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

Abstract

The present invention provides: a composition with which it is possible to form a coating that is formed in a specific region of a substrate and suppresses film formation by atomic layer deposition processing; a method for manufacturing a modified substrate; a method for manufacturing a laminate; and a method for manufacturing an electronic device. This composition is for forming a coating that suppresses film formation by atomic layer deposition processing, and contains a compound having a functional group that interacts with a substrate, an organic solvent, and water, wherein the water content is 10-90 mass% with respect to the total mass of the organic solvent and the water.

Description

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

[0001] The present invention relates to a composition, a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

[0002] As semiconductor devices become more powerful, smaller and more precise semiconductor elements are required. Traditionally, top-down photolithography has been used to form semiconductor elements, but achieving the required precision is becoming increasingly difficult due to mechanical and optical factors, etc. Therefore, as a bottom-up method for forming semiconductor elements, a method for selectively modifying a substrate has been considered, in which a film of a compound is formed on a region of a substrate made of a specific material by selectively adsorbing the compound to the specific material, and the film is then used to modify regions of the substrate other than the region made of the specific material. Specifically, for example, a method has been devised in which a material that selectively adsorbs to a specific component is used to selectively form a coating that inhibits material deposition on a specific region of the substrate surface, followed by atomic layer deposition (ALD) processing to selectively deposit material in regions where the coating is not present, thereby modifying the substrate.

[0003] As a method for selectively modifying a substrate as described above, Patent Document 1 describes a chemical solution containing a compound A having a specific functional group, an organic solvent, and a specific metal atom, wherein the content of the compound A is more than 10 ppm by mass with respect to the total mass of the chemical solution, the total content of the specific metal atoms is 1000 ppt by mass or less with respect to the total mass of the chemical solution, and the mass ratio of the content of the compound A to the content of the specific metal atoms is 10 ４ ~10 ９ "A method for producing a modified substrate using a chemical solution in which the water content in the chemical solution is 1 mass % or less."

[0004] International Publication No. 2023 / 136042

[0005] The coating used for selectively modifying a substrate as described above is formed on a specific region of the substrate, and when the coating is subjected to atomic layer deposition (ALD) processing, the amount of material deposited on the coating is suppressed, i.e., the coating is required to have excellent ALD inhibition properties. The present inventors formed a coating using the composition disclosed in Patent Document 1 and subjected the coating to ALD processing, and found that there is room for further improvement in ALD inhibition properties.

[0006] Therefore, an object of the present invention is to provide a composition that can form a coating that is formed on a specific region of a substrate and that suppresses film formation by atomic layer deposition. Another object of the present invention is 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 extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A composition for forming a coating that inhibits film formation by atomic layer deposition, comprising: a compound having a functional group that interacts with a substrate; an organic solvent; and water, wherein the content of the water is 10 to 90 mass% based on the total mass of the organic solvent and the water. [2] The composition according to [1], wherein the compound has a hydrocarbon group having 3 or more carbon atoms. [3] The composition according to [1] or [2], wherein the functional group is a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, a carboxy group or a salt thereof, a phosphonic acid ester, a hydroxy group, and a thiol group. [4] The composition according to any one of [1] to [3], wherein the compound has a linear or branched alkyl group having 3 to 18 carbon atoms, or an aromatic ring group which may have a substituent. [5] The composition according to any one of [1] to [4], wherein the compound has a linear or branched alkyl group having 3 to 12 carbon atoms, or an aromatic ring group which may have a substituent. [6] The composition according to any one of [1] to [5], wherein the compound is a compound represented by the following formula (1): X-R (1) In formula (1), X represents a group selected from the group consisting of an amino group, a guanidine group, a phosphonic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, and a thiol group. In formula (1), R represents an alkyl group having 3 to 18 carbon atoms. [7] The composition according to [6], wherein in formula (1), X represents a phosphonic acid group or a salt thereof, or a thiol group. [8] The composition according to any one of [1] to [7], wherein the organic solvent comprises one or more solvents selected from the group consisting of alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, amine-based solvents, sulfoxide-based solvents, and sulfone-based solvents.[9] The composition according to any one of [1] to [8], wherein the organic solvent comprises one or more solvents selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methanol, tetraethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol, tetrahydrofuran, ethyl lactate, γ-butyrolactone, dimethyl sulfoxide, sulfolane, dimethylformamide, N-methylpyrrolidone, and pyridine.

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

[11] The method for producing a modified substrate according to

[10] , wherein the substrate has at least two surfaces, a first surface and a second surface, each of which is made of a different material.

[12] The method for producing a modified substrate according to

[10] or

[11] , wherein the substrate has a metal surface.

[13] A method for producing a modified substrate according to

[12] , wherein the metal surface is a surface composed of at least one metal selected from copper, cobalt, tungsten, molybdenum, and ruthenium.

[14] A method for producing a laminate, comprising: Step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface composed of different materials, with the composition according to any one of [1] to [9] to form a first coating on the first surface; and Step 2 of subjecting the substrate obtained in Step 1 to atomic layer deposition to form a second coating on the second surface.

[15] A method for producing an electronic device, comprising the method for producing a modified substrate according to any one of

[10] to

[13] .

[0009] The present invention provides a composition that can form a coating that is formed on a specific region of a substrate and that suppresses film formation by atomic layer deposition. The present invention also provides methods for producing a modified substrate, a laminate, and an electronic device.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components.

[0012] In the present specification, when there are multiple substituents, linking groups, etc. (hereinafter referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are simultaneously specified, this means that the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. The compounds described in the present specification may contain structural isomers, optical isomers, and isotopes, unless otherwise specified. Furthermore, one type of structural isomer, optical isomer, and isotope may be contained alone, or two or more types may be contained. In the present specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -CO-O-) is such that when Y in a compound represented by "X-Y-Z" is -CO-O-, the compound may be either "X-O-CO-Z" or "X-CO-O-Z."

[0013] [Composition] The composition of the present invention (hereinafter also referred to as "the composition") is described in detail below. The composition is for forming a coating that inhibits film formation by atomic layer deposition processing, and includes a compound having a functional group that interacts with a substrate (hereinafter also referred to as "specific compound"), an organic solvent, and water, wherein the content of water is 10 to 90 mass % based on the total mass of the organic solvent and the water.

[0014] Although the reason why the composition having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. 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 the one described below, it is still within the scope of the present invention. The functional group of the specific compound that interacts with the substrate can bind to or adsorb to a surface of the substrate, such as a metal surface, and therefore a coating can be formed using the composition. Furthermore, since the composition contains not only an organic solvent but also water, it is believed that the dispersibility of the specific compound in the composition changes, improving its adsorption to the substrate. As a result, it is presumed that the formed coating has a greater effect of inhibiting film formation by ALD processing. Hereinafter, the ability to form a coating that is formed on a specific region of a substrate and that better inhibits film formation by atomic layer deposition processing using the composition is also referred to as "excellent effects of the present invention."

[0015] [Specific Compound] The present composition contains a specific compound. As described above, the specific compound is a compound having a functional group that interacts with the substrate (hereinafter also referred to as a "specific functional group"). The specific functional group will be described in detail below.

[0016] <Specific Functional Group> The number of specific functional groups possessed by the specific compound is not particularly limited, but is preferably 1 to 3, and more preferably 1 or 2. Specific examples of the interaction between the specific functional group and the substrate include, for example, a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, an acid-base interaction, a van der Waals bond, and a metallic bond. When the composition is used to form a coating on a metal surface of a substrate composed of a material containing metal atoms, a coordinate bond or an ionic bond is preferred, and a coordinate bond is more preferred. When the composition is used to form a coating on a non-metal surface of a substrate composed of a non-metal material, a hydrogen bond, an acid-base interaction, or a covalent bond is preferred. Details of the substrate and the surface of the substrate will be described later.

[0017] The specific functional group is preferably either a group that bonds to or adsorbs onto a metal surface of the substrate (also referred to as "specific functional group A") or a group that bonds to or adsorbs onto a non-metal surface of the substrate (also referred to as "specific functional group B"), and more preferably specific functional group A. The specific functional group A is preferably a functional group that can form a coordinate bond with a metal.

[0018] Examples of the specific functional group include a nitrogen-containing group and a phosphonic acid group (-PO ３ H ２ ) or a salt thereof, a phosphate group (—PO ４ H ２ ) or a salt thereof, a sulfonic acid group (—SO ３ Examples of the specific functional group include groups selected from the group consisting of carboxyl (-H) or salts thereof, carboxyl (-COOH) or salts thereof, phosphonic acid ester, hydroxyl (-OH), and thiol (-SH) groups (hereinafter also referred to as "substituent group S"). Among these, in terms of superior effects of the present invention, a nitrogen-containing group, a thiol group, or a phosphonic acid or a salt thereof is preferred, an amino group, a phosphonic acid group or a salt thereof is more preferred, and a primary amino group, a phosphonic acid group or a salt thereof is even more preferred. When the specific functional group is a group selected from the above-mentioned substituent group S, it is easy to selectively form a coating that inhibits film formation by atomic layer deposition on the substrate of Aspect A described below.

[0019] Examples of the nitrogen-containing group include an amino group (—NR Ｎ ２ ), quaternary ammonium group (-N ＋ R Ｎ ３ ), a hydrazine group, a guanidine group, and a nitrogen-containing heterocyclic group. Ｎeach independently represents a hydrogen atom or an organic group (a group containing at least one carbon atom). As the organic group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferred, an aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferred, and an alkyl group having 1 to 6 carbon atoms is even more preferred. The aliphatic hydrocarbon group and alkyl group may be linear, branched, or cyclic. Examples of the nitrogen-containing heterocyclic group include nitrogen-containing aromatic heterocyclic groups such as a pyrrole group, an imidazole group, a pyrazole group, an oxazolyl group, a triazole group, a benzimidazole group, a benztriazole group, a pyridyl group, and a triazine group, as well as nitrogen-containing aliphatic heterocyclic groups such as a pyrrolidinyl group, a piperidinyl group, and a piperazinyl group. Aromatic heterocyclic groups having 5 or 6 ring atoms, such as an imidazole group and a pyridyl group, are preferred.

[0020] The nitrogen-containing group is preferably an amino group, a hydrazine group, or a guanidine group, more preferably a primary amino group, a secondary amino group, or a tertiary amino group, and even more preferably a primary amino group. When the amino group is a secondary amino group or a tertiary amino group, the number of carbon atoms contained in the secondary amino group or the tertiary amino group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0021] The salt of a phosphonic acid group is —PO ３ ２－ Ct ｎ＋ ２／ｎ Ct ｎ＋ represents an n-valent cation, where n is 1 or 2. Examples of monovalent cations include Li ＋ , Na ＋ , K. ＋ , and NH ４ ＋ The divalent cations include Mg ２＋ , and Ca ２＋ The phosphonate ester is a phosphonate ester such as -PO ３ R Ｐ ２ R Ｐ each independently represents a hydrogen atom or an organic group, provided that two R ＰAt least one of the R represents an organic group. The phosphonate ester is preferably a monoester. That is, the two R Ｐ Among these, it is preferable that one is a hydrogen atom and the other is an organic group. As the organic group, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, an aliphatic hydrocarbon group having 1 to 6 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is even more preferable. The aliphatic hydrocarbon group and the alkyl group may be linear, branched, or cyclic.

[0022] The salt of the phosphate group is -PO ４ ２－ Ct ｎ＋ ２／ｎ It is to be noted that Ct ｎ＋ represents an n-valent cation, where n is 1 or 2. Examples of the monovalent cation and the divalent cation include the same cations as those explained above for the salts of the phosphonic acid group. The salts of the sulfo group include -SO ３ － Ct ＋ The salt of a carboxy group refers to a group represented by the formula: － Ct ＋ Ct ＋ represents a monovalent cation, and examples thereof include the same monovalent cations as those explained above for the salts of phosphonic acid groups.

[0023] The hydroxy group may be either an alcoholic hydroxy group (a hydroxy group bonded to an aliphatic hydrocarbon) or a phenolic hydroxy group (a hydroxy group bonded to an aromatic hydrocarbon), with an alcoholic hydroxy group being preferred.

[0024] The specific compound preferably further contains a hydrophobic group, as this enhances the effects of the present invention. Examples of hydrophobic groups include hydrocarbon groups. The specific compound preferably contains at least one group selected from the group consisting of an aliphatic hydrocarbon group, an aromatic ring group optionally having a substituent, and a group formed by combining these. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The aliphatic hydrocarbon group may be a monovalent group or a divalent or higher valent group. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups. The linear or branched aliphatic hydrocarbon group preferably contains 2 to 30 carbon atoms, more preferably 3 to 18 carbon atoms, and even more preferably 3 to 15 carbon atoms. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The cyclic aliphatic hydrocarbon group preferably contains 6 to 30 carbon atoms, more preferably 7 to 30 carbon atoms, and even more preferably 8 to 20 carbon atoms.

[0025] The aromatic ring constituting the aromatic ring group may be either a monocycle or a polycycle. Examples of polycycles include fused rings formed by condensing two or more monocycles, and linked rings formed by connecting two or more rings selected from monocycles and fused rings with a single bond. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, 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 a benzene ring, a naphthalene ring, a pyrene ring, a thiophene ring, an indole ring, a carbazole ring, a benzothiophene ring, a dibenzothiophene ring, a porphyrin ring, a 9,9-bisphenylfluorene ring, and an aromatic ring formed by connecting two or more of these with a single bond. 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. Furthermore, examples of the substituent that the aromatic ring group may have include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a halogen atom.

[0026] Among these, the specific compound preferably has a hydrocarbon group having 3 or more carbon atoms, more preferably has a linear or branched alkyl group having 3 to 18 carbon atoms or an aromatic ring group which may have a substituent, still more preferably has a linear or branched alkyl group having 3 to 16 carbon atoms or an aromatic ring group which may have a substituent, and particularly preferably has a linear or branched alkyl group having 3 to 12 carbon atoms or an aromatic ring group which may have a substituent.

[0027] The specific compound is preferably a compound represented by formula (M1), more preferably a compound represented by formula (1) or formula (2).

[0028]

[0029] In formula (M1), X represents a group selected from the group consisting of an amino group, a guanidine group, a phosphonic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, and a thiol group. The amino group is preferably a primary amino group, a secondary amino group, or a tertiary amino group, and more preferably a primary amino group. When the amino group is a secondary amino group or a tertiary amino group, the number of carbon atoms contained in the secondary amino group or the tertiary amino group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. Among these, X is preferably a group selected from the group consisting of a primary amino group, a phosphonic acid group or a salt thereof, a sulfonic acid group or a salt thereof, and a carboxy group or a salt thereof. L ａ represents a single bond or an alkylene group. The number of carbon atoms in the alkylene group is preferably 2 to 30, more preferably 3 to 18, and still more preferably 3 to 12. n represents an integer of 1 or more, and n is preferably 1 to 3, and more preferably 1 or 2.

[0030] In the above formula (M1), L １represents a single bond or an (n+1)-valent linking group. Examples of the (n+1)-valent linking group include -O- (oxygen atom), >N- (nitrogen atom), -S- (thioether sulfur atom), an (n+1)-valent aromatic ring group, and groups formed by combining these. Examples of groups formed by combining these include -O-(n+1)-valent aromatic ring group-O-(n+1)-valent aromatic ring group-. The (n+1)-valent aromatic ring group may be either an (n+1)-valent aromatic hydrocarbon group or an (n+1)-valent aromatic heterocyclic group, with an (n+1)-valent aromatic hydrocarbon group being preferred. The aromatic ring constituting the (n+1)-valent aromatic ring group may be either a monocyclic or polycyclic ring. Examples of polycyclic rings include fused rings formed by condensing two or more monocyclic rings, and linked rings formed by connecting two or more rings selected from monocyclic rings and fused rings with a single bond. The (n+1)-valent aromatic ring group preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.

[0031] In the above formula (M1), Y represents a hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group are as described in detail for the hydrophobic group, but among them, a hydrocarbon group having 3 to 40 carbon atoms is preferred, an aliphatic hydrocarbon group, an aromatic ring group which may have a substituent, or a group formed by combining these is more preferred, and an aliphatic hydrocarbon group having 3 to 30 carbon atoms, an aromatic ring group having 4 to 30 carbon atoms, or a group formed by combining these is even more preferred.

[0032] Next, formula (1) will be described in detail. X-R Formula (1) In formula (1), X represents a group selected from the group consisting of an amino group, a guanidine group, a phosphonic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, and a thiol group. Specific examples and preferred embodiments of X are the same as the specific examples and preferred embodiments of X in formula (M1). X is preferably a group selected from the group consisting of an amino group, a phosphonic acid group or a salt thereof, and a thiol group, and more preferably a phosphonic acid group or a salt thereof, or a thiol group. In formula (1), R represents an alkyl group having 3 to 18 carbon atoms. R is preferably a linear or branched alkyl group having 3 to 18 carbon atoms.

[0033] Next, equation (2) will be described in detail.

[0034]

[0035] In formula (2), X represents a group selected from the group consisting of an amino group, a guanidine group, a phosphonic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, and a thiol group. Specific examples and preferred embodiments of X are the same as those of X in formula (M1). ２ represents a single bond or —O— (oxygen atom). ２ As the group, —O— is preferred.

[0036] In the above formula (2), L represents a single bond or a (q+1)-valent linking group. Examples of the (q+1)-valent linking group include a (q+1)-valent aliphatic hydrocarbon group, a (q+1)-valent aromatic ring group, —O— (etheric oxygen atom), —S— (thioetheric sulfur atom), —CO— (carbonyl group), and —NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ), -N< (nitrogen atom), and groups formed by combining two or more of these groups. Examples of groups formed by combining two or more of the above groups include an -O-(q+1)-valent aromatic ring group.

[0037] The (q+1)-valent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched. Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, with an alkylene group being preferred. The (q+1)-valent aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.

[0038] The (q+1)-valent aromatic ring group may be either a (q+1)-valent aromatic hydrocarbon group or a (q+1)-valent aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The aromatic ring constituting the (q+1)-valent aromatic ring group may be either a monocyclic ring or a polycyclic ring. Examples of polycyclic rings include fused rings formed by condensing two or more monocyclic rings, and linked rings formed by connecting two or more rings selected from monocyclic rings and fused rings with a single bond. The number of carbon atoms in the (q+1)-valent aromatic ring group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0039] In the above formula (2), Y represents a hydrocarbon group. Specific examples and preferred embodiments of the hydrocarbon group represented by Y in formula (2) are the same as the specific examples and preferred embodiments of the hydrocarbon group represented by Y in formula (M1), with an aliphatic hydrocarbon group having 1 to 18 carbon atoms being particularly preferred.

[0040] In the formula (2), k, p, and q each independently represent an integer of 1 or more, and m represents an integer of 0 or more. ２ represents a single bond, q represents 1. k is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. p is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. q is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. m is preferably 0 to 2, and more preferably 0 or 1.

[0041] The molecular weight of the specific compound is preferably 100 to 1,000, more preferably 100 to 700, and even more preferably 100 to 500.

[0042] The specific compound may be used alone or in combination of two or more. In order to obtain a more excellent effect of the present invention, the content of the specific compound is preferably 5.00% by mass or less, more preferably 3.00% by mass or less, and even more preferably 1.00% by mass or less, relative to the total mass of the composition. The lower limit is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.008% by mass or more, even more preferably 0.01% by mass or more, and particularly preferably 0.05% by mass or more. In addition, the total amount of the specific compound, the organic solvent described below, 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, relative to the total mass of the composition. The upper limit is 100% by mass or less, and preferably 99.9999% by mass or less.

[0043] [Solvent] As described above, the present composition contains an organic solvent and water, and the content of water is 10 to 90% by mass, based on the total mass of the organic solvent and water. In order to achieve superior effects of the present invention, the content of water is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more, based on the total mass of the organic solvent and water. The upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less. The content of the organic solvent is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the organic solvent and water. The upper limit is preferably 70% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less. 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.

[0044] Examples of alcohol-based solvents include monoalcohol-based solvents, polyol-based solvents, and glycol monoether-based solvents. Examples of monoalcohol-based solvents include aliphatic monoalcohol-based solvents having 1 to 18 carbon atoms, such as methanol, ethanol (EtOH), 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, isopentyl alcohol, and 4-methyl-2-pentanol (methyl isobutylcarbinol); alicyclic monoalcohol-based solvents having 3 to 18 carbon atoms, such as cyclohexanol; aromatic monoalcohol-based solvents such as benzyl alcohol; and ketone monoalcohol-based solvents such as diacetone alcohol. Examples of polyol-based solvents include glycol-based solvents having 2 to 18 carbon atoms, such as ethylene glycol, tetraethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol.Examples of glycol monoether solvents include glycol monoether solvents having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether. The alcohol solvent preferably has 1 to 19 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms.

[0045] Examples of ether solvents include dialkyl ether solvents such as tetraethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dihexyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and cyclohexyl methyl ether; cyclic ether solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, and tetrahydropyran; anisole; and diphenyl ether.

[0046] Examples of ester solvents include glycol ester solvents, monocarboxylic acid ester solvents such as ethyl acetate, n-butyl acetate, and ethyl lactate, lactone solvents such as γ-butyrolactone (GBL) and δ-valerolactone, and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, ethylene carbonate, and propylene carbonate. Examples of glycol ester solvents include 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, and methoxybutyl acetate, as well as propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the ester-based solvent include glycol monoether carboxylate solvents having 5 to 21 carbon atoms, such as ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, tetraethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate. The number of carbon atoms in the ester-based solvent is preferably 3 to 22, and more preferably 4 to 12.

[0047] Examples of ketone solvents include chain ketone solvents such as acetaldehyde, methyl isobutyl ketone, acetone, methyl ethyl ketone, diethyl ketone, methyl-n-butyl ketone, 2-heptanone, 4-methyl-2-pentanone, ethyl-n-butyl ketone, methyl-n-ketone, diisobutyl ketone, and trimethylnonane; cyclic ketone solvents such as cyclohexanone, cyclopentanone, cycloheptanone, and methylcyclohexanone; and acetophenone.

[0048] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone (N-methyl-2-pyrrolidinone).

[0049] Examples of sulfur-containing solvents include sulfoxide solvents and sulfone solvents, and more specific examples include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0050] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane and n-hexane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbon solvents such as toluene and xylene.

[0051] In addition to the above, amine solvents such as pyridine, and nitrile solvents such as acetonitrile, propionitrile, and benzonitrile can also be suitably used as the solvent. The organic solvent preferably contains one or more solvents selected from the group consisting of alcohol solvents, ether solvents, ester solvents, ketone solvents, amide solvents, sulfoxide solvents, and sulfone solvents, and more preferably one or more solvents selected from the above group. Among these, the organic solvent preferably contains one or more solvents selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methanol, tetraethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol, tetrahydrofuran, ethyl lactate, γ-butyrolactone, dimethyl sulfoxide, sulfolane, dimethylformamide, N-methylpyrrolidone, and pyridine, and more preferably one or more solvents selected from the above group.

[0052] The organic solvent may be used alone or in combination of two or more. The content of water is preferably 25.0 mass% or more, more preferably 45.0 mass% or more, and even more preferably 65.0 mass% or more, based on the total mass of the composition. The upper limit is preferably 80.0 mass% or less. The content of the organic solvent is preferably 10.0 mass% or more, more preferably 20.0 mass% or more, based on the total mass of the composition. The upper limit is preferably 80.0 mass% or less, more preferably 50.0 mass% or less, and even more preferably 30.0 mass% or less.

[0053] [Other Components] The composition may contain other components in addition to the specific compound, organic solvent, and water. Examples of other components include polymerization inhibitors. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, free radical compounds, amine compounds, and phosphine compounds.

[0054] [Method for producing the present composition] The method for producing the present composition is not particularly limited, and the composition can be produced, for example, by mixing the above-mentioned components. The order or timing of mixing the components is not particularly limited, and the composition can be produced, for example, by adding the specific compound to a stirrer such as a mixer containing purified organic solvent and water, and then thoroughly stirring. In order to achieve better effects of the present invention, it is preferable that the raw materials of the present composition (e.g., the specific compound, organic solvent, and water) have been subjected to a purification treatment.

[0055] The production process of the present composition may include a step selected from the group consisting of a distillation step of distilling raw materials, a dehydration step of dehydrating the present composition, a metal removal step of removing metal components from the present composition, a filtration step of filtering the present composition, and a destaticization step of destaticizing the present composition.

[0056] This composition can be filled into a known container for storage, transportation, and use. As a container, a container with a high degree of cleanliness within the container for semiconductor applications and which suppresses the elution of impurities from the inner wall of the container's storage section into each liquid is preferred. Examples of such containers include various containers commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these. Furthermore, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used as containers, and the contents of these containers are incorporated herein.

[0057] [Uses of the Composition] The composition is a composition for forming a coating that inhibits film formation by atomic layer deposition, and is preferably used in a substrate modification process in the manufacturing process of a semiconductor device. In the above process, a modified substrate having a coating formed on the substrate surface is obtained by using the composition to form a coating that inhibits film formation by atomic layer deposition. The composition is also preferably used to manufacture a laminate in which a material is deposited in areas where no coating has been formed by the above process, by subjecting the modified substrate to an ALD process. Methods for manufacturing a modified substrate and a laminate will be described in detail below.

[0058] <Substrate> The substrate is not particularly limited, but is preferably a substrate having at least one of a metal surface made of a material containing metal atoms and a non-metal surface made of a non-metal material, and more preferably a substrate having a metal surface. The metal surface is preferably a surface made of at least one metal selected from copper, cobalt, tungsten, molybdenum, and ruthenium.

[0059] The metal atoms contained in the metal surface are not particularly limited, but are preferably tungsten atoms, copper atoms, ruthenium atoms, cobalt atoms, titanium atoms, tantalum atoms, molybdenum atoms, germanium atoms, zirconium atoms, aluminum atoms, tin atoms, nickel atoms, palladium atoms, indium atoms, zinc atoms, gold atoms, silver atoms, or platinum atoms, more preferably tungsten atoms, ruthenium atoms, molybdenum atoms, copper atoms, or cobalt atoms, and even more preferably tungsten atoms or copper atoms. The form of the metal atoms on the metal surface is not particularly limited, but includes elemental metals, alloys, nitrides, oxides, and silicides, with elemental metals or alloys being preferred. Examples of alloys include alloys containing two or more of the metal atoms contained in the metal surface described above. The method for forming the metal surface is not particularly limited, and known methods can be used. For example, CVD, plating, and physical vapor deposition methods can be mentioned.

[0060] Examples of non-metallic materials constituting the non-metallic surface include insulators, such as non-metallic elements such as silicon and carbon, non-metallic oxides such as silicon oxide, non-metallic nitrides such as silicon nitride, non-metallic oxynitrides such as silicon oxynitride, and organic materials. The material constituting the non-metallic surface is preferably a non-metallic material containing silicon atoms, more preferably silicon or silicon oxide. Specific examples of silicon oxide include SiO ｙ (y is preferably 0.5 to 2.0, more preferably 1.0 to 2.0), and SiO ｚ C ｗ(wherein z is preferably 0.5 to 2.0, more preferably 1.0 to 2.0, and w is preferably 0.5 to 2.0, more preferably 1.0 to 2.0). ｙ and SiO ｚ C ｗ The material represented by the composition may further contain hydrogen. ｚ C ｗ Examples of the material represented by the composition include Si(OC ２ H ５ ) ４ (tetraethyl orthosilicate, TEOS). Silicon oxides include SiO ２ A material represented by the formula (silicon dioxide) or TEOS is preferred.

[0061] The method for forming the nonmetallic surface is not particularly limited, and examples thereof include CVD, physical vapor deposition, plasma irradiation, and application of a precursor compound. It is also preferable that the nonmetallic surface is a surface treatment performed on a region made of silicon or silicon oxide. Examples of the treatment include contact with a treatment liquid such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride water), plasma treatment, corona treatment, and ozone treatment.

[0062] The substrate is also preferably a substrate having at least two types of surfaces, a first surface and a second surface, made of different materials. The first surface is a surface that interacts with a specific functional group possessed by the specific compound. The second surface may be made of a material different from the first surface, but is preferably a surface on which a coating does not form when contacted with the composition. In particular, at least one of the first surface and the second surface is preferably a metal surface or a non-metal surface, and more preferably at least one of the first surface and the second surface is a metal surface. In particular, the first surface is preferably a metal surface made of at least one metal selected from copper, cobalt, tungsten, molybdenum, and ruthenium.

[0063] A preferred embodiment of the substrate is embodiment 1, in which the first surface is a metal surface. In embodiment 1, the specific functional group possessed by the specific compound is the specific functional group A described above. In embodiment 1, the metal atom contained in the metal surface that is the first surface is preferably a metal element, an alloy, a conductive metal nitride, or a metal silicide, and more preferably a metal element or an alloy. Examples of the metal element and alloy include the metal elements and alloys thereof exemplified as the metal contained in the metal surface. 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.

[0064] In Aspect 1, the second surface is preferably a metal surface or a non-metal surface different from the first surface, more preferably a non-metal surface. In Aspect 1, the metal atoms in the metal surface constituting the second surface are preferably contained in the form of a metal oxide, a metal nitride, or a metal oxynitride, more preferably a metal oxide. Examples of metal oxides include aluminum oxide, tantalum oxide, iron oxide, and copper oxide.

[0065] A preferred embodiment of the substrate also includes embodiment 2, in which the first surface is a non-metallic surface. In embodiment 2, the specific functional group possessed by the specific compound is the above-described specific functional group B. In embodiment 2, the second surface is preferably a metal surface. In embodiment 2, the metal atom contained in the metal surface that is the second surface is preferably an elemental metal, an alloy, a conductive metal nitride, or a metal silicide, and more preferably an elemental metal or an alloy.

[0066] The shape of the first surface and the second surface is not particularly limited, and examples thereof include a planar shape, a dotted shape, and a striped shape. The shape of the substrate is also not particularly limited, and any shape commonly used as a semiconductor substrate can be used. The substrate may be a substrate having the above-described surface, and may be a single layer or a multilayer structure.

[0067] <Coating> The coating formed on a substrate using the present composition is a coating containing components other than the solvent contained in the composition (e.g., a specific compound). The coating preferably functions as a mask when depositing a material in an ALD process. That is, when an ALD process is performed on a modified substrate on which a coating using the present composition has been formed on a specific region, the material preferably does not deposit in the region where the coating has been formed, but deposits in the region where the coating has not been formed, forming a film (hereinafter also referred to as an "ALD film"). This results in a laminate in which an ALD film is selectively formed in regions other than the region where the coating has been formed.

[0068] The coating also preferably functions as a mask when forming a metal-containing film by chemical vapor deposition (CVD) other than ALD. That is, in a CVD process, deposition of a film by CVD (hereinafter also referred to as a "CVD film") can be suppressed in the region where the coating is formed, and a CVD film can be deposited in the region where the coating is not formed. This results in a laminate in which a CVD film is selectively formed in the region other than the region where the coating is formed. Examples of CVD other than ALD that can be preferably applied to the modified substrate include known techniques such as thermal CVD and plasma CVD. As raw materials for the CVD film used in the CVD process, raw materials for the ALD film described below can be used.

[0069] The thickness of the 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.

[0070] In order to obtain superior effects of the present invention, the water contact angle of the coating is preferably 60° or more, more preferably 80° or more, and even more preferably 90° or more. There is no particular upper limit, and it is often 120° or less. The water contact angle is the average value of three measurements of the contact angle 500 milliseconds after a water droplet contacts the surface of the measurement object using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.).

[0071] [Method for Producing a Modified Substrate] The method for producing a modified substrate of the present invention includes a step of contacting a substrate with the present composition to form a coating on the substrate. This results in a modified substrate having a coating formed on the substrate. The method for producing a modified substrate of the present invention can be suitably used, for example, in the production of electronic devices (semiconductor devices). Specific examples and preferred embodiments of the substrate are as described above. The method for contacting the substrate with the present composition is not particularly limited, and known methods can be used. Examples include a method of applying (e.g., spin coating) or spraying the present composition onto the substrate, and a method of immersing the substrate in the present composition. When immersing the substrate in the composition, the present composition may be subjected to convection. The temperature of the composition when contacting the substrate with the present composition is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. The time for contacting the substrate with the present composition is also 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.

[0072] After contacting the substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and known methods can be used, such as an oven or 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.

[0073] After contacting the substrate with the composition, it is also preferable to perform a rinsing treatment. The rinsing treatment can remove at least one of the composition and impurities adhering to regions on the substrate other than the desired region (e.g., the region that interacts with the specific functional group contained in the specific compound) from the substrate. The rinsing method is not particularly limited, and examples include a method of contacting the substrate with a rinsing liquid. As the contacting method, the same method as the method of contacting the substrate with the composition can be used. The temperature of the rinsing liquid during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. As the rinsing liquid, a known organic solvent can be used, such as the alcohol-based solvents, ether-based solvents, and ester-based solvents described above.

[0074] [Method for Producing Laminate] The method for producing a laminate of the present invention includes step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each made of a different material (hereinafter also referred to as a "specific substrate") with the present composition to form a first coating on the first surface, and step 2 of subjecting the substrate obtained in step 1 to an ALD treatment to form a second coating on the second surface. This results in a laminate having a second coating (ALD film) on the second surface.

[0075] [Step 1: Method for producing modified substrate] Step 1 is a step of contacting a specific substrate with the present composition to form a first coating on the first surface. Step 1 results in a modified substrate 1 in which a first coating is formed on the first surface of the specific substrate. The first coating is a coating containing the specific compound contained in the present composition. Specific examples and preferred embodiments of the specific substrate are as described above. There are no particular limitations on the method for contacting the specific substrate with the present composition, and the method of contacting the present composition with a substrate can be used in the above-described method for producing a modified substrate.

[0076] After contacting the specific substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and the heating methods in the above-mentioned method for producing a modified substrate can be used.

[0077] It is also preferable to perform a rinse treatment on the modified substrate 1 having the first coating formed on the first surface. The rinse treatment can remove at least one of the composition and impurities adhering to regions other than the first surface (e.g., the second surface) of the specific substrate from the specific substrate. The rinse method can be the same as the rinse method in the method for producing a modified substrate described above.

[0078] [Step 2: ALD Treatment] Step 2 is a step of subjecting the modified substrate 1 obtained in step 1 to ALD treatment to form a second coating on the second surface. Step 2 results in a laminate 1 having a first coating formed on the first surface and a second coating formed on the second surface. The second coating is a film formed by ALD treatment (ALD film). Note that the modified substrate 1 may be any substrate having a first coating formed on the first surface of the specific substrate in step 1, and may be subjected to the above-mentioned heating treatment, rinsing treatment, etc. after step 1.

[0079] The ALD process method is not particularly limited, and known methods can be used. For example, a method can be used in which a precursor gas serving as a raw material for the ALD film is supplied to the surface of the modified substrate 1, and then the raw material is decomposed and / or chemically reacted with an oxidizing agent or a reducing agent, etc., to deposit the material, thereby forming 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, such as organometallic compounds. Examples of precursors that can be used include alumina, tantalum nitride, and titanium nitride. The oxidizing agent is not particularly limited, and known oxidizing agents used in ALD processes can be used, such as water, oxygen, and ozone.

[0080] The materials constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, etc. The materials of the formed ALD film are not particularly limited, and include 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 process, a treatment for modifying the surface of the region where the first coating is not formed may be performed.

[0081] After the ALD process, the thickness of the material deposited on the first coating 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 coating is formed to the thickness of the second coating 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 ratio is 0 or more.

[0082] [Step 3: Removal of Coating (Removal Treatment)] The method for producing a laminate of the present invention may include, after step 2, step 3 of removing the first coating formed on the first surface in step 1. Step 3 results in a laminate 2 that has no coating on the first surface and has the second coating on the second surface.

[0083] The method for removing the first coating is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof. As dry etching, known methods can be used, 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. As wet etching, a method in which an etching solution is supplied to the laminate 1 can be used. Examples of the etching solution include etching solutions containing oxidizing agents such as ozone and hydrofluoric acid, and etching solutions containing an organic solvent. Examples of the organic solvent include the organic solvents contained in the above-mentioned chemical solutions, and alcohol-based solvents, ester-based solvents, ketone-based solvents, and hydrocarbon-based solvents are preferred.

[0084] The present invention will be described in more detail below with reference to examples. The materials, amounts, ratios, treatment details, and treatment 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 construed as being limited by the examples shown below. All of the main components used in the examples were classified as semiconductor grade or equivalent high-purity grades, and the preparation, filling, and storage of the compositions were all carried out in a clean room meeting ISO Class 2 or lower. Furthermore, the containers used for the preparation, filling, and storage of the compositions were cleaned with the solvent used in the preparation or the prepared composition before use.

[0085] The materials used in preparing the compositions of the Examples and Comparative Examples are shown below.

[0086] [Specific compounds] M-1: Dodecylphosphonic acid M-2: Decylphosphonic acid M-3: Octylphosphonic acid M-4: Hexylphosphonic acid M-5: Octanol M-6: Octanethiol M-7: Octylcarboxylic acid M-8: Octylamine M-9: Phenylphosphonic acid

[0087]

[0088] [Solvents] S-1: Water, S-2: Propylene glycol monomethyl ether, S-3: Methanol, S-4: Tetraethylene glycol dimethyl ether, S-5: Tetraethylene glycol, S-6: Tetrahydrofuran, S-7: Ethyl lactate, S-8: γ-butyrolactone, S-9: Dimethyl sulfoxide, S-10: Sulfolane, S-11: Dimethylformamide, S-12: N-methylpyrrolidone, S-13: Pyridine, S-14: Triethylene glycol butyl methyl ether

[0089] [Liquid Preparation] The compositions of each of the Examples and Comparative Examples were prepared by mixing the specific compound, organic solvent, and water to obtain the compositions shown in the table below.

[0090] [Preparation of Modified Substrate (Sample for Evaluating ALD Inhibition)] A commercially available silicon wafer (diameter 12 inches) was prepared as a substrate. On one surface of this silicon wafer, a tungsten (W) layer, a ruthenium (Ru) layer, a molybdenum (Mo) layer, a copper (Cu) layer, a cobalt (Co) layer, and a tetraethyl orthosilicate (Si(OC ２ H ５ ) ４ By forming a TEOS (tetraethoxysilane) layer and a silicon oxycarbide (SiOC) layer, respectively, a W layer wafer, a Ru layer wafer, a Mo layer wafer, a Cu layer wafer, a Co layer wafer, a TEOS layer wafer, and a SiOC layer wafer (hereinafter, these are also collectively referred to as "layered wafers") were prepared. The W layer, Ru layer, Mo layer, TEOS layer, and SiOC layer were formed by CVD, and the Cu layer and Co layer were formed by sputtering. The film formation conditions were adjusted so that the thickness of each layer was 20 nm.

[0091] Each layered wafer was cut into 2 cm squares and rinsed by immersion in isopropyl alcohol (IPA). The rinse was performed while stirring the IPA at 250 rpm, at an IPA temperature of 25°C, and for 30 seconds. The cleaned wafers were dried by spraying with nitrogen gas. Furthermore, for the W-layer wafer, Ru-layer wafer, Mo-layer wafer, Cu-layer wafer, and Co-layer wafer, each wafer after the rinse was immersed in a pretreatment solution and then dried by spraying with nitrogen gas. The immersion was performed while stirring the pretreatment solution at 250 rpm, at a temperature of 25°C, and for 1 minute. For the W-layer wafer, Cu-layer wafer, and Co-layer wafer, a 1% by mass aqueous citric acid solution was used as the pretreatment solution, while for the Ru-layer wafer and Mo-layer wafer, a 0.1% by mass hydrofluoric acid solution was used as the pretreatment solution. An unmodified substrate (untreated sample) was prepared according to the above procedure.

[0092] Next, each unmodified substrate prepared by the above procedure was immersed in each composition to perform a modification treatment on the substrate. The immersion was performed while stirring the composition at a stirring speed of 250 rpm, the composition temperature was 25°C, and the immersion time was 10 minutes. After immersion, each substrate was rinsed by immersing it in IPA. The rinsing treatment was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25°C, and the immersion time was 30 seconds. After rinsing, the wafer was dried by spraying nitrogen gas. Using the above procedure, modified substrates (samples with coatings formed on each layer) were obtained.

[0093] [Evaluation] [Evaluation of ALD Inhibition (Deposition Inhibition)] A titanium nitride (TiN) layer (ALD film) was formed by ALD using an atomic layer deposition system (Flex-AL manufactured by Oxford Electronics) on each modified substrate (evaluation sample) obtained by [Preparation of Modified Substrate] and on a substrate (untreated sample) before immersion in each composition. TDMAT (tetrakis(dimethylamino)titanium) was used as the organometallic source and ammonia as the reducing agent, and the ALD treatment temperature was 300°C. Other conditions were adjusted so that the ALD film formed on the untreated sample would have a thickness of 2 nm. For example, in Example 1, ALD films were formed on the modified substrates under conditions such that the ALD film would have a thickness of 2 nm on the Cu layer wafer and the Co layer wafer before immersion in the composition. The thickness of the ALD film of each sample after the ALD treatment was measured using an X-ray fluorescence (XRF) analyzer (AZX400 manufactured by Rigaku Corporation). The thickness of the ALD film was measured at five points on the substrate, and the average value was taken as the film thickness. The ALD inhibition amount (nm) (deposition inhibition) was evaluated from the value obtained according to the following formula (A). The larger the ALD inhibition amount, the more difficult it is to deposit a film by the ALD treatment, i.e., the better the ALD inhibition. Formula (A): ALD inhibition amount (nm) = (thickness of the ALD film of the untreated sample (2 nm)) - (thickness of the ALD film of the evaluation sample (nm))

[0094] [Results] The composition and evaluation results of each composition are shown in Tables 1 to 6. In the tables, the values ​​shown in the "Specific Compound" and "Solvent" columns represent the content of the specific compound and the content of the solvent (unit: parts by mass).

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] The results in Tables 1 to 6 confirm that the compositions of the present invention can form coatings that are formed in specific regions of a substrate and that inhibit film formation by atomic layer deposition (ALD films). For example, taking the evaluation results of Example 1 as an example, the ALD inhibition amount was 2 nm for the Cu layer wafer and the Co layer wafer, while the ALD inhibition amount was 0 nm for the TEOS layer wafer and the SiOC layer wafer, indicating that coatings that inhibit ALD films can be selectively formed in the Cu layer and the Co layer. However, the ALD inhibition properties of the comparative compositions were poor.

[0102] Furthermore, comparisons of Examples 26 to 28 and the like confirmed that the effects of the present invention are better when the water content is 30% by mass or more, even better when the water content is 50% by mass or more, and particularly better when the water content is 70% by mass or more, relative to the total mass of the organic solvent and water. Comparisons of Examples 1 to 7 and 9 and the like confirmed that when the specific compound has at least one of a phosphonic acid group and a thiol group, the amount of ALD inhibition for the Cu layer and the Co layer is better. Comparisons of Examples 8 and 10 to 15 and the like confirmed that when the specific compound has a nitrogen-containing group, the amount of ALD inhibition for the W layer, the Ru layer, and the Mo layer is better.

[0103] Furthermore, in the above-mentioned step of [Evaluation of ALD inhibition (deposition inhibition)], a tantalum nitride layer was formed on each evaluation sample by using PDMAT (pentakis(dimethylamino)tantalum) instead of TDMAT, and the other steps were carried out in the same manner as in the above-mentioned [Evaluation of ALD inhibition (deposition inhibition)], even when the amount of ALD inhibition was evaluated.

Claims

1. A composition for forming a coating that inhibits film formation by atomic layer deposition, the composition comprising: a compound having a functional group that interacts with a substrate; an organic solvent; and water, wherein the content of the water is 10 to 90 mass % based on the total mass of the organic solvent and the water.

2. The composition of claim 1, wherein the compound has a hydrocarbon group having 3 or more carbon atoms.

3. The composition according to claim 1, wherein the functional group is a group selected from the group consisting of a nitrogen-containing group, a phosphonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a sulfonic acid group or a salt thereof, a carboxy group or a salt thereof, a phosphonic acid ester, a hydroxy group, and a thiol group.

4. The composition according to claim 1, wherein the compound has a linear or branched alkyl group having 3 to 18 carbon atoms, or an aromatic ring group which may have a substituent.

5. The composition according to claim 1, wherein the compound has a linear or branched alkyl group having 3 to 12 carbon atoms, or an aromatic ring group which may have a substituent.

6. The composition according to claim 1, wherein the compound is a compound represented by the following formula (1): X-R (1) In formula (1), X represents a group selected from the group consisting of an amino group, a guanidine group, a phosphonic acid group or a salt thereof, a sulfonic acid group or a salt thereof, a carboxy group or a salt thereof, a hydroxy group, and a thiol group. In formula (1), R represents an alkyl group having 3 to 18 carbon atoms.

7. The composition according to claim 6, wherein in formula (1), X is a phosphonic acid group or a salt thereof, or a thiol group.

8. The composition of claim 1, wherein the organic solvent comprises one or more solvents selected from the group consisting of alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, amine-based solvents, sulfoxide-based solvents, and sulfone-based solvents.

9. The composition of claim 1, wherein the organic solvent comprises one or more solvents selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methanol, tetraethylene glycol dimethyl ether, triethylene glycol butyl methyl ether, tetraethylene glycol, tetrahydrofuran, ethyl lactate, gamma-butyrolactone, dimethyl sulfoxide, sulfolane, dimethylformamide, N-methylpyrrolidone, and pyridine.

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

11. The method for producing a modified substrate according to claim 10, wherein the substrate has at least two surfaces, a first surface and a second surface, which are made of different materials.

12. The method for producing a modified substrate according to claim 10, wherein the substrate is a substrate having a metal surface.

13. The method for producing a modified substrate according to claim 12, wherein the metal surface is a surface composed of at least one metal selected from copper, cobalt, tungsten, molybdenum, and ruthenium.

14. A method for producing a laminate, comprising: step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each surface being made of a different material, with the composition described in any one of claims 1 to 9 to form a first coating on the first surface; and step 2 of subjecting the substrate obtained in step 1 to atomic layer deposition to form a second coating on the second surface.

15. A method for producing an electronic device, comprising the method for producing the modified substrate according to claim 10.

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