific examples of ketal ester structures of carboxylic acids include: 1-methyl-1-methoxyethoxycarbonyl, 1-methyl-1-ethoxyethoxycarbonyl, 1-methyl- 1-propoxyethoxycarbonyl, 1-methyl-1-butoxyethoxycarbonyl, 1-methyl-1-cyclohexyloxyethoxycarbonyl, 2-(2-methyltetrahydrofuryl )oxycarbonyl, 2-(2-methyltetrahydropyranyl)oxycarbonyl, 1-methoxycyclopentyloxycarbonyl, 1-methoxycyclohexyloxycarbonyl and the like.

Among these, the functional group FM is generated by heat (specifically, heating at the time of film formation), thereby improving the effect of improving the adhesion with the metal contained in the plating layer 18. Polymerization The crosslinkable group possessed by the substance (I) is particularly preferably at least one selected from the group consisting of an acid anhydride group and a protected carboxyl group.

The main skeleton of the polymer (I) is not particularly limited. In terms of excellent heat resistance, a high degree of freedom in the selection of the monomer, and relatively easy introduction of the functional group F1, it is preferable to use a monomer having a polymerizable carbon-carbon unsaturated bond for the polymer (I). obtained polymers. The polymer (I) preferably includes a structural unit having a functional group F1 (hereinafter, also referred to as "structural unit U1"), and more preferably further includes a structural unit having a crosslinkable group (hereinafter, also referred to as "structural unit U1"). unit U2").

Regarding the monomer providing the structural unit U1, examples of the monomer having a silanol group include: dimethoxyhydroxysilylstyrene, diethoxyhydroxysilylstyrene, dimethylhydroxysilylbenzene Ethylene, diethylhydroxystyrene, etc.; Examples of monomers having an alkoxysilyl group include: 4-dimethylmethoxysilylstyrene, 4-diethylmethoxystyrene, 4 -Methylethylmethoxysilylstyrene, 3-(meth)acryloxypropyldimethylmethoxystyrene, 3-(meth)acryloxypropyldiethylmethyl Oxystyrene, etc.; Examples of monomers having the group "-N(Si(R ⁵ ) ₃ ) ₂ " include compounds represented by the following formulas (UA-1) to (UA-3), etc. ; As a monomer having an amino group, it can be enumerated: (meth)aminomethyl acrylate, 2-aminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, etc.; Monomers of hydroxyl groups include: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxypropyl (meth)acrylate Butyl ester, etc.; As a monomer having a conjugated nitrogen-containing heterocyclic group, N-vinylcarbazole, N-vinylbenzocarbazole, N-vinyldibenzocarbazole, 2- Fluoro-9-vinylcarbazole, 2-nitro-9-vinylcarbazole, 2-methoxy-9-vinylcarbazole and the like. [Chem 3]

In the polymer (I), the content of the structural unit U1 is preferably at least 1 mol%, more preferably at least 2 mol%, and still more preferably 5 mol%, relative to all the structural units constituting the polymer (I). above. By setting the content of the structural unit U1 to 1 mol % or more, the adhesiveness with the insulating layer 14 in the second organic film 17 can be sufficiently improved, which is preferable in this point. In addition, from the viewpoint of ensuring good matrix selectivity, the content of the structural unit U1 is preferably 30 mol% or less, more preferably 25 mol% or less, relative to all structural units constituting the polymer (I), More preferably, it is 20 mol% or less. If the content of the structural unit U1 is within the above range, by uniformly introducing the functional group F1 into the polymer (I), the unevenness of the functional group F1 in the coating film can be suppressed, and it can also be used as a permanent film. It is preferable in terms of the above.

（式（U2-2）～式（U2-4）中，R ^A為氫原子、碳數1～5的一價烴基、鹵素原子、或碳數1～5的鹵化烷基。R ⁹為熱分離性基。R ¹¹為碳數1～5的一價烴基、碳數1～5的鹵化烷基、碳數1～5的烷氧基或鹵素原子。d為0～4的整數。d為2以上的情況下，多個R ¹¹為相同或不同） Examples of the structural unit U2 include structural units represented by the following formulas (U2-1) to (U2-4), respectively. [chemical 4]

(In formula (U2-2) to formula (U2-4), R ^A is a hydrogen atom, a monovalent hydrocarbon group with 1 to 5 carbons, a halogen atom, or a halogenated alkyl group with 1 to 5 carbons. R ⁹ is heat Separable group. R ¹¹ is a monovalent hydrocarbon group with 1 to 5 carbons, a halogenated alkyl group with 1 to 5 carbons, an alkoxyl group with 1 to 5 carbons or a halogen atom. d is an integer of 0 to 4. d is 2 or more, multiple R ¹¹ are the same or different)

When the polymer (I) contains a structural unit U2, the content of the structural unit U2 is preferably at least 5 mol %, more preferably at least 10 mol %, relative to all structural units constituting the polymer (I), More preferably, it is 20 mol% or more. By setting the content of the structural unit U2 to 5 mol % or more, the crosslinked structure can be sufficiently introduced into the second organic film 17 and the dielectric breakdown resistance can be improved, which is preferable in this point. In addition, from the viewpoint of securing the toughness of the second organic film 17, the content of the structural unit U2 is preferably 70 mol% or less, more preferably 60 mol% relative to all structural units constituting the polymer (I). the following.

（式（1）中，R為氫原子、碳數1～5的一價烴基、鹵素原子、或碳數1～5的鹵化烷基。R ²為碳數1～5的一價烴基。R ³為碳數1～5的烷氧基。R ¹⁰為碳數1～5的一價烴基、碳數1～5的鹵化烷基、碳數1～5的烷氧基或鹵素原子。a為0～2的整數，b為1～3的整數。其中，a+b=3。c為0～4的整數。a為2的情況下，多個R ²為相同或不同。b為2或3的情況下，多個R ³為相同或不同。c為2以上的情況下，多個R ¹⁰為相同或不同） Among them, the polymer (I) is preferably a polymer having a functional group F1 and at least one crosslinkable group selected from the group consisting of an acid anhydride group and a protected carboxyl group, as the polymer containing the functional group F1 The structural unit preferably includes a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit U3"). [chemical 5]

(In formula (1), R is a hydrogen atom, a monovalent hydrocarbon group with 1 to 5 carbons, a halogen atom, or a halogenated alkyl group with ¹ to 5 carbons. R2 is a monovalent hydrocarbon group with 1 to 5 carbons. R ³ is an alkoxy group with 1 to 5 carbons. R ¹⁰ is a monovalent hydrocarbon group with 1 to 5 carbons, a halogenated alkyl group with 1 to 5 carbons, an alkoxy group with 1 to 5 carbons or a halogen atom. a is An integer of 0 to 2, b is an integer of 1 to 3. Among them, a+b=3. c is an integer of 0 to 4. When a is 2, a plurality of R ² are the same or different. b is 2 or In the case of 3, multiple R ³ are the same or different. When c is 2 or more, multiple R ¹⁰ are the same or different)

In the formula (1), examples of the monovalent hydrocarbon group in R ² include alkyl groups, cycloalkyl groups, and the like. Among these, R ² is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. b is preferably 1 or 2, more preferably 1, since the selectivity to the substrate (more specifically, the insulating layer 14 ) can be improved. c is preferably 0-2, more preferably 0.

When the polymer (I) contains the structural unit U3, the content of the structural unit U3 is preferably at least 1 mol %, more preferably at least 2 mol %, relative to all the structural units constituting the polymer (I), More preferably, it is 5 mol% or more. By setting the content of the structural unit U3 to 1 mol % or more, the effect of improving the adhesion between the insulating layer 14 and the second organic film 17 can be increased, which is preferable in this point. In addition, from the viewpoint of securing good matrix selectivity, the content of the structural unit U3 is preferably 40 mol% or less, more preferably 30 mol% or less, based on all structural units constituting the polymer (I).

The polymer (I) may further include a structural unit different from the structural unit U1 to structural unit U3 together with the structural unit U1 (hereinafter also referred to as "other structural unit U4"). The other structural unit U4 is not particularly limited as long as it can be copolymerized with the structural unit U1. The monomer providing the other structural unit U4 is preferably a monomer having a polymerizable carbon-carbon unsaturated bond. Specifically, for example, the group selected from alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, aromatic vinyl compounds, N -Substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, olefins, vinyl cycloalkanes, cycloalkenes, and unsaturated dicarboxylic acid dialkyl esters At least one monomer in the group consisting of compounds. Specific examples and preferable examples thereof include the same compounds as the monomers exemplified in the description of the polymer (A). In addition, as the monomer providing the other structural unit U4, a monomer having the functional group FM and different from the monomer providing the structural unit U2 can be used.

In the polymer (I), relative to all the structural units constituting the polymer (I), the content of other structural units U4 is preferably 80 mol % or less, more preferably 70 mol % or less, further preferably 60 mol % Ear % below.

From the viewpoint of obtaining an organic film with high heat resistance, the polymer (I) preferably further includes a structural unit derived from a monomer having an aromatic ring (hereinafter also referred to as "structural unit U5"). The monomer providing the structural unit U5 may be one of the structural units U1 to U4, or two or more. As a specific example of the monomer providing the structural unit U5, a monomer having an aromatic ring can be arbitrarily selected and used from the monomers exemplified as the monomer providing the structural unit U1 to U4. In addition, the aromatic ring which structural unit U5 has may have a substituent in a ring part. Examples of the substituent include a monovalent hydrocarbon group having 1 to 5 carbons, a halogenated alkyl group having 1 to 5 carbons, an alkoxy group having 1 to 5 carbons, or a halogen atom.

In the polymer (I), relative to all the structural units contained in the polymer (I), the content of the structural unit U5 is preferably at least 10 mol %, more preferably at least 20 mol %, and even more preferably at least 30 mol % %above. In addition, the content of the structural unit U5 is preferably 99 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less, relative to all structural units contained in the polymer (I).

The method for synthesizing the polymer (I) is also not particularly limited, and it can be produced using known polymerization methods such as radical polymerization and anionic polymerization. Among them, when using radical polymerization, the polymer (I) can be easily synthesized and the cost of the composition can be reduced, which is preferable. Regarding the polymer (I), any polymerization forms such as random polymerization and block (co)polymerization can also be applied.

In the case of radical polymerization, examples of polymerization initiators include: 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile) ), 2,2'-azobis(isobutyrate) dimethyl ester, 2,2'-dimethyl azobis(2-methylpropionate) and other azo compounds. It is preferable that the usage-amount of a polymerization initiator is 0.01 mass part - 30 mass parts with respect to 100 mass parts of total amounts of the monomer used for reaction. As a polymerization medium, alcohols, ethers, ketones, esters, hydrocarbons, etc. are mentioned, for example. The amount of the polymerization solvent used is preferably an amount such that the total amount of monomers used in the reaction is 0.1% by mass to 60% by mass relative to the entire amount of the reaction solution.

During polymerization, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the type of the polymerization initiator and the monomer, or the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the above reaction may be directly used in the preparation of the composition in the state of being dissolved in the reaction solution, or may be used in the preparation of the composition after being separated from the reaction solution. The polymer can be separated by, for example, a method of injecting the reaction solution into a large amount of poor solvent, drying the precipitate thus obtained under reduced pressure, or a method of removing the reaction solution by distillation under reduced pressure using an evaporator, etc. to proceed.

The polymer (I) preferably has a weight average molecular weight (Mw) in terms of polystyrene by GPC of 1,000 or more. When Mw is 1,000 or more, a sufficiently high organic film such as heat resistance or chemical resistance can be obtained, which is preferable in this point. Mw is more preferably at least 2,000, further preferably at least 3,000. In addition, from the viewpoint of improving film-forming properties, the Mw of the polymer (I) is preferably at most 10,000, more preferably at most 9,000, and still more preferably at most 8,000. The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.

〔Solvent〕 The second composition is preferably a liquid composition in which the polymer (I) is dissolved or dispersed in a solvent. The solvent used in the preparation of the second composition is preferably an organic solvent capable of dissolving the polymer (I) and not reacting with each component. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents.

As specific examples of these, as alcohol solvents, aliphatic monohydric alcohol solvents such as 4-methyl-2-pentanol and n-hexanol having 1 to 18 carbon atoms; cyclohexanol and the like having 3 to 18 carbon atoms Alicyclic monohydric alcohol-based solvents; 1,2-propanediol and other polyol-based solvents with 2 to 18 carbon atoms; propylene glycol monomethyl ether and other polyol-based partial ether solvents with 3-19 carbon atoms. Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; Cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; ether solvents containing aromatic rings such as diphenyl ether and anisole (methyl phenyl ether), etc.

Examples of ketone solvents include acetone, methyl ethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, diethyl ketone, methyl isobutyl ketone, 2-heptanone (methyl n- amyl ketone), ethyl n-butyl ketone, methyl n-hexyl ketone, diisobutyl ketone, trimethyl nonanone and other chain ketone solvents; cyclopentanone, cyclohexanone, cycloheptanone, cyclooctyl Cyclic ketone solvents such as ketone and methylcyclohexanone; 2,4-pentanedione, acetylacetone, acetophenone, etc. Examples of amide-based solvents include cyclic amide-based solvents such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; N-methylformamide, N,N-dimethyl Chain amides such as methylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylacrylamide Amine solvents, etc. Examples of ester-based solvents include: monocarboxylate-based solvents such as n-butyl acetate and ethyl lactate; polyhydric alcohol carboxylate-based solvents such as propylene glycol acetate; Ester-based solvents; lactone-based solvents such as γ-butyrolactone and δ-valerolactone; polycarboxylic acid diester-based solvents such as diethyl oxalate; dimethyl carbonate, diethyl carbonate, ethyl carbonate, Carbonate-based solvents such as propylene carbonate, etc. Examples of the hydrocarbon solvent include: aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane and n-hexane; and aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene and xylene.

Among these, the solvent used in the preparation of the second composition is preferably at least one selected from the group consisting of alcohol solvents, ether solvents, ketone solvents and ester solvents, more preferably selected from At least one selected from the group consisting of ketone solvents and ester solvents. Among these, it is preferable that the solvent is a mixed solvent containing a ketone solvent and an ester solvent from the viewpoint of solubility. In the case where the solvent is a mixed solvent comprising a ketone-based solvent and an ester-based solvent, specifically, the solvent is preferably selected from the group consisting of acetone, methyl ethyl ketone, and methyl n-propyl ketone. At least one, mixed solvent with propylene glycol monomethyl ether acetate.

When using a mixed solvent containing a ketone solvent and an ester solvent as a solvent, the ratio (mass ratio) of the ketone solvent (X) to the ester solvent (Y) is not particularly limited. The total amount of the solvent is 100 parts by mass (X+Y), and the ester solvent (Y) is preferably 20 to 95 parts by mass, more preferably 30 to 90 parts by mass.

The amount of the polymer (I) contained in the second composition is preferably at least 0.1% by mass, more preferably at least 0.2% by mass, and still more preferably at least 0.5% by mass, based on the total amount of the polymer (I) and the solvent. . When the content of the polymer (I) is 0.1% by mass or more, a coating film having a sufficiently secured film thickness can be formed on the inner wall surface 12 of the through hole 11 . In addition, the content of the polymer (I) is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 10% by mass, based on the total amount of the polymer (I) and the solvent. When the content of the polymer (I) is 30% by mass or less, the film thickness of the organic film does not become too large, and the viscosity of the second composition does not become too high, so that good applicability can be ensured.

[other ingredients] The second composition may further contain other components than these in addition to the polymer (I) and the solvent. Examples of other components include polymers having no functional group F1, surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc.), antioxidants, and the like. The compounding quantity of other components can be suitably selected according to each component in the range which does not impair the effect of this invention.

The solid content concentration of the second composition (the ratio of the total mass of components other than the solvent in the composition to the total mass of the composition) can be appropriately set in consideration of viscosity, volatility, and the like. The solid content concentration of the second composition is preferably in the range of 0.1% by mass to 30% by mass. When the solid content concentration is 0.1% by mass or more, the film thickness of the organic film can be sufficiently ensured, which is preferable in this point. In addition, if the solid content concentration is 30% by mass or less, the film thickness of the organic film will not become too large, and the viscosity of the second composition can be moderately increased, thereby ensuring good applicability. In terms of better. The solid content concentration of the second composition is more preferably from 0.5% by mass to 20% by mass, and still more preferably from 0.7% by mass to 10% by mass.

＜Third composition＞ Next, each component contained in the 3rd composition, and other components mix|blended as needed are demonstrated. The third composition is a polymer composition for forming the second layer 17 b in the second organic film 17 . When the polymer (I) has a crosslinkable group, the third composition preferably contains the polymer (II) having a crosslinkable group with the polymer (I) and a solvent. The linking group forms a bonded functional group (hereinafter also referred to as "functional group F2"). By using the second organic film 17 as a laminated film of the first layer 17a and the second layer 17b, a cross-linked structure is formed between the first layer 17a and the second layer 17b, and it is possible to form a film having excellent heat resistance and dielectric breakdown resistance. of organic membranes. Furthermore, the functional group F2 corresponds to the "third functional group".

[Polymer (II)] ·Functional group F2 The functional group F2 of the polymer (II) is not particularly limited as long as it can react with the crosslinkable group of the polymer (I) to form a bond. The functional group F2 is preferably oxazoline group and at least one of the epoxy groups. In addition, in this specification, an "epoxy group" means including an oxiranyl group and an oxetanyl group.

Among them, it is particularly preferred that the polymer (I) has at least one crosslinking group selected from the group consisting of an acid anhydride group and a protected carboxyl group, and the functional group F2 is at least one of an oxazoline group and an epoxy group. one. In this case, the dielectric breakdown resistance of the second organic film 17 can be improved by forming a crosslinked structure by utilizing the reaction between the crosslinkable group of the polymer (I) and the functional group F2 . In addition, it is considered that an acid anhydride group or a protected carboxyl group reacts with an oxazoline group to form an amide group, and the dielectric breakdown resistance can be further improved by the interaction of the amide bond. Furthermore, when a polymer (I) has an acid anhydride group, it is preferable at the point which can further improve the adhesiveness with the plating layer 18 by the carboxyl group produced|generated by a crosslinking reaction. The carboxyl group generated by the reaction of the crosslinkable group possessed by the polymer (I) and the functional group F2 corresponds to the functional group FM (second functional group).

Furthermore, when a protected carboxyl group is introduced into the polymer (I) as a crosslinkable group to obtain the second organic film 17 having a carboxyl group as the functional group FM, the crosslinkable group possessed by the polymer (I) The number can be designed to be more than the number of functional groups F2 of the polymer (II), so that the second organic film 17 has the functional group FM after the cross-linking reaction.

The main skeleton of the polymer (II) is not particularly limited. Polymer (II) preferably has polymerizable carbon-carbon unsaturation in terms of excellent heat resistance, high degree of freedom in the selection of monomers, and relatively easy introduction of functional group F2. A polymer obtained from the monomer of the bond. The polymer (II) preferably includes a structural unit having a functional group F2 (hereinafter also referred to as "structural unit U6").

Regarding the monomer providing the structural unit U6, examples of the monomer having an epoxy group include: glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, (methyl) ) 3,4-epoxycyclohexylmethyl acrylate, 2-(3,4-epoxycyclohexyl) ethyl (meth)acrylate, 3,4-epoxycyclohexyl[5.2.1.0 ^2,6 ]( Decyl methacrylate, (3-methyloxetan-3-yl)methyl (meth)acrylate, 4-glycidyl styrene, 3-glycidyl styrene, (methyl) (3-Ethyloxetane-3-yl)acrylate, (Oxetan-3-yl)(meth)methylacrylate, (3-Ethyloxetane-3- group) methyl (meth)acrylate, etc.; Examples of monomers having an oxazoline group include 2-vinyl-2-oxazoline, isopropenyloxazoline, and the like.

In the polymer (II), the content of the structural unit U6 is preferably at least 3 mol%, more preferably at least 5 mol%, and still more preferably 10 mol%, relative to all the structural units constituting the polymer (II). above. By setting the content of the structural unit U6 to be 3 mol % or more, the effect of improving the dielectric breakdown resistance and the adhesion with the plating layer 18 can be sufficiently obtained, which is preferable in this point. In addition, from the viewpoint of ensuring good matrix selectivity, the content of the structural unit U6 is preferably 40 mol% or less, more preferably 35 mol% or less, relative to all structural units constituting the polymer (II), More preferably, it is 30 mol% or less. If the content of the structural unit U6 is within the above range, by uniformly introducing the functional group F2 into the polymer (II), the unevenness of the functional group F2 in the coating film can be suppressed, and it can also be used as a permanent film. It is preferable in terms of the above.

·Other structural units The polymer (II) may further include, together with the structural unit U6, a structural unit different from the structural unit U6 (hereinafter also referred to as “other structural unit U7”). The other structural unit U7 is not particularly limited as long as it can be copolymerized with the structural unit U6. The monomer providing the other structural unit U7 is preferably a monomer having a polymerizable carbon-carbon unsaturated bond. Specifically, for example, the group selected from alkyl (meth)acrylates, (meth)acrylates having an alicyclic structure, (meth)acrylates having an aromatic ring structure, aromatic vinyl compounds, N -Substituted maleimide compounds, vinyl compounds having a heterocyclic structure, conjugated diene compounds, nitrogen-containing vinyl compounds, olefins, vinyl cycloalkanes, cycloalkenes, and unsaturated dicarboxylic acid dialkyl esters At least one monomer in the group consisting of compounds. Specific examples and preferable examples thereof include the same compounds as the monomers exemplified in the description of the polymer (A).

In the polymer (II), the content of other structural units U7 is preferably 97 mol % or less, more preferably 95 mol % or less, and more preferably 90 mol % relative to all structural units constituting the polymer (II). Ear % below.

From the viewpoint of obtaining an organic film with high heat resistance, the polymer (II) preferably further includes a structural unit derived from a monomer having an aromatic ring (hereinafter also referred to as "structural unit U8"). The monomer providing the structural unit U8 may be one of the structural unit U6 and the structural unit U7, or two or more. As a specific example of the monomer providing the structural unit U8, a monomer having an aromatic ring can be arbitrarily selected from the monomers exemplified as the monomer providing the structural unit U6 and the structural unit U7. In the polymer (II), relative to all the structural units contained in the polymer (II), the content of the structural unit U8 is preferably 10 mol % or more, more preferably 20 mol % or more, and more preferably 30 mol % ear% or more.

In addition, the synthesis method of polymer (II) is not specifically limited similarly to polymer (I) and polymer (A). The details of the synthesis method of the polymer (II) are the same as those of the polymer (I).

The polymer (II) preferably has a weight average molecular weight (Mw) in terms of polystyrene by GPC of 800 or more. When Mw is 800 or more, a sufficiently high organic film such as heat resistance and chemical resistance can be obtained, which is preferable in this point. Mw is more preferably at least 1,000, further preferably at least 1,500. In addition, from the viewpoint of improving film-forming properties, the Mw of the polymer (II) is preferably 8,000 or less, more preferably 7,000 or less, still more preferably 6,000 or less. The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less.

〔Solvent〕 The third composition is preferably a liquid composition obtained by dissolving or dispersing the polymer (II) in a solvent. The solvent used in the preparation of the third composition is preferably an organic solvent capable of dissolving the polymer (II) and not reacting with each component. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ketone-based solvents, amide-based solvents, ester-based solvents, and hydrocarbon-based solvents. Specific examples and preferred examples of these solvents include the same compounds as those described as specific examples and preferred examples of the solvent usable for the preparation of the second composition.

The amount of the polymer (II) contained in the third composition is preferably at least 0.1% by mass, more preferably at least 0.2% by mass, and still more preferably at least 0.5% by mass, based on the total amount of the polymer (II) and the solvent. . When the content of the polymer (II) is 0.1% by mass or more, a coating film having a sufficiently secured film thickness can be formed, which is preferable in this point. In addition, the content of the polymer (II) is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 10% by mass, based on the total amount of the polymer (II) and the solvent. When the content of the polymer (II) is 30% by mass or less, the film thickness of the organic film does not become too large, and the viscosity of the third composition does not become too high, so that good applicability can be ensured.

[other ingredients] The third composition may further contain other components other than these polymers (II) and the solvent. Examples of other components include polymers having no functional group F2, surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc.), antioxidants, and the like. The compounding quantity of other components can be suitably selected according to each component in the range which does not impair the effect of this invention.

The solid content concentration of the third composition is preferably in the range of 0.1% by mass to 30% by mass. When the solid content concentration is 0.1% by mass or more, the film thickness of the organic film can be sufficiently ensured, which is preferable in this point. In addition, if the solid content concentration is 30% by mass or less, the film thickness of the organic film will not become too large, and the viscosity of the third composition can be moderately increased, whereby good applicability can be ensured. The solid content concentration of the third composition is more preferably from 0.5% by mass to 20% by mass, and still more preferably from 0.7% by mass to 10% by mass.

＜Fourth composition＞ Next, each component contained in the 4th composition, and other components mix|blended as needed are demonstrated. The fourth composition contains a polymer (III) having a functional group F1 capable of interacting with a group on the surface layer of the insulating layer 14 , and a solvent capable of interacting with a metal contained in the plating layer 18 , and a solvent. The element forms a bonded functional group FM or a functional group FP that generates the functional group FM by heating.

The main skeleton of the polymer (III) is not particularly limited, but is preferably a polymer obtained by using a monomer having a polymerizable carbon-carbon unsaturated bond. Specific examples of the polymer (III) include: [1] a polymer comprising a structural unit having a functional group F1 and a structural unit having a functional group FM or a functional group FP, [2] a polymer comprising a structural unit having a functional group F1 A polymer with a functional group FM or a functional group FP at the end of the polymer, etc. In addition, the synthesis method of polymer (III) is also the same as that of polymer (I), polymer (II), and polymer (A), and it does not specifically limit. For details of the synthesis method of the polymer (III), the description of the synthesis method of the polymer (I) can be referred to.

The polymer (III) preferably includes a structural unit U1 having a functional group F1 and a structural unit having at least one selected from the group consisting of an acid anhydride group and a protected carboxyl group. The details of the functional group F1 and the structural unit U1 are the same as the description of the specific examples and preferred examples of the functional group F1 and the structural unit U1 contained in the polymer (I) contained in the first composition. The acid anhydride group and the protected carboxyl group are the same as those exemplified for the crosslinkable group that the polymer (I) may have. The details of the structural unit having these groups are the same as the description of specific examples and preferred examples of the structural unit U2 that the polymer (I) may have. In addition, the polymer (III) may have crosslinkable groups capable of forming bonds with each other through the same group. In this case, the heat resistance and dielectric breakdown resistance of the second organic film 17 can be improved. The preferred content of each structural unit in the polymer (III) is the same as the range described for each structural unit in the polymer (I).

In the fourth composition, components other than the polymer (III) and the solvent may be formulated in addition to the above-mentioned polymer (III) and the solvent. Examples of other components include polymers having no functional group F1, thermal acid generators (TAG), surfactants, antioxidants, and the like. Specific examples of the thermal acid generator include diphenyliodonium nonafluorobutanesulfonate and the like. In the case where a thermal acid generator is blended in the fourth composition, from the viewpoint of suppressing sinking when the fourth composition is applied to the base material while obtaining the effect of the blending of the thermal acid generator, compared with the first The total amount of the four components is preferably less than 10 mol%, more preferably 1-5 mol%.

According to the structure of the second organic film 17 as a single-layer film, the steps of forming the organic film on the inner wall surface 12 of the through hole 11 can be reduced as much as possible, and the manufacturing process can be simplified. In addition, an organic film having excellent adhesion to the plating layer 18 can be formed on the inner wall surface 12 of the through hole 11 while further reducing the thickness of the organic film formed on the inner wall surface 12 of the through hole 11 .

"Laminated Film Formation Kit" The laminated film forming kit (hereinafter also simply referred to as "film forming kit") of the present invention is used for preprocessing when forming the plating layer 18 inside the through hole 11 in the manufacturing process of the multilayer wiring board. The form of the set is not particularly limited as long as it contains the polymer (I) and the polymer (II). One aspect of the film-forming kit of the present invention is a kit including a first agent containing a polymer (I) and a second agent containing a polymer (II). In this case, it is preferable that the first agent is the second composition and the second agent is the third composition.

According to the film forming kit of the present invention, the second organic film 17 (first layer 17a and second organic film 17a) can be selectively formed on the inner wall surface 12 of the through hole 11 in the wiring forming step of forming multilayer wiring on the substrate. second floor 17b). The second organic film 17 formed on the inner wall surface 12 functions as a barrier layer and can suppress the diffusion of the metal element embedded in the via hole to the insulating layer 14 . In addition, according to the method of embedding metal into the inside of the through-hole 11 whose side surface is covered with the second organic film 17 by plating, the plating layer 18 can be formed with less generation of voids or seams. Therefore, according to the film forming kit of the present invention, a highly reliable element can be obtained.

"Constituents" The composition of the present invention is a composition used in the pre-processing of embedding metal in the inside of the through-hole 11 by a plating process in the manufacturing process of the multilayer wiring board. The composition contains a polymer having a crosslinkable group and a functional group F1 as at least one selected from the group consisting of an acid anhydride group and a protected carboxyl group, and a solvent. The details of the polymer and the solvent are as described above. According to such a composition, an organic film excellent in adhesion to the insulating layer 14 and to the plating layer 18 can be formed on the inner wall surface 12 of the via hole 11 . [Example]

Hereinafter, although an Example demonstrates more concretely, this invention is not limited by these Examples.

In the following examples and comparative examples, the measuring methods of the weight average molecular weight and the number average molecular weight of the polymer are as follows. [Weight average molecular weight and number average molecular weight] The weight average molecular weight (Mw) and number average molecular weight (Mn) of the polymer were determined by gel permeation chromatography (GPC) using Tosoh GPC columns (two "G2000HXL", one "G3000HXL" and "G4000HXL ” one piece), and the measurement was carried out under the following conditions. Eluent: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 mL/min Sample concentration: 1.0% by mass Sample injection volume: 100 μL Column temperature: 40°C Detector: Differential refractometer Standard material: monodisperse polystyrene

1. Synthesis of Polymer [Synthesis Example 1] Synthesis of Polymer (A-1) After a 500 mL flask reaction vessel was dried under reduced pressure, 120 g of tetrahydrofuran subjected to distillation and dehydration was injected under a nitrogen atmosphere, and cooled to -78℃. Then, 2.38 mL of a 1 N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this tetrahydrofuran, and then, 13.3 mL of styrene was added dropwise over 30 minutes to remove Polymerization inhibitors were separated by adsorption, filtration and distillation dehydration on silica gel, and the polymerization system was confirmed to be orange. During this dropwise injection, care should be taken that the internal temperature of the reaction solution should not be higher than -60°C. After the dropwise addition was completed, it was matured for 30 minutes. After that, 0.18 ml of N,N-dimethylformamide was injected to stop the polymerization terminal. The reaction solution was warmed up to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Thereafter, 1,000 g of a 2% aqueous solution of oxalic acid was injected and stirred, and the bottom water layer was removed after standing still. This operation was repeated three times to remove metallic Li. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. After this operation was repeated three times to remove oxalic acid, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. This polymer was dried under reduced pressure at 60°C to obtain 11.9 g of a white polymer. Mw of the obtained polymer was 5000, Mn was 4800, and Mw/Mn was 1.04. Next, 10.0 g of the white polymer was dissolved in 40 g of toluene, 0.21 g of malononitrile, 0.25 g of ammonium acetate, and 0.038 g of acetic acid were added, and heated and dry-distilled under a nitrogen atmosphere for 4 hours. The temperature of the reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Afterwards, 500 g of sodium bicarbonate 2% aqueous solution was injected and stirred, and the bottom water layer was removed after standing. This operation was repeated three times to remove metallic Li. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. After removing acetic acid by repeating this operation three times, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. The obtained polymer was dried under reduced pressure at 60° C. to obtain 9.8 g of a white polymer (A-1). Mw of this polymer (A-1) was 5300, Mn was 5100, and Mw/Mn was 1.04. [chemical 6]

[Synthesis Example 2] Synthesis of Polymer (A-2) After drying a 500 mL flask reaction container under reduced pressure, 120 g of distilled and dehydrated tetrahydrofuran was injected under a nitrogen atmosphere, and cooled to -78°C. Then, 2.30 mL of a 1 N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this tetrahydrofuran, and then, 13.3 mL of styrene was added dropwise over 30 minutes to remove Polymerization inhibitors were separated by adsorption, filtration and distillation dehydration on silica gel, and the polymerization system was confirmed to be orange. During this dropwise injection, care should be taken that the internal temperature of the reaction solution should not be higher than -60°C. After the dropwise addition was completed, it was matured for 30 minutes. After that, 0.47 ml of diisopropyl bromoethyl borate was injected to perform a stop reaction of the polymerization terminal. The temperature of the reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Thereafter, 1,000 g of a 2% aqueous solution of oxalic acid was injected and stirred, and the bottom water layer was removed after standing still. This operation was repeated three times to remove metallic Li. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. This operation was repeated three times to remove oxalic acid. Thereafter, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. This polymer was dried under reduced pressure at 60°C to obtain 11.7 g of a white polymer. Mw of the obtained polymer was 5000, Mn was 4700, and Mw/Mn was 1.06. Next, 0.96 g of triethylamine, 10 g of ultrapure water, 4 g of propylene glycol monomethyl ether, and 40 g of propylene glycol monomethyl ether acetate were added to 10.0 g of this polymer, and heated and stirred at 80° C. under a nitrogen atmosphere. . The temperature of the reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Afterwards, 500 g of sodium bicarbonate 2% aqueous solution was injected and stirred, and the bottom water layer was removed after standing. This operation was repeated three times to remove metallic Li. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. This operation was repeated three times to remove acetic acid. Thereafter, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. This polymer was dried under reduced pressure at 60°C to obtain 9.8 g of a white polymer (A-2). Mw of the obtained polymer (A-2) was 5100, Mn was 4800, and Mw/Mn was 1.04. [chemical 7]

[Synthesis Example 3] Synthesis of Polymer (A-3) After drying a 500 mL flask reaction container under reduced pressure, 120 g of distilled and dehydrated tetrahydrofuran was injected under a nitrogen atmosphere, and cooled to -78°C. Then, 2.30 mL of a 1 N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this tetrahydrofuran, and then, 13.3 mL of styrene was added dropwise over 30 minutes to remove Polymerization inhibitors were separated by adsorption, filtration and distillation dehydration on silica gel, and the polymerization system was confirmed to be orange. During this dropwise injection, care should be taken that the internal temperature of the reaction solution should not be higher than -60°C. After the dropwise addition was completed, it was matured for 30 minutes. After that, 0.33 ml of diethyl chlorophosphate was injected to stop the polymerization terminal. The temperature of the reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Thereafter, 1,000 g of a 2% aqueous solution of oxalic acid was injected and stirred, and the bottom water layer was removed after standing still. This operation was repeated three times to remove metallic Li. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. This operation was repeated three times to remove oxalic acid. Thereafter, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. This polymer was dried under reduced pressure at 60°C to obtain 11.5 g of a white polymer. Mw of the obtained polymer was 5100, Mn was 4900, and Mw/Mn was 1.04. Next, 0.81 g of triethylamine, 4 g of propylene glycol monomethyl ether, and 40 g of propylene glycol monomethyl ether acetate were added to 10.0 g of this polymer, and heated and stirred at 80° C. under a nitrogen atmosphere. The temperature of the reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Thereafter, 500 g of oxalic acid 2% aqueous solution was injected and stirred, and the bottom water layer was removed after standing. This operation was repeated three times to remove metallic Li. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. This operation was repeated three times to remove acetic acid. Thereafter, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. This polymer was dried under reduced pressure at 60° C. to obtain 9.2 g of a white polymer (A-3). Mw of the obtained polymer (A-3) was 5100, Mn was 4800, and Mw/Mn was 1.06. [chemical 8]

[Synthesis Example 4] Synthesis of Polymer (A-4) After drying a 500 mL flask reaction vessel under reduced pressure, 120 g of distilled and dehydrated tetrahydrofuran was injected under a nitrogen atmosphere, and cooled to -78°C. Then, 2.38 mL of a 1 N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this tetrahydrofuran, and then, 13.3 mL of styrene was added dropwise over 30 minutes to remove Polymerization inhibitors were separated by adsorption, filtration and distillation dehydration on silica gel, and the polymerization system was confirmed to be orange. During this dropwise injection, care should be taken that the internal temperature of the reaction solution should not be higher than -60°C. After the dropwise addition was completed, it was matured for 30 minutes. After that, 0.20 mL of allyl bromide was injected to stop the polymerization terminal. The temperature of the reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Thereafter, 1,000 g of a 2% aqueous solution of oxalic acid was injected and stirred, and the bottom water layer was removed after standing still. This operation was repeated three times to remove metallic Li. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. This operation was repeated three times to remove oxalic acid. Thereafter, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. This solid was dried under reduced pressure at 60°C to obtain 11.4 g of a white polymer (A-4). The obtained polymer (A-4) had Mw of 5700, Mn of 5200, and Mw/Mn of 1.10. [chemical 9]

[Synthesis Example 5] Synthesis of Polymer (A-5) After a 500 mL flask reaction container was dried under reduced pressure, 120 g of THF subjected to distillation and dehydration was injected under a nitrogen atmosphere, and cooled to -78°C. 2.40 mL of a 1 N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this THF, and 99.9 mL of styrene and 3.24 g of 4-vinylbenzocyclobutene were added dropwise over 30 minutes. , the styrene was subjected to adsorption filtration separation and distillation dehydration treatment using silica gel in advance to remove polymerization inhibitors, and it was confirmed that the polymerization system was orange. After the dropwise addition was completed, it was matured for 30 minutes. Furthermore, 1.0 g of hexamethylcyclotrisiloxane was added, aged for 30 minutes, and 1 ml of methanol was injected to stop the polymerization terminal reaction. The reaction solution was warmed up to room temperature, and the obtained reaction solution was concentrated and replaced with MIBK. After that, 1,000 g of ultrapure water was injected and stirred to remove the bottom water layer. After repeating this operation five times, the solution was concentrated and added dropwise to 500 g of methanol to precipitate a polymer, and the solid was collected using a Buchner funnel. This polymer was dried under reduced pressure at 60°C to obtain 11.2 g of a white polymer (A-5). Mw of the obtained polymer (A-5) was 6200, Mn was 6000, and Mw/Mn was 1.04. [chemical 10]

[Synthesis Example 6] Synthesis of Polymer (A-6) 10 g of 1,4-dioxane and a magnetic stirrer bar were placed in a 300 ml three-necked flask replaced with nitrogen, and heated to 80°C. Then, 5.10 g of styrene, 3.28 g of 4-(1-propoxyethyl) vinyl benzoate, 1.35 g of N-vinyl carbazole, 2,2-dimethyl 0.48 g of azobis(2-methylpropionate) (3 mol% relative to the total moles of all monomers), and 20 g of methyl isobutyl ketone. After that, ripen for 3 hours. The obtained polymerization solution was purified by precipitation in 500 g of methanol to precipitate a white solid, which was collected by Buchner funnel and dried under reduced pressure to recover 5.63 g of polymer (A-6). The obtained polymer (A-6) had Mw of 4000, Mn of 3000, and Mw/Mn of 1.33. [chemical 11]

[Synthesis Example 7] Synthesis of Polymer (A-7) 10 g of 1,4-dioxane and a magnetic stirrer bar were placed in a 300 ml three-necked flask replaced with nitrogen, and heated to 80°C. Then, 5.10 g of styrene, 1.96 g of maleic anhydride, 2.60 g of 4-vinylbenzocyclobutene, 1.93 g of 4-dimethylmethoxysilylstyrene, 2,2 - 0.46 g of dimethyl azobis (2-methyl propionate) (2 mol% relative to the total moles of all monomers), 20 g of methyl isobutyl ketone. After that, ripen for 3 hours. The obtained polymer solution was purified by precipitation in 500 g of diisopropyl ether to precipitate a white solid, which was collected by Buchner funnel and then dried under reduced pressure to recover polymer (A-7) 7.31 g. Mw of the obtained polymer (A-7) was 4660, Mn was 3140, and Mw/Mn was 1.48. [chemical 12]

[Synthesis Example 8] Synthesis of Polymer (A-8) 10 g of 1,4-dioxane and a magnetic stirrer bar were placed in a 300 ml three-necked flask replaced with nitrogen, and heated to 80°C. Then, 8.32 g of styrene, 2.22 g of isopropenyloxazoline, and 0.46 g of 2,2-dimethylazobis(2-methylpropionate) were added dropwise at a constant speed over 3 hours (with respect to the total monomer The total number of moles is 2 mol%), methyl isobutyl ketone 20 g. After that, ripen for 3 hours. The obtained polymerization solution was purified by precipitation in 500 g of hexane to precipitate a white solid, which was collected by Buchner funnel and dried under reduced pressure to recover 4.31 g of polymer (A-8). Mw of the obtained polymer (A-8) was 3140, Mn was 2410, and Mw/Mn was 1.30. [chemical 13]

[Synthesis Example 9] Synthesis of Polymer (A-9) 10 g of methyl ethyl ketone and a magnetic stirrer bar were placed in a 300 ml three-necked flask replaced with nitrogen, and heated to 80°C. Then, 9.37 g of styrene, 1.76 g of 4-glycidyl styrene, and 0.46 g of 2,2-dimethylazobis(2-methylpropionate) were added dropwise at a constant speed over 3 hours (with respect to all mono The total number of moles of the body is 2 mol%), and 20 g of methyl isobutyl ketone. After that, ripen for 3 hours. The obtained polymerization solution was purified by precipitation in 500 g of hexane to precipitate a white solid, which was collected by Buchner funnel and dried under reduced pressure to recover 4.36 g of polymer (A-9). The obtained polymer (A-9) had Mw of 3090, Mn of 2240, and Mw/Mn of 1.38. [chemical 14]

[Synthesis Example 10] Synthesis of Polymer (A-10) 10 g of 1,4-dioxane and a magnetic stirrer bar were placed in a 300 ml three-necked flask replaced with nitrogen, and heated to 80°C. Then, 5.10 g of styrene, 4.68 g of 1-propoxyethylvinylbenzoic acid, 2.60 g of 4-vinylbenzocyclobutene, 4-dimethylmethoxysilyl Styrene 1.93 g, 2,2-dimethylazobis(2-methylpropionate) 0.46 g (2 mol% relative to the total moles of all monomers), methyl isobutyl Ketones 20 g. After that, ripen for 3 hours. The obtained polymer solution was purified by precipitation in 500 g of diisopropyl ether to precipitate a white solid, which was collected by Buchner funnel and then dried under reduced pressure to recover the polymer (A-10) 6.38 g. Mw of the obtained polymer (A-10) was 4050, Mn was 3260, and Mw/Mn was 1.24. [chemical 15]

2. Preparation of composition for selective surface modification [Preparation Example 1 to Preparation Example 10] 98.8 g of propylene glycol monomethyl ether acetate (PGMEA) was added as a solvent to 1.20 g of the polymer (A-1), and after stirring, a high-density polyethylene filter having pores of 0.45 μm was used. Filtration was performed to prepare a composition (S-1). In addition, Composition (S-2) to Composition (S-10) were prepared in the same manner (see Table 1).

[Table 1] Table 1 Selective surface modification composition Preparation Example 1 Preparation example 2 Preparation example 3 Preparation Example 4 Preparation Example 5 Preparation example 6 Preparation Example 7 Preparation example 8 Preparation Example 9 Preparation Example 10 Composition (g) polymer A-1 1.2 A-2 1.2 A-3 1.2 A-4 1.2 A-5 1.2 A-6 1.2 A-7 1.2 A-8 1.2 A-9 1.2 A-10 1.2 solvent B-1 98.8 98.8 98.8 98.8 98.8 98.8 49.4 98.8 98.8 98.8 B-2 49.4 Composition name S-1 S-2 S-3 S-4 S-5 S-6 S-7 S-8 S-9 S-10

In Table 1, the abbreviations of the solvents represent the following compounds. B-1: Propylene glycol monomethyl ether acetate B-2: Methyl ethyl ketone

3. Evaluation [Example 1] <Film formation> A 12-inch low-k substrate (manufactured by Advantec) was cut into 3 cm×3 cm, and manufactured by (Ulvac, Luminous (Luminous) NA-1300, chamber pressure: 30 Pa, flow rate: 300 sccm, treatment time: 5 minutes) under the N ₂ /3%H ₂ ashing process. Next, the composition (S-6) was spin-coated at 1,500 rpm for 20 seconds using a spin coater (manufactured by Mikasa Co., Ltd., MS-B300) on the surface of the ashed substrate, and the composition (S-6) was sprayed under nitrogen flow 1. Burn at 150°C for 180 seconds. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove unadsorbed polymer. Next, the composition (S-8) was spin-coated on the film-forming surface made of the composition (S-6) at 1,500 rpm for 20 seconds, and baked at 250°C for 300 seconds under a nitrogen stream. . Next, the substrate was cleaned with propylene glycol monomethyl ether acetate to remove uncrosslinked polymer. Furthermore, instead of the 12-inch low-k substrate, a test piece substrate obtained by cutting a 12-inch TEOS substrate (manufactured by Advantec) into 3 cm x 3 cm, and a 12-inch thermal oxide silicon substrate were used respectively. A substrate (manufactured by Advantec) was cut into 3 cm×3 cm sample substrates, and the same treatment as described above was performed to form a film.

＜Electroless Cu plating test＞ Add 100 g of ultrapure water, 1.6 g of sodium hydroxide, 2.5 g of copper sulfate pentahydrate, 4 g of formalin, and 5.6 g of sodium tartrate into a 300 ml polypropylene beaker to prepare an aqueous solution with pH = 12 or higher, and adjust the temperature to 50°C. Next, two single-diameter alkaline storage batteries are connected in series, and a small amount of electricity is passed through the electroless plating aqueous solution through stainless steel clips to activate the plating solution and make the composition (S-6) and composition (S-8) Electroless plating was performed by immersing the low-k substrate of the crosslinked film for 3 minutes. After the plating assembly, the substrate was cleaned with ultrapure water, and then baked in a reduced-pressure oven at 150 degrees Celsius (Cdeg.) for 30 minutes. Next, after cutting the plated Cu film with a knife in the form of a grid, a cellophane tape was used to perform an adhesion peeling test, and the case where the metal film was not peeled to the tape side was rated as "○", and the case where the metal film was peeled was rated as " ×". The same evaluation was performed on substrates in which a crosslinking reaction film of the composition (S-6) and the composition (S-8) was formed on the TEOS substrate and the thermally oxidized silicon substrate. The evaluation results are shown in Table 2.

[Example 2-Example 4 and Comparative Example 1-Comparative Example 3] Except having changed the composition for selective surface modification used as described in Table 2, it carried out similarly to Example 1, and performed the film formation and electroless-plating Cu adhesion test. The evaluation results are shown in Table 2.

[Example 25] Except having changed the composition for selective surface modification used as described in Table 2, it carried out similarly to Example 1, and performed the film formation and electroless-plating Cu adhesion test. In addition, in Table 2, "None" means that the film formation in the corresponding column was not performed (the same applies to Table 3 and Table 4). The evaluation results are shown in Table 2.

[Table 2] Table 2 Plating Cu adhesion test film forming Evaluation First SAM Second SAM low-k th-SiO ₂ TEOS Example 1 S-6 S-8 ○ ○ ○ Example 2 S-6 S-9 ○ ○ ○ Example 3 S-7 S-8 ○ ○ ○ Example 4 S-7 S-9 ○ ○ ○ Example 25 S10 none ○ ○ ○ Comparative example 1 S-5 none x x x Comparative example 2 S-5 S-8 x x x Comparative example 3 S-5 S-9 x x x

[Example 5] ＜Film formation＞ For 12-inch low-k substrates, 12-inch TEOS substrates, and 12-inch thermal oxide silicon substrates, use the composition (S-6) and composition (S-8) to perform the same operations as in Example 1, thereby performing film forming.

＜Electroless Co plating test＞ Add 100 ml of ultrapure water, 1.55 g of cobalt sulfate, 2.12 g of sodium hypophosphite hydrate, 6.6 g of ammonium sulfate, and 10.6 g of sodium pyrophosphate into a 300 ml polypropylene beaker to prepare an aqueous solution with pH = 10.0 to 10.5, and adjust the temperature to 60°C. Next, electroless plating was performed by immersing the low-k substrate having the film cross-linked by the composition (S-6) and the composition (S-8) for 3 minutes. After the plating assembly, the substrate was cleaned with ultrapure water, and then baked in a 150Cdeg. decompression oven for 30 minutes. Next, after cutting the incisions in a grid pattern on the plated Co film with a knife, a cellophane tape was used to perform an adhesion peeling test, and the case where the metal film was not peeled to the tape side was rated as "○", and the case where the metal film was peeled was rated as " ×". The same evaluation was performed on substrates in which a crosslinking reaction film of the composition (S-6) and the composition (S-8) was formed on the TEOS substrate and the thermally oxidized silicon substrate. Table 3 shows the evaluation results.

[Example 6-Example 8 and Comparative Example 4-Comparative Example 6] Film formation and electroless plating Co adhesion tests were performed in the same manner as in Example 5, except that the selective surface modification composition used was changed as described in Table 3. Table 3 shows the evaluation results.

[Example 26] Film formation and electroless plating Co adhesion tests were performed in the same manner as in Example 5, except that the selective surface modification composition used was changed as described in Table 3. Table 3 shows the evaluation results.

[table 3] Table 3 Plating Co adhesion test film forming Evaluation First SAM Second SAM low-k th-SiO ₂ TEOS Example 5 S-6 S-8 ○ ○ ○ Example 6 S-6 S-9 ○ ○ ○ Example 7 S-7 S-8 ○ ○ ○ Example 8 S-7 S-9 ○ ○ ○ Example 26 S-10 none ○ ○ ○ Comparative example 4 S-5 none x x x Comparative Example 5 S-5 S-8 x x x Comparative example 6 S-5 S-9 x x x

According to the results of Table 2 and Table 3, it is clear that Example 1 for making an organic film formed by using a polymer (I) having a functional group F1 (first functional group) and having a functional group FM (second functional group) In Example 8, the metal film did not peel off to the cellophane tape side in the adhesion test, and the adhesion between the organic film and the metal film was excellent. On the other hand, in Comparative Examples 1 to 6 in which organic films having no functional group FM (second functional group) were formed, the metal film was peeled to the cellophane tape side in the adhesion test, and the adhesion between the metal film and the organic film was poor. .

In addition, in Examples 25 and 26 in which the organic film was formed using the polymer (III), the metal film did not peel off to the cellophane tape side in the adhesion test, and the organic film and the metal film had excellent adhesion.

[Example 9] ＜Research on pattern embedding of trench via hole with Cu on the bottom surface＞ A 12-inch substrate (manufactured by Advanced Material Technologies, Inc.) with sidewalls consisting of thermal silicon oxide, bottom surface consisting of copper thin film, and patterned with trench vias containing 50 nm wide/100 nm deep was cut into 3 cm x 3 cm, immersed in 2.38% trimethylammonium hydroxide aqueous solution for 10 minutes. Then, immerse in ultrapure water to remove alkali and complete surface modification. The composition (S-1) was coated on the substrate, spin-coated (manufactured by Mikasa, MS-B300) at 1,500 rpm for 20 seconds, and baked at 150°C for 180 seconds under a nitrogen stream. bell. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove unadsorbed polymer. Next, the composition (S-6) was spin-coated at 1,500 rpm for 20 seconds, and baked at 150° C. for 180 seconds under nitrogen flow. Next, the substrate was cleaned with propylene glycol monomethyl ether acetate to remove polymers not adsorbed on the oxide. Furthermore, similarly, the composition (S-8) was spin-coated at 1,500 rpm for 20 seconds, and baked at 250° C. for 300 seconds under nitrogen flow. Next, the substrate was rinsed with propylene glycol monomethyl ether acetate to remove uncrosslinked polymer. Finally, the substrate was immersed in an acetic acid stock solution for 10 minutes, and washed with ultrapure water, thereby peeling off only the film containing the composition (S-1) adsorbed on the copper thin film on the bottom surface. Through the above operations, the composition (S-6) and the composition (S-8) were provided on the inner wall surface of the via hole, and the trench substrate in which the Cu layer was exposed on the bottom surface inside the via hole was obtained. This substrate was immersed in an electroless plating Cu solution to grow Cu in the grooves. After the plating assembly, the substrate was cleaned with ultrapure water, and then baked in a 150Cdeg. decompression oven for 30 minutes. Cross-sectional scanning electron microscopy (SEM) observation of the obtained substrate confirmed that Cu was embedded in the trench without voids. From the wide-angle view, the case where all 10 grooves were buried was rated as "◯", and the case where there was poor filling was rated as "×". The evaluation results are shown in Table 4.

＜Research on pattern embedding of trench via hole with Co on the bottom surface＞ A 12-inch substrate (manufactured by Advanced Material Technologies, Inc.) with sidewalls comprising thermal silicon oxide, bottom surface comprising thin copper film, and a via pattern comprising trenches 50 nm wide/100 nm deep was cut into 3 cm × 3 cm, immersed in 2.38% trimethylammonium hydroxide aqueous solution for 10 minutes, followed by immersion in ultrapure water to remove the alkali to complete the surface modification. The composition (S-1) was coated on the substrate, spin-coated (manufactured by Mikasa, MS-B300) at 1,500 rpm for 20 seconds, and baked at 150° C. for 180 seconds under a nitrogen stream. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove unadsorbed polymer. Next, the composition (S-6) was spin-coated at 1,500 rpm for 20 seconds, and baked at 150° C. for 180 seconds. Next, the substrate was cleaned with propylene glycol monomethyl ether acetate to remove polymers not adsorbed on the oxide. Furthermore, similarly, the composition (S-8) was spin-coated at 1,500 rpm for 20 seconds, and baked at 250° C. for 300 seconds under nitrogen flow. Next, the substrate was rinsed with propylene glycol monomethyl ether acetate to remove uncrosslinked polymer. Finally, the substrate was immersed in the stock solution of acetic acid for 10 minutes, and washed with ultrapure water, thereby peeling off only the film containing the composition (S-1) adsorbed on the copper thin film on the bottom surface. Through the above operations, a trench substrate in which the Co layer was exposed on the inner wall surface of the through hole with the insoluble film of the composition (S-6) and the composition (S-8) provided on the inner wall surface of the through hole was obtained. This substrate was immersed in an electroless Co plating solution to grow Co in the grooves. After the plating assembly, the substrate was cleaned with ultrapure water, and then baked in a 150Cdeg. decompression oven for 30 minutes. Cross-sectional SEM observation of the obtained substrate (manufactured by Hitachi High-technologies, CG5000) confirmed that Co was embedded in the trench without voids. From the wide-angle view, the case where all 10 grooves were buried was rated as "◯", and the case where there was poor filling was rated as "×". The evaluation results are shown in Table 4.

[Example 10 to Example 24 and Comparative Example 7 to Comparative Example 9] Examination of embedding of trench via pattern with Cu on the bottom surface and trench via pattern with Co on the bottom surface were carried out in the same manner as in Example 9, except that the composition for selective surface modification used was changed as described in Table 4. Embed research. The evaluation results are summarized in Table 4.

[Example 27 to Example 32] Examination of embedding of trench via pattern with Cu on the bottom surface and trench via pattern with Co on the bottom surface were carried out in the same manner as in Example 9, except that the composition for selective surface modification used was changed as described in Table 4. Embed research. The evaluation results are summarized in Table 4.

[Table 4] Table 4 Trench Via Electroless Plating Buried Study film forming Evaluation Through hole bottom SAM Sidewall first SAM Side wall second SAM Copper Bottom Via Trench Cobalt Bottom Via Trench Example 9 S-1 S-6 S-8 ○ ○ Example 10 S-1 S-6 S-9 ○ ○ Example 11 S-1 S-7 S-8 ○ ○ Example 12 S-1 S-7 S-9 ○ ○ Example 13 S-2 S-6 S-8 ○ ○ Example 14 S-2 S-6 S-9 ○ ○ Example 15 S-2 S-7 S-8 ○ ○ Example 16 S-2 S-7 S-9 ○ ○ Example 17 S-3 S-6 S-8 ○ ○ Example 18 S-3 S-6 S-9 ○ ○ Example 19 S-3 S-7 S-8 ○ ○ Example 20 S-3 S-7 S-9 ○ ○ Example 21 S-4 S-6 S-8 ○ ○ Example 22 S-4 S-6 S-9 ○ ○ Example 23 S-4 S-7 S-8 ○ ○ Example 24 S-4 S-7 S-9 ○ ○ Example 27 S-1 S-6 none ○ ○ Example 28 S-1 S-7 none ○ ○ Example 29 S-1 S-10 none ○ ○ Example 30 S-2 S-10 none ○ ○ Example 31 S-3 S-10 none ○ ○ Example 32 S-4 S-10 none ○ ○ Comparative Example 7 S-1 S-5 none x x Comparative Example 8 S-8 none none x x Comparative Example 9 S-9 none none x x

From the results in Table 4, it can be seen that, with regard to Examples 9 to 24 and Examples 27 to 32, in which the metal was embedded in the through hole by this manufacturing method, there is no void in the trench and the metal embedding property is good. . On the other hand, regarding Comparative Example 7 in which an organic film was formed on the inner wall surface of the through-hole using the composition (S-5), and only the composition (S-8) or the composition (S-9) was used in the through-hole In Comparative Example 8 and Comparative Example 9, in which the organic film was formed on the surface, voids were generated in the trenches, and the metal embedding properties were poor.

10: Wiring substrate 11: Through hole 12: Inner wall surface 13: Wiring 14: Insulation layer 15: Bottom 16: The first organic film 17: The second organic film 17a: First floor 17b: Second floor 18: Plating layer

FIG. 1 is a schematic view showing the steps of forming an organic film inside a via hole. (a) indicates before forming the organic film, (b) indicates after forming the first organic film, (c) indicates after forming the first layer of the second organic film, (d) indicates after forming the second layer of the second organic film, (e) shows after removing the first organic film, and (f) shows after forming a plating layer.

10: Wiring substrate

11: Through hole

12: Inner wall surface

13: Wiring

14: Insulation layer

15: Bottom

16: The first organic film

17: The second organic film

17a: First floor

17b: Second floor

18: Plating layer

Claims (18)

A method for manufacturing a multilayer wiring substrate is a method for manufacturing a multilayer wiring substrate, the method for manufacturing a multilayer wiring substrate comprising: The first forming step is to form a first organic film on the wiring inside the through hole, and the through hole is formed on the insulating layer provided on the wiring to penetrate the insulating layer in the thickness direction; A second forming step, after forming the first organic film, forming a second organic film on the inner wall surface of the through hole; a removing step of removing the first organic film after forming the second organic film; and a plating step of forming a metal layer by a plating process inside the through hole after removing the first organic film, The second organic film is formed using a polymer (I) having a first functional group capable of interacting with a group of the insulating layer on a surface layer, and having a functional group capable of forming a bond with a metal contained in the metal layer. second functional group. The method for producing a multilayer wiring board according to claim 1, wherein the polymer (I) has the first functional group and a crosslinkable group, The second organic film is a laminated film of the first layer and the second layer, the first layer is formed on the inner wall using the polymer (I), and the second layer is made of The polymer (II) in which the crosslinkable group forms a bonded third functional group is formed on the first layer. The method for manufacturing a multilayer wiring board according to claim 2, wherein the crosslinkable group is at least one selected from the group consisting of an acid anhydride group and a protected carboxyl group. The method for manufacturing a multilayer wiring board according to Claim 2 or Claim 3, wherein the third functional group is at least one of an oxazoline group and an epoxy group. The method for producing a multilayer wiring board according to any one of claim 2 to claim 4, wherein the polymer (II) has a structural unit derived from a monomer having an aromatic ring. The method of manufacturing a multilayer wiring board according to claim 1, wherein the second organic film is a single-layer film. The method for manufacturing a multilayer wiring substrate according to any one of claim 1 to claim 6, wherein the insulating layer has a surface layer with a silicon atom bonded to a silicon atom selected from a hydrogen atom, a hydroxyl group, a side oxygen group, and -N (R 1 ) At least one group of groups consisting of (R ¹ ) ₂ , wherein R ¹ are each independently a hydrogen atom or a monovalent organic group with 1 to 20 carbons, and the first functional group is selected from the group consisting of silanol At least one of the group consisting of alkoxysilyl group, alkoxysilyl group, -N(Si(R ⁵ ) ₃ ) ₂ , amino group, hydroxyl group, and conjugated nitrogen-containing heterocyclic group, wherein R ⁵ are independently Ground is a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms. The method for producing a multilayer wiring board according to any one of claim 1 to claim 7, wherein the polymer (I) has a structural unit derived from a monomer having an aromatic ring. The method for manufacturing a multilayer wiring board as described in any one of claim 1 to claim 8, wherein the first organic film is made of , a phosphonate group, a thiol group, a disulfide group, and a group consisting of a carbon-carbon unsaturated bond-containing group. The manufacturing method of any one of claim 1 to claim 9, wherein the wiring contains Cu or Co. The method for manufacturing a multilayer wiring board according to any one of claim 1 to claim 10, wherein the plating step is a step of performing electroless plating inside the through hole. The method of manufacturing a multilayer wiring board according to any one of claim 1 to claim 11, wherein the metal layer contains Cu or Co. The method for manufacturing a multilayer wiring substrate according to any one of claim 1 to claim 12 further includes the following steps: using N on the substrate surface before the first organic film is formed in the first forming step ₂ /H ₂ gas or O ₂ gas for ashing treatment. The method for manufacturing a multilayer wiring board as described in any one of claim ₁ to claim 13 further includes the following steps: making the A treatment solution of tetramethylammonium fluoride (TMAF) or citric acid is in contact with the surface of the substrate before the first organic film is formed by the first forming step. The method for manufacturing a multilayer wiring board according to any one of claim 1 to claim 14, wherein the removing step is to remove the first organic film by contacting the first organic film with an organic acid step, It further includes the step of contacting the surface of the substrate after the removing step with an alkali. A set for forming a laminated film used for pretreatment for forming a metal layer inside a through-hole of a multilayer wiring board by plating treatment, the set for forming a laminated film comprising: a polymer (I) having A functional group and a crosslinking group, the functional group can be bonded to a silicon atom with at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, a side oxygen group, and -N(R ¹ ) ₂ group interaction, wherein R ¹ are each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbons; and the polymer (II) has a functional group capable of forming a bond with the crosslinkable group. A composition for pretreatment for forming a metal layer inside a through-hole of a multilayer wiring board by plating, the composition comprising: a polymer having a functional group, and a polymer selected from an acid anhydride group and a At least one crosslinking group in the group consisting of protected carboxyl groups, the functional group can be bonded to a silicon atom selected from a hydrogen atom, a hydroxyl group, a side oxygen group, and -N(R ¹ ) ₂ Group interaction of at least one of the group consisting of, wherein R ¹ are each independently a hydrogen atom or a monovalent organic group with 1 to 20 carbons; and a solvent. The composition according to claim 17, wherein the polymer has a structural unit represented by the following formula (1) as a structural unit having the functional group,

In formula (1), R is a hydrogen atom, a monovalent hydrocarbon group with 1 to 5 carbons, a halogen atom, or a halogenated alkyl group with 1 to 5 carbons; R ² is a monovalent hydrocarbon group with 1 to 5 carbons; R ³ is an alkoxy group with 1 to 5 carbons; R ¹⁰ is a monovalent hydrocarbon group with 1 to 5 carbons, a halogenated alkyl group with 1 to 5 carbons, an alkoxy group with 1 to 5 carbons or a halogen atom; a is 0 An integer of ~2, b is an integer of 1 to 3; wherein, a+b=3; c is an integer of 0 to 4; when a is 2, multiple R ² are the same or different; b is 2 or 3 In the case of , multiple R ^3s are the same or different; when c is 2 or more, multiple R ^10s are the same or different.

Images