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 capable of sufficiently suppressing film formation due to an atomic layer deposition process; a method for producing a modified substrate; a method for producing a laminate; and a method for producing an electronic device. A composition according to the present invention is for forming, on a substrate, a coating film that suppresses film formation due to an atomic layer deposition process, and contains: a compound having a functional group that interacts with the substrate; water; and a specific component selected from the group consisting of an organic solvent, a nonionic surfactant, and a pH adjuster. The compound has a ClogP of 5.0 or more. The content of the water is 60.000 mass% or more relative to the total mass of the composition. The organic solvent has a ClogP of - 1.0 to 1.5, and the Hansen solubility parameter distance between the organic solvent and the compound is 13.0 MPa1 / 2 or less. The nonionic surfactant has a hydrophilic-lipophilic balance value of 12.0-18.0. The minimum value of the acid dissociation constant in the pH adjuster is 4.5 or less, or the maximum value of the acid dissociation constant is 9.0 or more.

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 involves using 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 using 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 film that inhibits material deposition is selectively formed on a specific region of the substrate surface using a material that selectively adsorbs to a specific component, 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 agent, a surface treatment method, and a region-selective film formation method for a substrate surface that includes adjacent metal and insulating regions, and can suppress the water repellency of insulating regions and more selectively make the metal regions water repellent, and states that "a surface treatment agent used for treating the surface of a substrate, wherein the surface includes two or more regions, and the two or more regions include at least one metal region and at least one insulating region, and at least one of the two or more regions is adjacent to the metal region and at least one insulating region, and the following general formula (P-1): HO-P(=O)R １ R ２ ...(P-1) [wherein, R １ and R ２ Each of these is an aromatic hydrocarbon group that is independently bonded to a phosphorus atom and may have a hydrogen atom, an alkyl group, a fluorinated alkyl group, or a substituent, however R １ and R２ A method is disclosed for using a surface treatment agent containing a compound (P) represented by [ ] and an organic solvent (S ], which is also not a hydrogen atom.

[0004] Japanese Patent Publication No. 2023-017484

[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. In particular, in recent years, there has been a demand for the ability to selectively deposit any material onto a substrate by ALD, and since some materials require harsh ALD conditions such as high temperatures, the above-mentioned coatings are required to have sufficiently excellent ALD inhibitory properties even under harsh ALD conditions. Furthermore, in recent years, water-based compositions have also been requested from an environmental perspective. The present inventors attempted to selectively modify a substrate using a composition containing compound (P) (e.g., octadecylphosphinic acid) and water disclosed in Patent Document 1, under harsh ALD conditions (e.g., deposition of tantalum nitride), and found that the ALD inhibitory properties were insufficient, indicating room for further improvement.

[0006] Therefore, the present invention aims to provide a composition that can form a coating that can sufficiently suppress film formation by atomic layer deposition. 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 having a functional group that interacts with the substrate; water; and a specific component selected from the group consisting of an organic solvent, a nonionic surfactant, and a pH adjuster, wherein the ClogP of the compound is 5.0 or higher; the water content is 60.000% by mass or more relative to the total mass of the composition; the ClogP of the organic solvent is -1.0 to 1.5; and the distance of the Hansen solubility parameter to the compound is 13.0 MPa １／２A composition wherein the hydrophilic-lipophilic balance value of the nonionic surfactant is 12.0 to 18.0, and the minimum value of the acid dissociation constant in the pH adjuster is 4.5 or less, or the maximum value of the acid dissociation constant is 9.0 or more. [2] The composition according to [1], wherein the water content is 99.000% by mass or less. [3] The composition according to [1] or [2], wherein the compound is a compound having a structure represented by formula (1) described later. [4] The composition according to any one of [1] to [3], wherein the content of the specific component is 0.01 to 40% by mass of the total mass of the composition. [5] The composition according to any one of [1] to [4], wherein the organic solvent contains one or more selected from the group consisting of ether-based solvents, ester-based solvents, and alcohol-based solvents. [6] The composition according to any one of [1] to [5], wherein the organic solvent comprises one or more aprotic organic solvents selected from the group consisting of ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether acetate, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, and tetraethylene glycol dimethyl ether. [7] The composition according to any one of [1] to [6], wherein the specific component is the nonionic surfactant. [8] The composition according to any one of [1] to [6], wherein the specific component comprises at least a combination of the organic solvent and the pH adjuster, a combination of the organic solvent and the nonionic surfactant, or a combination of the nonionic surfactant and the pH adjuster. [9] The composition according to [3], comprising at least the compound having the structure represented by formula (1) in which X is a phosphonic acid group, and a basic compound having a nitrogen atom as the pH adjusting agent.

[10] A method for producing a modified substrate, comprising the step of contacting a substrate with the composition according to any one of [1] to [9] to form a film on the substrate.

[11] A method for producing a laminate, comprising: step 1 of bringing a substrate having at least two types of surfaces, a first surface and a second surface, which are composed of mutually different materials, into contact with the composition according to any one of [1] to [9] to form a first coating film on the first surface; and step 2 of subjecting the substrate obtained in step 1 to an atomic layer deposition treatment to form a second coating film on the second surface.

[12] The method for producing a laminate according to

[11] , wherein the first surface is a copper surface or a cobalt surface, and the second surface is an aluminum oxide surface.

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

[10] .

[0009] According to the present invention, there can be provided a composition capable of forming a coating film that can sufficiently suppress film formation by atomic layer deposition. Further, the present invention can also provide a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

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

[0011] In the present specification, a numerical range expressed using "to" means a range including the numerical values described before and after "to" as the lower limit and the upper limit. In the present specification, "ppm" means "parts-per-million (10 －６ )", "ppb" means "parts-per-billion (10 －９ )", and "ppt" means "parts-per-trillion (10 －１２ )". In the present specification, (meth)acrylate represents at least one of acrylate and methacrylate. Further, (meth)acrylic acid represents at least one of acrylic acid and methacrylic acid. In the present specification, when two or more types of a certain component are present, the "content" of the component means the total content of the two or more types of the component.

[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] [Composition] The composition of the present invention (hereinafter also referred to as "this composition") will be described in detail below. This composition is a composition for forming a film on a substrate that suppresses film formation by atomic layer deposition, and comprises a compound having a functional group that interacts with the substrate (hereinafter also referred to as "specific compound"), water, and a specific component selected from the group consisting of an organic solvent, a nonionic surfactant, and a pH adjuster, wherein the ClogP of the compound is 5.0 or higher, the water content is 60.000% by mass or more relative to the total mass of the composition, the ClogP of the organic solvent is -1.0 to 1.5, and the distance of the Hansen solubility parameter to the compound is 13.0 MPa １／２ The following conditions apply: the hydrophilic-lipophilic balance value of the above nonionic surfactant is 12.0 to 18.0; and the minimum value of the acid dissociation constant in the above pH adjuster is 4.5 or less, or the maximum value of the acid dissociation constant is 9.0 or more.

[0015] 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 groups of the above-mentioned specific compound interact with the substrate to form a film on the substrate. Furthermore, because the specific compound has a ClogP of 5.0 or higher, the ALD inhibitory effect is improved when a film is formed on the substrate. Also, because the ClogP value of the above-mentioned specific compound is within the above range, uniform dispersion in water is difficult as is. However, by adding each of the above-mentioned specific components, whose parameters are within the above range, it becomes possible to effectively make the water and the specific compound compatible, and to uniformly disperse (or emulsify) the specific compound in water, resulting in the formation of a film with excellent ALD inhibitory properties. As described above, it is presumed that the problems of the present invention have been solved by defining the specific component with the parameters described above. Hereinafter, the ability to form a coating that can further suppress film formation by atomic layer deposition using this composition is also referred to as "the effects of the present invention being superior."

[0016] [Compounds having functional groups that interact with the substrate] This composition contains a compound (specific compound) having a functional group that interacts with the substrate and having a ClogP of 5.0 or higher. The ClogP value is a value calculated using the program "CLOGP" available from Daylight Chemical Information System, Inc. This program provides a "calculated logP" value calculated by Hansch, Leo's fragment approach. The fragment approach is based on the chemical structure of the compound, and estimates the logP value of the compound by dividing the chemical structure into substructures (fragments) and summing the logP contributions assigned to those fragments. Unless otherwise specified in this specification, Fragment database ver. 23 (Biobyte) was used as the fragment value. ChemDraw was used as the calculation software, but Bio Room ver 1.5 can also be used.

[0017] The ClogP value of the specific compound is not particularly limited as long as it is within the above range, but in terms of superior effects of the present invention, it is preferably 5.0 to 30.0, and more preferably 5.5 to 25.0. Furthermore, 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 350 or more. As an upper limit, it is preferably 1500 or less, more preferably 1000 or less, and even more preferably 900 or less.

[0018] Furthermore, while the specific compound is not particularly limited as long as it has a functional group that interacts with the above-mentioned substrate, it is preferable that it further has at least one of a structure having π electrons and a hydrophobic group. The above-mentioned structure and group will be described in detail below.

[0019] <Functional groups that interact with the substrate> The number of functional groups that a particular compound has that interact with the substrate is preferably 1 to 3, and more preferably 1 or 2. Specific examples of the above functional groups include phosphonic acid groups or their salts, sulfonic acid groups or their salts, carboxyl groups or their salts, phosphinic acid groups or their salts, phosphonic acid ester groups, phosphoric acid groups, hydroxyl groups (-OH), thiol groups (-SH), nitrogen-containing groups, cyano groups (-CN), sulfonic acid ester bond-containing groups, and boronic acid groups (-BO) ２ H ２ ) are examples, but among them, acidic functional groups or basic functional groups are preferred, and acidic functional groups are more preferred.

[0020] The above acidic functional group is a phosphonic acid group (-PO ３ H ２ ) or its salt, phosphinic acid group (-PO ２ H ２ ) or its salt, phosphate group (-PO ４ H ２ ) or its salt, sulfonic acid group (-SO ３ Examples include H) or its salts, a carboxyl group (-COOH) or its salts, and a phenolic hydroxyl group, with phosphonic acid groups or their salts, phosphinic acid groups or their salts, phosphate groups or their salts, sulfonic acid groups or their salts, or carboxyl groups or their salts being preferred, and phosphonic acid groups or their salts, or phosphinic acid groups or their salts being more preferred.

[0021] 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, among which amino groups are preferred, and primary amino groups are more preferred. Ｎ Each of these independently represents a hydrogen atom or an organic group (a group containing at least one carbon atom), preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

[0022] <Structures containing π electrons> The structure containing π electrons is not particularly limited; for example, it may or may not be aromatic, but it is preferable that it be aromatic. The structure containing π electrons may also be an ion. Examples of aromatic structures include aromatic groups, and divalent to trivalent aromatic groups are preferred. The aromatic group may also be a structure in which multiple aromatic rings are bonded together (for example, biphenyl). The aromatic rings constituting the aromatic group may be monocyclic or polycyclic, and may be aromatic hydrocarbons or aromatic heterocyclics, but aromatic hydrocarbons are 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 14. The aromatic group may have substituents, but it is preferable that it does not. The number of substituents is preferably 0 to 2. Preferred aromatic rings constituting the aromatic group include benzene rings, naphthalene rings, anthracene rings, imidazole rings, pyridine rings, pyrimidine rings, quinoline rings, thiophene rings, furan rings, thiazole rings, oxazole rings, benzofuran rings, benzothiophene rings, or thienothiophene rings.

[0023] Examples of structures that have π electrons but are not aromatic include intramolecular alkenes such as vinylene structures.

[0024] <Hydrophobic Groups> Hydrophobic groups preferably have 2 or more carbon atoms, more preferably 4 or more, and even more preferably 6 or more. The upper limit is preferably 150 or less, more preferably 100 or less, and even more preferably 80 or less. Examples of hydrophobic groups include hydrocarbon groups which may have ether bonds, and groups which include organopolysiloxane chains. The number of ether bonds which the hydrocarbon group may have is preferably 1 to 3. More specifically, examples of hydrocarbon groups include aliphatic hydrocarbon groups which may have substituents, aromatic hydrocarbon groups which may have substituents, and groups which are combinations thereof, with aliphatic hydrocarbon groups which may have substituents being preferred.

[0025] The above aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear is preferred. The number of carbon atoms in the linear or branched aliphatic hydrocarbon group is preferably 1 to 30, more preferably 2 to 30, and even more preferably 4 to 30. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 5 to 30, more preferably 5 to 30, and even more preferably 6 to 20. Examples of substituents that the aliphatic hydrocarbon group may have include halogen atoms and alkynyl groups having 1 to 3 carbon atoms, with fluorine atoms being preferred. The alkyl group having a fluorine atom may be a perfluoroalkyl group.

[0026] The aromatic ring constituting the above aromatic hydrocarbon group may be monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 14. The aromatic hydrocarbon group may have substituents, but it is preferable that it does not. The number of substituents is preferably 0 to 2. The aromatic ring constituting the aromatic hydrocarbon group is preferably a benzene ring, a naphthalene ring, or an anthracene ring.

[0027] The group containing the polyorganosiloxane chain is preferably a monovalent hydrocarbon group containing a polyorganosiloxane chain and which may have ether bonds. The number of ether bonds in the monovalent hydrocarbon group is preferably 1 to 3. More specifically, the hydrocarbon group may be an aliphatic hydrocarbon group which may have substituents, an aromatic hydrocarbon group which may have substituents, and a group which is a combination thereof, with an aliphatic hydrocarbon group which may have substituents being preferred, and an alkyl group which may have substituents being more preferred. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred. The number of carbon atoms in the linear or branched alkyl group is preferably 1 to 30, more preferably 2 to 20, and even more preferably 4 to 10.

[0028] In terms of superior effects of the present invention, the specific compound is preferably a compound having the structure represented by the following formula (1), and more preferably a compound represented by the formula (2) described later. X-L-Y ...Formula (1) In formula (1), Y represents a structure having π electrons. Specific examples and preferred embodiments of the structure having π electrons are as described above. X represents a group selected from the group consisting of a phosphonic acid group or a salt thereof, an amino group, a guanidine group, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group, a thiol group, a phosphinic acid group, a quaternary ammonium group, a hydrazine group, a phosphonic acid ester group, a phosphoric acid group, a cyano group, a sulfonic acid ester bond-containing group, and a boronic acid group. As X, a phosphonic acid group or a salt thereof and an amino group are preferred, and a phosphonic acid group or a salt thereof, a primary amino group, a secondary amino group having an alkyl group with 1 to 3 carbon atoms, and a tertiary amino group having an alkyl group with 1 to 3 carbon atoms are more preferred.

[0029] In formula (1) above, L represents a single bond or a divalent linking group. Examples of divalent linking groups include the hydrophobic groups mentioned above, specifically divalent aliphatic hydrocarbon groups, divalent aromatic groups, -O- (ether bond), -CO-, -NR Ｃ - (R Ｃ ) represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. Examples of linking groups formed by combining two or more of these groups include -O-2 valent aliphatic hydrocarbon group-, -2 valent aromatic group-O-2 valent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-2 valent aromatic group-, -CONH-2 valent aromatic group-, -COO-2 valent aliphatic hydrocarbon group-, -2 valent aliphatic hydrocarbon group-O-2 valent aliphatic hydrocarbon group-, and -CONH-2 valent aliphatic hydrocarbon group-. Among these, a single bond, an ether bond, a divalent aliphatic hydrocarbon group, or an -O-2 valent aliphatic hydrocarbon group- is preferred for L.

[0030] 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 alkynylene 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. 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 arylene groups are 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.

[0031] As mentioned above, the compound represented by the following formula (2) is preferred as the specific compound: X-L-Y-(L １ -R) ｍ ...Equation (2) In equation (2), X, L, and Y are the same as X, L, and Y in equation (1) above. L １ L represents a single bond or a divalent linking group. １ A specific example of a divalent linking group represented by is L, １ Among these, single bonds, ether bonds, or ethynylene groups are preferred. R represents a hydrophobic group. Specific examples and preferred embodiments of the hydrophobic group are as described above, but groups selected from the group consisting of alkyl groups having 2 or more carbon atoms, which may have substituents, and groups containing organopolysiloxane chains are preferred. m represents an integer of 1 or more, with 1 or 2 being preferred.

[0032] Furthermore, the specific compound may be a compound represented by the following formula (3): X １ -Z...Formula (3) In formula (3), X １ is a guanidine group, or -NR １ ２ Represents R １represents an alkyl group having an amino group, and an alkyl group having 1 to 3 carbon atoms and having a primary amino group is preferred. Z represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 2 to 30, and even more preferably 4 to 30.

[0033] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 5.00% by mass or less, more preferably 1.00% by mass or less, and even more preferably 0.1% by mass or less, based on the total mass of the composition. There is no particular lower limit, but it is preferably 0.00001% by mass or more, and more preferably 0.0001% by mass or more, based on the total mass of the composition. Furthermore, in terms of achieving superior effects of the present invention, the total amount of the specific compound, the specific component described later, and water 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.

[0034] [Specific Components] This composition contains the above-mentioned specific components. The specific components are compounds selected from the group consisting of organic solvents, nonionic surfactants, and pH adjusters, as described above, and are compounds having the characteristics detailed later, and are different from the specific compounds described above. This composition preferably contains at least an organic solvent as a specific component. Furthermore, if this composition contains two or more specific components, it is preferable to contain at least a combination of an organic solvent and a pH adjuster, a combination of an organic solvent and a nonionic surfactant, or a combination of a nonionic surfactant and a pH adjuster, and it is more preferable to contain at least a combination of an organic solvent and a pH adjuster.

[0035] For superior effects of the present invention, the content of a specific component is preferably 0.01 to 40% by mass, more preferably 0.05 to 30% by mass, and even more preferably 0.1 to 15% by mass, relative to the total mass of the composition. If the composition contains two or more specific components, the above content is the total amount of the two or more specific components. Furthermore, if the composition contains an organic solvent as a specific component, the content of the organic solvent is preferably 1 to 75% by mass, more preferably 5 to 70% by mass, and even more preferably 10 to 45% by mass, relative to the water content described later. Furthermore, if the composition contains a nonionic surfactant as a specific component, the content of the nonionic surfactant is preferably 0.01 to 20% by mass, more preferably 0.05 to 15% by mass, and even more preferably 0.1 to 10% by mass, relative to the water content described later. Furthermore, if the composition contains a pH adjuster as a specific component, the content of the pH adjuster is preferably 1 to 1500 times, more preferably 10 to 1000 times, by mass, relative to the content of the specific compound. The following provides a detailed description of each specific component.

[0036] <Organic solvent> The above organic solvent has a ClogP of -1.0 to 1.5, and the distance of the Hansen solubility parameter to the above compound is 13.0 MPa. １／２ The following applies. The method for calculating ClogP is as described in the section above under [Compounds having functional groups that interact with the substrate]. Furthermore, the above Hansen solubility parameter (HSP) is defined as the dispersion term (δ ｄ ), polar term (δ ｐ ), and the hydrogen bond term (δ ｈ It is a type of solubility parameter expressed by three components (δ). Furthermore, Hansen's solubility parameter distance (HSP distance) is a point in a three-dimensional space where the three components of HSP of a given substance are used as coordinates. ｄ , δ ｐ , δ ｈ When considering the relationship between two different substances, the HSP distance is a parameter that corresponds to the distance between their coordinates. The smaller the HSP distance, the higher the affinity between the two substances can be estimated.

[0037] The HSP of the first substance is δ ｄ１ , δ ｐ１ , δ ｈ１Therefore, the HSP of the second substance is δ ｄ２ , δ ｐ２ , δ ｈ２ In this case, the HSP distance between the first substance and the second substance can be calculated by formula (2).

[0038]

[0039] Here, HSP can uniquely calculate the values ​​at 25°C from the chemical structure of the components by using the computer software Hansen Solubility Parameter in Practice (HSPiP) (http: / / www.hansen-solubility.com). Unless otherwise specified in this specification, HSPiP ver. 6.0.03 (sold by Eizo Kobo Question Co., Ltd.) is used to calculate the dispersion term (δ) of each component at 25°C. ｄ ), polar term (δ ｐ ), and hydrogen bond term (δ ｈ The HSP distance between each of the above components was calculated by calculating the respective values ​​of ).

[0040] The ClogP value of the organic solvent as a specific component is not particularly limited as long as it is within the above range, but -0.5 to 1.3 is preferred, 0.0 to 1.3 is more preferred, and 0.5 to 1.3 is even more preferred in terms of superior effects of the present invention. Furthermore, the HSP distance between the above compound and the above organic solvent is not particularly limited as long as it is within the above range, but 11.0 MPa is preferred. １／２ The following is preferred: 9.0 MPa １／２ The following is more preferable: 6.5 MPa １／２ The following is even more preferable: The lower limit is not particularly limited, and 1.0 MPa １／２ The above is preferable, 2.5 MPa １／２ The above is preferable.

[0041] The above organic solvent is not particularly limited as long as the ClogP value and the HSP distance are within a predetermined range, but specifically, examples include organic solvents containing one or more selected from the group consisting of ether-based solvents, ester-based solvents, ketone-based solvents, and alcohol-based solvents. The organic solvent preferably contains an aprotic solvent, and more preferably an aprotic polar solvent. Specifically, the organic solvent preferably contains one or more selected from the group consisting of ether-based solvents, ester-based solvents, and alcohol-based solvents, and more preferably contains at least one of an ether-based solvent and an ester-based solvent.

[0042] Examples of ether-based solvents include dialkyl ether solvents such as ethylene glycol dimethyl ether (dimethoxyethane), diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol dimethyl ether, propylene glycol dimethyl ether, 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. Among these, dialkyl ether solvents are preferred.

[0043] Examples of ester solvents include glycol ester solvents, monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate, lactone solvents, and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. Among these, glycol ester solvents are preferred. The number of carbon atoms in the ester solvent is preferably 3 to 22, and more preferably 4 to 12.

[0044] Specifically, glycol ester solvents include propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene 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, and diethylene glycol butyl ether acetate. Examples include glycol monoether carboxylate solvents having 5 to 21 carbon atoms, such as nitrate, tripropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate, as well as glycol dicarboxylate solvents having 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.

[0045] Examples of alcohol-based solvents include monoalcohol-based solvents, polyol-based solvents, and glycol ether-based solvents, with glycol ether-based solvents being preferred. 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.

[0046] 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 ether solvents include propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, 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 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.

[0047] As a specific component, the organic solvent is preferably one or more aprotic organic solvents selected from the group consisting of ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol ethyl ether acetate, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, and tetraethylene glycol dimethyl ether.

[0048] <Nonionic Surfactants> The above nonionic surfactants have a hydrophilic-lipophilic balance value of 12.0 to 18.0. The above hydrophilic-lipophilic balance (HLB) value indicates the affinity of the surfactant for water and oil; a higher value indicates greater hydrophilicity, and a lower value indicates greater lipophilicity. For example, it is defined by the following formula (Griffin method), but values ​​calculated by other methods may also be used. HLB value = 20 × [(molecular weight of hydrophilic groups contained in the surfactant) / (molecular weight of the surfactant)] Unless otherwise specified in this specification, the manufacturer's stated value as listed in the manufacturer's product catalog, etc., shall be adopted.

[0049] The HLB value of the nonionic surfactant as a specific component is not particularly limited as long as it is within the above range, but 13.0 to 17.5 is preferred, and 13.5 to 17.0 is more preferred, in terms of superior effects of the present invention. Furthermore, the ClogP value of the above nonionic surfactant is not particularly limited, but 1.0 to 15.0 is preferred, 5.0 to 13.0 is more preferred, and 8.0 to 12.0 is even more preferred, in terms of superior effects of the present invention. The method for calculating ClogP is as described in the section above under [Compounds having functional groups that interact with the substrate].

[0050] The above-mentioned nonionic surfactants differ from ionic surfactants such as anionic surfactants and cationic surfactants in that they are compounds that have surfactant function by possessing hydrophilic and hydrophobic groups that do not exhibit ionicity. While there are no particular limitations on the nonionic surfactant as long as the HLB value is within a predetermined range, it is preferable that the nonionic surfactant has a polyoxyalkylene chain as the hydrophilic group. The polyoxyalkylene chain is -(R ａ O) ｎ It is a structure represented by -. R ａ R represents an alkylene group, and n represents an integer greater than or equal to 2. There are multiple R groups. ａ These may be different from each other or the same. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 2 to 6, and even more preferably 2 or 3. n is preferably 2 to 200, more preferably 5 to 150, and even more preferably 5 to 100. The polyoxyalkylene chain is an oxyethylene group (-CH ２ -CH ２ -O-), and oxypropylene group (-CH ２ -CH(CH ３ )-O- or -(CH ２ ) ３ It is preferable that the group consists of a group selected from the group consisting of -O-). The polyoxyalkylene chain may have a structure consisting of only one of the oxyethylene group and the oxypropylene group, or a structure consisting of both, but it is preferable that it is a polyoxyethylene chain consisting of only the oxyethylene group, or a polyoxyethylene-polyoxypropylene chain consisting of the oxyethylene group and the oxypropylene group.

[0051] Furthermore, examples of hydrophobic groups in nonionic surfactants include hydrocarbon groups, more specifically, aliphatic hydrocarbon groups, aromatic ring groups which may have substituents, and groups formed by combining these. The valency of each of the above-mentioned groups is not particularly limited, for example, it can be 1 to 4-valent, and is often monovalent or divalent. In particular, nonionic surfactants preferably have hydrocarbon groups having 3 to 30 carbon atoms as hydrophobic groups, and more preferably have hydrocarbon groups having 8 to 25 carbon atoms. Among the above hydrophobic groups, aliphatic hydrocarbon groups are preferred, aliphatic hydrocarbon groups having 3 to 30 carbon atoms are more preferred, and alkyl groups having 3 to 30 carbon atoms are even more preferred.

[0052] The above aliphatic hydrocarbon group may be linear, branched, or cyclic. Furthermore, the aliphatic hydrocarbon group may be monovalent or divalent or more. 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 3 to 30, more preferably 8 to 25, and even more preferably 10 to 20. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 6 to 30, more preferably 7 to 30, and even more preferably 8 to 20.

[0053] The aromatic ring constituting the above aromatic ring group may be monocyclic or polycyclic. Examples of polycyclic rings include fused rings formed by the fusion of two or more monocyclic rings, and linked rings formed by the single bonding of two or more rings selected from monocyclic and fused rings. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, but an aromatic hydrocarbon ring is preferred. The number of carbon atoms in the aromatic ring is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 15. Specific examples of aromatic rings include benzene rings and naphthalene rings. The number of substituents that the aromatic ring group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Examples of substituents that the aromatic ring group may have include aliphatic hydrocarbon groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms, and halogen atoms.

[0054] Specific examples of nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene polyoxyalkylene alkyl ethers, polyoxyalkylene distyrene-phenyl ethers, polyoxyalkylene alkylphenyl ethers, polyoxyalkylene polyoxyalkylene alkylphenyl ethers, polyoxyalkylene polyalkylphenyl ethers, polyalkylene glycols, polyoxyalkylene alkyl esters, polyoxyalkylene polyoxyalkylene alkyl esters, polyoxyalkylene glycols, polyoxyalkylene polyoxyalkylene glycols, polyoxyalkylene polyoxyalkylene block copolymers, polyoxyalkylene glycerin fatty acid esters, polyoxyalkylene polyoxyalkylene glycerin fatty acid esters, polyalkylene glycol fatty acid esters, polyoxyalkylene polyoxyalkylene glycols Examples include polyoxyalkylene fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene polyoxyalkylene sorbitol fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyalkylene polyoxyalkylene fatty acid esters, polyoxyalkylene castor oil, polyoxyalkylene polyoxyalkylene castor oil, polyoxyalkylene hydrogenated castor oil, polyoxyalkylene polyoxyalkylene hydrogenated castor oil, polyoxyalkylene phytosterols, polyoxyalkylene polyoxyalkylene phytosterols, polyoxyalkylene alkyl fatty acid amides, polyoxyalkylene polyoxyalkylene alkyl fatty acid amides, polyoxyalkylene alkylamines, polyoxyalkylene polyoxyalkylene alkylamines, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol, and polyoxyethylene sorbitol beeswax. In the above specific examples, "polyoxyalkylene polyoxyalkylene" refers to a state in which two different polyoxyalkylene groups are bonded together. As the oxyalkylene group, an oxyethylene group or an oxypropylene group is preferred.The above fatty acid ester may also be a partial fatty acid ester in which a portion has been esterified. Among the specific examples described above, polyoxyalkylene alkyl ethers, polyoxyalkylene polyoxyalkylene alkyl ethers, or polyoxyalkylene distyrene-phenyl ethers are particularly preferred as nonionic surfactants as specific components.

[0055] The above polyoxyalkylene alkyl ether and polyoxyalkylene polyoxyalkylene alkyl ether are preferably compounds represented by the following general formula (N): R-L １ - (L ２ O) ｎ -H ...General formula (N) In general formula (N), R represents an alkyl group. L １ L represents a single bond, an oxygen atom, or an alkylene group which may have an oxygen atom. ２ L represents an alkylene group with 2 or 3 carbon atoms, and there are multiple L groups. ２ These may be the same or different. n represents a number of 2 or more. In the general formula (N), the number of carbon atoms in the alkyl group represented by R is preferably 3 to 30, more preferably 8 to 25, and even more preferably 10 to 20. The alkyl group may be linear or branched. L １ The number of carbon atoms in the alkylene group which may have an oxygen atom, represented by -O-CH, is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. Examples of alkylene groups which may have an oxygen atom include -O-CH ２ -CH ２ - and -O-CH ２ -CH ２ -CH ２ - are examples. n is preferably 2 to 200, more preferably 5 to 150, and even more preferably 5 to 100.

[0056] Examples of commercially available nonionic surfactants include Kao Corporation's "Emulgen LS-106 (HLB value 12.5)", "Emulgen LS-110 (HLB value 13.4)", "Emulgen LS-114 (HLB value 14.0)", "Emulgen MS-110 (HLB value 12.7)", "Emulgen 108 (HLB value 12.1)", "Emulgen 109P (HLB value 13.6)", "Emulgen 120 (HLB value 15.3)", "Emulgen 123P (HLB value 16.9)", "Emulgen 147 (HLB value 16.3)", "Emulgen 220 (HLB value 14.2)", and "Emulgen 123P (HLB value 16.9)". Examples include "Emulgen 320P (HLB value 13.9)", "Emulgen 409P (HLB value 12.0)", "Emulgen 420 (HLB value 13.6)", "Emulgen 430 (HLB value 16.2)", "Emulgen 707 (HLB value 12.1)", "Emulgen 709 (HLB value 13.3)", "Emulgen 1108 (HLB value 13.5)", "Emulgen 1118S-70 (HLB value 16.4)", "Emulgen 1135S-70 (HLB value 17.9)", "Emulgen 2020G-HA (HLB value 13.0)", and "Emulgen 2025G (HLB value 15.7)". Furthermore, examples of commercially available nonionic surfactants include the products described in paragraphs

[0092] to

[0095] of the press release of Japanese Patent Publication No. 2009-074133, the contents of which are incorporated herein by reference.

[0057] <pH Adjusters> The above pH adjusters are compounds whose minimum acid dissociation constant is 4.5 or less, or whose maximum acid dissociation constant is 9.0 or more. While known methods and software can be used to calculate the above acid dissociation constant (pKa), unless otherwise specified in this specification, the structure will be drawn using ChemDrawProfessional (version 20.1.1.1) from PerkinElmer, and the value will be calculated using the following software package 1 based on a database of Hammett substituent constants and publicly available literature values. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V20.1.1 for Solaris (1994-2007 ACD / Labs) If pKa cannot be calculated using the above method, the value obtained by molecular orbital calculation will be used. As a specific method using molecular orbital calculations, we adopt values ​​obtained using Gaussian 16 based on DFT (density functional theory).

[0058] The acid dissociation constant of the pH adjuster as a specific component is not particularly limited as long as it is within the above range, however, in the case of acidic compounds, the minimum value of the acid dissociation constant is preferably -10.0 to 4.0, and more preferably -7.5 to 3.5. In the case of basic compounds, the maximum value of the acid dissociation constant is preferably 9.5 to 15.0, and more preferably 10.0 to 14.5.

[0059] The pH adjusting agent is preferably an acidic compound and a basic compound different from the specified compound. However, it is permissible to adjust the pH of the treatment solution by adjusting the amount of the specified compound added. Furthermore, the pH adjusting agent is preferably one that does not have a hydrocarbon group with 6 or more carbon atoms.

[0060] The pH adjusting agent is preferably a low molecular weight component. The molecular weight of the pH adjusting agent is preferably 600 or less, more preferably 450 or less, and even more preferably 300 or less. The lower limit of the above molecular weight is preferably 30 or more, and more preferably 50 or more.

[0061] An acidic compound is a compound that exhibits acidity in an aqueous solution. As a pH adjuster, any acidic compound that becomes an acid or an acid ion (anion) in an aqueous solution may be used; salts of such acidic compounds may also be used. Examples of acidic compounds include acidic organic compounds (organic acids) and acidic inorganic compounds, with organic acids being preferred. Organic acids preferably have 1 to 15 carbon atoms, and more preferably 2 to 15. Examples of acidic inorganic compounds include hydrochloric acid, sulfuric acid, nitric acid, nitrite, sulfurous acid, phosphoric acid, and boric acid.

[0062] Examples of acidic groups that organic acids possess include carboxyl groups, phosphonic acid groups, sulfonic acid groups, and phenolic hydroxyl groups. The number of acidic groups that organic acids possess is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. Organic acids used as pH adjusters preferably have at least one of a carboxyl group and a phosphonic acid group, and are preferably carboxylic acid-based organic acids or phosphonic acid-based organic acids, as detailed below.

[0063] <Carboxylic Acids> Carboxylic acid-based organic acids refer to organic acids that have at least one carboxyl group in their molecule. Examples of carboxylic acid-based organic acids include aminopolycarboxylic acid-based organic acids, amino acid-based organic acids, and aliphatic carboxylic acid-based organic acids, with aliphatic carboxylic acid-based organic acids being preferred.

[0064] Aliphatic carboxylic acid organic acids may further have hydroxyl groups. Examples of aliphatic carboxylic acid organic acids include malonic acid, citric acid, lactic acid, tartaric acid, oxalic acid, succinic acid, glutaric acid, gluconic acid, adipic acid, pimelic acid, sebacic acid, maleic acid, and malic acid.

[0065] Among the carboxylic acid-based organic acids, compounds represented by formula (D) are preferred, and compounds represented by formula (D1) are more preferred.

[0066]

[0067] In formula (D), L ｄrepresents a single bond or a divalent linking group. Examples of the above divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, and -SO ２ Examples include -, -NT-, divalent hydrocarbon groups (e.g., alkylene groups, alkenylene groups, alkylylene groups, and arylene groups) and groups formed by combining these. T represents a hydrogen atom or substituent. The above divalent linking group may have further substituents. Examples of the above substituents include alkyl groups, aryl groups, hydroxyl groups, carboxyl groups, amino groups, and halogen atoms, with hydroxyl groups or carboxyl groups being preferred. Among these, L ｄ The linking group is preferably a single bond or a divalent hydrocarbon group, and more preferably an alkylene group which may have substituents. The number of substituents on the divalent linking group is preferably 1 to 5, and more preferably 1 to 3. The number of carbon atoms on the divalent linking group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5.

[0068]

[0069] In formula (D1), R ｄ１ and R ｄ２ Each of these independently represents a hydrogen atom, a hydroxyl group, or a carboxyl group. n represents an integer from 0 to 5.

[0070] The total number of hydroxyl groups in the compound represented by formula (D1) is preferably 0 to 4, more preferably 0 to 2. The total number of carboxyl groups in the compound represented by formula (D1) is preferably 0 to 4, more preferably 0 to 2, and even more preferably 1. The total number of hydroxyl and carboxyl groups in the compound represented by formula (D1) is preferably 0 to 8, more preferably 0 to 4, and even more preferably 0 to 2. Multiple R ｄ１ Fellow and R ｄ２ The same or different elements may be identical to each other.

[0071] n represents an integer between 0 and 5. Preferably, n is between 1 and 4, and more preferably between 1 and 3.

[0072] <Phosphonic Acid-Based Organic Acids> Phosphonic acid-based organic acids are organic acids having at least one phosphonic acid group in their molecule. Note that if an organic acid has both a phosphonic acid group and a carboxyl group, it is classified as a carboxylic acid-based organic acid. Examples of phosphonic acid-based organic acids include aliphatic phosphonic acid-based organic acids and aminophosphonic acid-based organic acids. In addition to the phosphonic acid group and aliphatic group, aliphatic phosphonic acid-based organic acids may also have a hydroxyl group. The number of phosphonic acid groups in a phosphonic acid-based organic acid is preferably 2 to 5, more preferably 2 to 4, and even more preferably 2 to 3. The number of carbon atoms in a phosphonic acid-based organic acid is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 8. Examples of phosphonic acid-based organic acids include ethylidenediphosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid (HEDPO), 1-hydroxypropylidene-1,1'-diphosphonic acid, 1-hydroxybutylidene-1,1'-diphosphonic acid, ethylaminobis(methylenephosphonic acid), dodecylaminobis(methylenephosphonic acid), nitrilotris(methylenephosphonic acid) (NTPO), ethylenediaminebis(methylenephosphonic acid) (EDDPO), 1,3-propylenediaminebis(methylenephosphonic acid), and ethylenediaminetetra(methylenephosphonic acid) (ED Examples include TPO), ethylenediaminetetra(ethylenephosphonic acid), 1,3-propylenediaminetetra(methylenephosphonic acid) (PDTMP), 1,2-diaminopropanetetra(methylenephosphonic acid), 1,6-hexamethylenediaminetetra(methylenephosphonic acid), diethylenetriaminepenta(methylenephosphonic acid) (DEPPO), diethylenetriaminepenta(ethylenephosphonic acid), triethylenetetraminehexa(methylenephosphonic acid), and triethylenetetraminehexa(ethylenephosphonic acid), with ethylidenediphosphonic acid or HEDPO being preferred.

[0073] Basic compounds are compounds that exhibit basicity in aqueous solutions, and examples include basic inorganic compounds and basic organic compounds. Examples of basic inorganic compounds include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides. Examples of basic organic compounds include basic compounds containing a nitrogen atom, and more specifically, quaternary ammonium compounds and amine compounds different from specific compounds.

[0074] Examples of quaternary ammonium compounds include tetraalkylammonium compounds such as tetramethylammonium hydroxide (TMAH), tris(hydroxyethyl)methylammonium hydroxide (THEMAH), trimethylethylammonium hydroxide (TMEAH), dimethyldiethylammonium hydroxide (DMDEAH), methyltriethylammonium hydroxide (MTEAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH), and tetrabutylammonium hydroxide (TBAH), as well as tris(hydroxymethyl)aminomethane, 2-hydroxyethyltrimethylammonium hydroxide, and benzyltrimethylammonium hydroxide (BTMAH).

[0075] Amine compounds other than the specified compounds mentioned above (hereinafter also simply referred to as "amine compounds") are compounds other than the specified compounds or salts thereof that have at least one group selected from the group consisting of primary amino groups, secondary amino groups, and tertiary amino groups in their molecule. If an amine compound has amino groups of different grades, it is classified as an amine having the highest grade group among them. Amine compounds may be linear (straight-chain or branched-chain) or cyclic. Examples of amine compounds include aliphatic amines, amino alcohols (alkanolamines), and alicyclic amines. Examples of salts of amine compounds include salts with inorganic acids in which at least one nonmetal selected from the group consisting of Cl, S, N, and P is bonded to a hydrogen atom, and hydrochloride salts, sulfate salts, or nitrate salts are preferred.

[0076] <Aliphatic Amines> Examples of aliphatic amines other than amino alcohols include primary aliphatic amines (aliphatic amines having a primary amino group), secondary aliphatic amines (aliphatic amines having a secondary amino group), and tertiary aliphatic amines (aliphatic amines having a tertiary amino group).

[0077] Examples of primary aliphatic amines include methylamine, ethylamine, propylamine, dimethylamine, diethylamine, n-butylamine, 3-methoxypropylamine, tert-butylamine, n-hexylamine, n-octylamine, and 2-ethylhexylamine. Examples of secondary aliphatic amines include alkylenediamines such as ethylenediamine (EDA), 1,3-propanediamine (PDA), 1,2-propanediamine, 1,3-butanediamine, and 1,4-butanediamine; and polyalkyl polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), bis(aminopropyl)ethylenediamine (BAPEDA), and tetraethylenepentamine. Examples of tertiary aliphatic amines include tertiary alkylamines such as trimethylamine and triethylamine; alkylenediamines such as 1,3-bis(dimethylamino)butane; and polyalkyl polyamines such as N,N,N',N'',N''-pentamethyldiethylenetriamine.

[0078] <Amino Alcohols> Amino alcohols are compounds of amines that further have at least one hydroxyalkyl group in their molecule. Amino alcohols may have any of primary, to tertiary amino groups, but it is preferable that they have a tertiary amino group. The number of amino groups in an amino alcohol is, for example, 1 to 5, and is preferably 1 to 3. The number of hydroxyl groups in an amino alcohol is, for example, 1 to 5, and is more preferably 1 to 3.

[0079] Examples of amino alcohols include monoethanolamine (MEA), 3-amino-1-propanol, 1-amino-2-propanol, trishydroxymethylaminomethane (Tris), 2-amino-2-methyl-1-propanol (AMP), 2-dimethylamino-2-methyl-1-propanol (DMAMP), 2-amino-2-methyl-1,3-propanediol (AMPDO), 2-amino-2-ethyl-1,3-propanediol (AEPDO), 2-amino-1,3-propanediol (2-APDO), 3-amino-1,2-propanediol (3-APDO), 3-methylamino-1,2-propanediol (MAPDO), and 2-(methylamino)-2-methyl-1-propanediol (N Examples include DMAMP, 2-(aminoethoxy)ethanol (AEE), 2-(2-aminoethylamino)ethanol (AAE), diethanolamine (DEA), triethanolamine (TEA), N-methylethanolamine, N-butylethanolamine, N-cyclohexylethanolamine, 2-(ethylamino)ethanol, propylaminoethanol, diethylene glycolamine (DEGA), N,N'-bis(2-hydroxyethyl)ethylenediamine, 1,2-bis(2-aminoethoxy)ethane, N-methyldiethanolamine, N-tert-butyldiethanolamine, N-butyldiethanolamine, 1-piperidineethanol, and 1-(2-hydroxyethyl)piperazine. Among these, DMAMP or N-methyldiethanolamine is preferred.

[0080] <Alicyclic Amines> Examples of alicyclic amines include cyclic amidine compounds and piperazine compounds. Note that compounds contained in amino alcohols are not included in the category of alicyclic amines.

[0081] A cyclic amidine compound is a compound having a heterocycle containing an amidine structure (>N-C=N-) within the ring. The number of ring members in the heterocycle of the cyclic amidine compound is preferably 5 to 6, and more preferably 6. Examples of cyclic amidine compounds include diazabicycloundecene (1,8-diazabicyclo[5.4.0]undeca-7-ene: DBU), diazabicyclononene (1,5-diazabicyclo[4.3.0]nona-5-ene: DBN), 3,4,6,7,8,9,10,11-octahydro-2H-pyrimido[1.2-a]azosine, 3,4,6,7,8,9-hexahydro-2H-pyrido[1.2-a]pyrimidine, 2,5,6,7-tetrahydro-3H-pyrrolo[1.2-a]imidazole, 3-ethyl-2,3,4,6,7,8,9,10-octahydropyrimido[1.2-a]azepine, and creatinine.

[0082] Piperazine compounds are compounds having a heterosix-membered ring (piperazine ring) in which the opposite >CH- group of a cyclohexane ring is replaced by a tertiary amino group (>N-). Examples of piperazine compounds include piperazine, 1-methylpiperazine, 2-methylpiperazine, 1-ethylpiperazine, 1-propylpiperazine, 1-butylpiperazine, 1,4-dimethylpiperazine, 2,5-dimethylpiperazine, 2,6-dimethylpiperazine, 1-phenylpiperazine, and 1,4-diazabicyclo[2.2.2]octane (DABCO).

[0083] [Water] This composition contains water, and the water content is 60.000% by mass or more based on the total mass of this composition. For the effects of the present invention to be more superior, the water content is preferably 65.000% by mass or more, more preferably 70.000% by mass or more, and even more preferably 75.000% by mass or more, based on the total mass of this composition. Furthermore, there is no particular upper limit, but it is preferably 99.999% by mass or less, more preferably 99.500% by mass or less, and even more preferably 99.000% by mass or less.

[0084] [Specific Components and Solvents Other Than Water] This composition may contain solvents other than specific components and water. Organic solvents are preferred as solvents other than specific components and water, and organic solvents that are miscible with water in any proportion are 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, provided they do not fall under the category of specific components.

[0085] The specific components and solvents other than water may be used individually or in combination of two or more. The content of the specific components and solvents other than water is preferably 20,000% by mass or less, more preferably 10,000% by mass or less, and even more preferably 5,000% by mass or less, based on the total mass of the composition. The lower limit is preferably 0,000% by mass or more, and more preferably 0,100% by mass or more.

[0086] [Other Ingredients] This composition may contain other ingredients besides those listed above.

[0087] [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 predetermined components to a stirrer such as a mixing mixer containing a purified solvent 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., specific compound, specific component, and water) has been purified.

[0088] 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.

[0089] 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.

[0090] [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.

[0091] <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.

[0092] The method for forming the metal surface A is not particularly limited, and known methods can be used. Examples include CVD, plating, and physical vapor deposition. The metal atoms contained in the metal surface A are not particularly limited, but copper atoms, cobalt atoms, aluminum atoms, tungsten atoms, ruthenium atoms, molybdenum atoms, titanium atoms, tantalum atoms, germanium atoms, zirconium atoms, tin atoms, nickel atoms, palladium atoms, indium atoms, zinc atoms, gold atoms, silver atoms, or platinum atoms are preferred, copper atoms, cobalt atoms, aluminum atoms, tungsten atoms, molybdenum atoms, or ruthenium atoms are more preferred, and copper atoms or cobalt atoms are even more preferred. The form of the metal atoms on the metal surface A is not particularly limited, but examples include elemental metals, alloys, nitrides, oxides, and silicides, with elemental metals, oxides, or alloys being preferred. Examples of alloys include alloys containing two or more of the metal atoms contained in the metal surface A as described above.

[0093] Here, depending on the material of the substrate being treated, although the detailed mechanism is unknown, when using a composition containing the basic compound having a nitrogen atom and a specific compound having the structure represented by formula (1) in which X is a phosphonic acid group (hereinafter also referred to as "Composition A"), there may be differences in the degree to which film formation by ALD treatment is suppressed. Specifically, when Composition A is used on a substrate such as AlOx (alumina), there may be a difference in the effect of suppressing film formation by ALD treatment compared to when it is used on a substrate such as Cu (copper) or Co (cobalt). As described above, if there are differences in the degree to which film formation by ALD treatment is suppressed depending on the material and type of the substrate, it is possible to perform film formation by ALD treatment selectively in areas according to the material and type of the substrate. Details will be explained later, but as a specific substrate described later, for example, a substrate can be used in which the first surface is a copper surface or a cobalt surface and the second surface is an aluminum oxide surface.

[0094] Examples of the nonmetallic material constituting the nonmetallic surface B include insulators, for example, simple nonmetals such as silicon and carbon, nonmetallic oxides such as silicon oxide, nonmetallic nitrides such as silicon nitride, nonmetallic oxynitrides such as silicon oxynitride, and organic substances. As the material constituting the nonmetallic surface B, a nonmetallic material containing a silicon atom is preferable, and silicon or silicon oxide is more preferable. Specific examples of the silicon oxide include SiO ｙ represented by the composition of (y preferably represents 0.5 to 2.0, more preferably 1.0 to 2.0), and SiO ｚ C ｗ represented by the composition of (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). 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 atoms. Examples of the material represented by the composition of SiO ｚ C ｗ include, for example, Si(OC ２ H ５ ) ４ (tetraethyl orthosilicate, TEOS). As the silicon oxide, a material represented by the composition of SiO ２ (silicon dioxide), TEOS, or a material represented by the composition of SiO ｚ C ｗ is preferable.

[0095] There is no particular limitation on the method for forming the nonmetallic surface B, and examples include CVD, physical vapor deposition, plasma irradiation, and coating of a precursor compound. It is also preferable that the nonmetallic surface B is obtained by subjecting a region made of silicon or silicon oxide to a surface treatment. Examples of the above treatment include treatment with a treatment liquid such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride water), plasma treatment, corona treatment, and ozone treatment.

[0096] 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 functional groups of a specific compound that interact with the substrate. 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 cobalt atoms, copper atoms, tungsten atoms, molybdenum atoms, and ruthenium atoms.

[0097] A preferred embodiment of the substrate is Embodiment 1, in which the first surface is a metal surface A. In Embodiment 1, the metal atoms in the first surface, the metal surface A, 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 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.

[0098] 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.

[0099] A preferred embodiment of the substrate is embodiment 2, in which the first surface is a non-metallic surface B. In embodiment 2, the second surface is preferably a metallic surface A. In embodiment 2, the metal atoms in 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 metallic silicide, with elemental metal or an alloy being more preferred.

[0100] The shapes of the first and second surfaces are not particularly limited and include, for example, planar, dotted, and striped.

[0101] 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.

[0102] <Coating> The coating formed on the substrate by this composition is a coating containing components other than the solvent contained in this composition (for example, specific compounds). Preferably, the above coating functions as a mask when depositing material in ALD processing. That is, when ALD processing 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 "ALD film"). As a result, a laminate is obtained in which the ALD film is selectively formed in areas other than the area where the coating is formed.

[0103] 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.

[0104] 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.

[0105] 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.).

[0106] [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.

[0107] 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.

[0108] It is also preferable to perform a rinsing treatment after bringing the substrate and the composition into contact. The rinsing treatment can remove at least one of the composition and impurities adhering to areas on the substrate other than the desired area. 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.

[0109] [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.

[0110] [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.

[0111] 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.

[0112] 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.

[0113] [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.

[0114] 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.

[0115] 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.

[0116] 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.

[0117] [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.

[0118] 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.

[0119] 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. In addition, all main components used in the examples were classified as semiconductor grade or equivalent high-purity grade, and 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 the prepared composition before use.

[0120] The materials used in preparing the compositions of the examples and comparative examples are listed below.

[0121] [Specific compound]

[0122]

[0123] [Comparative Compounds] ・M-7: Octylphosphonic acid ・M-8: Octylcarboxylic acid ・M-9: Octylamine

[0124] [Solvent] ・S-1: Water (ultrapure water)

[0125] [Organic solvents] A-1: ​​Triethylene glycol butyl methyl ether, A-2: Diethylene glycol diethyl ether, A-3: Diethylene glycol monoethyl ether, A-4: Diethylene glycol ethyl ether acetate, A-5: Ethyl benzoate, A-6: Dimethyl sulfoxide, A-7: γ-Butyrolactone

[0126] [Nonionic surfactants] ・A-8: Emulgen LS-114 (HLB: 14.0) ・A-9: Emulgen 123P (HLB: 16.9) ・A-10: Emulgen 105 (HLB: 9.7)

[0127] [pH adjusters] ・A-11: n-propylamine (pKa: 10.6) ・A-12: tetramethylammonium hydroxide (pKa: >14) ・A-13: malonic acid (pKa: 2.8) ・A-14: hydrochloric acid (pKa: -7.0) ・A-15: acetic acid (pKa: 4.8) Note that the above pKa values ​​represent the maximum values ​​for A-11 and A-12, and the minimum values ​​for A-13 to A-15.

[0128] [Preparation of Solution] The compositions for each example and comparative example were prepared by mixing the specific compound or comparative compound, solvent (water), and additives to the composition shown in the table below.

[0129] [Fabrication of Modified Substrates (Evaluation Samples) (First Film Formation Method)] A commercially available silicon wafer (12 inches in diameter) was prepared as the substrate. A copper (Cu) layer, a cobalt (Co) layer, a tungsten (W) layer, a molybdenum (Mo) layer, a ruthenium (Ru) layer, and an aluminum oxide (ALOx) layer were formed on one surface of this silicon wafer, thereby preparing Cu-layered wafers, Co-layered wafers, W-layered wafers, Mo-layered wafers, Ru-layered wafers, and ALOx-layered wafers (hereinafter collectively referred to as "layered wafers"). The Cu and Co layers were formed by sputtering, while the W, Mo, Ru, and ALOx layers were formed by CVD (Chemical Vapor Deposition). The film formation conditions were adjusted so that the thickness of each layer was 20 nm.

[0130] Next, unmodified substrates (untreated samples) were prepared according to the following procedure. Each of the above layered wafers was cut into 2 cm squares, rinsed with isopropyl alcohol (IPA), and then dried by blowing nitrogen gas onto each wafer. The rinsing was performed by immersing the substrate in IPA. The immersion was carried out at 250 rpm while stirring the IPA in a container with a magnetic stirrer, the IPA temperature was 25°C, and the immersion time was 30 seconds. Furthermore, for the Cu layer wafers, Co layer wafers, W layer wafers, Mo layer wafers, and Ru layer wafers, pretreatment was performed by immersing each wafer after the rinsing in a pretreatment solution and then drying it by blowing nitrogen gas onto it. The immersion was carried out at 250 rpm while stirring the pretreatment solution in a container with a magnetic stirrer, the pretreatment solution temperature was 25°C, and the immersion time was 1 minute. For Cu layer wafers, Co layer wafers, and W layer wafers, a 1% by mass aqueous solution of citric acid was used as the pretreatment solution, while for Mo layer wafers and Ru layer wafers, a 0.1% by mass hydrofluoric acid was used as the pretreatment solution.

[0131] Finally, samples were prepared by forming a first coating on each layer using the compositions listed in the table below, following the procedure described below. Each unmodified substrate prepared in the above procedure was modified by immersing it in each composition. Immersion of each unmodified substrate into each composition was carried out while stirring the composition in a container with a magnetic stirrer at 250 rpm, the temperature of the composition was 25°C, and the immersion time was 10 minutes. After the above immersion treatment, each substrate was rinsed with IPA using the same procedure as above, and then dried with nitrogen gas to obtain modified substrates (evaluation samples with a first coating formed on each layer).

[0132] [Evaluation] [ALD Inhibition (Deposition Inhibition) Evaluation] Tantalum nitride (TaN) layers (ALD coatings) were formed on each modified substrate (evaluation sample) obtained by [Fabrication of Modified Substrates], and on the sample in which the first coating was not formed (untreated sample), using an atomic layer deposition system (Oxford Flex-AL). PDMAT (pentakis(dimethylamino)tantalum) was used as the organometallic raw material, and ammonia was used as the reducing agent. The ALD treatment temperature was set to 350°C, and each sample in which the first coating was not formed (untreated sample) was treated with ALD under conditions that resulted in an ALD coating (TaN layer) thickness of 2 nm. The thickness of the ALD coating in each sample after the above ALD treatment was measured using an X-ray fluorescence analyzer (XRF: X-ray Fluorescence) (Rigaku AZX400). The film thickness of the ALD coating was measured at five points on the sample, and the average value was taken as the film thickness. The ALD inhibitory activity (deposition inhibitory activity) was evaluated from the ALD inhibitory amount (nm) obtained according to the following formula (A). The larger the ALD inhibitory amount (nm), the more difficult it is for the coating to deposit due to ALD treatment, and the better the ALD inhibitory activity. In practice, a value of 1.0 nm or more is preferable for Cu layer wafers, Co layer wafers, W layer wafers, Mo layer wafers, and Ru layer wafers, and 0.3 nm or more is preferable for ALOx layer wafers. ALD inhibitory amount (nm) = (Film thickness of the ALD coating on the untreated sample (2 nm)) - (Film thickness of the ALD coating on the evaluation sample (nm)) ...Formula (A)

[0133] [Results] The following tables show the composition and evaluation results of each composition. Table 1 shows examples of evaluation of Cu layer wafers and Co layer wafers, Table 2 shows examples of evaluation of W layer wafers, Mo layer wafers, and Ru layer wafers, and Table 2 shows the results of comparative examples when each wafer was evaluated. In the tables, the content of each component in each composition is the content (unit: parts by mass) when the total mass of the composition is 100 parts by mass. In the tables, the "HSP distance" column is the distance (MPa) of the Hansen solubility parameter between the organic solvent (A-1 to A-7) and the specific compound or comparative compound. １／２ ) represents.

[0134]

[0135]

[0136]

[0137]

[0138] Furthermore, if we consider Example 25 as an example in which a composition was prepared using M-10 as shown below as a specific compound, as described in [Preparation] above, and an evaluation was carried out using the obtained composition as described in [Evaluation], then in Example 25, the amount of ALD inhibition for the W layer wafer, Mo layer wafer, and Ru layer wafer was 2 nm for all wafers.

[0139]

[0140] Furthermore, the ClogP value of M-10 is 14.7, and the distance of the Hansen solubility parameter between the organic solvent (A-1) and M-10 is 4.4 MPa. １／２ That was the case.

[0141] Furthermore, the composition of the composition prepared in Example 25 is as follows: • M-10: 0.001 parts by mass • Water (ultrapure water): 79.999 parts by mass • Triethylene glycol butyl methyl ether (A-1): 20 parts by mass

[0142] From the results in the table and Example 25, it was confirmed that the composition of the present invention is an aqueous composition that can form a film that sufficiently suppresses film formation by atomic layer deposition (excellent ALD inhibition) even when an ALD film is formed under harsh conditions (high temperature conditions, and raw materials that are difficult to form films with, etc.). Furthermore, from the comparison of Examples 1 to 3 in Table 1 and the comparison of Examples 11 to 12 in Table 2, it was confirmed that the ALD inhibition is even better when the specific component contained in the composition is an aprotic organic solvent. Furthermore, from the comparison of Examples 1 to 3 and 6 to 10, it was confirmed that when the composition contains a basic compound having a nitrogen atom and a specific compound having the structure represented by formula (1) in which X is a phosphonic acid group, the ALD inhibition against the AlOx layer is reduced compared to the Cu layer and the Co layer. Furthermore, from the comparison of Examples 13 to 16 in Table 2, it was confirmed that the ALD inhibition is even better when the specific compound is a compound having the structure represented by formula (1).

Claims

1. A composition for forming a coating on a substrate that suppresses film formation by atomic layer deposition, comprising: a compound having a functional group that interacts with the substrate; water; and a specific component selected from the group consisting of an organic solvent, a nonionic surfactant, and a pH adjuster, wherein the ClogP of the compound is 5.0 or higher; the water content is 60.000% by mass or more relative to the total mass of the composition; the ClogP of the organic solvent is -1.0 to 1.5; and the distance of the Hansen solubility parameter between the compound and the organic solvent is 13.0 MPa. １／２ A composition wherein the hydrophilic-lipophilic balance value of the nonionic surfactant is 12.0 to 18.0, and the minimum value of the acid dissociation constant in the pH adjuster is 4.5 or less, or the maximum value of the acid dissociation constant is 9.0 or more.

2. The composition according to claim 1, wherein the water content is 99,000% by mass or less.

3. The composition according to claim 1, wherein the compound is a compound having a structure represented by the following formula (1): X-L-Y ...Formula (1) In formula (1), X represents a group selected from the group consisting of a phosphonic acid group or a salt thereof, an amino group, a guanidine group, a sulfonic acid group or a salt thereof, a carboxyl group or a salt thereof, a hydroxyl group, a thiol group, a phosphinic acid group, a quaternary ammonium group, a hydrazine group, a phosphonic acid ester group, a phosphoric acid group, a cyano group, a sulfonic acid ester bond-containing group, and a boronic acid group. L represents a single bond or a divalent linking group. Y represents a structure having π electrons.

4. The composition according to claim 1, wherein the content of the specified component is 0.01 to 40% by mass of the total mass of the composition.

5. The composition according to claim 1, wherein the organic solvent comprises one or more selected from the group consisting of ether-based solvents, ester-based solvents, and alcohol-based solvents.

6. The composition according to claim 1, wherein the organic solvent comprises one or more aprotic organic solvents selected from the group consisting of ethylene glycol monomethyl ether acetate, propylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether acetate, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, and tetraethylene glycol dimethyl ether.

7. The composition according to claim 1, wherein the specified component is the nonionic surfactant.

8. The composition according to claim 1, wherein the specified component comprises at least a combination of the organic solvent and the pH adjuster, a combination of the organic solvent and the nonionic surfactant, or a combination of the nonionic surfactant and the pH adjuster.

9. The composition according to claim 3, comprising at least the compound having the structure represented by formula (1) in which X is a phosphonic acid group, and a basic compound having a nitrogen atom as the pH adjusting agent.

10. A method for manufacturing a modified substrate, comprising the step of bringing a substrate into contact with a composition according to any one of claims 1 to 9 to form a coating on the substrate.

11. 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 a composition according to any one of claims 1 to 9 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.

12. The method for manufacturing a laminate according to claim 11, wherein the first surface is a copper surface or a cobalt surface, and the second surface is an aluminum oxide surface.

13. A method for manufacturing an electronic device, comprising the method for manufacturing a modified substrate as described in claim 10.

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