Method for manufacturing multilayer wiring board, kit for forming laminated film, and composition

Abstract

To provide a method for manufacturing a multilayer wiring board that can form an organic film with excellent adhesion to the plating layer on the inner surface of a via, and is excellent in metal embedding into the via by plating process.SOLUTION: The method for manufacturing a multilayer wiring board has a film forming process for forming an organic film 17 on a wiring 13 and on an inner wall surface 12 inside a via 11 formed in an insulating layer 14 provided on the wiring 13, and a plating process for forming a plating layer 18 inside the via 11 after the organic film 17 is formed. The organic film 17 is formed using a polymer (I) having a first functional group that can interact with a group that the insulating layer 14 has on the surface layer, and has a second functional group that can form a bond with the metal in the plating layer 18.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a multilayer wiring board, a kit for forming a laminated film, and a composition.

Background Art

[0002] In the semiconductor manufacturing process, as a method for forming multilayer wiring on a semiconductor wafer, a technique is known in which a via is formed in an interlayer insulating film and metal is embedded inside the via by plating treatment. In this technique, in order to suppress the diffusion of the metal filled inside the via into the insulating film, a barrier film is formed on the inner surface of the via before embedding the metal (see, for example, Patent Document 1).

[0003] Patent Document 1 discloses that a barrier film composed of a Co-W-B alloy or the like is formed on the bottom surface of a via in a wafer in which a via is formed in an insulating film on a wiring, and then an electroless plating film is formed from the bottom surface of the via using the barrier film exposed on the bottom surface of the via as a catalyst to embed metal inside the via.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] In semiconductor manufacturing processes, further miniaturization is being considered in order to meet requirements such as increased capacity and speed. Also, attempts are being made to develop new materials to achieve fine processing. Regarding the barrier film formed inside the via in the multilayer wiring formation process, a new material with even higher performance is required in place of the conventional metal layer. As the performance of the barrier film, in addition to the adhesion to the insulating film, it has excellent adhesion to the metal embedded in the via, and there are few voids and seams generated in the metal embedded in the via, and it has excellent metal embedding properties, etc.

[0006] The present invention has been made in view of the above problems, and a main object thereof is to provide a method for manufacturing a multilayer wiring board capable of forming an organic film excellent in adhesion to a plating layer on the inner surface of a via and having excellent metal embedding properties in the via by a plating process.

Means for Solving the Problems

[0007] In order to solve the above problems, the following means are provided according to the present invention.

[0008] [1] A method for manufacturing a multilayer wiring board, comprising: a film forming step of forming an organic film on the wiring and the inner wall surface inside the via formed so as to penetrate the insulating layer in the thickness direction of the insulating layer provided on the wiring; and a plating step of forming a metal layer by plating inside the via after forming the organic film, wherein the organic film is formed using a polymer (I) having a first functional group capable of interacting with a group on the surface layer of the insulating layer, and having a second functional group capable of forming a bond with a metal contained in the metal layer. A method for manufacturing a multilayer wiring board.

[0009] [2] A laminate film forming kit used for pretreatment for forming a metal layer by plating inside a via in a multilayer wiring board including wiring containing one or more selected from the group consisting of Co, Ni, W, and Ru, the kit comprising a crosslinkable group and a silicon atom having a hydrogen atom, a hydroxyl group, an oxo group, and -N(R 1 ) 2 (However, R 1Each independently is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. A functional group (excluding the crosslinkable group) capable of interacting with a group to which at least one selected from the group consisting of) is bonded, and a polymer (I) having, a polymer (II) having a functional group capable of forming a bond with the crosslinkable group, a laminate film forming kit.

[0010] [3] A composition used for pretreatment for forming a metal layer by plating inside a via in a multilayer wiring board provided with a wiring containing one or more selected from the group consisting of Co, Ni, W, and Ru, and at least one selected from the group consisting of an acid anhydride group and a protected carboxyl group A crosslinkable group, and a hydrogen atom, a hydroxyl group, an oxo group, and -N(R 1 ) 2 (However, R 1 Each independently is a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) A functional group (excluding the crosslinkable group) capable of interacting with a group to which at least one selected from the group consisting of) is bonded, and a polymer, a solvent, a composition containing. [Advantages of the Invention]

[0011] According to the production method of the present invention, an organic film excellent in adhesion to a plating layer can be formed on the inner surface of the via (on the wiring and the inner wall surface of the via). Further, the via having an organic film formed on the inner surface by the production method of the present invention is excellent in the embedding property of the metal by the plating treatment. According to the production method of the present invention, an organic film exhibiting such excellent characteristics can be obtained by a simple operation such as coating. [Brief Description of the Drawings]

[0012]

Figure 1

[0013] Hereinafter, matters related to the embodiments will be described in detail. In this specification, a numerical range described using "~" means that the numerical values described before and after "~" are included as the lower limit value and the upper limit value, respectively.

[0014] 《Method for Manufacturing Multilayer Wiring Substrate》 The manufacturing method of the present disclosure (hereinafter, also referred to as "the present manufacturing method") includes, as a pretreatment for the step of embedding metal inside a via in a wiring formation step of forming multilayer wiring on a substrate to obtain a multilayer wiring substrate, a step of performing a process of forming an organic film on the inner surface of the via provided in the insulating layer on the wiring. The organic film on the inner surface of the via is formed using a surface modification composition that is an organic material. The organic film formed on the inner surface of the via then has a barrier function of suppressing the diffusion of the metal embedded inside the via into the insulating layer by plating treatment. Specifically, the present manufacturing method includes the following film formation step and plating step. (Film Formation Step) A step of forming an organic film on the wiring and the inner wall surface inside the via formed in the insulating layer on the wiring. (Plating Step) A step of forming a plating layer inside the via after forming the organic film. Hereinafter, the details of the present manufacturing method will be described with reference to the drawings as appropriate.

[0015] Figs. 1(a) to 1(d) are schematic diagrams showing a series of steps when forming an organic film inside a via provided in the wiring substrate 10. Note that Figs. 1(a) to 1(d) show a partially enlarged view of the via 11 and its peripheral portion. Fig. 1(a) represents a state before an organic film is formed on the wiring 11 inside the via and the inner wall surface 12 using a surface modification composition.

[0016] As shown in Fig. 1(a), the wiring board 10 includes wiring 13. The wiring 13 is formed of a metal material. In this embodiment, the wiring 13 is formed of a conductive material containing one or more selected from the group consisting of cobalt (Co), nickel (Ni), tungsten (W), and ruthenium (Ru). Note that the metal contained in the wiring 13 may be a single metal, an alloy, a conductive nitride, a metal oxide, or the like. An insulating layer 14 is provided adjacent to the wiring 13 above the wiring 13.

[0017] The insulating layer 14 is formed of a silicon-containing material. The insulating layer 14 preferably has, on its surface, a group (hereinafter also referred to as a "silicon-containing group") to which at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an oxo group, and -N(R 1 ) 2 (wherein each R 1 is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms. The same applies hereinafter) is bonded. Specific examples of the silicon-containing group include, for example, Si-H, Si-OH (silanol group), Si=O, Si-N(R 1 ) 2 , etc. Examples of the material constituting the insulating layer 14 include semiconductor materials such as silicon oxide, silicon nitride, and silicon oxynitride (SiO 2 , SiOC, Si 3 N 4 , SiNx, SiON, etc.).

[0018] A via 11 is provided in the insulating layer 14. The via 11 is formed in the insulating layer 14 so as to penetrate the insulating layer 14 in the thickness direction. As a result, at the bottom 15 inside the via, the wiring 13 is exposed. Note that the method of forming the via 11 in the insulating layer 14 is not particularly limited, and a conventionally known method such as dry etching can be appropriately employed.

[0019] In the wiring board 10 where plating embedding is performed by this manufacturing method, it is preferable that a treatment for surface modification of the wiring board 10 (more specifically, surface modification of the insulating layer 14) is performed (substrate modification step). The treatment for substrate modification may be a dry type or a wet type. In the case of the dry type, the substrate modification treatment performed in this manufacturing method is N 2 / H 2 gas or O 2 ashing treatment with gas is preferable. In the case of the wet type, from the viewpoint of improving the coatability and adhesion of the surface modification composition, the substrate modification treatment to be applied is preferably a treatment in which a treatment liquid containing tetramethylammonium hydroxide (TMAH), hydrogen fluoride (HF), ammonia (NH 3 ), tetramethylammonium fluoride (TMAF), or citric acid is brought into contact.

[0020] <Film formation step> In this manufacturing method, in the film formation step, an organic film 17 is formed on the exposed wiring 13 and the inner wall surface 12 at the bottom 15 of the via 11 (see FIGS. 1(b) and (c)). The organic film 17 is a film that covers the bottom 15 and the inner wall surface 12 of the via 11, and is directly formed on the wiring 13 at the bottom 15 and the inner wall surface 12 using a polymer composition containing a polymer and a solvent. Specifically, it is preferable to form the organic film 17 on the bottom 15 and the inner wall surface 12 of the via 11 by a method including the following steps 1 and 2. (Step 1) A step of applying a polymer composition to the surface of the wiring board 10. (Step 2) A step of removing the solvent from the polymer composition applied to the substrate surface.

[0021] ·Step 1: Coating step In this step, the polymer composition is applied to at least the inner surface of the via 11 in the wiring board 10. Examples of the method of applying the polymer composition include a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, an inkjet method, and the like. Among these, it is preferable to apply the composition by a spin coating method, a slit die coating method, or a bar coating method.

[0022] On the surface of the substrate to which the polymer composition is applied, for example, H 2 , N 2 and H 2 mixed gas with, O 2 gas, etc., plasma treatment using gas, etc., or pretreatment such as wet modification treatment for hydrophilizing the substrate surface may be performed. By performing plasma treatment on the surface of the substrate to which the polymer composition is applied, it is possible to sufficiently generate at least any one of Si-OH, Si-H, and Si-N on the coating surface of the polymer composition, which is preferable in that it can improve the coatability and sufficiently promote the surface modification by the polymer composition.

[0023] · Step 2: Solvent removal step In this step, preferably, heat treatment is performed to remove the solvent from the polymer composition applied to the substrate surface. Thereby, the organic film 17 is formed on the wiring 13 and the inner wall surface 12 inside the via. The heat treatment can be performed using a heating device such as an oven or a hot plate. When performing the heat treatment, the heating temperature is preferably 80°C or higher, more preferably 100°C or higher, and still more preferably 120°C or higher. Also, the heating temperature is preferably 300°C or lower, more preferably 280°C or lower. The heating time is preferably 0.5 to 30 minutes, more preferably 1 to 20 minutes. The thickness of the formed organic film 17 is, for example, 1 to 10 nm, preferably 1 to 5 nm, and more preferably 1 to 3 nm.

[0024] In addition, in order to remove unadsorbed polymers, etc., a rinsing treatment such as washing with an organic solvent or running water washing may be performed on the surface of the substrate on which the organic film is formed. Examples of the organic solvent used as the rinsing liquid include propylene glycol monomethyl ether acetate, isopropanol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, and a mixed solvent of two or more of these.

[0025] The organic film 17 has a functional group (hereinafter also referred to as "functional group FM") that can form a bond with the metal contained in the plating layer 18 (see FIG. 1(d)) formed inside the via by the plating process described later. The functional group FM is preferably a functional group capable of forming a coordination bond with a metal element, and examples thereof include a carboxy group, a sulfide group, a dithiocarbonyl group (-C(=S)-S-), a thiourethane group (-NR 20 -C(=O)-S-), and a thioamide group (-C(=S)-NR 20 -), and at least one selected from the group consisting of these is preferable. Note that the functional group FM corresponds to the "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 monovalent hydrocarbon groups having 1 to 10 carbon atoms.

[0026] One embodiment of the organic film 17 is a multilayer structure. Specifically, as shown in FIGS. 1(b) and 1(c), the organic film 17 is a laminated film including a first layer 17a formed on the inner wall surface 12 and a second layer 17b formed on the first layer 17a. The first layer 17a is formed on the wiring 13 inside the via and the inner wall surface 12 by using a composition (hereinafter also referred to as "first composition") including a polymer (I) having a functional group (hereinafter also referred to as "functional group F1") that can interact with the group on the surface layer of the insulating layer 14 and a solvent (see FIG. 1(b)). Further, the second layer 17b is formed on the first layer 17a by using a composition (hereinafter also referred to as "second composition") including a polymer (II) and a solvent (see FIG. 1(c)).

[0027] In addition, in order to form the laminated film including the first layer 17a and the second layer 17b, first, the first layer 17a is formed by steps 1 and 2 using the first composition, and then the steps 1 and 2 are performed again using the second composition to form the second layer 17b.

[0028] When the organic film 17 has a multilayer structure, examples of the method for obtaining the organic film 17 having the functional group FM include using, as the polymer (I), a polymer having the functional group FM or a functional group that generates the functional group FM by heat (hereinafter also referred to as "functional group FP"); using, as the polymer (II), a polymer having the functional group FM or the functional group FP; a method of generating the functional group FM by the reaction between the functional group of the polymer (I) and the functional group of the polymer (II) during film formation; and the like.

[0029] Another aspect of the organic film 17 is a single-layer structure. When the organic film 17 is a single-layer film, the organic film 17 is formed using a polymer (I) that is a functional group F1 capable of interacting with the group (silicon-containing group) on the surface layer of the insulating layer 14. In this case, the organic film 17 preferably contains a polymer (hereinafter also referred to as "polymer (III)") having the functional group F1 and a functional group FM capable of forming a bond with the metal contained in the plating layer 18 or a functional group FP that generates the functional group FM by heat, and a solvent (hereinafter also referred to as "third composition"), and is formed on the bottom 15 and the inner wall surface 12 by performing the above steps 1 and 2.

[0030] <Plating process> In this manufacturing method, after forming the organic film 17 on the bottom 15 and the inner wall surface 12 of the via 11, subsequently, a plating treatment is performed while leaving the organic film 17 to form a plating layer 18 as a metal layer inside the via (see Fig. 1(d)). The plating method is not particularly limited, and known electroplating, electroless plating, fusion plating, vacuum plating, vapor plating, etc. can be adopted. When applied to a semiconductor manufacturing process, among these, electroplating or electroless plating is preferably used, and electroless plating is particularly preferred. Specifically, a method of forming an electroless plating layer by using the exposed wiring 13 on the bottom 15 as a catalyst and bottom-up from the bottom 15 can be mentioned. Note that after the plating treatment, a planarization treatment of the substrate surface or the like may be performed as necessary.

[0031] 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 materials of the wiring 13. Among these, the plating layer 18 preferably contains one or more selected from the group consisting of Co, Ni, W, and Ru.

[0032] The plating layer 18 formed in this way has few voids and seams, and thus a highly reliable multilayer wiring board can be obtained.

[0033] Next, the modifying compositions (the first composition, the second composition, and the third composition) used in this manufacturing method will be described. As each component constituting the composition, unless otherwise specified, one kind may be used alone or two or more kinds may be used in combination.

[0034] <The First Composition> The first composition is a polymer composition used to form the first layer 17a on the bottom 15 and the inner wall surface 12 of the via 11. This first composition contains a polymer (I) having a functional group (functional group F1) capable of interacting with the groups on the surface layer of the insulating layer 14 and a solvent. Note that the functional group F1 corresponds to the "first functional group". In this specification, "interaction" means forming a chemical bond between molecules or a physical force acting between molecules, and is also referred to as "adsorption". This interaction includes covalent bonds, ionic bonds, and metal bonds, as well as coordination bonds, hydrogen bonds, and van der Waals forces.

[0035] 〔Polymer (I)〕 ·Functional Group F1 The functional group F1 possessed by the polymer (I) is preferably a functional group capable of interacting with a group (silicon-containing group) to which at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an oxo group, and -N(R 1 ) 2 is bonded to a silicon atom. More specifically, the functional group F1 is a silanol group, an alkoxysilyl group, a halogenated silyl group, -N(Si(R 5 ) 3 ) 2, it is preferably at least one selected from the group consisting of an amino group, a hydroxyl group, a conjugated nitrogen-containing heterocyclic group, an acid anhydride group, a carboxy group, and a protected carboxy group. Here, R 5 is each independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

[0036] When the functional group F1 is the group “-N(Si(R 5 )) 3 ) 2 ”, examples of the monovalent organic group having 1 to 10 carbon atoms for R 5 include monovalent hydrocarbon groups having 1 to 10 carbon atoms. The conjugated nitrogen-containing heterocyclic group is a group having a conjugated nitrogen-containing heterocycle, and specifically includes groups having ring structures such as a carbazole ring, a benzocarbazole ring, a dibenzocarbazole ring, an indole ring, a pyrrole ring, an imidazole ring, a pyridine ring, a triazole ring, and a triazine ring. Note that the conjugated nitrogen-containing heterocyclic group may have a substituent on the heterocyclic moiety. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, a halogen atom, and the like.

[0037] The functional group F1 is more preferably at least one selected from the group consisting of a silanol group, an alkoxysilyl group, and a conjugated nitrogen-containing heterocyclic group in terms of having high affinity with the silicon-containing group on the surface layer of the insulating layer 14 and being able to improve the storage stability of the first composition, and is more preferably further including an alkoxysilyl group in terms of showing high adsorptivity to silicon oxide and being able to further enhance the effect of improving the adhesion between the first layer 17a and the insulating layer 14. Also, in terms of showing crosslinkability while interacting with the silicon-containing group on the surface layer of the insulating layer 14, the functional group F1 is preferably an acid anhydride group, a carboxy group, or a protected carboxy group, and more preferably an acid anhydride group.

[0038] ·Crosslinkable group The polymer (I) preferably has a crosslinkable group. Here, in the present specification, the "crosslinkable group" refers to a group that reacts with the same or different functional groups by heat application or the like to form a covalent bond. However, the crosslinkable group possessed by the polymer (I) is a group different from the functional group F1 possessed by the polymer (I). When the polymer (I) has a crosslinkable group, the polymer (I) preferably has, as the functional group F1, a group that interacts with the group on the surface layer of the insulating layer 14 and does not exhibit crosslinkability. The fact that the polymer (I) has a crosslinkable group is preferable in that an organic film having high heat resistance and dielectric breakdown resistance can be formed. Further, a crosslinked structure can be formed between the first layer 17a and the second layer 17b by using the crosslinkable group possessed by the polymer (I), and the effect of improving the adhesion of the organic film 17 can be enhanced. 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, a carboxy group, a protected carboxy group, and the like.

[0039] Note that the crosslinkable group is a group different from the functional group F1. Therefore, when the polymer (I) has an acid anhydride group, a carboxy group, or a protected carboxy group as the functional group F1, the crosslinkable group possessed by the polymer (I) is a group different from the acid anhydride group, the carboxy group, and the protected carboxy group (for example, 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). Further, when the polymer (I) has a group different from the acid anhydride group, the carboxy group, and the protected carboxy group as the functional group F1, the crosslinkable group possessed by the polymer (I) may be an acid anhydride group, a carboxy group, or a protected carboxy group.

[0040] Specific examples of the crosslinkable group include, as a group having a carbon-carbon unsaturated bond, for example, a vinyl group, a vinyloxy group, an allyl group, a (meth)acryloyl group, a vinylphenyl group, etc.; as a 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 a cyclic ether group, for example, an oxiranyl group, an oxetanyl group, etc.; as a protected carboxy group, a group “-COOR 9 ” (however, R 9 is a thermally dissociable group.), etc. can be respectively cited.

[0041] Specific examples of the group “-COOR 9 ” include, for example, a structure represented by the following formula (X-1), an acetal ester structure of a carboxylic acid, a ketal structure of a carboxylic acid, etc. can be respectively cited.

Chemical formula

[0042] Specific examples of the structure represented by the above formula (X-1) include a tert-butoxycarbonyl group, a 1-cyclopentylethoxycarbonyl group, a 1-cyclohexylethoxycarbonyl group, a 1-norbornylethoxycarbonyl group, a 1-phenylethoxycarbonyl group, a 1-(1-naphthyl)ethoxycarbonyl group, a 1-benzylethoxycarbonyl group, a 1-phenethyl ethoxycarbonyl group, and the like.

[0043] Specific examples of the acetal ester structure of a carboxylic acid include, for example, a 1-methoxyethoxycarbonyl group, a 1-ethoxyethoxycarbonyl group, a 1-propoxyethoxycarbonyl group, a 1-butoxyethoxycarbonyl group, a 1-cyclohexyloxyethoxycarbonyl group, a 2-tetrahydropyranyloxycarbonyl group, a 1-phenoxyethoxycarbonyl group, a 2-tetrahydrofuranyloxycarbonyl group, and the like.

[0044] Specific examples of the ketal ester structure of a carboxylic acid include a 1-methyl-1-methoxyethoxycarbonyl group, a 1-methyl-1-ethoxyethoxycarbonyl group, a 1-methyl-1-propoxyethoxycarbonyl group, a 1-methyl-1-butoxyethoxycarbonyl group, a 1-methyl-1-cyclohexyloxyethoxycarbonyl group, a 2-(2-methyltetrahydrofuranyl)oxycarbonyl group, a 2-(2-methyltetrahydropyranyl)oxycarbonyl group, a 1-methoxycyclopentyloxycarbonyl group, a 1-methoxycyclohexyloxycarbonyl group, and the like.

[0045] Among these, in terms of being able to enhance the effect of improving the adhesion to the metal contained in the plating layer 18 by generating the functional group FM by heat (preferably, heating during film formation), the crosslinkable group possessed by the polymer (I) is particularly preferably at least one selected from the group consisting of an acid anhydride group and a protected carboxy group. The polymer (I) particularly has a silanol group, an alkoxysilyl group, -N(Si(R 5 ) 3 ) 2It is preferable to have at least one selected from the group consisting of an amino group, a hydroxyl group, and a conjugated nitrogen-containing heterocyclic group, and at least one selected from the group consisting of an acid anhydride group and a protected carboxy group. Among them, in terms of high affinity with the silicon-containing group on the surface of the insulating layer 14 and the ability to improve the storage stability of the first composition, the polymer (I) preferably has at least one selected from the group consisting of a silanol group, an alkoxysilyl group, and a conjugated nitrogen-containing heterocyclic group, and more preferably has an alkoxysilyl group.

[0046] The main skeleton of the polymer (I) is not particularly limited. In terms of excellent heat resistance, high degree of freedom in monomer selection, and relatively easy introduction of the functional group F1, the polymer (I) is preferably a polymer obtained using a monomer having a polymerizable carbon-carbon unsaturated bond. The polymer (I) preferably contains a structural unit having a functional group F1, and more preferably contains a structural unit having a functional group F1 (excluding a crosslinkable group) (hereinafter also referred to as "structural unit U1") and a structural unit having a crosslinkable group (hereinafter also referred to as "structural unit U2").

[0047] When the polymer (I) has a structural unit U1 and a structural unit U2, as the monomer that gives the structural unit U1, a monomer having at least one selected from the group consisting of a silanol group, an alkoxysilyl group, -N(Si(R 5 ) 3 ) 2 , an amino group, a hydroxyl group, and a conjugated nitrogen-containing heterocyclic group (wherein each R 5 is independently a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms) can be preferably used.

[0048] Specific examples thereof include, as the monomer having a silanol group, dimethoxyhydroxysilylstyrene, diethoxyhydroxysilylstyrene, dimethylhydroxysilylstyrene, diethylhydroxystyrene, etc.; As monomers having an alkoxysilyl group, 4-dimethylmethoxysilylstyrene, 4-diethylmethoxystyrene, 4-methylethylmethoxysilylstyrene, 3-(meth)acryloyloxypropyldimethylmethoxysilylstyrene, 3-(meth)acryloyloxypropyldiethylmethoxysilylstyrene, etc.; As monomers having a group “-N(Si(R 5 ) 3 ) 2 ”, compounds represented by each of the following formulas (UA-1) to (UA-3), etc.; As monomers having an amino group, aminomethyl (meth)acrylate, 2-aminoethyl (meth)acrylate, 3-aminopropyl (meth)acrylate, etc.; As monomers having a hydroxyl group, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, etc.; As monomers 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, etc. can be respectively mentioned. [Chemical formula]

[0049] In the polymer (I), the content of the structural unit U1 is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 5 mol% or more, based on all the structural units constituting the polymer (I). By setting the content of the structural unit U1 to 1 mol% or more, it is suitable in that the adhesion between the organic film 17 and the insulating layer 14 can be made sufficiently high. Further, from the viewpoint of ensuring good substrate selectivity, the content of the structural unit U1 is preferably 30 mol% or less, more preferably 25 mol% or less, and still more preferably 20 mol% or less, based on all the structural units constituting the polymer (I). When the content of the structural unit U1 is within the above range, the functional group F1 is evenly introduced into the polymer (I), so that unevenness of the functional group F1 in the coating film can be suppressed, and it is preferable in that it can be used as a permanent film.

[0050] Examples of the structural unit U2 include structural units represented by the following formulas (U2-1) to (U2-4).

Chemical formula

[0051] When the polymer (I) contains the structural unit U2, the content of the structural unit U2 is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more based on all the structural units constituting the polymer (I). By setting the content of the structural unit U2 to 5 mol% or more, a crosslinked structure can be sufficiently introduced into the organic film 17, which is preferable in terms of enhancing the dielectric breakdown resistance. Further, from the viewpoint of ensuring the toughness of the organic film 17, the content of the structural unit U2 is preferably 70 mol% or less, more preferably 60 mol% or less based on all the structural units constituting the polymer (I).

[0052] Among the above, the polymer (I) is preferably a polymer having a functional group F1 (excluding an acid anhydride group and a protected carboxy group) and at least one crosslinkable group selected from the group consisting of an acid anhydride group and a protected carboxy group, and particularly preferably contains a structural unit represented by the following formula (1) (hereinafter also referred to as "structural unit U3") as the structural unit having the functional group F1.

Chemical formula

[0053] In the above formula (1), R 2Examples of the monovalent hydrocarbon group include an alkyl group and a cycloalkyl group. Among these, R 2 is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group.

[0054] When the polymer (I) contains the structural unit U3, the content of the structural unit U3 is preferably 1 mol% or more, more preferably 2 mol% or more, and still more preferably 5 mol% or more with respect to all the structural units constituting the polymer (I). By setting the content of the structural unit U3 to 1 mol% or more, it is preferable in terms of being able to enhance the effect of improving the adhesion between the insulating layer 14 and the organic film 17. Further, from the viewpoint of ensuring good substrate selectivity, the content of the structural unit U3 is preferably 40 mol% or less, more preferably 30 mol% or less with respect to all the structural units constituting the polymer (I).

[0055] The polymer (I) may further contain a structural unit different from the structural units U1 to U3 (hereinafter also referred to as "other structural unit U4") together with the structural unit U1. The other structural unit U4 only needs to be copolymerizable with the structural unit U1 and is not particularly limited. The monomer that gives the other structural unit U4 is preferably a monomer having a polymerizable carbon-carbon unsaturated bond. Specifically, for example, at least one monomer selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters 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, alkenes, vinylcycloalkanes, cycloalkenes, and unsaturated dicarboxylic acid dialkyl ester compounds can be mentioned. Further, as the monomer that gives the other structural unit U4, a monomer having a functional group FM and different from the monomer that gives the structural unit U2 may be used. In the present specification, "(meth)acryloyl" means including acryloyl and methacryloyl. "(meth)acrylic" means including acrylic and methacrylic.

[0056] Specific examples of the above monomers include, as (meth)acrylic acid alkyl esters, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-lauryl (meth)acrylate, n-stearyl (meth)acrylate, etc.; As (meth)acrylic acid esters having an alicyclic structure, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 decane-8-yl, tricyclo[5.2.1.0 2,5 decane-8-yloxyethyl, isobornyl (meth)acrylate, etc.; As (meth)acrylic acid esters having an aromatic ring structure, phenyl (meth)acrylate, benzyl (meth)acrylate, etc.; As aromatic vinyl compounds, styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 5-t-butyl-2-methylstyrene, divinylbenzene, trivinylbenzene, t-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-t-butylstyrene, 3-t-butylstyrene, 4-t-butylstyrene, diphenylethylene, methyl (4-vinylphenyl)sulfane, ethyl (4-vinylphenyl)sulfane, vinylnaphthalene, etc.; Examples of N-substituted maleimide compounds include N-cyclohexylmaleimide, N-cyclopentylmaleimide, N-(2-methylcyclohexyl)maleimide, N-(4-methylcyclohexyl)maleimide, N-(4-ethylcyclohexyl)maleimide, N-(2,6-dimethylcyclohexyl)maleimide, N-norbornylmaleimide, N-tricyclodecylmaleimide, 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-dioxan-5-ylmethyl (meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl (meth)acrylate, 2-(meth)acryloxymethyl-1,4,6-trioxaspiro[4,6]undecane, (γ-butyrolactone-2-yl) (meth)acrylate, glycerin carbonate (meth)acrylate, (γ-lactam-2-yl) (meth)acrylate, N-(meth)acryloxyethylhexahydrophthalimide, N-vinyl-2-pyrrolidone, vinylpyridine, etc.; Examples of conjugated diene compounds include 1,3-butadiene, isoprene, etc.; examples of nitrogen-containing vinyl compounds include 2-(dimethylamino)ethyl (meth)acrylate, etc.; Examples of alkenes include propene, butene, pentene, etc.; Examples of vinylcycloalkanes include vinylcyclopentane, vinylcyclohexane, etc.; Examples of cycloalkenes include cyclopentene, cyclohexene, etc.; Examples of unsaturated dicarboxylic acid dialkyl ester compounds include diethyl itaconate, etc., and each can be listed accordingly.

[0057] Among the monomers constituting the polymer (I), at least one selected from the group consisting of (meth)acrylic acid alkyl esters, (meth)acrylic acid esters having an alicyclic structure, (meth)acrylic acid esters having an aromatic ring structure, aromatic vinyl compounds, conjugated diene compounds, alkenes, vinylcycloalkanes, and cycloalkenes is preferable.

[0058] In the polymer (I), the content of the other structural unit U4 is preferably 80 mol% or less, more preferably 70 mol% or less, and still more preferably 60 mol% or less, based on all the structural units constituting the polymer (I).

[0059] From the viewpoint of obtaining an organic film with high heat resistance, the polymer (I) preferably further contains a structural unit (hereinafter also referred to as "structural unit U5") derived from a monomer having an aromatic ring. The monomer that gives the structural unit U5 may be one of the monomers that give the structural units U1 to U4, or two or more of them. As specific examples of the monomer that gives the structural unit U5, a monomer having an aromatic ring can be arbitrarily selected from the monomers exemplified as the monomers that give the structural units U1 to U4. Note that the aromatic ring of the structural unit U5 may have a substituent on the ring portion. Examples of the substituent include a monovalent hydrocarbon group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioalkoxy group having 1 to 5 carbon atoms (-SR 12 , provided that R 12 is an alkyl group having 1 to 5 carbon atoms) or a halogen atom, etc.

[0060] In the polymer (I), the content of the structural unit U5 is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more, based on all the structural units contained in the polymer (I). Also, 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, based on all the structural units contained in the polymer (I).

[0061] The method for synthesizing the polymer (I) is not particularly limited. For example, when obtaining the polymer (I) by polymerizing a monomer having a polymerizable unsaturated carbon-carbon bond, using the above-described monomer, in a suitable solvent, in the presence of a polymerization initiator, etc., the polymer (I) can be produced according to known methods such as radical polymerization and anionic polymerization. Among these, in the case of radical polymerization, it is preferable in that the synthesis of the polymer (I) can be easily carried out and the cost of the composition can be reduced. The polymerization mode for obtaining the polymer (I) is not particularly limited, and examples include random polymerization and block (co)polymerization.

[0062] In the case of radical polymerization, examples of the polymerization initiator include azo compounds such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(isobutyrate), and 2,2'-dimethylazobis(2-methylpropionate). The amount of the polymerization initiator used is preferably 0.01 to 30 parts by mass with respect to 100 parts by mass of the total amount of the monomers used in the reaction. Examples of the polymerization solvent include alcohols, ethers, ketones, esters, hydrocarbons, etc. The amount of the polymerization solvent used is preferably such that the total amount of the monomers used in the reaction is 0.1 to 60% by mass with respect to the total amount of the reaction solution.

[0063] In the polymerization, the reaction temperature is usually 30°C to 180°C. The reaction time varies depending on the types of the polymerization initiator and the monomer and the reaction temperature, but is usually 0.5 to 10 hours. The polymer obtained by the above reaction may be used for the preparation of the composition while being dissolved in the reaction solution, or may be used for the preparation of the composition after being isolated from the reaction solution. The isolation of the polymer can be carried out by known isolation methods such as a method of pouring the reaction solution into a large amount of poor solvent and drying the precipitate obtained thereby under reduced pressure, and a method of distilling off the reaction solution under reduced pressure using an evaporator.

[0064] Regarding the polymer (I), the weight average molecular weight (Mw) in terms of polystyrene by GPC is preferably 1,000 or more. When Mw is 1,000 or more, it is preferable in that an organic film having sufficiently high heat resistance, chemical resistance, etc. can be obtained. Mw is more preferably 2,000 or more, and still more preferably 3,000 or more. Also, from the viewpoint of improving the film-forming property, the Mw of the polymer (I) is preferably 10,000 or less, more preferably 9,000 or less, and still more preferably 8,000 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, and still more preferably 2.5 or less.

[0065] 〔Solvent〕 The first composition is preferably a liquid composition in which the polymer (I) is dissolved or dispersed in a solvent. The solvent used for preparing the first composition is preferably an organic solvent that can dissolve the polymer (I) and does not react with each component. Examples of such organic solvents include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like.

[0066] Specific examples of these include, as alcohol solvents, aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as 4-methyl-2-pentanol and n-hexanol; alicyclic monoalcohol solvents having 3 to 18 carbon atoms such as cyclohexanol; polyhydric alcohol solvents having 2 to 18 carbon atoms such as 1,2-propylene glycol; and polyhydric alcohol partial ether solvents having 3 to 19 carbon atoms such as propylene glycol monomethyl ether. Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diisoamyl ether, dihexyl ether, and diheptyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; and aromatic ring-containing ether solvents such as diphenyl ether and anisole (methyl phenyl ether).

[0067] Examples of ketone solvents include chain ketone solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, diethyl ketone, methyl-iso-butyl ketone, 2-heptanone (methyl-n-pentyl ketone), ethyl-n-butyl ketone, methyl-n-hexyl ketone, di-iso-butyl ketone, trimethylnonanone, etc.; cyclic ketone solvents such as cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, methylcyclohexanone, etc.; 2,4-pentanedione, acetonylacetone, acetophenone, etc. Examples of amide solvents include cyclic amide solvents such as N,N'-dimethylimidazolidinone, N-methylpyrrolidone, etc.; chain amide solvents such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide, etc. Examples of ester solvents include monocarboxylic acid ester solvents such as n-butyl acetate, ethyl lactate, etc.; polyhydric alcohol carboxylate solvents such as propylene glycol acetate, etc.; polyhydric alcohol partial ether carboxylate solvents such as propylene glycol monomethyl ether acetate, etc.; lactone solvents such as γ-butyrolactone, δ-valerolactone, etc.; polycarboxylic acid diester solvents such as diethyl oxalate, etc.; carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, etc. Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents having 5 to 12 carbon atoms such as n-pentane, n-hexane, etc.; aromatic hydrocarbon solvents having 6 to 16 carbon atoms such as toluene, xylene, etc.

[0068] Among these, the solvent used for preparing the first composition is preferably at least one selected from the group consisting of alcohol solvents, ether solvents, ketone solvents, and ester solvents, and more preferably at least one selected from the group consisting of ketone solvents and ester solvents. Among them, from the viewpoint of solubility, it is preferable that the solvent is a mixed solvent containing a ketone solvent and an ester solvent. When the solvent is a mixed solvent containing a ketone solvent and an ester solvent, specifically, it is particularly preferable that the solvent is a mixed solvent containing at least one selected from the group consisting of acetone, methyl ethyl ketone, and methyl-n-propyl ketone and propylene glycol monomethyl ether acetate.

[0069] When a mixed solvent containing a ketone solvent and an ester solvent is used as the solvent, the ratio (mass ratio) of the ketone solvent (X) and the ester solvent (Y) is not particularly limited, but with respect to a total of 100 parts by mass (X + Y) of the ketone solvent and the ester solvent, it is preferable that the ester solvent (Y) is 20 to 95 parts by mass, and more preferably 30 to 90 parts by mass.

[0070] The amount of the polymer (I) contained in the first composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more with respect to 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 with a sufficient film thickness can be formed on the bottom 15 and the inner wall surface 12 of the via 11. Also, the content of the polymer (I) is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less with respect to 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 first composition does not become too high, and good coatability can be ensured.

[0071] 〔Other Components〕 In addition to the above-described polymer (I) and solvent, the first composition may further contain other components other than these. Examples of the other components include a polymer having no functional group F1, a surfactant (such as a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, etc.), an antioxidant, and the like. The blending amount of the other components can be appropriately selected according to each component as long as the effects of the present invention are not impaired.

[0072] The solid content concentration of the first composition (the ratio of the total mass of the 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 first composition is preferably in the range of 0.1 to 30% by mass. When the solid content concentration is 0.1% by mass or more, it is suitable in that a sufficient film thickness of the organic film can be ensured. Further, when the solid content concentration is 30% by mass or less, it is suitable in that the film thickness of the organic film does not become excessively large, and good coatability can be ensured by appropriately increasing the viscosity of the first composition. The solid content concentration of the first composition is more preferably 0.5 to 20% by mass, and still more preferably 0.7 to 10% by mass.

[0073] <The second composition> Next, each component contained in the second composition and other components blended as necessary will be described. The second composition is a polymer composition used for forming the second layer 17b of the organic film 17. When the polymer (I) has a crosslinkable group, the second composition preferably contains a polymer (II) having a functional group (hereinafter also referred to as "functional group F2") capable of forming a bond with the crosslinkable group of the polymer (I) and a solvent. By forming the organic film 17 as a laminated film of the first layer 17a and the second layer 17b and forming a crosslinked structure between the first layer 17a and the second layer 17b, an organic film excellent in heat resistance and dielectric breakdown resistance can be formed. Note that the functional group F2 corresponds to the "third functional group".

[0074] 〔Polymer (II)〕 · Functional group F2 The functional group F2 possessed by the polymer (II) may be any functional group that can react with the crosslinkable group possessed by the polymer (I) to form a bond, and is not particularly limited. In terms of being able to form an organic film excellent in adhesion to the plating layer 18 while maintaining good storage stability of the first composition and the second composition, the functional group F2 is preferably at least one of an oxazoline group and an epoxy group. In this specification, the "epoxy group" means including an oxiranyl group and an oxetanyl group.

[0075] Among them, in particular, it is preferable that the polymer (I) has at least one crosslinkable group selected from the group consisting of an acid anhydride group and a protected carboxy group, and the functional group F2 is at least one of an oxazoline group and an epoxy group. In this case, a crosslinked structure is formed by the reaction between the crosslinkable group possessed by the polymer (I) and the functional group F2, so that the dielectric breakdown resistance of the organic film 17 can be improved. Also, in the reaction between an acid anhydride group or a protected carboxy group and an oxazoline group, an amide group is generated, and it is considered that the dielectric breakdown resistance can be further improved by the interaction by the amide bond. Furthermore, when the polymer (I) has an acid anhydride group, it is suitable in that the adhesion to the plating layer 18 can be further improved by the carboxy group generated by the crosslinking reaction. The carboxy group generated by the reaction between the crosslinkable group possessed by the polymer (I) and the functional group F2 corresponds to the functional group FM (the second functional group).

[0076] In addition, when a protected carboxy group is introduced into the polymer (I) as a crosslinkable group to obtain an organic film 17 having a carboxy group as the functional group FM, by designing so that the number of crosslinkable groups possessed by the polymer (I) is larger than the number of functional groups F2 possessed by the polymer (II), the organic film 17 may have the functional group FM after the crosslinking reaction.

[0077] The main skeleton of the polymer (II) is not particularly limited. In terms of excellent heat resistance, a high degree of freedom in monomer selection, and the relatively easy introduction of the functional group F2, the polymer (II) is preferably a polymer obtained using a monomer having a polymerizable carbon-carbon unsaturated bond. The polymer (II) preferably contains a structural unit having a functional group F2 (hereinafter also referred to as "structural unit U6").

[0078] As the monomer that provides the structural unit U6, as the monomer having an epoxy group, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 2-(3,4-epoxycyclohexyl) ethyl (meth) acrylate, 3,4-epoxytricyclo[5.2.1.0 2,6 decyl (meth) acrylate, (3-methyloxetan-3-yl) methyl (meth) acrylate, 4-glycidylstyrene, 3-glycidylstyrene, (3-ethyloxetan-3-yl) (meth) acrylate, (oxetan-3-yl) methyl (meth) acrylate, (3-ethyloxetan-3-yl) methyl (meth) acrylate, etc.; As the monomer having an oxazoline group, 2-vinyl-2-oxazoline, isopropenyloxazoline, etc. can be respectively mentioned.

[0079] In the polymer (II), the content of the structural unit U6 is preferably 3 mol% or more, more preferably 5 mol% or more, and still more preferably 10 mol% or more based on all the structural units constituting the polymer (II). By setting the content of the structural unit U6 to 3 mol% or more, it is preferable in that the effect of improving the dielectric breakdown resistance and the adhesion to the plating layer 18 can be sufficiently obtained. Further, from the viewpoint of ensuring good substrate selectivity, the content of the structural unit U6 is preferably 40 mol% or less, more preferably 35 mol% or less, and still more preferably 30 mol% or less based on all the structural units constituting the polymer (II). When the content of the structural unit U6 is within the above range, unevenness of the functional group F2 in the coating film can be suppressed by uniformly introducing the functional group F2 into the polymer (II), which is preferable in that it can be used as a permanent film.

[0080] · Other structural units The polymer (II) may further contain a structural unit different from the structural unit U6 (hereinafter also referred to as "other structural unit U7") together with the structural unit U6. The other structural unit U7 only needs to be copolymerizable with the structural unit U6 and is not particularly limited. The monomer that gives the other structural unit U7 is preferably a monomer having a polymerizable carbon-carbon unsaturated bond. Specifically, for example, at least one monomer selected from the group consisting of (meth) acrylic acid alkyl esters, (meth) acrylic acid esters having an alicyclic structure, (meth) acrylic acid esters 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, alkenes, vinylcycloalkanes, cycloalkenes, and unsaturated dicarboxylic acid dialkyl ester compounds can be mentioned. Specific examples and preferred examples thereof include the same compounds as the monomers exemplified in the description of the polymer (I).

[0081] In the polymer (II), the content of the other structural unit U7 is preferably 97 mol% or less, more preferably 95 mol% or less, and still more preferably 90 mol% or less based on all the structural units constituting the polymer (II).

[0082] From the viewpoint of obtaining an organic film with high heat resistance, the polymer (II) preferably further contains a structural unit derived from a monomer having an aromatic ring (hereinafter also referred to as "structural unit U8"). The monomer that provides the structural unit U8 may be one of the structural unit U6 and the structural unit U7, or two or more thereof. As specific examples of the monomer that provides the structural unit U8, a monomer having an aromatic ring can be arbitrarily selected and used from the monomers exemplified as the monomers that provide the structural unit U6 and the structural unit U7. In the polymer (II), the content of the structural unit U8 is preferably 10 mol% or more, more preferably 20 mol% or more, and still more preferably 30 mol% or more based on all the structural units contained in the polymer (II).

[0083] Note that the synthesis method of the polymer (II) is also not particularly limited, similar to the polymer (I). The details of the synthesis method of the polymer (II) are the same as those of the polymer (I).

[0084] For the polymer (II), the weight average molecular weight (Mw) in terms of polystyrene by GPC is preferably 800 or more. When Mw is 800 or more, it is preferable in terms of being able to obtain an organic film with sufficiently high heat resistance, chemical resistance, etc. Mw is more preferably 1,000 or more, and still more preferably 1,500 or more. Also, from the viewpoint of good film-forming properties, the Mw of the polymer (II) is preferably 8,000 or less, more preferably 7,000 or less, and 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, and still more preferably 2.5 or less.

[0085] 〔Solvent〕 The second composition is preferably a liquid composition in which the polymer (II) is dissolved or dispersed in a solvent. The solvent used for preparing the second composition is preferably an organic solvent that can dissolve the polymer (II) and does not react with each component. Examples of the organic solvent include alcohol solvents, ether solvents, ketone solvents, amide solvents, ester solvents, hydrocarbon solvents, and the like. Specific examples and preferred examples of these solvents include the same compounds as those described as specific examples and preferred examples of the solvents that can be used for preparing the first composition.

[0086] The amount of the polymer (II) contained in the second composition is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.5% by mass or more 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, it is preferable in that a coating film with a sufficient film thickness can be formed. Further, the content of the polymer (II) is preferably 30% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less 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 second composition does not become too high, and good coatability can be ensured.

[0087] 〔Other components〕 In addition to the above-described polymer (II) and solvent, the second composition may further contain other components other than these. Examples of the other components include polymers having no functional group F2, surfactants (fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, etc.), antioxidants, and the like. The blending amount of the other components can be appropriately selected according to each component within a range that does not impair the effects of the present invention.

[0088] The solid content concentration of the second composition is preferably in the range of 0.1 to 30% by mass. When the solid content concentration is 0.1% by mass or more, it is suitable in that the film thickness of the organic film can be sufficiently ensured. Further, when the solid content concentration is 30% by mass or less, the film thickness of the organic film does not become too large, and good coatability can be ensured by appropriately increasing the viscosity of the second composition. The solid content concentration of the second composition is more preferably 0.5 to 20% by mass, and still more preferably 0.7 to 10% by mass.

[0089] <Third Composition> Next, each component contained in the third composition and other components blended as necessary will be described. The third 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 functional group FM capable of forming a bond with a metal element contained in the plating layer 18 or a functional group FP that generates the functional group FM by heating, and a solvent. It is preferable that the functional group FM and the functional group FP of the polymer (III) are different functional groups from the functional group F1. For example, the polymer (III) may have a group that does not show an interaction with the group on the surface layer of the insulating layer 14 as the functional group FM.

[0090] The main skeleton of the polymer (III) is not particularly limited, but a polymer obtained using a monomer having a polymerizable carbon-carbon unsaturated bond is preferable. Specific examples of the polymer (III) include [1] a polymer containing a structural unit having a functional group F1 and a structural unit having a functional group FM or a functional group FP, and [2] a polymer containing a structural unit having a functional group F1 and having a functional group FM or a functional group FP at the polymer terminal. In addition, the synthesis method of the polymer (III) is also not particularly limited, similar to the polymers (I) and (II). Regarding the details of the synthesis method of the polymer (III), the description of the synthesis method of the polymer (I) can be cited.

[0091] The polymer (III) preferably has a crosslinkable group. In this case, the crosslinkable group possessed by the polymer (III) is a group different from the functional group FM and the functional group FP possessed by the polymer (III). When the polymer (III) has a crosslinkable group, the polymer (III) may have, as the functional group FM or the functional group FP, a group that forms a bond with the metal contained in the plating layer 18 and does not exhibit crosslinkability. Note that the crosslinkable group is a group different from the functional group F1.

[0092] One preferred embodiment of the polymer (III) is a polymer containing the above-described structural unit U1, the structural unit U2, and a structural unit having a functional group FM or a functional group FP (however, it is a group different from the functional group F1 and the crosslinkable group). The details of the functional group F1 and the structural unit U1 possessed by the polymer (III) are the same as the descriptions of the specific examples and preferred examples of the functional group F1 and the structural unit U1 possessed by the polymer (I) contained in the first composition. The details of the crosslinkable group possessed by the polymer (III) are the same as the description of the crosslinkable group that the polymer (I) may have. Among these, as the crosslinkable group, a group capable of forming a bond between the same kind of groups can be preferably used. Note that 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).

[0093] In polymer (III), examples of the structural unit having functional group FM or functional group FP include structural units derived from monomers having a carboxy group, a protected carboxy group, a sulfide group, a dithiocarbonyl group, a thiourethane group, or a thioamide group. From the viewpoint of adhesion to the plating layer 18, among them, at least one selected from the group consisting of a carboxy group, a protected carboxy group, and a sulfide group is preferable for the functional group FM or functional group FP possessed by polymer (III), and a sulfide group is more preferable. In polymer (III), the content of the structural unit having functional group FM or functional group FP is preferably 5 mol% or more, more preferably 10 mol% or more, based on all the structural units constituting polymer (III). Further, the content of the structural unit is preferably 70 mol% or less, more preferably 60 mol% or less, based on all the structural units constituting polymer (III).

[0094] In addition to the above-described polymer (III) and solvent, the third composition may also contain other components other than 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. When a thermal acid generator is blended in the third composition, the blending amount is preferably 10 mol% or less, more preferably 1 to 5 mol%, based on the total amount of the third composition, from the viewpoint of suppressing repelling when applying the third composition to a substrate while obtaining the effect of blending the thermal acid generator.

[0095] According to the configuration in which the organic film 17 is a single-layer film, the number of steps for forming an organic film on the inner surface of the via 11 can be minimized as much as possible, and the manufacturing process can be simplified. Further, while further thinning the organic film formed on the inner surface of the via 11, an organic film excellent in adhesion to the plating layer 18 can be formed on the inner surface of the via.

[0096] 《Kit for Forming a Stacked Film》 The kit for forming a laminated film of the present invention (hereinafter, also simply referred to as "film-forming kit") is used for the pretreatment when forming a plating layer 18 inside the via 11 in the manufacturing process of a multilayer wiring board, and is particularly suitable for the manufacturing process of a multilayer wiring board including wiring containing one or more selected from the group consisting of Co, Ni, W, and Ru. The mode of the kit is not particularly limited as long as it contains the above-described polymer (I) and polymer (II). One mode of the film-forming kit of the present invention is a kit including a first agent containing polymer (I) and a second agent containing polymer (II). In this case, it is preferable that the first agent is a first composition and the second agent is a second composition.

[0097] According to such a film-forming kit of the present invention, in the wiring formation process of forming multilayer wiring on a substrate, an organic film 17 (first layer 17a and second layer 17b) can be formed on the bottom 15 and the inner wall surface 12 of the via 11. This organic film 17 functions as a barrier layer and can suppress the diffusion of metal elements embedded inside the via into the insulating layer 14. Further, according to the method of embedding metal by plating inside the via 11 coated with the organic film 17, a plating layer 18 with less generation of voids and seams can be formed. Therefore, according to the film-forming kit of the present invention, a highly reliable device can be obtained.

[0098] 《Composition》 The composition of the present invention is a composition used for the pretreatment of embedding metal by plating inside the via 11 in the manufacturing process of a multilayer wiring board. This composition can be preferably used particularly in the manufacturing process of a multilayer wiring board including wiring containing one or more selected from the group consisting of Co, Ni, W, and Ru. The composition contains a polymer having at least one crosslinkable group selected from the group consisting of an acid anhydride group and a protected carboxy group and a functional group F1 (excluding the crosslinkable group), and a solvent. 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 adhesion to the plating layer 18 can be formed on the bottom 15 and the inner wall surface 12 of the via 11.

Example

[0099] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

[0100] In the following examples and comparative examples, the measurement methods of the weight average molecular weight and 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 measured by gel permeation chromatography (GPC) using Tosoh's GPC columns (two "G2000HXL", one "G3000HXL", and one "G4000HXL") under the following conditions. Eluent: Tetrahydrofuran (Wako Pure Chemical Industries, Ltd.) Flow rate: 1.0 mL / min Sample concentration: 1.0 mass% Sample injection volume: 100 μL Column temperature: 40 °C Detector: Differential refractometer Standard substance: Monodisperse polystyrene

[0101] 1a. Synthesis of monomer [Synthesis of methyl (4-vinylphenyl) sulfide] To a 500 ml three-necked flask equipped with a Dimroth condenser and a dropping funnel, 32.2 g (90.2 mmol) of methyltriphenylphosphonium bromide, 4.32 g (90.2 mmol) of sodium hydride, and 150 ml of dry THF were stirred at room temperature for 1 hour under a nitrogen atmosphere to synthesize an ylide. Next, 11.4 g (75.1 mmol) of 4-methythiobenzaldehyde and 150 ml of dry THF were added dropwise, and the mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere to obtain a pale yellow suspension. Next, 50 g of diisopropyl ether was added to precipitate salt and phosphine oxide, and the mixture was filtered through a pleated filter paper, and the filtrate was concentrated. The filtrate was dissolved in CH 2 Cl 2Washed three times with brine, the organic layer was recovered. Further, 30 g of n-hexane / ethyl acetate = 10 / 1 was added to precipitate salts, and the filtered product was purified by column chromatography (n-hexane / ethyl acetate = 2 / 1). The yield was 71%, and the structure was confirmed by 1 1H NMR. 1 1H NMR (400 MHz, CDCl 3 3) δ; 7.33 (Ph, m, 2H), 7.24(Ph, m, 2H), 6.72 (CH, q, 1H), 5.76 (CH 2 , d, 1H), 5.25 (CH 2 , d, 1H), 2.38 (CH 3 , s, 3H).

[0102] 1. Synthesis of Polymer [Synthesis Example 1] Synthesis of Polymer (A-1) After drying a 500 mL flask reaction vessel under reduced pressure, 120 g of tetrahydrofuran that had been subjected to distillation dehydration treatment was injected under a nitrogen atmosphere and cooled to -78°C. Then, 2.38 mL of a 1N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected into this tetrahydrofuran. Subsequently, 13.3 mL of styrene that had been subjected to adsorption filtration through silica gel and distillation dehydration treatment to remove the polymerization inhibitor was dropwise injected over 30 minutes, and it was confirmed that the polymerization system was orange. During this dropwise injection, care was taken so that the internal temperature of the reaction solution did not exceed -60°C. After the dropwise injection was completed, it was aged for 30 minutes. Then, 0.19 ml of 3-bromopropionitrile was injected to carry out a termination reaction at the polymerization end. The temperature of this reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with methyl isobutyl ketone (MIBK). Then, 1,000 g of a 2% aqueous oxalic acid solution was injected and stirred. After standing, the lower aqueous layer was removed. This operation was repeated 3 times to remove metallic Li. Then, 1,000 g of ultrapure water was injected and stirred, and the lower aqueous layer was removed. After repeating this operation 3 times to remove oxalic acid, the solution was concentrated and dropped into 500 g of methanol to precipitate the polymer, and the solid was recovered with a Buchner funnel. This polymer was dried under reduced pressure at 60°C to obtain 11.9 g of a white polymer. The obtained polymer had an Mw of 5,600, an Mn of 5,200, and an Mw / Mn of 1.08. [Chemical formula]

[0103] [Synthesis Example 2] Synthesis of Polymer (A-2) After drying the 500 mL flask reaction vessel under reduced pressure, 120 g of THF that had been subjected to distillation dehydration treatment was injected under a nitrogen atmosphere and cooled to -78°C. To this THF, 2.40 mL of a 1N cyclohexane solution of sec-butyllithium (sec-BuLi) was injected. Further, 99.9 mL of styrene and 3.24 g of 4-vinylbenzocyclobutene, which had been previously subjected to adsorption filtration through silica gel and distillation dehydration treatment to remove polymerization inhibitors, were dropwise injected over 30 minutes, and it was confirmed that the polymerization system was orange. After completion of the dropwise addition, it was aged for 30 minutes. Further, 1.0 g of hexamethylcyclotrisiloxane was added, aged for 30 minutes, and 1 mL of methanol was injected to carry out a termination reaction at the polymerization end. The temperature of this reaction solution was raised to room temperature, and the obtained reaction solution was concentrated and replaced with MIBK. Thereafter, 1,000 g of ultrapure water was injected and stirred, and the lower aqueous layer was removed. After repeating this operation 5 times, the solution was concentrated and dropped into 500 g of methanol to precipitate a polymer, and the solid was recovered with a Buchner funnel. By drying this polymer under reduced pressure at 60°C, 11.2 g of a white polymer (A-5) was obtained. The obtained polymer (A-2) had a Mw of 6,200, a Mn of 6,000, and a Mw / Mn of 1.04. [Chemical formula]

[0104] [Synthesis Example 3] Synthesis of Polymer (A-3) 10 g of 1,4-dioxane and a magnetic stirrer bar were placed in a 300 ml three-necked flask purged with nitrogen and heated to 80°C. Subsequently, 5.10 g of styrene, 3.28 g of 4-(1-propoxyethyl)vinyl benzoate, 1.35 g of N-vinylcarbazole, 0.48 g of 2,2-dimethylazobis(2-methylpropionate) (3 mol% based on the total number of moles of all monomers), and 20 g of methyl isobutyl ketone were added dropwise at a constant rate over 3 hours. Thereafter, it was aged for 3 hours. The obtained polymerization solution was precipitated and purified in 500 g of methanol to precipitate a white solid, which was filtered off with a Buchner funnel and then dried under reduced pressure to recover 5.63 g of polymer (A-3). The obtained polymer (A-3) had a Mw of 4,000, a Mn of 3,000, and a Mw / Mn of 1.33. [Chemical formula]

[0105] [Synthesis Example 4] Synthesis of Polymer (A-4) 10 g of 1,4-dioxane and a magnetic stirrer bar were placed in a 300 ml three-necked flask purged with nitrogen and heated to 80°C. Subsequently, 5.10 g of styrene, 1.96 g of maleic anhydride, 2.60 g of 4-vinylbenzocyclobutene, 1.93 g of 4-dimethylmethoxysilylstyrene, 0.46 g of 2,2-dimethylazobis(2-methylpropionate) (2 mol% based on the total number of moles of all monomers), and 20 g of methyl isobutyl ketone were added dropwise at a constant rate over 3 hours. Then, it was aged for 3 hours. With respect to the obtained polymerization solution, a white solid was precipitated by precipitation purification in 500 g of diisopropyl ether, filtered off with a Buchner funnel, and then dried under reduced pressure to recover 7.31 g of Polymer (A-4). The obtained Polymer (A-4) had an Mw of 4,660, an Mn of 3,140, and an Mw / Mn of 1.48. [Chemical formula]

[0106] [Synthesis Example 5] Synthesis of Polymer (A-5) 10 g of 1,4-dioxane and a magnetic stirrer bar were placed in a 300 ml three-necked flask purged with nitrogen and heated to 80°C. Subsequently, 8.32 g of styrene, 2.22 g of isopropenyloxazoline, 0.46 g of 2,2-dimethylazobis(2-methylpropionate) (2 mol% based on the total number of moles of all monomers), and 20 g of methyl isobutyl ketone were added dropwise at a constant rate over 3 hours. Then, it was aged for 3 hours. With respect to the obtained polymerization solution, a white solid was precipitated by precipitation purification in 500 g of hexane, filtered off with a Buchner funnel, and then dried under reduced pressure to recover 4.31 g of Polymer (A-5). The obtained Polymer (A-5) had an Mw of 3,140, an Mn of 2,410, and an Mw / Mn of 1.30. [Chemical formula]

[0107] [Synthesis Example 6] Synthesis of Polymer (A-6) 10 g of methyl ethyl ketone and a magnetic stirrer bar were placed in a 300 ml three-necked flask purged with nitrogen, and the mixture was heated to 80°C. Subsequently, 9.37 g of styrene, 1.76 g of 4-glycidylstyrene, 0.46 g of 2,2-dimethylazobis(2-methylpropionate) (2 mol% based on the total number of moles of all monomers), and 20 g of methyl isobutyl ketone were added dropwise at a constant rate over 3 hours. Thereafter, the mixture was aged for 3 hours. With respect to the obtained polymerization solution, a white solid was precipitated by precipitation purification in 500 g of hexane, filtered off with a Buchner funnel, and then dried under reduced pressure to recover 4.36 g of polymer (A-6). The obtained polymer (A-6) had an Mw of 3,090, an Mn of 2,240, and an Mw / Mn of 1.38. [Chemical Formula]

[0108] [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 purged with nitrogen, and the mixture was heated to 80°C. Subsequently, 5.10 g of styrene, 3.00 g of methyl(4-vinylphenyl)sulfane, 2.60 g of 4-vinylbenzocyclobutene, 1.93 g of 4-dimethylmethoxysilylstyrene, 0.46 g of 2,2-dimethylazobis(2-methylpropionate) (2 mol% based on the total number of moles of all monomers), and 20 g of methyl isobutyl ketone were added dropwise at a constant rate over 3 hours. Thereafter, the mixture was aged for 3 hours. With respect to the obtained polymerization solution, a white solid was precipitated by precipitation purification in 500 g of diisopropyl ether, filtered off with a Buchner funnel, and then dried under reduced pressure to recover 6.38 g of polymer (A-7). The obtained polymer (A-7) had an Mw of 4220, an Mn of 3140, and an Mw / Mn of 1.34. [Chemical Formula]

[0109] Preparation of Composition for Surface Modification [Preparation Examples 1 - 7] To 1.20 g of polymer (A - 1), 98.8 g of propylene glycol monomethyl ether acetate (PGMEA) as a solvent was added. After stirring, the composition (S - 1) was prepared by filtering through a high - density polyethylene filter having pores of 0.45 μm. Similarly, compositions (S - 2) to (S - 7) were prepared respectively (see Table 1).

[0110] [Table 1]

[0111] In Table 1, the abbreviations of the solvents represent the following compounds. B - 1: Propylene glycol monomethyl ether acetate B - 2: Methyl ethyl ketone

[0112] 3. Evaluation [Example 1] [Film Formation] A 12 - inch low - k substrate (manufactured by Advantec) was cut into 3 cm × 3 cm, and an N 2 / 3% H 2 ashing process was carried out (manufactured by Ulvac, Luminous NA - 1300, chamber pressure; 30 Pa, flow rate; 300 sccm, treatment time; 5 minutes). Subsequently, on the surface of the substrate subjected to the ashing treatment, using a spin coater (manufactured by Mikasa, MS - B300), the composition (S - 3) was spin - coated at 1,500 rpm for 20 seconds and baked at 150 °C for 180 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the unadsorbed polymer. Next, on the film - forming surface by the composition (S - 3), the composition (S - 5) was spin - coated under the conditions of 1,500 rpm for 20 seconds and baked at 250 °C for 300 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the uncrosslinked polymer. Furthermore, instead of the 12-inch low-k substrate, a coupon substrate obtained by cutting a 12-inch TEOS substrate (manufactured by Advantech Co., Ltd.) into 3 cm × 3 cm pieces and a coupon substrate obtained by cutting a 12-inch thermally oxidized silicon substrate (manufactured by Advantech Co., Ltd.) into 3 cm × 3 cm pieces were each used to perform the same treatment as above, and then film formation was carried out.

[0113] <Electroless Nickel Adhesion Test> In a 300 ml polypropylene beaker, 100 g of ultrapure water, 2.5 g of nickel(II) sulfate hexahydrate, 2.0 g of sodium hypophosphite hydrate, 1 g of sodium acetate trihydrate, and 1.0 g of trisodium citrate dihydrate were added to prepare an aqueous solution with a pH of 10 to 10.5, and the temperature was adjusted to 90°C. Next, a low-k substrate having a film crosslinked with composition (S-3) and composition (S-5) was immersed for 1 minute to perform electroless plating. After plating, the substrate was washed with ultrapure water and then baked in a vacuum oven at 150°C for 30 minutes. Next, after making lattice-shaped scratches on the plated Ni film with a cutter, an adhesion peel test was performed with cellophane tape. Those in which the metal film did not peel off on the tape side were marked as "○", and those in which it peeled off were marked as "×". The same evaluation was also performed on the substrates on which films crosslinked with composition (S-3) and composition (S-5) were formed on the TEOS substrate and the thermally oxidized silicon substrate. The evaluation results are shown in Table 2.

[0114] [Examples 2 to 4 and Comparative Examples 1 to 4] Film formation and electroless nickel adhesion test were carried out in the same manner as in Example 1, except that the surface modification composition used was changed as shown in Table 2. The evaluation results are shown in Table 2.

[0115] [Example 17] Film formation and electroless nickel adhesion test were carried out in the same manner as in Example 1, except that the surface modification composition used was changed as shown in Table 2. In Table 2, "None" indicates that film formation was not performed in the corresponding column (the same applies to Tables 3 to 5). The evaluation results are shown in Table 2.

[0116]

Table 2

[0117] [Example 5] [Film Formation] For each of a 12-inch low-k substrate, a 12-inch TEOS substrate, and a 12-inch thermally oxidized silicon substrate, film formation was carried out by performing the same operations as in Example 1 using Composition (S-3) and Composition (S-5).

[0118] [Electroless Plating Co / W Alloy Adhesion Test] In a 300-ml polypropylene beaker, 100 g of ultrapure water, 2.0 g of potassium hydroxide, 2.4 g of cobalt(II) chloride hexahydrate, 2.0 g of sodium hypophosphite hydrate, 8.8 g of trisodium citrate dihydrate, 1.0 g of sodium tungstate, and 0.12 g of dimethylaminoborane were added to prepare an aqueous solution with pH = 8.5 to 10.5, and the temperature was adjusted to 70°C. Next, a low-k substrate having a film crosslinked with Composition (S-3) and Composition (S-5) was immersed for 3 minutes to perform electroless plating. After plating, the substrate was washed with ultrapure water and then baked in a reduced-pressure oven at 150°C for 30 minutes. Next, after making lattice-shaped scratches on the plated Co / W alloy film with a cutter, an adhesion peel test was performed with cellophane tape. Those in which the metal film did not peel off on the tape side were marked as "○", and those in which it peeled off were marked as "×". The same evaluation was also performed on the substrates on which films crosslinked with Composition (S-3) and Composition (S-5) were formed on the TEOS substrate and the thermally oxidized silicon substrate. The evaluation results are shown in Table 3.

[0119] [Examples 6 - 8 and Comparative Examples 5 - 8] Film formation and electroless plating Co / W alloy adhesion test were carried out in the same manner as in Example 5 except that the surface modification composition used was changed as shown in Table 3. The evaluation results are shown in Table 3.

[0120] [Example 18] Film formation and electroless plating Co / W alloy adhesion test were carried out in the same manner as in Example 5 except that the surface modification composition used was changed as shown in Table 3. The evaluation results are shown in Table 3.

[0121]

Table 3

[0122] [Example 9] <Film formation> For each of a 12-inch low-k substrate, a 12-inch TEOS substrate, and a 12-inch thermally oxidized silicon substrate, film formation was carried out by performing the same operations as in Example 1 using Composition (S-3) and Composition (S-5).

[0123] <Electroless plating Ru adhesion test> NP-1900 (ruthenium plating solution manufactured by Sanming Chemical Co., Ltd.) was poured into a 300 ml polypropylene beaker and the temperature was adjusted to 70°C. Next, a low-k substrate having a film crosslinked with Composition (S-3) and Composition (S-5) was immersed for 3 minutes to perform electroless plating. After plating, the substrate was washed with ultrapure water and then baked in a vacuum oven at 150°C for 30 minutes. Next, after making scratches in a grid pattern on the plated Ru film with a cutter, an adhesion peeling test was performed with cellophane tape, and those in which the metal film did not peel off on the tape side were marked as "○", and those in which it peeled off were marked as "×". The same evaluation was also performed on substrates on which films crosslinked with Composition (S-3) and Composition (S-5) were formed on a TEOS substrate and a thermally oxidized silicon substrate. The evaluation results are shown in Table 4.

[0124] [Examples 10 to 12 and Comparative Examples 9 to 12] Film formation and electroless plating Ru adhesion test were carried out in the same manner as in Example 9 except that the surface modification composition used was changed as shown in Table 4. The evaluation results are shown in Table 4.

[0125] [Example 19] Film formation and electroless plating Ru adhesion test were carried out in the same manner as in Example 9 except that the surface modification composition used was changed as shown in Table 4. The evaluation results are shown in Table 4.

[0126]

Table 4

[0127] As is clear from the results in Tables 2 to 4, in Examples 1 to 12 in which the organic film having the functional group F1 (first functional group) was formed using the polymer (I) and having the functional group FM (second functional group), the metal film did not peel off on 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 12 in which the organic film did not have at least either the functional group F1 or the functional group FM, the metal film peeled off on the cellophane tape side in the adhesion test, and the adhesion between the metal film and the organic film was poor.

[0128] Also, regarding Examples 17 to 19 in which the organic film was formed using the polymer (III), the metal film did not peel off on the cellophane tape side in the adhesion test, and the adhesion between the organic film and the metal film was excellent.

[0129] [Example 13] [Examination of Embedding Trench Via Pattern with Ni on Bottom Surface] A 12-inch substrate (manufactured by Advanced Material Technology Co., Ltd.) having a trench via pattern with a width of 50 nm and a depth of 100 nm with a silicon thermal oxide on the side walls and a nickel thin film on the bottom surface was cut into 3 cm × 3 cm and immersed in a 2.38% aqueous solution of trimethylammonium hydroxide for 10 minutes. Subsequently, it was immersed in ultrapure water to remove the alkali, and the surface modification was completed. The composition (S-3) was applied to this substrate and spin-coated (manufactured by Mikasa Co., Ltd., MS-B300) under the conditions of 1,500 rpm for 20 seconds, and baked at 150 °C for 180 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the polymer not adsorbed on the oxide. Next, the composition (S-5) was also spin-coated at 1,500 rpm for 20 seconds and baked at 250 °C for 300 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the uncrosslinked polymer. By the above operations, films insolubilized by the composition (S-3) and the composition (S-5) were provided on the bottom surface and the inner wall surface of the via. This substrate was immersed in electroless nickel plating solution to grow Ni in the trenches. After plating, the substrate was washed with ultrapure water and then baked in a vacuum oven at 150°C for 30 minutes. Cross-sectional SEM observation was performed on the obtained substrate, and it was confirmed that Ni was embedded in the trenches without voids. All 10 trenches embedded from a wide-angle view were marked as "○", and those with embedding defects were marked as "×". The evaluation results are shown in Table 5.

[0130] <Study on Embedding of Trench Via Pattern with Bottom W> A 12-inch substrate (manufactured by Advanced Material Technology) with a trench via pattern consisting of 50 nm in width and 100 nm in depth, having thermally oxidized silicon on the sidewalls and a tungsten thin film on the bottom surface, was cut into 3 cm × 3 cm and immersed in a 2.38% aqueous solution of trimethylammonium hydroxide for 10 minutes. Subsequently, it was immersed in ultrapure water to remove the alkali and complete the surface modification. Composition (S-3) was applied to this substrate and spin-coated (manufactured by Mikasa, MS-B300) under the conditions of 1,500 rpm for 20 seconds, and then baked at 150°C for 180 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the unadsorbed polymer on the oxide. Next, composition (S-5) was also spin-coated at 1,500 rpm for 20 seconds and baked at 250°C for 300 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the uncrosslinked polymer. By the above operations, films insolubilized by composition (S-3) and composition (S-5) were imparted to the bottom surface and inner wall surface of the via. This substrate was immersed in electroless Co / W plating solution to grow Co / W alloy in the trenches. After plating, the substrate was washed with ultrapure water and then baked in a vacuum oven at 150°C for 30 minutes. Cross-sectional SEM observation was performed on the obtained substrate, and it was confirmed that Co / W was embedded in the trenches without voids. All 10 trenches embedded from a wide-angle view were marked as "○", and those with embedding defects were marked as "×". The evaluation results are shown in Table 5.

[0131] <Consideration of Embedding Trench Via Pattern with Ru on the Bottom Surface> A 12-inch substrate (manufactured by Advanced Material Technology Co., Ltd.) with a trench via pattern having a width of 50 nm and a depth of 100 nm, with a thermal oxide silicon sidewall and a ruthenium thin film on the bottom surface, was cut into 3 cm × 3 cm pieces and immersed in a 2.38% aqueous solution of trimethylammonium hydroxide for 10 minutes. Subsequently, it was immersed in ultrapure water to remove the alkali and complete the surface modification. The composition (S-3) was applied to this substrate and spin-coated (manufactured by Mikasa Co., Ltd., MS-B300) under the conditions of 1,500 rpm for 20 seconds, and then baked at 150 °C for 180 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the unadsorbed polymer on the oxide. Next, the composition (S-5) was similarly spin-coated at 1,500 rpm for 20 seconds and baked at 250 °C for 300 seconds under a nitrogen flow. Next, the substrate was washed with propylene glycol monomethyl ether acetate to remove the uncrosslinked polymer. By the above operations, films insolubilized by the composition (S-3) and the composition (S-5) were applied to the bottom surface and the inner wall surface of the via. This substrate was immersed in an electroless plating Ru solution to grow Ru in the trench. After plating, the substrate was washed with ultrapure water and then baked in a reduced-pressure oven at 150 °C for 30 minutes. Cross-sectional SEM observation was performed on the obtained substrate, and it was confirmed that Ru was embedded in the trench without voids. All 10 trenches from a wide-angle view that were embedded were marked as "○", and those with poor embedding were marked as "×". The evaluation results are shown in Table 5.

[0132] [Examples 14 to 16 and Comparative Examples 13 to 16] Except that the surface modification composition used was changed as described in Table 5, consideration of embedding a trench via pattern with Ni on the bottom surface, consideration of embedding a trench via pattern with W on the bottom surface, and consideration of embedding a trench via pattern with Ru on the bottom surface were carried out in the same manner as in Example 13. The evaluation results are summarized in Table 5.

[0133] [Examples 20 to 23] Except that the surface modification composition to be used was changed as shown in Table 5, the study of trench via pattern embedding with Ni on the bottom surface, the study of trench via pattern embedding with W on the bottom surface, and the study of trench via pattern embedding with Ru on the bottom surface were conducted in the same manner as in Example 13. The evaluation results are summarized in Table 5.

[0134]

Table 5

[0135] As can be seen from the results in Table 5, in Examples 13 to 16 and 20 to 23 where metal embedding was performed in the via by this manufacturing method, there were no voids in the trench and the metal embedding property was good. On the other hand, in Comparative Example 13 using only Composition (S-1), Comparative Example 14 using only Composition (S-2), Comparative Example 15 using Composition (S-2) and Composition (S-5), and Comparative Example 16 using Composition (S-2) and Composition (S-6) when forming the organic film on the inner surface of the via, voids occurred in the trench and the metal embedding property was poor.

Explanation of Symbols

[0136] 10... Wiring board, 11... Via, 12... Inner wall surface, 13... Wiring, 14... Insulating layer, 15... Bottom, 17... Organic film, 17a... First layer, 17b... Second layer, 18... Plating layer.

Claims

1. A method for manufacturing a multilayer wiring board, comprising: a film forming step of forming an organic film on the wiring and the inner wall surface inside a via formed to penetrate the insulating layer in the thickness direction in the insulating layer provided on the wiring; a plating step of forming a metal layer by plating inside the via after forming the organic film; and the organic film is formed using a polymer (I) having a first functional group capable of interacting with a group on the surface layer of the insulating layer, and having a second functional group capable of forming a bond with a metal contained in the metal layer. A method for manufacturing a multilayer wiring board.

2. The polymer (I) has the first functional group and a crosslinkable group (however, a group different from the first functional group). The organic film is a laminated film of a first layer formed on the wiring and the inner wall surface using the polymer (I) and a second layer formed on the first layer using a polymer (II) having a third functional group capable of forming a bond with the crosslinkable group. The method for manufacturing a multilayer wiring board according to claim 1.

3. The crosslinkable group is at least one selected from the group consisting of an acid anhydride group and a protected carboxy group. The method for manufacturing a multilayer wiring board according to claim 2.

4. The third functional group is at least one of an oxazoline group and an epoxy group. The method for manufacturing a multilayer wiring board according to claim 2 or 3.

5. The polymer (II) has a structural unit derived from a monomer having an aromatic ring. The method for manufacturing a multilayer wiring board according to any one of claims 2 to 4.

6. The organic film is a single-layer film. The method for manufacturing a multilayer wiring board according to claim 1.

7. The second functional group is at least one selected from the group consisting of a carboxy group, a sulfide group, a dithiocarbonyl group, a thiourethane group, and a thioamide group. The method for manufacturing a multilayer wiring board according to any one of claims 1 to 6.

8. The insulating layer has, on its surface layer, a group to which at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an oxo group, and -N(R １ ), ２ wherein R １ is each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms). The first functional group is a silanol group, an alkoxysilyl group, a halogenated silyl group, a -N(Si(R ５ ) ３ ) ２ , an amino group, a hydroxyl group, a conjugated nitrogen-containing heterocyclic group, an acid anhydride group, a carboxy group, and a protected carboxy group (wherein R ５ each independently represents a hydrogen atom or a monovalent organic group having 1 to 10 carbon atoms.

9. The polymer (I) has a structural unit derived from a monomer having an aromatic ring. The method for manufacturing a multilayer wiring board according to any one of claims 1 to 8.

10. The wiring contains one or more selected from the group consisting of Co, Ni, W, and Ru. The method for manufacturing a multilayer wiring board according to any one of claims 1 to 9.

11. The plating step is a step of performing electroless plating inside the via. The method for manufacturing a multilayer wiring board according to any one of claims 1 to 10.

12. The method for manufacturing a multilayer wiring board according to any one of claims 1 to 11, wherein the metal layer contains one or more selected from the group consisting of Co, Ni, W, and Ru.

13. Before forming the organic film by the film formation step, an ashing treatment is further performed on the substrate surface with N ２ / H ２ gas or O ２ gas, and the method for manufacturing a multilayer wiring board according to any one of claims 1 to 12.

14. Before forming the organic film by the film formation step, a treatment liquid containing tetramethylammonium hydroxide (TMAH), hydrogen fluoride (HF), ammonia (NH ３ ), tetramethylammonium fluoride (TMAF), or citric acid is brought into contact with the substrate surface. The method for manufacturing a multilayer wiring board according to any one of claims 1 to 13, further comprising this step.

15. A laminate film forming kit used for pretreatment for forming a metal layer by plating inside a via in a multilayer wiring board including a wiring containing one or more selected from the group consisting of Co, Ni, W, and Ru, A polymerizable group and a functional group (excluding the polymerizable group) capable of interacting with a group to which at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an oxo group and -N(R １ )) ２ (wherein each R １ is independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms)), and a polymer (I) having the same. a polymer (II) having a functional group capable of forming a bond with the crosslinkable group, A laminate film forming kit comprising:

16. A composition used for pretreatment for forming a metal layer by plating inside a via in a multilayer wiring board including a wiring containing one or more selected from the group consisting of Co, Ni, W, and Ru, At least one crosslinkable group selected from the group consisting of an acid anhydride group and a protected carboxy group, and a functional group (excluding the crosslinkable group) capable of interacting with a group to which at least one selected from the group consisting of a hydrogen atom, a hydroxyl group, an oxo group, and -N(R １ ), where R ２ is each independently a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms.) is bonded to a polymer having １ ​ a solvent, A composition containing:

17. The composition according to claim 16, wherein the polymer has a structural unit represented by the following formula (1) as a structural unit having the functional group. 【Chemical 1】 (In formula (1), R is a hydrogen atom, a monovalent hydrocarbon group having 1 to 5 carbon atoms, a halogen atom, or a halogenated alkyl group having 1 to 5 carbon atoms. R ２ is a monovalent hydrocarbon group having 1 to 5 carbon atoms. R ３ is an alkoxy group having 1 to 5 carbon atoms. R １０ is a monovalent hydrocarbon group having 1 to 5 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. a is an integer from 0 to 2, and b is an integer from 1 to 3. However, a + b = 3. c is an integer from 0 to 4. When a is 2, the plurality of R ２ are the same or different, and when b is 2 or 3, the plurality of R ３ are the same or different. When c is 2 or more, the plurality of R １０ are the same or different.)

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