Composition, method for manufacturing modified substrate, method for manufacturing laminate, and method for manufacturing electronic device

Abstract

The present invention provides a composition capable of forming a coating film in which the occurrence of defects is suppressed and film formation due to atomic layer deposition processing can be sufficiently suppressed. The present invention also provides a method for manufacturing a modified substrate, a method for manufacturing a laminate, and a method for manufacturing an electronic device. A composition according to the present invention is for forming a coating film that suppresses film formation due to atomic layer deposition processing, and contains: a compound C1 having a functional group A that binds or adsorbs to a substrate, and a specific structure B1 that is a polyoxyalkylene structure and / or a betaine structure; and a solvent containing water. The water content is 10 mass% or more with respect to the total mass of the solvent containing water.

Description

Composition, method for manufacturing a modified substrate, method for manufacturing a laminate, method for manufacturing an electronic device

[0001] The present invention relates to compositions, methods for manufacturing modified substrates, methods for manufacturing laminates, and methods for manufacturing electronic devices.

[0002] As semiconductor devices become more high-performance, there is a growing demand for finer and more precise semiconductor elements. Conventionally, top-down photolithography has been used to form semiconductor elements, but due to mechanical and optical factors, it is becoming increasingly difficult to achieve the required precision. Therefore, as a bottom-up method for forming semiconductor elements, a selective modification method for substrates is being investigated, which utilizes the selective adsorption of compounds to specific materials to form a film of the compound on a region of a specific material on the substrate, and then uses that film to modify regions of the substrate other than those formed by the specific material. Specifically, for example, a method has been devised in which a material that selectively adsorbs to specific components is used to selectively form a film that inhibits material deposition on a specific region of the substrate surface, and then atomic layer deposition (ALD) is performed to selectively deposit material in the regions where the film does not exist, thereby modifying the substrate.

[0003] For example, Patent Document 1 describes a surface treatment method for a substrate having a surface including two or more regions of different materials, using a surface treatment agent that can shorten the processing time, and a method for selectively forming a film on the substrate surface to which the surface treatment method is applied, which is described as "a substrate having a surface including two or more regions of different materials, wherein at least one of the two or more regions contains a metal surface, and a surface treatment agent used to treat the substrate that has been pre-treated with an oxidizing agent, comprising a compound (P) represented by the following general formula (P-1) and an organic solvent (S) having a relative dielectric constant of 35 or less (wherein R １ R is an alkyl group, etc. ２ and R ３ (where is a hydrogen atom or an alkyl group, etc.) is disclosed. １ -P (=O) (OR ２ ) ( OR ３ ) ... (P-1)

[0004] Japanese Patent Publication No. 2022-100079

[0005] The coatings used for the selective modification of substrates as described above are required to have excellent ALD inhibitory properties, meaning that when atomic layer deposition (ALD) is performed on the coating, the amount of material deposited on the coating is suppressed. Furthermore, in recent years, there has been a growing demand for compositions that use water as a solvent from an environmental perspective. When the present inventors attempted to selectively modify a substrate using a composition containing compound (P) (e.g., octadecylphosphonic acid) and water disclosed in Patent Document 1, they found that defects occurred in the resulting coating, indicating that there is room for further improvement.

[0006] Therefore, the present invention aims to provide a composition that can form a coating in which the occurrence of defects is suppressed and film formation by atomic layer deposition is sufficiently suppressed. Furthermore, the present invention also aims to provide a method for manufacturing a modified substrate, a method for manufacturing a laminate, and a method for manufacturing an electronic device.

[0007] As a result of diligent research to solve the above problems, the inventors have found that the problems can be solved by the following configuration.

[0008] [1] A composition for forming a film on a substrate that suppresses film formation by atomic layer deposition, comprising: a compound C1 having a functional group A that binds to or adsorbs to the substrate, and a specific structure B1 which is at least one of a polyoxyalkylene structure and a betaine structure; and a solvent containing water, wherein the water content is 10% by mass or more of the total mass of the solvent containing water. [2] The composition according to [1], wherein the polyoxyalkylene structure is a polyoxyethylene structure or a polyoxypropylene structure, and the betaine structure has a cationic portion selected from the group consisting of a quaternary ammonium cation, a sulfonium cation, and a phosphonium cation, and an anionic portion selected from the group consisting of a phosphate ester anion, a sulfonic acid anion, and a carboxylic acid anion. [3] The composition according to [1] or [2], wherein the compound C1 further has a hydrocarbon group having 4 or more carbon atoms in addition to the functional group A and the specific structure B1. [4] The composition according to any one of [1] to [3], wherein, if the functional group A is a basic functional group, the acid dissociation constant of the conjugate acid of the compound C1 obtained by adding a proton to the basic functional group is 7.0 or more, and if the functional group A is an acidic functional group, the acid dissociation constant of the compound C1 when a proton dissociates from the acidic functional group is 5.0 or less. [5] The composition according to any one of [1] to [4], wherein the molecular weight of the compound C1 is 400 or more. [6] The composition according to any one of [1] to [5], wherein the polyoxyalkylene structure is a structure represented by formula (1) or formula (2), and the betaine structure is a structure represented by any one of formulas (3) to (6). [7] The composition according to any one of [1] to [6], wherein the compound C1 is a compound further having an unsaturated group. [8] The composition according to any one of [1] to [7], wherein the content of compound C1 is 5.00% by mass or less based on the total mass of the composition. [9] The composition according to any one of [1] to [8], wherein the total amount of compound C1 and the solvent containing water is 99.90% by mass or more based on the total mass of the composition.

[10] A composition for forming a film on a substrate that suppresses film formation by atomic layer deposition, comprising: a functional group A that binds to or adsorbs to the substrate; a compound C2 that does not contain the functional group A, has a molecular weight of 130 or more, and exhibits a specific structure B2 having a ClogP of -0.50 or less; and a solvent containing water, wherein the water content is 10% by mass or more of the total mass of the solvent containing water.

[11] The composition according to

[10] , wherein the compound C2 further has a hydrocarbon group having 4 or more carbon atoms in addition to the functional group A and the specific structure B2.

[12] The composition according to

[10] or

[11] , wherein, when the functional group A is a basic functional group, the acid dissociation constant of the conjugate acid of the compound C2 obtained by adding a proton to the basic functional group is 7.0 or more; and when the functional group A is an acidic functional group, the acid dissociation constant of the compound C2 when a proton dissociates from the acidic functional group is 5.0 or less.

[13] The composition according to any one of

[10] to

[12] , wherein the molecular weight of compound C2 is 400 or more.

[14] The composition according to any one of

[10] to

[13] , wherein the content of compound C2 is 5.00% by mass or less with respect to the total mass of the composition.

[15] The composition according to any one of

[10] to

[14] , wherein the total amount of compound C2 and the solvent containing water is 99.90% by mass or more with respect to the total mass of the composition.

[16] The composition according to any one of [1] to

[15] , wherein the content of water is 30% by mass or more with respect to the total mass of the solvent containing water.

[17] The composition according to any one of [1] to

[16] , wherein the functional group A is a basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group.

[18] The composition according to

[17] , wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group.

[19] The composition according to any one of [1] to

[16] , wherein the functional group A is an acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxyl group.

[20] A method for producing a modified substrate, comprising the step of contacting a substrate with the composition according to any one of [1] to

[19] to form a film on the substrate.

[21] A step 1 of forming a first film on the first surface by bringing a substrate having at least two surfaces of a first surface and a second surface made of different materials into contact with the composition according to any one of [1] to

[19] ; and A step 2 of subjecting the substrate obtained in the step 1 to an atomic layer deposition treatment to form a second film on the second surface. A method for manufacturing a laminate, comprising:

[22] A method for manufacturing an electronic device, comprising the method for manufacturing a modified substrate according to

[20] .

[0009] According to the present invention, it is possible to provide a composition that can form a film in which the occurrence of defects is suppressed and the film formation by atomic layer deposition treatment can be sufficiently suppressed. Further, the present invention can also provide a method for manufacturing a modified substrate, a method for manufacturing a laminate, and a method for manufacturing an electronic device.

[0010] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. In this specification, "ppm" means "parts-per-million (10 －６ )", "ppb" means "parts-per-billion (10 －９ )", and "ppt" means "parts-per-trillion (10 －１２ )". In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Also, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid. In this specification, when there are two or more kinds of a certain component, the "content" of that component means the total content of those two or more kinds of components.

[0012] In this specification, when there are multiple substituents and linking groups, etc. (hereinafter referred to as substituents, etc.) indicated by specific symbols, or when multiple substituents, etc. are specified simultaneously, it means that each substituent, etc. may be identical or different from the others. The same applies to the specification of the number of substituents, etc. Compounds described in this specification may include structural isomers, optical isomers, and isotopes unless otherwise specified. Furthermore, structural isomers, optical isomers, and isotopes may be present individually or in groups of two or more. In this specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -CO-O-) is such that, in a compound represented as "X-Y-Z", if Y is -CO-O-, the compound may be either "X-O-CO-Z" or "X-CO-O-Z".

[0013] In this specification, unless otherwise specified, the molecular weight of a compound with a molecular weight distribution is the weight-average molecular weight. Also in this specification, unless otherwise specified, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI) (Mw / Mn) of a polymer are defined as polystyrene equivalent values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector (Refractitive Index Detector)).

[0014] In this specification, ClogP is the value obtained by calculation of the common logarithm logP of the partition coefficient P between 1-octanol and water. While known methods and software can be used to calculate ClogP, unless otherwise specified, this invention uses ChemDrawProfessional (version 20.1.1.1) from PerkinElmer to plot the structure and employs the value calculated using the following software package 1. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V20.1.1 for Solaris (1994-2007 ACD / Labs)

[0015] While known methods and software can be used to calculate the acid dissociation constant (pKa), in this invention, unless otherwise specified, the values ​​are obtained by calculation using the above-mentioned software package 1, based on a database of Hammett substituent constants and publicly known literature values. If pKa cannot be calculated by the above method, the value obtained by molecular orbital calculation is adopted. Specifically, the molecular orbital calculation method uses the value obtained using Gaussian 16 based on DFT (density functional theory).

[0016] [Composition] The composition of the present invention (hereinafter also referred to as "this composition") will be described in detail below. The first embodiment of this composition is a composition for forming a film on a substrate that suppresses film formation by atomic layer deposition, and comprises a compound C1 having a functional group A that binds to or adsorbs to the substrate, and a specific structure B1 which is at least one of a polyoxyalkylene structure and a betaine structure, and a solvent containing water, wherein the water content is 10% by mass or more of the total mass of the solvent containing water. The second embodiment of this composition is a composition for forming a film on a substrate that suppresses film formation by atomic layer deposition, and comprises a functional group A that binds to or adsorbs to the substrate, and a compound C2 that does not contain the functional group A, has a molecular weight of 130 or more, and exhibits a specific structure B2 which shows a ClogP of -0.50 or less, and a solvent containing water, wherein the water content is 10% by mass or more of the total mass of the solvent containing water.

[0017] The reason why a composition having the above configuration can solve the problems of the present invention is not necessarily clear, but the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than those described below, it is still within the scope of the present invention. The functional group A of compound C1 and compound C2 can form a film on the substrate by bonding to or adsorbing to the substrate. Furthermore, compound C1 has the above-mentioned specific structure B1, and compound C2 has the above-mentioned specific structure B2, so that the film formed by the composition of the present invention can be made water-soluble in compound C1 or compound C2 without reducing the effect of inhibiting film formation by ALD treatment. As described above, it is presumed that the problem of the present invention has been solved because the specific compound has the above-mentioned structure. Hereinafter, when at least one of the following effects is obtained—that the occurrence of defects in the film made by the composition is suppressed, or that the composition can form a film that sufficiently suppresses film formation by atomic layer deposition—it is also referred to as "the effect of the present invention is superior."

[0018] [Specific Compound] This composition contains compound C1 or compound C2. Hereinafter, compound C1 and compound C2 are collectively referred to as the "specific compound." The molecular weight of the specific compound is not particularly limited, but in terms of superior effects of the present invention, it is preferably 200 or more, more preferably 300 or more, and even more preferably 400 or more. The upper limit is preferably 1500 or less, more preferably 1000 or less, and even more preferably 700 or less. Furthermore, if the specific compound is a polymer compound (has a molecular weight distribution), the weight-average molecular weight of the specific compound is preferably 2000 or more, more preferably 5000 or more, and even more preferably 8000 or more. The upper limit is preferably 300,000 or less, more preferably 100,000 or less, and even more preferably 75,000 or less.

[0019] As described above, compound C1 is a compound having a functional group A that binds to or adsorbs to a substrate, and a specific structure B1 which is at least one of a polyoxyalkylene structure and a betaine structure. Compound C2 is a compound having a functional group A that binds to or adsorbs to a substrate, and a specific structure B2 which has a ClogP of -0.50 or less, does not contain the above functional group A, and has a molecular weight of 130 or more. Furthermore, in terms of achieving superior effects of the present invention, it is preferable that the specific compounds (compounds C1 and C2) further have a hydrophobic group in addition to the above-described group and structure. Moreover, the hydrophobic group may be an unsaturated group containing an unsaturated bond. In other words, it is preferable that the specific compounds further have an unsaturated group. The functional group A and the hydrophobic group will be described in detail below.

[0020] <Functional Group A> Functional group A is a functional group that binds to or adsorbs to the substrate. The number of functional groups A in a particular compound is preferably 1 to 3, and more preferably 1 or 2. Specific examples of bonding or adsorption between functional group A and the substrate include, for example, covalent bonds, coordination bonds, ionic bonds, hydrogen bonds, acid-base interactions, van der Waals bonds, and metallic bonds.

[0021] When forming a film with this composition on a metal surface A made of a material containing metal atoms of the substrate, coordination bonds or ionic bonds are preferred, and coordination bonds are more preferred. When forming a film on a nonmetallic surface B made of a nonmetallic material of the substrate, hydrogen bonds, acid-base interactions, or covalent bonds are preferred. Details of the substrate and the surface of the substrate will be described later. Functional group A is preferably either a group that bonds to or adsorbs to the metal surface A of the substrate (also called "functional group AA"), or a group that bonds to or adsorbs to the nonmetallic surface B of the substrate (also called "functional group AB"), and functional group AA is more preferred. Functional group AA is preferably a functional group capable of forming coordination bonds with the metal.

[0022] For superior effects of the present invention, functional group A is preferably a basic functional group or an acidic functional group. When functional group A is a basic functional group, the acid dissociation constant of the conjugate acid of the specific compound (compound C1 or compound C2) obtained by the addition of a proton to the basic functional group is preferably 7.0 or higher, more preferably 8.0 or higher, and even more preferably 9.0 or higher. An upper limit, for example, is 30.0 or lower. When functional group A is an acidic functional group, the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is preferably 5.0 or lower, more preferably 4.0 or lower, and even more preferably 3.0 or lower. A lower limit, for example, is -5.0 or higher.

[0023] Examples of the basic functional groups mentioned above include nitrogen-containing groups. Examples of the nitrogen-containing groups include amino groups (-NR Ｎ ２ ), quaternary ammonium group (-N ＋ R Ｎ ３ Examples include imide groups, hydrazine groups, guanidine groups, and nitrogen-containing heterocyclic groups. ＮEach of these independently represents a hydrogen atom or an organic group (a group containing at least one carbon atom), with a hydrogen atom or an alkyl group being preferred, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms being more preferred, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms being even more preferred. Examples of the nitrogen-containing heterocyclic groups include nitrogen-containing aromatic heterocyclic groups such as pyrrole group, imidazole group, pyrazole group, oxazolyl group, triazole group, benzimidazole group, benztriazole group, pyridyl group, and triazine group, as well as nitrogen-containing aliphatic heterocyclic groups such as pyrrolidinyl group, piperidinyl group, and piperazinyl group, with aromatic heterocyclic groups having 5 or 6 ring member atoms, such as imidazole group and pyridyl group, being preferred.

[0024] When functional group A is a basic functional group, the basic functional group is preferably an amino group, a hydrazine group, or a guanidine group, more preferably a primary amino group, a secondary amino group, or a tertiary amino group, and even more preferably a primary amino group. When the amino group is a secondary or tertiary amino group, the number of carbon atoms in the organic group of the secondary or tertiary amino group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0025] The above acidic functional group is a phosphonic acid group (-PO ３ H ２ ), phosphinic acid group (-PO ２ H ２ ), phosphate group (-PO ４ H ２ ), sulfo group (-SO ３ Examples include H), carboxyl groups (-COOH), and phenolic hydroxyl groups. When functional group A is an acidic functional group, the acidic functional group is preferably a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxyl group, more preferably a phosphonic acid group or a sulfo group, and even more preferably a phosphonic acid group.

[0026] <Hydrophobic Group> The valency of the hydrophobic group is not particularly limited; for example, it can be 1 to 3, with 2 being preferred. Examples of hydrophobic groups include hydrocarbon groups. The number of carbon atoms in the hydrocarbon group is preferably 2 or more, more preferably 4 or more, and even more preferably 6 or more. The upper limit is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less. In particular, it is preferable for the specific compound to further have a hydrocarbon group with 4 or more carbon atoms as a hydrophobic group.

[0027] More specifically, hydrocarbon groups include aliphatic hydrocarbon groups which may have substituents, aromatic groups which may have substituents, and groups which are combinations thereof. The above aliphatic hydrocarbon groups may be linear, branched, or cyclic. Examples of aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups. The number of carbon atoms in linear or branched aliphatic hydrocarbon groups is preferably 1 to 30, more preferably 2 to 30, and even more preferably 4 to 30. Cyclic aliphatic hydrocarbon groups may be monocyclic, such as cyclohexane rings, or polycyclic, such as adamantane. The number of carbon atoms in cyclic aliphatic hydrocarbon groups is preferably 5 to 30, more preferably 5 to 30, and even more preferably 6 to 20. Examples of substituents which aliphatic hydrocarbon groups may have include halogen atoms.

[0028] The aromatic ring constituting the above aromatic group may be monocyclic or polycyclic. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. The number of carbon atoms in the aromatic group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10. Examples of substituents that the aromatic group may have include the above aliphatic hydrocarbon group. Specific embodiments and preferred embodiments of the aliphatic hydrocarbon group are as described above. Among the aliphatic hydrocarbon groups that the aromatic group may have, aliphatic hydrocarbon groups having 1 to 30 carbon atoms are preferred, aliphatic hydrocarbon groups having 1 to 20 carbon atoms are more preferred, and alkyl groups having 1 to 20 carbon atoms are even more preferred. The number of substituents that the aromatic group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0029] Examples of groups formed by combining an optionally substituted aliphatic hydrocarbon group and an optionally substituted aromatic group include a -divalent aliphatic hydrocarbon group-aromatic group, or an aromatic group having an aliphatic hydrocarbon group as a substituent. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear or branched is preferred. Examples of divalent aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, and alkylylene groups, with alkylene groups being preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 10, and more preferably 1 to 6. Specific examples and preferred embodiments of the above aliphatic hydrocarbon group and aromatic group are as described above.

[0030] As described above, the hydrophobic group may be an unsaturated group containing an unsaturated bond. In other words, it is preferable for the specific compound to further contain an unsaturated group. The presence of an unsaturated group in the specific compound allows for crosslinking of the specific compounds by heating during the ALD treatment, enabling the formation of a stable ALD inhibitory film. The hydrophobic group may contain either a double bond or a triple bond. When the hydrophobic group is an unsaturated group containing an unsaturated bond, an alkenyl group or an alkynyl group is preferred, more preferably an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, and even more preferably a vinyl group, a styryl group, a vinylnaphthyl group, a vinyl ether group, or an alkynyl group having 2 to 18 carbon atoms. The vinylnaphthyl group is preferably a group obtained by removing the hydrogen atom at position 6 from 2-vinylnaphthalene.

[0031] The specific structure B1 possessed by compound C1 and the specific structure B2 possessed by compound C2 will be described in detail below.

[0032] -Specific Structure B1- Compound C1 has a specific structure B1 which is at least one of a polyoxyalkylene structure and a betaine structure. If compound C1 is a polymer, compound C1 may have the specific structure B1 in either the main chain or the side chain, but it is preferable that the specific structure B1 be in the side chain.

[0033] Of the specific structures B1, the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure, and more preferably a structure represented by formula (1) or formula (2).

[0034]

[0035] In formula (1), n ​​represents an integer of 2 or more. n is preferably 3 or more, and more preferably 5 or more. The upper limit is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and particularly preferably 10 or less. In formula (2), m represents an integer of 2 or more. m is preferably 3 or more, and more preferably 5 or more. The upper limit is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and particularly preferably 10 or less.

[0036] Among the specific structures B1, the betaine structure described above is not particularly limited as long as it has both a cationic and anionic portion within its structure. Examples of betaine structures include a carbobetaine structure, a sulfobetaine structure, or a phosphobetaine structure. In a carbobetaine structure, the dissociated carboxyl group constitutes the anionic portion (negative charge), in a sulfobetaine structure, the dissociated sulfo group constitutes the anionic portion, and in a phosphobetaine structure, the phosphate ester anion or the dissociated phosphate group constitutes the anionic portion of the betaine structure. Examples of cationic portions include a quaternary ammonium cation structure, a sulfonium cation structure, and a phosphonium cation structure, and it is preferable that the betaine structure has a quaternary ammonium cation portion. In terms of superior effects of the present invention, it is preferable that the betaine structure has a cationic portion selected from the group consisting of a quaternary ammonium cation, a sulfonium cation, and a phosphonium cation, and an anionic portion selected from the group consisting of a phosphate ester anion, a phosphate anion, a sulfonic acid anion, and a carboxylic acid anion.

[0037] Furthermore, in terms of achieving superior effects of the present invention, the betaine structure is preferably a structure represented by any of formulas (3) to (6).

[0038]

[0039] In formulas (3) to (6), L １ ~L ４ Each of these independently represents a divalent linking group. １ Examples of divalent linking groups represented by include divalent aliphatic hydrocarbon groups, divalent aromatic groups, -O-, -CO-, and -NR Ｃ - (R Ｃ ) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), and groups formed by combining two or more of these groups are examples of linking groups formed by combining two or more of the above groups. Examples of linking groups formed by combining two or more of the above groups include -O-divalent aliphatic hydrocarbon group-, -divalent aromatic group-O-divalent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aromatic group-, -CONH-divalent aromatic group-, -COO-divalent aliphatic hydrocarbon group-, -divalent aliphatic hydrocarbon group-O-divalent aliphatic hydrocarbon group-, and -CONH-divalent aliphatic hydrocarbon group-.

[0040] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear is preferred. Examples of divalent aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, and alkylylene groups, with alkylene groups being preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0041] The above-mentioned divalent aromatic group may be either a divalent aromatic hydrocarbon group (arylene group) or a divalent aromatic heterocyclic group (heteroarylene group), but the arylene group is preferred. The aromatic ring constituting the divalent aromatic group may be monocyclic or polycyclic. The number of carbon atoms in the divalent aromatic group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0042] The above-mentioned divalent aliphatic hydrocarbon group and the above-mentioned divalent aromatic group may have substituents. Examples of substituents that the divalent aliphatic hydrocarbon group may have include hydroxyl groups or halogen atoms. Examples of substituents that the divalent aromatic group may have include C1-C6 alkyl groups, C1-C6 alkoxy groups, hydroxyl groups, and halogen atoms. １ ~L ４ Among these, divalent aliphatic hydrocarbon groups are preferred, alkylene groups are more preferred, and alkylene groups having 2 to 6 carbon atoms are even more preferred.

[0043] In formulas (3), (5), and (6) above, X, V, and W each independently represent a monovalent anionic group. The anionic group is not particularly limited, but it can be an acid group that releases a proton (H ＋ A dissociated group is preferred. As for the anionic group, a dissociated sulfo group, a dissociated carboxyl group, or a dissociated phosphate group is preferred, and a dissociated sulfo group or a dissociated carboxyl group is more preferred.

[0044] In the above formula (3), R １ R represents an alkyl group with 1 to 8 carbon atoms. There are multiple R's. １ These may be identical or different from one another. １ Among these, alkyl groups having 1 to 3 carbon atoms are preferred, and methyl groups are more preferred.

[0045] In formula (4) above, Y represents a monovalent cationic group. The cationic group is not particularly limited, but examples include cationic groups containing any of a quaternary ammonium cation, a sulfonium cation, and a phosphonium cation. As a monovalent cationic group, a cationic group represented by the following formula (C) is preferred. In formula (C), * represents the bond position.

[0046]

[0047] In formula (C), R ａ ~R ｃ Each of these independently represents an alkyl group which may have substituents. Also, R ａ ~R ｃAn alkyl group which may have two substituents selected from the above may be bonded to each other to form a ring. The alkyl group may be linear or branched, with linear being preferred. The number of carbon atoms in the alkyl group portion of the alkyl group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and particularly preferably 1 or 2. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl groups. Examples of substituents include hydroxyl and phenyl groups. Examples of alkyl groups having substituents include 2-hydroxyethyl, 2-hydroxypropyl, and benzyl groups. Furthermore, the methylene group constituting the alkyl group may be substituted with a divalent substituent such as -O-. ａ ~R ｃ The total number of carbon atoms in the compound is not particularly limited, but is preferably 4 to 20, and more preferably 5 to 15.

[0048] In the above formulas (5) and (6), R ２ and R ３ Each of these independently represents an optionally substituted alkyl group or an optionally substituted phenyl group. ３ These may be the same or different from each other. Examples of substituents that the alkyl group may have include a hydroxyl group or a halogen atom, and examples of substituents that the phenyl group may have include C1-C6 alkyl groups, C1-C6 alkoxy groups, hydroxyl groups, and halogen atoms. The alkyl group may be linear, branched, or cyclic. Furthermore, the number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0049] -Specific Structure B2- Compound C2 has a specific structure B2 in which ClogP is -0.50 or less, does not contain the above-mentioned functional group A, and has a molecular weight of 130 or more. Specific examples and preferred embodiments of functional group A are as described above. When compound C2 is a polymer, compound C2 may have the specific structure B2 in either the main chain or the side chain, but it is preferable that the specific structure B2 be in the side chain.

[0050] Specific structure B2 is a structure in compound C2 in which ClogP is -0.50 or less and the molecular weight is 130 or more. In this specification, structural unit B2 is defined as the unit with the smallest molecular weight among the above structures. For example, if compound C2 is compound E-1 shown below, the polyoxyethylene structure corresponds to a structure in which ClogP is -0.50 or less, but among the above structures -O-(CH ２ CH ２ O) ３ The unit represented by - has a molecular weight of 130 or more and is the smallest unit, and is therefore structural unit B2 shown by the dashed line in the structural formula below. There is no particular upper limit to the molecular weight of structural unit B2, but it is preferably 700 or less, more preferably 500 or less, and even more preferably 300 or less.

[0051]

[0052] Furthermore, the ClogP value of specific structure B2 is preferably -0.7 or less, more preferably -1.0 or less, and even more preferably -1.3 or less. There is no particular lower limit, but -10.0 or more is preferred.

[0053] Specific examples of structural unit B2 include the polyoxyalkylene structure and the betaine structure described above. Specific examples and preferred embodiments of each structure are as detailed in the description of structural unit B1.

[0054] The specific compounds (compound C1 and compound C2) are preferably compounds represented by formula (X1) or formula (X2), or polymer compounds having at least one of repeating unit Y1 and functional group A, and repeating unit Y2. In particular, the specific compound is preferably a compound represented by formula (7), which will be described later.

[0055] <Compound represented by formula (X1) or formula (X2)> Formula (X1) or formula (X2) will be described in detail below. A-Lx-B １ -R...Formula (X1) A-Lx-B ２ ...Formula (X2) In formulas (X1) and (X2), A represents the functional group A. Specific examples and preferred embodiments of the functional group A are as described above. Lx represents a single bond or a divalent linking group. Specific examples and preferred embodiments of the divalent linking group are as described above. １ This is the same as the divalent linking group represented by . Among Lx, a divalent aliphatic hydrocarbon group which may have a hydroxyl group is preferred, an alkylene group which may have a hydroxyl group is more preferred, and an alkylene group having 2 to 6 carbon atoms which may have a hydroxyl group is even more preferred.

[0056] In formula (X1), B １ R represents a polyoxyalkylene structure. Specific examples and preferred embodiments of the polyoxyalkylene structure are as described above. R represents a monovalent hydrocarbon group, an -O-1valent hydrocarbon group, an -CO-O-1valent hydrocarbon group, or an -O-CO-1valent hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group are the same as those for the hydrocarbon group exemplified as a hydrophobic group above.

[0057] In formula (X2), B ２ This represents a betaine structure represented by any of the above formulas (3) to (6). Formulas (3) to (6) are as described above.

[0058] <Compound represented by formula (7)>

[0059]

[0060] In equation (7), n represents an integer greater than or equal to 2. ５ represents a single bond or a divalent linking group. Ar represents a divalent aromatic group. R ４ represents a hydrogen atom or an alkyl group.

[0061] In formula (7) above, n is preferably 3 or greater, and more preferably 5 or greater. The upper limit is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and particularly preferably 10 or less.

[0062] In the above formula (7), L ５ Examples of divalent linking groups represented by include -O-, -CO-, and -NR Ｃ - (R Ｃ ) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples include a divalent aliphatic hydrocarbon group, a divalent aromatic group, and a group formed by combining two or more of these groups. Examples of linking groups formed by combining two or more of the above groups include -O-divalent aromatic group-O-, -O-divalent aliphatic hydrocarbon group-, -divalent aromatic group-O-divalent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aromatic group-, -CONH-divalent aromatic group-, -COO-divalent aliphatic hydrocarbon group-, -divalent aliphatic hydrocarbon group-O-divalent aliphatic hydrocarbon group-, and -CONH-divalent aliphatic hydrocarbon group-.

[0063] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear is preferred. Examples of divalent aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, and alkylylene groups, with alkylene groups being preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0064] The above-mentioned divalent aromatic group may be either a divalent aromatic hydrocarbon group (arylene group) or a divalent aromatic heterocyclic group (heteroarylene group). The aromatic ring constituting the divalent aromatic group may be monocyclic or polycyclic. The number of carbon atoms in the divalent aromatic group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10. Specific examples of aromatic rings constituting the above-mentioned divalent aromatic group include, for example, a benzene ring, naphthalene ring, anthracene ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, tetrazine ring, quinoxaline ring, pyrrole ring, furan ring, thiophene ring, carbazole ring, imidazole ring, oxazole ring, thiazole ring, benzopyrrole ring, benzofuran ring, benzothiophene ring, benzimidazole ring, benzoxazole ring, and benzothiazole ring.

[0065] The above-mentioned divalent aliphatic hydrocarbon group and the above-mentioned divalent aromatic group may have substituents. Examples of substituents that the divalent aliphatic hydrocarbon group may have include a hydroxyl group or a halogen atom. Examples of substituents that the divalent aromatic group may have include C1-C6 alkyl groups, C1-C6 alkoxy groups, hydroxyl groups, and halogen atoms.

[0066] L ５ Among these, -O-, -O-divalent aromatic groups -O-, or -O-divalent aliphatic hydrocarbon groups - are preferred.

[0067] In formula (7) above, the divalent aromatic group represented by Ar may be either a divalent aromatic hydrocarbon group (arylene group) or a divalent aromatic heterocyclic group (heteroarylene group). For specific examples of aromatic rings constituting the divalent aromatic group, see L ５ As detailed above, the divalent linking group represented by is as follows.

[0068] In the above formula (7), R ４ The alkyl group represented by may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 10, and even more preferably 2 to 6.

[0069] <Polymer compound having at least one of repeating unit Y1 and functional group A, and repeating unit Y2> Repeating unit Y1 is a repeating unit having functional group A, and repeating unit Y2 is a repeating unit having a specific structure B1 and not having functional group A. Repeating unit Y1 may further have the specific structure B1. Specific examples and preferred embodiments of functional group A and specific structure B1 are as described above. When the specific compound has functional group A in addition to repeating unit Y1, it is preferable that the functional group A is at the main chain end of the specific compound. The content of repeating unit Y1 is preferably 5 to 100 mol%, more preferably 10 to 95 mol%, relative to the total repeating units in the specific compound. The content of repeating unit Y2 is preferably 5 to 60 mol%, more preferably 5 to 50 mol%, relative to the total repeating units in the specific compound.

[0070] The repeating unit Y1 is preferably a repeating unit represented by formula (Y1), and the repeating unit Y2 is preferably a repeating unit represented by formula (Y2).

[0071]

[0072] In formula (Y1), R Ｙ１１ ~R Ｙ１３ Each of these independently represents a hydrogen atom, a fluorine atom, or a methyl group. Ｙ１１ ~R Ｙ１３ A hydrogen atom is preferred as the element.

[0073] In the above formula (Y1), X １ This represents functional group A. Specific examples and preferred embodiments of functional group A are as described above. L １ represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic hydrocarbon groups, divalent aromatic groups, -O-, -CO-, and -NR Ｃ - (R Ｃ) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), and groups formed by combining two or more of these groups are examples of linking groups formed by combining two or more of the above groups. Examples of linking groups formed by combining two or more of the above groups include -O-divalent aliphatic hydrocarbon group-, -divalent aromatic group-O-divalent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aromatic group-, -CONH-divalent aromatic group-, -COO-divalent aliphatic hydrocarbon group-, -divalent aliphatic hydrocarbon group-O-divalent aliphatic hydrocarbon group-, and -CONH-divalent aliphatic hydrocarbon group-.

[0074] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear is preferred. Examples of divalent aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, and alkylylene groups, with alkylene groups being preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.

[0075] The above-mentioned divalent aromatic group may be either a divalent aromatic hydrocarbon group (arylene group) or a divalent aromatic heterocyclic group (heteroarylene group), but the arylene group is preferred. The aromatic ring constituting the divalent aromatic group may be monocyclic or polycyclic. The number of carbon atoms in the divalent aromatic group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0076] The above-mentioned divalent aliphatic hydrocarbon group and the above-mentioned divalent aromatic group may have substituents. Examples of substituents that the divalent aliphatic hydrocarbon group may have include halogen atoms. Examples of substituents that the divalent aromatic group may have include C1-C6 alkyl groups, C1-C6 alkoxy groups, and halogen atoms. １ Among these, single bonds, divalent aromatic groups, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aliphatic hydrocarbon group-, or -CONH-divalent aliphatic hydrocarbon group- are preferred. Also, L １ The divalent linking group represented by may further have the above-mentioned specific structure B1.

[0077] In the above formula (Y1), R Ｙ１２ and L １ These elements may bond to each other to form a ring. Examples of such rings include aliphatic hydrocarbon rings and aliphatic heterocycles, and specifically, cyclic olefins and cyclic imides.

[0078] In formula (Y2), R Ｙ２１ ~R Ｙ２３ Each of these independently represents a hydrogen atom, a fluorine atom, or a methyl group. Ｙ２１ ~R Ｙ２３ As such, hydrogen atoms are preferred. ２ L represents a single bond or a divalent linking group. ２ Specific examples and preferred embodiments are shown in L １ This is the same as the specific examples and preferred embodiments. L ２ Among these, single bonds, divalent aromatic groups, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aliphatic hydrocarbon group-, or -CONH-divalent aliphatic hydrocarbon group- are preferred. Ｙ２１ and L ２ These elements may bond to each other to form a ring. Examples of such rings include aliphatic hydrocarbon rings and aliphatic heterocycles, and specifically, cyclic olefins and cyclic imides.

[0079] In the above formula (Y2), X ２ This represents a polyoxyalkylene group or a betaine structure represented by any of the above formulas (3) to (6). Formulas (3) to (6) are as described above. The polyoxyalkylene group is preferably a group represented by the following formula (OA): *-(AL-O) ｋ-R ...Formula (OA) In formula (OA), AL represents an ethylene group or a propylene group, with an ethylene group being preferred. k represents 2 to 100. k is preferably 2 or more, more preferably 3 or more, and even more preferably 5 or more. The upper limit is preferably 100 or less, more preferably 50 or less, even more preferably 30 or less, and particularly preferably 10 or less. R represents a monovalent hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group are as described in detail above for the hydrophobic group. Among the hydrocarbon groups, aliphatic hydrocarbon groups are preferred, aliphatic hydrocarbon groups having 1 to 6 carbon atoms are more preferred, and alkyl groups having 1 to 4 carbon atoms are even more preferred.

[0080] A polymer compound having repeating unit Y1 and at least one of functional group A, and repeating unit Y2 may also have repeating unit Y3 that does not correspond to either repeating unit Y1 or repeating unit Y2, in addition to the repeating units described above. When a specific compound has repeating unit Y3, the content of repeating unit Y3 is preferably 90 mol% or less, more preferably 25 mol% or less, and even more preferably 5 mol% or less, relative to the total repeating units of the specific compound. The lower limit is not particularly limited, but for example, it may be 0 mol% or more. Examples of repeating unit Y3 include repeating units derived from monomers such as aromatic vinyl compounds, (meth)acrylates, and (meth)acrylamide compounds. Among these, repeating units derived from styrene or N-alkylacrylamide compounds are preferred as repeating units that do not contain acidic functional groups. It is also preferable that repeating unit Y3 has the hydrophobic group described above.

[0081] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 10.00% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less, based on the total mass of the composition. There is no particular lower limit, but it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. Furthermore, in terms of achieving superior effects of the present invention, the total amount of the specific compound and the water-containing solvent, which will be described in detail later, is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 99.90% by mass or more, based on the total mass of the composition. The upper limit is 100% by mass or less, and preferably 99.9999% by mass or less.

[0082] [Water-containing solvent] The present composition (first and second embodiments) contains a water-containing solvent, wherein the water content is 10% by mass or more of the total mass of the water-containing solvent. For superior effects of the present invention, the water content is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more, based on the total mass of the water-containing solvent. The upper limit may be 100% by mass or less, preferably 95% by mass or less, and more preferably 80% by mass or less. As a solvent other than water, an organic solvent is preferred, and an organic solvent that is miscible with water in any proportion is more preferred. Examples of organic solvents include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and hydrocarbon-based solvents.

[0083] Examples of alcohol-based solvents include monoalcohol solvents, polyol solvents, and glycol monoether solvents. Examples of monoalcohol solvents include aliphatic monoalcohol solvents having 1 to 18 carbon atoms such as methanol, ethanol (EtOH), 1-propanol, 2-propanol (IPA), 2-butanol, isobutyl alcohol, tert-butyl alcohol, isopentyl alcohol, and 4-methyl-2-pentanol (methylisobutylcarbinol); alicyclic monoalcohol solvents having 3 to 18 carbon atoms such as cyclohexanol; aromatic monoalcohol solvents such as benzyl alcohol; and ketone monoalcohol solvents such as diacetone alcohol. Examples of polyol solvents include glycol solvents having 2 to 18 carbon atoms such as ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol. Examples of glycol monoether solvents include glycol monoether solvents having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.The number of carbon atoms in the alcohol-based solvent is preferably 1 to 19, more preferably 2 to 12, and even more preferably 3 to 8.

[0084] Examples of ether-based solvents include glycol ether solvents such as tetraethylene glycol dimethyl ether (TEGDME), triethylene glycol butyl methyl ether (TEGBME), ethylene glycol dimethyl ether (dimethoxyethane), dipropylene glycol methyl-n-propyl ether, and dipropylene glycol methyl-n-butyl ether; dialkyl ether solvents such as ethylene glycol dimethyl ether (dimethoxyethane), diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dihexyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, and cyclohexyl methyl ether; cyclic ether solvents such as tetrahydrofuran (THF) and tetrahydropyran; anisole; and diphenyl ether.

[0085] Examples of ester solvents include glycol ester solvents, monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate, lactone solvents such as γ-butyrolactone (GBL) and δ-valerolactone, and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. Glycol ester solvents include glycol dicarboxylate solvents with 6 to 22 carbon atoms such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, tetraethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, triacetin, and methoxybutyl acetate, as well as propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, and diethyl Examples of glycol monoether carboxylate solvents having 5 to 21 carbon atoms include ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, tetraethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, tripropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate. The number of carbon atoms in the ester solvent is preferably 3 to 22, and more preferably 4 to 12.

[0086] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane and n-hexane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbon solvents such as toluene and xylene.

[0087] Examples of ketone solvents include linear ketone solvents such as methyl isobutyl ketone, acetone, methyl ethyl ketone, diethyl ketone, methyl-n-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-ketone, diisobutyl ketone, and trimethylnonane; cyclic ketone solvents such as cyclohexanone, cyclopentanone, cycloheptanone, and methylcyclohexanone; and acetophenone.

[0088] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0089] Examples of sulfur-containing solvents include dimethyl sulfoxide (DMSO), dimethyl sulfone, and sulfolane.

[0090] In solvents containing water, preferred solvents other than water are alcohol-based solvents, ether-based solvents, sulfur-containing solvents, ester-based solvents, or ketone-based solvents; more preferred are aliphatic monoalcohol-based solvents, polyol-based solvents, glycol monoether-based solvents, ether-based solvents, or sulfur-containing solvents; and even more preferred are glycol monoether-based solvents or glycol ester-based solvents. In particular, the solvent preferably contains at least one selected from the group consisting of IPA, ethylene glycol, PGME, dimethoxyethane, THF, propylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, triacetin, 1,3-butylene glycol, diethylene glycol monoethyl ether, sulfolane, ethyl lactate, and DMSO.

[0091] Furthermore, the solvent may also preferably include at least one selected from the group consisting of TEGBE, TEGDME, TEGBME, PGME, diethylene glycol monomethyl ether, triethylene glycol butyl methyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, triacetin, 1,3-butylene glycol, ethylene glycol, IPA, dimethoxyethane, THF, propylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, sulfolane, ethyl lactate, and DMSO.

[0092] The water-containing solvent may consist of one solvent other than water alone, or a combination of two or more solvents. The water-containing solvent content is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 97.00% by mass or more, based on the total mass of the composition. The upper limit is preferably less than 100% by mass, more preferably 99.999% by mass or less, and even more preferably 99.9% by mass or less.

[0093] [Other Components] This composition may contain other components besides the specific compound (compound C1 or compound C2) and a solvent including water. Examples of other components include polymerization inhibitors. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, free radical compounds, amine compounds, and phosphine compounds.

[0094] [Method for Manufacturing the Composition] The method for manufacturing the composition is not particularly limited, but for example, it can be manufactured by mixing the above-mentioned components. The order or timing of mixing the components is not particularly limited, and for example, it can be manufactured by adding the specific compound to a stirrer such as a mixing mixer containing a solvent including purified water, and then stirring thoroughly. In terms of achieving superior effects of the present invention, it is preferable that each raw material of the composition (e.g., the solvent and the specific compound) has been purified.

[0095] The manufacturing process of this composition may include a step selected from the group consisting of a distillation step for distilling raw materials, a dehydration step for dehydrating the composition, a metal removal step for removing metal components from the composition, a filtration step for filtering the composition, and an electrostatic removal step for removing static electricity from the composition.

[0096] This composition can be stored, transported, and used by filling it into a known container. For semiconductor applications, a container with a high degree of cleanliness and suppressed elution of impurities from the inner wall of the container's compartment into the liquids is preferred. Examples of such containers include, but are not limited to, various commercially available containers for semiconductor processing solutions, such as the "Clean Bottle" series from Aicello Chemical Co., Ltd. and the "Pure Bottle" from Kodama Resin Industry Co., Ltd. Furthermore, containers exemplified in paragraphs

[0121] to

[0124] of International Publication No. 2022 / 004217 can also be used, and the contents of these paragraphs are incorporated herein by reference.

[0097] [Uses of this composition] As described above, this composition is for forming a coating on a substrate that suppresses film formation by atomic layer deposition (ALD) (hereinafter also simply referred to as "ALD inhibitory film"), and is preferably used in the substrate modification process in the semiconductor device manufacturing process. By forming an ALD inhibitory film using this composition, a modified substrate with a coating formed on the substrate (substrate surface) can be obtained. Furthermore, this composition is also preferably used in the manufacture of a laminate in which material is deposited in areas where a coating has not been formed by the above process, by applying ALD treatment to the modified substrate. The manufacturing methods for the modified substrate and the laminate will be described in detail later.

[0098] <Substrate> The substrate is not particularly limited, but it is preferable to have at least one of a metal surface A made of a material containing metal atoms and a nonmetal surface B made of a nonmetal material, and it is more preferable to include a metal surface A.

[0099] The metal atoms contained in the metal surface A are not particularly limited, but tungsten atoms, copper atoms, ruthenium atoms, cobalt atoms, titanium atoms, tantalum atoms, molybdenum atoms, germanium atoms, zirconium atoms, aluminum atoms, tin atoms, nickel atoms, palladium atoms, indium atoms, zinc atoms, gold atoms, silver atoms, or platinum atoms are preferable, tungsten atoms, molybdenum atoms, cobalt atoms, copper atoms, or ruthenium atoms are more preferable, and tungsten atoms, molybdenum atoms, or cobalt atoms are even more preferable. The form of the metal atoms on the metal surface A is not particularly limited, and examples include elemental metals, alloys, nitrides, oxides, and silicides, etc., and elemental metals or alloys are preferable. As the alloy, for example, an alloy containing two or more of the metal atoms contained in the above-described metal surface A can be mentioned. The method for forming the metal surface A is not particularly limited, and known methods can be used. For example, CVD method, plating, and physical vapor deposition method can be mentioned.

[0100] The non-metal materials constituting the non-metal surface B include insulators, for example, non-metal simple substances such as silicon and carbon, non-metal oxides such as silicon oxide, non-metal nitrides such as silicon nitride, non-metal oxynitrides such as silicon oxynitride, and organic substances, etc. As the material constituting the non-metal surface B, a non-metal material containing silicon atoms is preferable, and silicon or silicon oxide is more preferable. Specifically, as the silicon oxide, for example, a material represented by the composition of SiO ｙ (where y preferably represents 0.5 to 2.0, more preferably 1.0 to 2.0), and a material represented by the composition of SiO ｚ C ｗ (where z preferably represents 0.5 to 2.0, more preferably 1.0 to 2.0, and w preferably represents 0.5 to 2.0, more preferably 1.0 to 2.0) can be mentioned. The material represented by the composition of SiO ｙ and the material represented by the composition of SiO ｚ C ｗ may further contain hydrogen. As the material represented by the composition of SiO ｚ C ｗ , for example, Si(OC ２ H ５ )４ Examples include (tetraethyl orthosilicate, TEOS). Examples of silicon oxides include SiO ２ A material represented by the following composition (silicon dioxide) or TEOS is preferred.

[0101] The method for forming the nonmetallic surface B is not particularly limited and includes methods such as CVD, physical vapor deposition, plasma irradiation, and coating of precursor compounds. It is also preferable that the nonmetallic surface B is a region made of silicon or silicon oxide that has been surface-treated. Examples of such treatments include contact with a treatment solution such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride), plasma treatment, corona treatment, and ozone treatment.

[0102] The substrate may also preferably have at least two surfaces, a first surface and a second surface, composed of different materials. The first surface is a surface that interacts with a specific functional group of a specific compound. The second surface may be composed of a different material from the first surface, but it is preferable that it is a surface that does not form a film when in contact with the composition. In particular, it is preferable that at least one of the first surface and the second surface is a metallic surface A or a non-metallic surface B, and it is more preferable that at least one of the first surface and the second surface is a metallic surface A. Among the first surfaces, it is preferable that it is a metallic surface composed of at least one metal selected from tungsten atoms, molybdenum atoms, cobalt atoms, copper atoms, and ruthenium atoms.

[0103] A preferred embodiment of the substrate is Embodiment 1, in which the first surface is a metal surface A. In Embodiment 1, the specific functional group possessed by the specific compound is the specific functional group A described above. In Embodiment 1, the metal atoms on the first surface, the metal surface A, are preferably in the form of elemental metal, alloy, conductive metal nitride, or metal silicide, with elemental metal or alloy being more preferred. Examples of the elemental metal and alloy include the elemental metals and alloys thereof that are exemplified as metals contained in the metal surface A. Examples of the conductive metal nitride include tantalum nitride, titanium nitride, iron nitride, and aluminum nitride. Examples of the metal silicide include iron silicide, molybdenum silicide, and tungsten silicide.

[0104] In Embodiment 1, the second surface is preferably a different metal surface A or a non-metal surface B from the first surface, and more preferably a non-metal surface B. In Embodiment 1, the metal atoms in the metal surface A constituting the second surface are preferably in the form of a metal oxide, a metal nitride, or a metal oxynitride, and more preferably a metal oxide. Examples of metal oxides include aluminum oxide, tantalum oxide, iron oxide, and copper oxide.

[0105] A preferred embodiment of the substrate is Embodiment 2, in which the first surface is a nonmetallic surface B. In Embodiment 2, the specific functional group possessed by the specific compound is the specific functional group B described above. In Embodiment 2, the second surface is preferably a metallic surface A. In Embodiment 2, the metal atoms on the metallic surface A, which is the second surface, are preferably in the form of elemental metal, an alloy, a conductive metal nitride, or a metal silicide, with elemental metal or an alloy being more preferable.

[0106] The shapes of the first and second surfaces are not particularly limited and include, for example, planar, dotted, and striped.

[0107] The shape of the substrate is not particularly limited, and any shape commonly used for semiconductor substrates can be adopted. Furthermore, the substrate may have any surface as described above, and may be single-layer or multilayer in structure.

[0108] <Coating> The coating formed on the substrate by this composition is a coating containing components other than the water-containing solvent in this composition (for example, specific compounds). Preferably, the coating functions as a mask when depositing material in the ALD treatment. That is, when an ALD treatment is performed on a modified substrate on which a coating has been formed with this composition in a specific area, it is preferable that no material is deposited in the area where the coating is formed, and that material is deposited in the area where the coating is not formed, forming a film (hereinafter also referred to as the "ALD film"). This makes it possible to obtain a laminate in which the ALD film is selectively formed in areas other than the area where the coating is formed.

[0109] The above-mentioned coating also functions favorably as a mask when forming a metal-containing film by chemical vapor deposition (CVD) other than ALD. That is, in CVD processing, the deposition of a CVD film (hereinafter also referred to as "CVD film") is suppressed in the region where the above-mentioned coating is formed, and a CVD film can be deposited in the region where the above-mentioned coating is not formed. As a result, a laminate is obtained in which a CVD film is selectively formed in regions other than the region where the coating is formed. Known methods other than ALD that can be favorably applied to the above-mentioned modified substrate include thermal CVD and plasma CVD. The raw materials for the ALD film described later can be used as the raw materials for the CVD film used in CVD processing.

[0110] The film thickness of the above coating is preferably 0.1 to 100.0 nm, more preferably 0.5 to 50.0 nm, and even more preferably 3.0 to 30.0 nm.

[0111] For the present invention to be more effective, the water contact angle of the above-mentioned coating is preferably 60° or higher, more preferably 80° or higher, and even more preferably 90° or higher. There is no particular upper limit, but it is often 120° or lower. The above-mentioned water contact angle is the average value obtained by measuring the contact angle three times 500 milliseconds after a water droplet contacts the surface of the object to be measured using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.).

[0112] [Method for Manufacturing a Modified Substrate] The method for manufacturing a modified substrate of the present invention includes the step of bringing a substrate into contact with the composition to form a film on the substrate. This yields a modified substrate with a film formed on it. The method for manufacturing a modified substrate of the present invention can be suitably used, for example, in the manufacture of electronic devices (semiconductor devices). The method for bringing the substrate into contact with the composition is not particularly limited, and known methods can be used. For example, methods include coating (e.g., spin coating) or spraying the composition onto the substrate, and immersing the substrate in the composition. When immersing the substrate in the composition, the composition may be circulated. The temperature of the composition when bringing it into contact with the substrate is not particularly limited, but is preferably 0 to 50°C, and more preferably 10 to 30°C. The contact time between the substrate and the composition is not particularly limited, but is preferably 30 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and even more preferably 5 to 15 minutes.

[0113] After bringing the substrate and the composition into contact, the coating film may be subjected to heat treatment. The heating method is not particularly limited, and known methods can be used, such as an oven and a hot plate. The heating temperature is preferably 50 to 400°C, more preferably 100 to 350°C, even more preferably 130 to 300°C, and particularly preferably 150 to 250°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 1 to 30 minutes, and even more preferably 3 to 10 minutes.

[0114] It is also preferable to perform a rinsing treatment after bringing the substrate and the composition into contact. Rinsing treatment can remove at least one of the composition and impurities adhering to areas of the substrate other than the desired area (for example, an area that interacts with a specific functional group contained in a specific compound). The rinsing method is not particularly limited and can be performed by bringing the rinsing solution into contact with the substrate. The same contact method as the method for bringing the composition and the substrate into contact can be used. The temperature of the rinsing solution at the time of contact is not particularly limited, but is preferably 0 to 50°C, and more preferably 10 to 30°C. As the rinsing solution, a known organic solvent can be used, for example, the alcohol-based solvents, ether-based solvents, and ester-based solvents mentioned above can be used.

[0115] [Method for Manufacturing a Laminate] The method for manufacturing a laminate of the present invention includes a step 1 of bringing a substrate having at least two surfaces, a first surface and a second surface, made of different materials (hereinafter also referred to as a "specific substrate"), into contact with the composition to form a first coating on the first surface, and a step 2 of applying ALD treatment to the substrate obtained in step 1 to form a second coating on the second surface. This provides a laminate having a second coating (ALD film) on the second surface.

[0116] [Step 1: Method for Manufacturing a Modified Substrate] Step 1 is a step of bringing a specific substrate and the composition into contact to form a first film on a first surface. Step 1 provides a modified substrate 1 in which a first film is formed on the first surface of the specific substrate. The first film is a film containing a specific compound included in the composition. The method of bringing the specific substrate and the composition into contact is not particularly limited, and the method of bringing the composition and the substrate into contact in the above-described method for manufacturing a modified substrate can be used.

[0117] After bringing a specific substrate into contact with the composition, the coating film may be subjected to heat treatment. The heating method is not particularly limited, and the heating method described above in the manufacturing method of the modified substrate can be used.

[0118] It is also preferable to subject the modified substrate 1, on which the first coating has been formed on the first surface, to a rinsing treatment. By rinsing, at least one of the composition and impurities adhering to areas other than the first surface on the specific substrate (for example, the second surface) can be removed from the specific substrate. As a rinsing method, the rinsing method described in the manufacturing method of the modified substrate above can be used.

[0119] [Step 2: ALD Treatment] Step 2 is a step in which the modified substrate 1 obtained in Step 1 is subjected to ALD treatment to form a second film on the second surface. Step 2 yields a laminate 1 in which a first film is formed on the first surface and a second film is formed on the second surface. The second film is a film (ALD film) formed by the ALD treatment. The modified substrate 1 can be any substrate in which the first film is formed on the first surface of a specific substrate in Step 1, and the heat treatment and rinsing treatment described above may be performed after Step 1.

[0120] The ALD treatment method is not particularly limited, and known methods can be used. For example, a method can be used in which a precursor gas, which is the raw material for the ALD film, is supplied to the surface of a modified substrate 1, and then the raw material is decomposed and / or chemically reacted with an oxidizing agent or reducing agent to deposit the material and form an ALD film. The precursor is not particularly limited, and known precursors can be used depending on the type of ALD film to be formed, for example, organometallic compounds. Alumina, tantalum nitride, or titanium nitride can be used as precursors. The oxidizing agent is not particularly limited, and known oxidizing agents used in ALD treatment can be used, for example, water, oxygen, and ozone.

[0121] The materials constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, and the oxidizing agent. The material of the formed ALD film is not particularly limited and includes metals, metal oxides, and metal nitrides. Examples of metals include aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, lanthanum, cerium, hafnium, tantalum, tungsten, platinum, and bismuth. Examples of metal oxides include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide. Examples of metal nitrides include titanium nitride and tantalum nitride. In the ALD treatment, a treatment may be performed to alter the surface of the region where the first film has not been formed.

[0122] After ALD treatment, the thickness of the material deposited on the first film is preferably as thin as possible, preferably 4.0 nm or less, more preferably 2.0 nm or less, and even more preferably 1.0 nm or less. The lower limit is 0 nm. The ratio of the thickness of the material deposited on the region where the first film is formed to the thickness of the second film is preferably 0.75 or less, more preferably 0.50 or less, and even more preferably 0.25 or less. The lower limit of the above ratio is 0 or more.

[0123] [Step 3: Removal of coating (removal process)] The method for manufacturing the laminate of the present invention may include, after step 2, step 3, in which the first coating formed on the first surface in step 1 is removed. Step 3 yields a laminate 2 having no coating on the first surface and a second coating on the second surface.

[0124] The method for removing the first coating is not particularly limited and includes dry etching, wet etching, and combinations thereof. Known methods can be used for dry etching, such as chemical dry etching, which supplies reactive ions or reactive radicals to the surface of the laminate 1, and physical dry etching such as sputter etching and ion beam etching. Among these, removal by plasma treatment is preferred. For wet etching, a method of supplying an etching solution to the laminate 1 can be used. Examples of etching solutions include etching solutions containing oxidizing agents such as ozone and hydrofluoric acid, and etching solutions containing organic solvents. Examples of organic solvents include organic solvents contained in the above-mentioned chemical solutions, and alcohol-based solvents, ester-based solvents, ketone-based solvents, or hydrocarbon-based solvents are preferred.

[0125] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the following examples. The preparation, filling, and storage of the compositions were all carried out in a cleanroom meeting ISO Class 2 or lower standards. Furthermore, the containers used for the preparation, filling, and storage of the compositions were washed with the solvent used for preparation or with the prepared compositions before use.

[0126] [Synthesis of specific compound E-8] E-8 was synthesized as follows.

[0127]

[0128] <Synthesis of Intermediate E-8A> Under a nitrogen flow (50 mL / min), tetraethylene glycol monobenzyl ether (10.0 g, 35.2 mmol, manufactured by Tokyo Chemical Industries, Ltd.), triphenylphosphine (13.84 g, 52.8 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), phthalimide (7.76 g, 52.8 mmol), and tetrahydrofuran (THF) (80 mL) were added to a three-necked flask and cooled to 0°C. Next, a solution was prepared separately by dissolving azodicarboxylate bis(2-methoxyethyl) (DMEAD®, 12.36 g, 52.8 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in THF (53 mL). While maintaining the internal temperature of the reaction mixture obtained above at 5°C or below, the above solution was added dropwise to the reaction mixture over 4 hours. After the addition was complete, the reaction mixture was stirred at 25°C for 12 hours. After the reaction was complete, the solvent was removed from the reaction mixture by distillation. Ethyl acetate (100 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and distilled water (100 mL) were added, and the resulting solution was transferred to a separatory funnel and stirred. The solution was then allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was collected. The solvent was removed from the obtained organic phase by distillation under reduced pressure at 40°C / 10 hPa. The crude product obtained was purified by silica gel column chromatography to obtain intermediate E-8A.

[0129] <Synthesis of Intermediate E-8B> In an autoclave, intermediate E-8A (10.0 g, 24.2 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), Pd / C (ASCA-2, 12.36 g, 52.8 mmol, manufactured by N.E. CHEMCAT), tetrahydrofuran (THF) (50 mL), and hydrogen (H ２ (0.08 MPa) was added and the mixture was stirred at 25°C for 8 hours. After the reaction was complete, the insoluble matter was filtered out using a Nutsche filter packed with Celite. The resulting filtrate was concentrated to obtain intermediate E-8B.

[0130] <Synthesis of Intermediate E-8C> Under a nitrogen flow (10 mL / min), 6-bromo-2-naphthol (50.0 g, 0.22 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and DMF (dimethylformamide, 670 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a three-necked flask and stirred. Further, triethylamine (453.6 g, 4.48 mol), 1-octadesine (84.2 g, 0.34 mmol, manufactured by Tokyo Chemical Industries, Ltd.), copper iodide (4.3 g, 0.02 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and tetrakis(triphenylphosphine)palladium (0) (13.0 g, 0.01 mmol, manufactured by Tokyo Chemical Industries, Ltd.) were added and stirred at 70°C for 12 hours. After the reaction was complete, the reaction mixture was cooled to 25°C and insoluble matter was filtered out using a Nutsche filter packed with Celite. The crude product obtained by concentrating the resulting filtrate was purified by silica gel chromatography to obtain intermediate E-8C.

[0131] <Synthesis of Intermediate E-8D> Under a nitrogen flow (50 mL / min), intermediate E-8C (10.0 g, 25.5 mmol), triphenylphosphine (10.02 g, 38.2 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), intermediate E-8B (9.23 g, 28.0 mmol), and tetrahydrofuran (THF) (100 mL) were added and cooled to 0°C. Next, a solution was prepared separately by dissolving azodicarboxylate bis(2-methoxyethyl) (DMEAD®, 8.95 g, 38.2 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in THF (100 mL). While maintaining the internal temperature of the reaction solution obtained above at 5°C or below, the above solution was added dropwise to the reaction solution over 4 hours. After the addition was complete, the reaction solution was stirred at 25°C for 12 hours. After the reaction was complete, the solvent was removed from the reaction mixture by distillation. Ethyl acetate (200 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and distilled water (100 mL) were added, and the resulting solution was transferred to a separatory funnel and stirred. The solution was then allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was collected. The solvent was removed from the obtained organic phase under reduced pressure at 40°C / 10 hPa. The crude product obtained was purified by silica gel column chromatography to obtain intermediate E-8D.

[0132] <Synthesis of Specific Compound E-8> Under a nitrogen flow (0.1 L / min), intermediate E-8D (15.00 g, 21.5 mmol) and ethanol (75 mL, manufactured by Fujifilm Wako Pure Chemical Corporation) were added to a three-neck flask and stirred. Hydrazine monohydrate (3.23 g, 64.5 mmol, manufactured by Fujifilm Wako Pure Chemical Corporation) was added to the resulting mixture, and the mixture was heated under reflux for 1 hour. After completion of the reaction, the solvent was distilled off from the reaction solution, and t-butyl methyl ether (100 mL, manufactured by Fujifilm Wako Pure Chemical Corporation) and 1 M aqueous sodium hydroxide solution (100 mL) were added thereto. The resulting solution was transferred to a separatory funnel and stirred. Then, the solution was allowed to stand, and the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. The solvent was distilled off from the obtained organic phase under reduced pressure at 40 °C / 10 hPa to obtain specific compound E-8. １ The 1H-NMR (Nuclear Magnetic Resonance) data are shown below. １ 1H-NMR (400 MHz, THF-d8): δ (ppm) = 7.67 (s, 1H), 7.56 (d, J = 9.2 Hz, 1H), 7.53 (d, J = 8.6 Hz, 1H), 7.23 (dd, J = 1.6 Hz, 8.4 Hz, 1H), 7.09 (d, J = 2.4 Hz, 1H), 7.02 (dd, J = 2.5 Hz, 8.9 Hz, 1H), 4.10 (t, J = 5.0 Hz, 2H), 3.74 (t, J = 5.0 Hz, 2H), 3.38 - 3.57 (m, 8H), 3.28 (t, J = 5.4 Hz, 2H), 2.59 (m, 2H), 2.32 (t, J = 7.0 Hz, 2H), 1.42 - 1.56 (m, 2H), 1.35 - 1.42 (m, 2H), 1.12 - 1.30 (m, 24H), 0.78 (t, J = 6.8 Hz, 3H).

[0133] For specific compounds other than E-8, they were synthesized by appropriately adjusting raw materials and reaction conditions according to the synthesis method of E-8 above. For specific compounds other than these, those synthesized using known synthesis methods or commercially available products were used as necessary.

[0134] The materials used for preparing the compositions of the examples and comparative examples are shown below.

[0135] [Specific Compounds] In the following specific compounds, the numerical values ​​indicated for each repeating unit represent the content (mol%) of each repeating unit relative to the total repeating units contained in the compound. However, the numerical values ​​indicated for E-16 and E-32 represent the number of each repeating unit, and the numerical values ​​indicated for the polyoxyalkylene structure represent the number of repeating units of each polyoxyalkylene unit. In the following structural formulas, the structure shown by the dashed line corresponds to specific structure B2, which has a molecular weight of 130 or more and a ClogP of -0.50 or less. Furthermore, specific structure B2 for E-9 to E-11, E-22, and E-25 to E-27, which do not have a structure shown by the dashed line, is the same as specific structure E-1.

[0136]

[0137]

[0138]

[0139]

[0140]

[0141] [Comparative Compounds]

[0142]

[0143] [Solvent] ・H ２ O: Ultrapure water, PGME: Propylene glycol monomethyl ether, IPA: Isopropyl alcohol, EG: Ethylene glycol, DMSO: Dimethyl sulfoxide, DME: 1,2-Dimethoxyethane, THF: Tetrahydrofuran, TEGBME: Triethylene glycol butyl methyl ether

[0144] [Preparation of Solution] The compositions for each example and comparative example were prepared by mixing the specific compound or comparative compound with a solvent containing water to the composition shown in the table below.

[0145] [Fabrication of Modified Substrates] A commercially available silicon wafer (12 inches in diameter) was prepared as the substrate. A tungsten (W) layer, a molybdenum (Mo) layer, and a cobalt (Co) layer were formed on one surface of this silicon wafer, respectively, to prepare W-layer wafers, Mo-layer wafers, and Co-layer wafers (hereinafter collectively referred to as "layered wafers"). The W layer and Mo layer were formed by CVD, and the Co layer was formed by sputtering. The deposition conditions were adjusted so that the thickness of each layer was 10 nm. Each layered wafer was cut into 2 cm squares and cleaned by immersion in isopropyl alcohol (IPA). The cleaning was performed while stirring the IPA at a stirring speed of 250 rpm, with the IPA temperature at 25°C and the cleaning time being 30 seconds. After cleaning, the wafers were dried by blowing nitrogen gas to prepare unmodified substrates.

[0146] Next, each unmodified substrate after the above cleaning was modified by immersing it in each composition. The immersion was performed while stirring the composition at a stirring speed of 250 rpm, the temperature of the composition was 25°C, and the immersion time was 10 minutes. After immersion, each substrate was rinsed by immersing it in IPA. The rinsing was performed while stirring the IPA at a stirring speed of 250 rpm, the temperature of the IPA was 25°C, and the rinsing time was 30 seconds. After rinsing, the wafers were dried by blowing nitrogen gas onto them. Modified substrates were obtained by following the above procedure.

[0147] [Evaluation] [ALD Inhibition (Deposition Inhibition) Evaluation] Tantalum nitride (TaN) layers (ALD films) were formed on each modified substrate (wafer with each layer) obtained in the [Fabrication of Modified Substrates] and on the substrate before immersion in each composition (unmodified substrate) using an atomic layer deposition apparatus (AD-230LP, Samco) by the ALD method. PDMAT (pentakis(dimethylamino)tantalum) was used as the organometallic raw material, ammonia as the reducing agent, and the ALD treatment temperature was set to 300°C. Other conditions were adjusted so that the thickness of the ALD film formed on the unmodified substrate was 5 nm. For example, in Table 1, ALD films were formed on the modified substrate under conditions that resulted in a thickness of 5 nm on the W-layer wafer before immersion in the composition. The thickness of the ALD film on each sample after ALD treatment was measured using an X-ray fluorescence analyzer (XRF: X-ray Fluorescence) (Rigaku AZX400). Measurements were taken at five points on the substrate, and the average value was used as the film thickness. From the obtained film thickness, the ALD inhibitory effect (deposition inhibitory effect) was evaluated according to the following evaluation criteria. The smaller the film thickness, the more difficult it is for the film to deposit due to ALD treatment, i.e., the better the ALD inhibitory effect. An ALD inhibitory effect of C or higher is preferable, and S is the most preferable.

[0148] (Evaluation Criteria) S: The thickness of the ALD film is less than 0.3 nm. A: The thickness of the ALD film is 0.3 nm or more and less than 0.5 nm. B: The thickness of the ALD film is 0.5 nm or more and less than 1.0 nm. C: The thickness of the ALD film is 1.0 nm or more and less than 1.3 nm. D: The thickness of the ALD film is 1.3 nm or more and less than 1.7 nm.

[0149] [Defect Evaluation of Modified Substrates] For each modified substrate (wafer with each layer) obtained through [Fabrication of Modified Substrates], the number of particles with a diameter of 19 nm or larger was measured using a wafer inspection system SP5 manufactured by KLA-Tencor, and defects after the substrate modification process were evaluated according to the evaluation criteria below.

[0150] (Evaluation Criteria) A: The number of particles is less than 100 per wafer. B: The number of particles is 100 or more per wafer, but less than 200 per wafer. C: The number of particles is 200 or more per wafer.

[0151] [Results] The following tables show the composition and evaluation results for each composition. Table 1 shows the evaluation results for W-layer wafers, Table 2 shows the evaluation results for Mo-layer wafers, and Table 3 shows the evaluation results for Co-layer wafers. Of the tables, "Table 1 (continued)" and "Table 1 (continued 2)" are parts of Table 1, respectively; "Table 2 (continued)" is a part of Table 2, and "Table 3 (continued)" is a part of Table 3. In the tables, the "amount (parts by mass)" of the specific compound or comparative compound represents the content (unit: parts by mass) of the specific compound or comparative compound when the total mass of the composition is 100 parts by mass. In the tables, the content of the solvent, including water, is the remainder after subtracting the content of the specific compound or comparative compound from the total mass of the composition. In the table, the value in the "pKa" column indicates the acid dissociation constant of the conjugate acid of the specific compound obtained by the addition of a proton to the basic functional group if the specific functional group is a basic functional group, or the acid dissociation constant of the specific compound when a proton dissociates from the acidic functional group if the specific functional group is an acidic functional group. As described above, the acid dissociation constant is a value calculated using the above software package 1, based on Hammett substituent constants and a database of publicly known literature values. In the table, the value in the "M.W." column in the "Specific Compound or Comparative Compound" column or the "Specific Structure" column indicates the molecular weight of each compound or specific structure. If the specific compound or comparative compound has a molecular weight distribution, it is the weight-average molecular weight (Mw) value obtained by GPC measurement under the above conditions. In the table, the value in the "ClogP" column indicates the ClogP value of each compound. As described above, the ClogP value is a value calculated using the above software package 1.

[0152]

[0153]

[0154]

[0155]

[0156]

[0157]

[0158]

[0159] From the results in the table, it was confirmed that the composition of the present invention can form a coating that suppresses the occurrence of defects and sufficiently inhibits film formation by atomic layer deposition (excellent ALD inhibitory properties). Furthermore, from a comparison between Examples A9 and A10, it was confirmed that when the functional group A of the specific compound is a basic functional group, and the acid dissociation constant of the conjugate acid of the specific compound obtained by adding a proton to the basic functional group is 7.0 or higher, the ALD inhibitory properties are even better. From a comparison between Examples A11 to A14, it was confirmed that when the functional group A of the specific compound is a basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group (more preferably a primary amino group, a secondary amino group, or a tertiary amino group), the ALD inhibitory properties are even better. From a comparison between Examples A2 to A7, it was confirmed that when the molecular weight of the specific compound is 400 or higher, the ALD inhibitory properties are even better. From a comparison between Examples A1 and A18, it was confirmed that when the content of the specific compound is 5.00% by mass or less of the total mass of the composition, the ALD inhibitory effect is superior. From a comparison between Examples A1 and A2, it was confirmed that when the specific compound is a compound further having at least one of a hydrophobic group and an unsaturated group, the ALD inhibitory effect is superior. From a comparison between Examples C14 to C16, it was confirmed that when functional group A of the specific compound is an acidic functional group, and the above acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxyl group, the ALD inhibitory effect is superior.

Claims

1. A composition for forming a film on a substrate that suppresses film formation by atomic layer deposition, comprising: a compound C1 having a functional group A that binds to or adsorbs to the substrate, and a specific structure B1 which is at least one of a polyoxyalkylene structure and a betaine structure; and a solvent containing water, wherein the water content is 10% by mass or more of the total mass of the solvent containing water.

2. The composition according to claim 1, wherein the polyoxyalkylene structure is a polyoxyethylene structure or a polyoxypropylene structure, and the betaine structure has a cationic portion selected from the group consisting of a quaternary ammonium cation, a sulfonium cation, and a phosphonium cation, and an anionic portion selected from the group consisting of a phosphate ester anion, a sulfonic acid anion, and a carboxylic acid anion.

3. The composition according to claim 1, wherein compound C1 further has a hydrocarbon group having 4 or more carbon atoms in addition to the functional group A and the specific structure B1.

4. The composition according to claim 1, wherein, when the functional group A is a basic functional group, the acid dissociation constant of the conjugate acid of the compound C1 obtained by the addition of a proton to the basic functional group is 7.0 or more, and when the functional group A is an acidic functional group, the acid dissociation constant of the compound C1 when a proton dissociates from the acidic functional group is 5.0 or less.

5. The composition according to claim 1, wherein the molecular weight of compound C1 is 400 or more.

6. The polyoxyalkylene structure is a structure represented by formula (1) or formula (2), and the betaine structure is a structure represented by any one of formulas (3) to (6), the composition according to claim 1. In formula (1), n represents an integer of 2 or more. In formula (2), m represents an integer of 2 or more. In formula (3), L １ represents a divalent linking group. X represents a monovalent anionic group. R １ represents an alkyl group having 1 to 8 carbon atoms. When there are a plurality of Rs １ they may be the same as or different from each other. In formula (4), L ２ represents a divalent linking group. Y represents a monovalent cationic group. In formula (5), L ３ represents a divalent linking group. V represents a monovalent anionic group. R ２ represents an alkyl group which may have a substituent or a phenyl group which may have a substituent. In formula (6), L ４ represents a divalent linking group. W represents a monovalent anionic group. R ３ represents an alkyl group which may have a substituent or a phenyl group which may have a substituent. When there are a plurality of Rs ３ they may be the same as or different from each other.

7. The composition according to claim 6, wherein the compound C1 is a compound further having an unsaturated group.

8. The composition according to claim 1, wherein the content of compound C1 is 5.00% by mass or less based on the total mass of the composition.

9. The composition according to claim 1, wherein the total amount of compound C1 and the solvent containing water is 99.90% by mass or more of the total mass of the composition.

10. A composition for forming a film on a substrate that suppresses film formation by atomic layer deposition, comprising: a functional group A that binds to or adsorbs to the substrate; a compound C2 that does not contain the functional group A, has a molecular weight of 130 or more, and exhibits a specific structure B2 having a ClogP of -0.50 or less; and a solvent containing water, wherein the water content is 10% by mass or more of the total mass of the solvent containing water.

11. The composition according to claim 10, wherein compound C2 further has a hydrocarbon group having 4 or more carbon atoms in addition to the functional group A and the specific structure B2.

12. The composition according to claim 10, wherein, when the functional group A is a basic functional group, the acid dissociation constant of the conjugate acid of the compound C2 obtained by the addition of a proton to the basic functional group is 7.0 or more, and when the functional group A is an acidic functional group, the acid dissociation constant of the compound C2 when a proton dissociates from the acidic functional group is 5.0 or less.

13. The composition according to claim 10, wherein the molecular weight of compound C2 is 400 or more.

14. The composition according to claim 10, wherein the content of compound C2 is 5.00% by mass or less with respect to the total mass of the composition.

15. The composition according to claim 10, wherein the total amount of compound C2 and the solvent containing water is 99.90% by mass or more of the total mass of the composition.

16. The composition according to claim 1 or 10, wherein the water content is 30% by mass or more relative to the total mass of the solvent containing the water.

17. The composition according to claim 1 or 10, wherein the functional group A is a basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group.

18. The composition according to claim 17, wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group.

19. The composition according to claim 1 or 10, wherein the functional group A is an acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxyl group.

20. A method for manufacturing a modified substrate, comprising the step of bringing a substrate into contact with the composition described in claim 1 or 10 to form a coating on the substrate.

21. A method for manufacturing a laminate, comprising: step 1, bringing a substrate having at least two surfaces, a first surface and a second surface, composed of different materials, into contact with the composition according to claim 1 or 10 to form a first coating on the first surface; and step 2, subjecting the substrate obtained in step 1 to atomic layer deposition to form a second coating on the second surface.

22. A method for manufacturing an electronic device, comprising the method for manufacturing a modified substrate as described in claim 20.

23. A compound represented by formula (7). In equation (7), n represents an integer greater than or equal to 2. ５ represents a single bond or a divalent linking group. Ar represents a divalent aromatic group. R ４ represents a hydrogen atom or an alkyl group.

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