Method for manufacturing surface-treated substrate, method for selectively modifying substrate surface, and composition for semiconductor treatment

Abstract

A method for manufacturing a surface-treated substrate according to the present invention includes a step for applying a composition to the surface of a substrate including a first region and a second region different in material from the first region to selectively modify the surface of the substrate. The composition contains: compound (A) that is at least one compound selected from the group consisting of a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3); and 1 mass% or more of water with respect to the total amount of the composition. R1, R4, and R8 are each independently a monovalent chain group having 9 or more carbon atoms.

Description

Method for producing surface-treated substrate, method for selectively modifying substrate surface, and composition for semiconductor processing

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to Japanese Patent Application No. 2023-143110, filed September 4, 2023, the entire contents of which are incorporated herein by reference. The present disclosure relates to a method for producing a surface-treated substrate, a method for selectively modifying a substrate surface, and a composition for semiconductor processing.

[0002] In a semiconductor manufacturing process, an organic film is formed on a portion of a substrate surface to cover and protect that portion, and the substrate after the organic film formation is subjected to various surface treatments such as forming a metal layer or etching. When forming an organic film on the substrate surface to protect that portion of the substrate surface, with the increasing miniaturization of semiconductor devices, it is required to be able to form the film with high selectivity on the region of the substrate surface that is to be protected (see, for example, Patent Document 1).

[0003] Patent Literature 1 discloses a method for selectively surface-modifying the first region with the first polymer by applying a composition containing a first polymer and a solvent, the first polymer having, at the end of its main chain or side chain, a group containing a first functional group that bonds to the metal contained in the first region, and then heating the coating film formed by applying the composition. Patent Literature 1 also discloses that the solvent used to prepare the composition is a solvent capable of dissolving or dispersing the first polymer, such as an alcohol solvent, an ether solvent, a ketone solvent, an amide solvent, or a hydrocarbon solvent.

[0004] International Publication No. 2018 / 043304

[0005] If the solvent in a composition used for selectively modifying a substrate surface can be made primarily of water, it is expected that the environmental impact can be reduced and the handling of the composition will be improved. On the other hand, when imparting water repellency or heat resistance to a substrate surface by selectively modifying the substrate surface, a highly hydrophobic material is generally used as the film-forming material. In this case, there is a concern that the solubility of the film-forming material in water may be insufficient or that the storage stability of the composition may be reduced.

[0006] Furthermore, when protecting a partial region on the surface of a substrate, it is necessary to selectively protect the region to be protected from the viewpoint of stabilizing the quality of products in semiconductor manufacturing processes, suppressing a decrease in product yield, etc. Furthermore, it is necessary to highly densely modify the region to be protected and make it difficult for impurities to adhere to the protected region (i.e., high blocking performance).

[0007] The present disclosure has been made in view of the above-mentioned problems, and has as its object to provide a method for highly selectively and densely modifying a substrate surface, which has high water solubility of the components and high storage stability of the composition, and another object to provide a semiconductor processing composition that has high storage stability and is capable of highly selectively and densely modifying a substrate surface.

[0008] According to one aspect of the present disclosure, there is provided a method for producing a surface-treated substrate, the method comprising: applying a composition to a surface of a substrate including a first region and a second region made of a material different from that of the first region, thereby selectively modifying the surface of the substrate; the composition containing compound (A) which is at least one compound selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3); and 1 mass % or more of water relative to the total amount of the composition: (In formula (1), formula (2) and formula (3), R １ , R ４ and R ８ are each independently a monovalent chain group having 9 or more carbon atoms. ２ , R ３ , R ５ , R ６ , R ９ and R １０ are each independently a hydrogen atom or a monovalent chain group having one or more carbon atoms. ７ is a hydrogen atom or a monovalent organic group having one or more carbon atoms. － represents an anion. － represents a monovalent anionic group.

[0009] According to another aspect of the present disclosure, there is provided a method for selectively modifying a substrate surface, the method comprising a step of applying a composition to a surface of a substrate including a first region and a second region made of a material different from that of the first region, the composition containing compound (A) which is at least one type selected from the group consisting of compounds represented by formula (1) above, compounds represented by formula (2) above, and compounds represented by formula (3) above, and 1 mass % or more of water relative to the total amount of the composition.

[0010] According to another aspect of the present disclosure, a composition containing at least one compound (A) selected from the group consisting of compounds represented by the above formula (1), compounds represented by the above formula (2), and compounds represented by the above formula (3), and 1 mass % or more of water relative to the total amount of the composition, wherein the amount of the compound (A) in the composition is M Ａ (mass%), the amount of metal components is M Ｂ (mass%), M Ａ M against Ｂ The ratio (M Ｂ / M Ａ ) is 1.0 x 10 －２ A semiconductor processing composition is provided, which is:

[0011] According to the present disclosure, the components have high solubility in water and the composition has high storage stability, and the substrate surface can be modified highly selectively and at high density.

[0012] Matters related to the embodiments will be described in detail below. In this specification, a numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower and upper limits. Unless otherwise specified, each component may be used alone or in combination of two or more.

[0013] Here, in this specification, the term "hydrocarbon group" includes chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. "Chain hydrocarbon group" refers to a straight-chain hydrocarbon group or a branched hydrocarbon group that does not contain a cyclic structure and is composed only of a chain structure. Chain hydrocarbon groups may be saturated or unsaturated. "Alicyclic hydrocarbon group" refers to a hydrocarbon group that contains only an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. An alicyclic hydrocarbon group does not necessarily have to be composed only of an alicyclic hydrocarbon structure, and also includes groups that have a chain structure as part of it. "Aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. However, it does not necessarily have to be composed only of an aromatic ring structure, and may contain a chain structure or an alicyclic hydrocarbon structure as part of it. "Chain group" refers to a straight-chain or branched group that does not contain a cyclic structure and is composed only of a chain structure.

[0014] <<Method and Composition>> The method of the present disclosure includes a step of applying a composition to the surface of a substrate. The composition is an aqueous liquid composition and contains water and a nitrogen-containing compound (hereinafter referred to as "compound (A)") having a specific partial structure in which a chain group is bonded to a nitrogen atom. Below, we will first explain the composition, and then explain a method of selectively modifying a substrate surface using the composition.

[0015] <Composition> One embodiment of the composition of the present disclosure is a semiconductor processing composition, and is used, for example, as a surface treatment liquid for semiconductor processing. More specifically, the composition is used as a surface treatment liquid for forming a film on the surface of a substrate to modify the surface of the substrate. The region where a film is formed by the composition is imparted with water repellency and heat resistance, and exhibits blocking performance. The film formed by the composition is typically a self-assembled monolayer (SAM) formed by adsorption of compound (A) onto the substrate surface. Below, each component contained in the composition of the present disclosure and components that are optionally blended as needed will be described.

[0016] Compound (A) Compound (A) is at least one selected from the group consisting of compounds represented by the following formula (1), compounds represented by the following formula (2), and compounds represented by the following formula (3): (In formula (1), formula (2) and formula (3), R １ , R ４ and R ８ are each independently a monovalent chain group having 9 or more carbon atoms. ２ , R ３ , R ５ , R ６ , R ９ and R １０ are each independently a hydrogen atom or a monovalent chain group having one or more carbon atoms. ７ is a hydrogen atom or a monovalent organic group having one or more carbon atoms. － represents an anion. － represents a monovalent anionic group.

[0017] By using the compound (A) as a monomolecular film forming material, the ability to adsorb to the substrate (particularly the metal region) is selectively expressed by nitrogen, and the monovalent chain group (R １ , R ４ or R ８ ) is thought to be responsible for the development of water repellency, heat resistance, and blocking performance. In particular, it is thought that nitrogen in compound (A) can modify metal regions highly selectively and densely by interacting with the metal. The "interaction" referred to here refers to, for example, chemical bonding, such as covalent bonding, ionic bonding, and coordinate bonding. When nitrogen in the above formulas (1) to (3) forms a coordinate bond with the metal, it is possible to increase the bonding strength between the metal atom and the nitrogen atom.

[0018] In the above formulas (1) to (3), R １ , R ４ or R ８ Examples of the monovalent chain group having 9 or more carbon atoms represented by the formula (I) include a linear or branched saturated hydrocarbon group having 9 to 40 carbon atoms, a linear or branched unsaturated hydrocarbon group having 9 to 40 carbon atoms, and a group having -O-, -S-, -CO-, -COO-, -O-CO-O-, -NR between the carbon-carbon bonds of the chain hydrocarbon group. ２１ --, --CONR ２１ -or-SO ２-, and monovalent groups having 9 to 40 carbon atoms in which any hydrogen atom in the monovalent group or chain hydrocarbon group has been substituted. ２１ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms (the same applies hereinafter).

[0019] Specific examples of linear or branched saturated hydrocarbon groups having 9 to 40 carbon atoms include nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, icosyl, henicosyl, docosyl, triacontyl, and tetracontyl groups. Specific examples of linear or branched unsaturated hydrocarbon groups having 9 to 40 carbon atoms include alkenyl groups such as nonenyl, decenyl, and dodecenyl groups; and alkynyl groups such as noninyl and dequinyl groups.

[0020] R １ , R ４ or R ８ may have a divalent heteroatom-containing group between the carbon-carbon bonds of the chain hydrocarbon group. The divalent heteroatom-containing group is selected from the group consisting of —O—, —S—, —CO—, —COO—, —O—CO—O—, and —NR ２１ --, --CONR ２１ -or-SO ２ - is preferred, and -NR ２１ -or-CONR ２１ - is more preferred, and -NR ２１ - is more preferred, and -NH- is even more preferred. １ , R ４ or R ８ When has a substituent, examples of the substituent include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a nitro group, an amino group, a carboxy group, and a hydroxy group.

[0021] From the viewpoint of imparting excellent water repellency, heat resistance, and blocking resistance to the substrate surface, R １ , R ４ or R ８is preferably a linear or branched monovalent saturated hydrocarbon group having 9 to 40 carbon atoms, a linear or branched monovalent unsaturated hydrocarbon group having 9 to 40 carbon atoms, a monovalent group having 9 to 40 carbon atoms having -NH- or -CONH- between the carbon-carbon bonds of the linear or branched hydrocarbon group, or a monovalent group having 9 to 40 carbon atoms in which any hydrogen atom in the monovalent group or chain hydrocarbon group has been substituted with a halogen atom or an amino group. １ , R ４ or R ８ is preferably a monovalent chain hydrocarbon group, more preferably a monovalent straight-chain hydrocarbon group.

[0022] R １ , R ４ or R ８ is preferably linear from the viewpoint of forming a film with higher density and imparting excellent water repellency, heat resistance, and blocking performance to the substrate surface. １ , R ４ or R ８ The number of carbon atoms in R is preferably 10 or more, and more preferably 12 or more. From the viewpoint of improving the solubility of the compound (A) in water and suppressing a decrease in the adsorption ability of the compound (A) to a substrate, １ , R ４ or R ８ The number of carbon atoms is preferably 30 or less, more preferably 25 or less, and even more preferably 22 or less.

[0023] Furthermore, from the viewpoint of imparting excellent water repellency, heat resistance and blocking performance to the substrate surface, R １ , R ４ or R ８ R preferably has a monovalent chain hydrocarbon group having 9 or more carbon atoms, more preferably has an alkyl group having 9 or more carbon atoms, and even more preferably has a linear alkyl group having 9 or more carbon atoms. １ , R ４ or R ８ A preferred specific example of R is a group represented by the following formula (1-A): １５ -R １１ -*...(1-A) (In formula (1-A), R１０ is an alkyl group having 9 or more carbon atoms. １１ is a single bond or a divalent linking group. "*" represents a bond to the nitrogen atom.

[0024] In the above formula (1-A), R １１ The divalent linking group represented by the formula (I) is a divalent linking group represented by the formula (I) ２１ -or-CONR ２１ and a divalent group having 1 to 10 carbon atoms and having -; or a divalent group in which one or more hydrogen atoms of a chain hydrocarbon group have been substituted with a primary amino group.

[0025] R ２ , R ３ , R ５ , R ６ , R ９ or R １０ Examples of the monovalent chain group represented by the formula (I) include a linear or branched saturated hydrocarbon group having 1 to 40 carbon atoms, a linear or branched unsaturated hydrocarbon group having 2 to 40 carbon atoms, and a linear or branched hydrocarbon group having -O-, -S-, -CO-, -COO-, -O-CO-O-, -NR ２１ --, --CONR ２１ -or-SO ２ and a monovalent group having 2 to 40 carbon atoms having -; and a monovalent group having 1 to 40 carbon atoms in which any hydrogen atom in the monovalent group or a linear or branched hydrocarbon group has been substituted.

[0026] Specific examples of linear or branched saturated hydrocarbon groups having 1 to 40 carbon atoms include the groups given as specific examples of linear or branched saturated hydrocarbon groups having 9 to 40 carbon atoms, as well as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, an n-hexyl group, an n-octyl group, etc. Specific examples of linear or branched unsaturated hydrocarbon groups having 1 to 40 carbon atoms, as well as the groups given as specific examples of linear or branched unsaturated hydrocarbon groups having 9 to 40 carbon atoms, include alkenyl groups such as a vinyl group, a propenyl group, a butenyl group, a hexenyl group, an octenyl group, a decenyl group, a dodecenyl group, etc.; alkynyl groups such as a propynyl group, a butynyl group, etc.

[0027] R ２ , R ３ , R ５ , R ６ , R ９ or R １０ When R has a substituent, examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a nitro group, an amino group, a carboxy group, a hydroxy group, etc. It is preferable that the compound (A) has a carboxy group, since this can improve the solubility of the compound (A) in the solvent component even when the proportion of water as the solvent component is increased while maintaining a high level of selective modification of the membrane. Specifically, R ２ , R ３ , R ５ , R ６ , R ９ or R １０ has a carboxy group, it is preferable in that the solubility of compound (A) in the solvent component can be improved even when the proportion of water as the solvent component is increased (i.e., when the proportion of the organic solvent is reduced) while maintaining a high degree of selective modification of the membrane.

[0028] R ７ Examples of the monovalent organic group having one or more carbon atoms represented by the formula (I) include a hydrocarbon group having 1 to 40 carbon atoms, a hydrocarbon group having -O-, -S-, -CO-, -COO-, -O-CO-O-, -NR ２１ --, --CONR ２１ -or-SO ２ and a divalent group having 1 to 40 carbon atoms in which any hydrogen atom in the monovalent group or a linear or branched hydrocarbon group has been substituted.

[0029] R ７ When R is a monovalent hydrocarbon group having 1 to 40 carbon atoms, specific examples include a monovalent chain hydrocarbon group having 1 to 40 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 40 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 40 carbon atoms. Specific examples of these include monovalent chain hydrocarbon groups having 1 to 40 carbon atoms, such as R ２ , R ３ , R ５ , R ６ , R ９ or R１０ Specific examples of the monovalent chain group represented by the following formula include the same groups as those given above.

[0030] Examples of the monovalent alicyclic hydrocarbon group having 3 to 40 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclopentyl group, an ethylcyclopentyl group, a methylcyclohexyl group, and an ethylcyclohexyl group; monocyclic aliphatic unsaturated hydrocarbon groups such as a cyclopentenyl group, a cyclohexenyl group, a methylcyclopentenyl group, and a methylcyclohexenyl group; polycyclic aliphatic saturated hydrocarbon groups such as a norbornyl group, an adamantyl group, and a tricyclodecyl group; and polycyclic aliphatic unsaturated hydrocarbon groups such as a norbornenyl group and a tricyclodecenyl group.

[0031] Examples of the monovalent aromatic hydrocarbon group having 6 to 40 carbon atoms include aryl groups such as a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, a vinylphenyl group, and an allylphenyl group; and aralkyl groups such as a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, a methylbenzyl group, a naphthylmethyl group, and an anthrylmethyl group.

[0032] R ７ When has a substituent, examples of the substituent include a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a nitro group, an amino group, a carboxy group, and a hydroxy group.

[0033] In the above formula (2), X － The anion represented by X is not particularly limited as long as it is an anionic counter ion. － The anion represented by X may be an inorganic anion or an organic anion. － Specific examples of the anion represented by the formula (I) include halide ions (e.g., chloride ions, bromide ions, and iodide ions), OH － , P.F. ６ － , B.F. ４ － , SbF ６ － , C.N. － , (CN)２ N － , SCN － , R １２ SO ３ － , R １２ COO － , R １２ SO ２ N － R １３ (However, R １２ and R １３ are each independently a monovalent organic group having one or more carbon atoms. From the viewpoint of improving the metal corrosion resistance of the composition, X － Among these, the anion represented by OH － , P.F. ６ － , B.F. ４ － , SbF ６ － , C.N. － , (CN) ２ N － , SCN － , R １２ SO ３ － , R １２ COO － or R １２ SO ２ N － R １３ is preferred.

[0034] In the above formula (3), Y － There is no particular limitation on the monovalent anionic group represented by Y － Specific examples of the monovalent anionic group represented by the formula: *-R １４ -SO ３ － , *-R １４ -COO － (However, R １４ is a divalent organic group having one or more carbon atoms, and "*" represents a bond to a nitrogen atom. １４ Examples of the divalent organic group having one or more carbon atoms represented by the formula (I) include a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group.

[0035] Compound (A) has one or more nitrogen atoms. From the viewpoints of being able to further increase the adsorption ability to the substrate, being able to improve the selective modification ability to the substrate, and being able to improve the heat resistance of the film, compound (A) preferably has two or more nitrogen atoms, more preferably two to four, and even more preferably two or three.

[0036] From the viewpoint of ensuring solubility in water, the molecular weight of the compound (A) is preferably 1,000 or less, more preferably 800 or less, even more preferably 700 or less, and even more preferably 600 or less. From the viewpoint of obtaining a film with good heat resistance, the molecular weight of the compound (A) is preferably 120 or more, more preferably 150 or more, and even more preferably 200 or more.

[0037] Specific examples of compound (A) include nonylamine, decylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, docosylamine, oleylamine, 9-fluorononan-1-amine, 12-fluorododecane-1-amine, 18-fluorooctadecane-1-amine, 22-fluorodocosane-1-amine, and the compounds represented by the following formulas (a1-1) to (a1-49):

[0038] From the viewpoint of high-density modification of the substrate surface, the content of compound (A) in the composition is preferably 0.0005% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.01% by mass or more, relative to the total amount of the composition. From the viewpoint of highly selective modification of the substrate surface, the content of compound (A) in the composition is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, even more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less, relative to the total amount of the composition.

[0039] The composition of the present disclosure is an aqueous composition containing water as a solvent component. From the viewpoint of ensuring the storage stability of the composition, the content of water in the composition is preferably 1% by mass or more, more preferably 5% by mass or more, even more preferably 15% by mass or more, still more preferably 25% by mass or more, and even more preferably 40% by mass or more, based on the total amount of the composition.

[0040] The solvent component of the composition may be water alone, or may further contain an organic solvent.By using a mixed solvent of water and an organic solvent as the solvent component of the composition containing compound (A), it is preferable that a film with few defects can be formed and that coating properties can be ensured.As the organic solvent, at least one selected from the group consisting of alcohols, ethers, ketones, sulfones, amides, cyclic amines, lactams and esters can be preferably used.

[0041] Specific examples of organic solvents that may be incorporated into the composition include alcohols, such as chain monoalcohols having 1 to 18 carbon atoms, such as methanol, ethanol, propanol, isopropyl alcohol, 4-methyl-2-pentanol, and n-hexanol; alicyclic monoalcohols having 3 to 18 carbon atoms, such as cyclohexanol; polyhydric alcohols having 2 to 18 carbon atoms, such as 1,2-propylene glycol; and partial ethers of polyhydric alcohols having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether (1-methoxy-2-propanol), 2-methoxy-1-propanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monobutyl ether (butyl cellosolve), propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol ethyl methyl ether, and diethylene glycol monobutyl ether (butyl diglycol).

[0042] Examples of ethers include tetrahydrofuran and triethylene glycol dimethyl ether. Examples of ketones include acetone, methyl ethyl ketone, acetonyl acetone, and diacetone alcohol. Examples of sulfones include sulfolane and dimethyl sulfoxide. Examples of amides include cyclic amides such as N,N'-dimethylimidazolidinone and N-methylpyrrolidone; and linear amides such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, and N-methylpropionamide. Examples of cyclic amines include morpholine and N-(3-aminopropyl)morpholine. Examples of lactams include 1-methyl-2-pyrrolidone. Examples of esters include linear esters such as monocarboxylic acid esters, such as ethyl lactate; and cyclic esters such as γ-butyrolactone and δ-valerolactone.

[0043] Of these, the organic solvent is preferably an alcohol, more preferably at least one selected from the group consisting of chain monoalcohols having 1 to 18 carbon atoms, polyhydric alcohols having 2 to 18 carbon atoms, and polyhydric alcohol partial ethers having 3 to 19 carbon atoms, and even more preferably a polyhydric alcohol partial ether having 3 to 19 carbon atoms. Furthermore, the number of carbon atoms in the at least one compound selected from the group consisting of chain monoalcohols having 1 to 18 carbon atoms, polyhydric alcohols having 2 to 18 carbon atoms, and polyhydric alcohol partial ethers having 3 to 19 carbon atoms is preferably 1 to 15, more preferably 1 to 12, and even more preferably 1 to 10.

[0044] When the composition of the present disclosure contains an organic solvent, the content of the organic solvent in the composition is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 80% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less, relative to the total amount of the composition, from the viewpoint of minimizing the amount of organic solvent used and improving storage stability. Also, from the viewpoint of ensuring the coatability of the composition and suppressing the occurrence of defects to form a high-density film, the content of the organic solvent in the composition is preferably 1% by mass or more, more preferably 2% by mass or more, even more preferably 5% by mass or more, even more preferably 7% by mass or more, even more preferably 10% by mass or more, and even more preferably 15% by mass or more, relative to the total amount of the composition.

[0045] In addition to the compound (A) and the solvent component described above, the composition of the present disclosure may further contain a component (hereinafter also referred to as "other component") that is different from both the compound (A) and the solvent component. Examples of other components include a pH adjuster, a cleaning component, etc.

[0046] (pH adjuster) The pH adjuster is a component for adjusting the hydrogen ion concentration in the composition. In terms of enhancing the storage stability of the composition, it is preferable that the composition contains a pH adjuster in addition to the compound (A) and water. The pH adjuster may be any of an inorganic acid, an organic acid, an inorganic base, and an organic base, or a salt thereof. A buffer solution may also be used as the pH adjuster.

[0047] Specific examples of pH adjusters include inorganic acids such as phosphoric acid, boric acid, hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as acetic acid, lactic acid, malonic acid, succinic acid, citric acid, maleic acid, gluconic acid, cis-2-butenedioic acid, and N-propylpiperazine-N'-ethanesulfonic acid; inorganic bases such as ammonia, potassium hydroxide, and sodium hydroxide; and organic bases such as monoethanolamine, diethanolamine, triethanolamine, trimethylamine, triethylamine, propylamine, dibutylamine, and tetramethylammonium hydroxide.

[0048] Examples of the salt include salts of the above-mentioned acids or bases, which are compounds that exhibit buffering properties. Specific examples include ammonium chloride, ammonium acetate, sodium citrate, and tetramethylammonium chloride. Examples of the buffer solution include sodium phosphate buffer, sodium acetate buffer, sodium citrate phosphate buffer, sodium tartrate buffer, potassium borate buffer, and sodium borate buffer. The organic acid and organic base used as the pH adjuster preferably have 10 or less carbon atoms, more preferably 8 or less carbon atoms, and even more preferably 7 or less carbon atoms.

[0049] From the viewpoint of minimizing the metal content in the composition, the pH adjuster is preferably at least one selected from the group consisting of organic acids, organic bases, and ammonia, and more preferably at least one selected from the group consisting of carboxyl group-containing chain compounds, chain monoamine compounds, and ammonia. The carboxyl group-containing chain compounds preferably have 8 or less carbon atoms, more preferably 2 to 7 carbon atoms. The chain monoamine compounds preferably have 6 or less carbon atoms, more preferably 2 to 4 carbon atoms.

[0050] Among the above, at least one pH adjuster selected from the group consisting of ammonia, monoethanolamine, diethanolamine, triethanolamine, citric acid, malonic acid, maleic acid, and cis-2-butenedioic acid can be preferably used as the pH adjuster. When a pH adjuster is blended into the composition, the content of the pH adjuster in the composition may be any amount that can adjust the composition to the desired pH, and can be set appropriately depending on the type of pH adjuster used.

[0051] When forming a film on a metal substrate, the pH of the composition is preferably less than 10.0 from the viewpoint of suppressing corrosion of the substrate surface by the composition (i.e., obtaining a composition with high metal corrosion resistance). From the viewpoint of further increasing the metal corrosion resistance of the composition, the pH of the composition is more preferably 8.0 or less, even more preferably 7.5 or less, and even more preferably less than 7.0. Furthermore, the pH of the composition is preferably 1.3 or more, more preferably 2.0 or more. In this specification, the pH of the composition is a value measured under conditions of 25°C and 1 atmosphere.

[0052] (Cleaning component) For the purpose of removing components remaining on the substrate before forming a monolayer on the substrate using the above composition (for example, residues from dry etching for hole formation, etc.), a cleaning component may be incorporated into the composition.By incorporating a cleaning component together with compound (A) in the composition of the present disclosure, it is possible to form a monolayer consisting of compound (A) on the substrate while removing components remaining on the substrate.This allows the step of removing components remaining on the substrate before forming a monolayer and the step of forming a monolayer to be carried out in a single step, which is advantageous in that it can simplify the process in semiconductor manufacturing.

[0053] From the viewpoint of forming a high-density film on the substrate by the compound (A) while obtaining a sufficient cleaning effect on the substrate surface, the molecular weight of the cleaning component is preferably smaller than the molecular weight of the compound (A). Specifically, the molecular weight of the cleaning component is preferably 300 or less, more preferably 200 or less, even more preferably 100 or less, and even more preferably 80 or less. In addition, the molecular weight of the cleaning component is preferably 10 or more, more preferably 15 or more.

[0054] Examples of cleaning components include fluorine-containing compounds, hydrogen peroxide, citric acid, ethylenediaminetetraacetic acid (EDTA), or two or more of these. Specific examples of fluorine-containing compounds include hydrofluoric acid (hydrofluoric acid), ammonium fluoride, tetramethylammonium fluoride, and hexafluorosilicic acid. Fluorine-containing compounds are preferably used as cleaning components because of their high cleaning effect.

[0055] The content of the cleaning component in the composition is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and even more preferably 0.005% by mass or more, based on the total amount of the composition, from the viewpoint of obtaining a sufficient cleaning effect on the substrate. Also, from the viewpoint of not interfering with the selective modification of the substrate surface by compound (A), the content of the cleaning component is preferably 10% by mass or less, more preferably 7% by mass or less, and even more preferably 5% by mass or less, based on the total amount of the composition.

[0056] In addition to the above, other components that may be blended into the composition include antioxidants, etc. The blending amounts of other components can be appropriately selected depending on each component within a range that does not impair the effects of the present disclosure.

[0057] (Metal Content) Considering that the composition of the present disclosure is applied to a semiconductor manufacturing process, it is preferable that the metal content is low. Specifically, the amount of compound (A) in the composition is M Ａ (mass%), the amount of metal components is M Ｂ (mass%), M Ａ M against Ｂ The ratio (M Ｂ / M Ａ ) is 1.0 × 10 －１ It is preferable that the ratio (M Ｂ / M Ａ ) is more preferably 0.5 × 10 －１ More preferably, it is 1.0 × 10 －２ and even more preferably 1.0 × 10 －３ The metal content in the composition is a value measured by inductively coupled plasma mass spectrometry (ICP-MS).

[0058] The composition of the present disclosure can be prepared by mixing compound (A), water, and other components that are blended as necessary, and dissolving compound (A) etc. in water. The concentration of components other than the solvent component in the composition (i.e., the proportion of the total mass of the components other than the solvent component in the composition to the total mass of the composition) is preferably 0.0001 to 4.0 mass%, more preferably 0.0002 to 1.0 mass%, from the viewpoint of forming a high-density film while ensuring good coatability.

[0059] <Method for producing a surface-treated substrate and method for selectively modifying a substrate surface> Next, a method for producing a surface-treated substrate and method for selectively modifying a substrate surface, which are carried out using the above-mentioned composition, will be described. The method for producing a surface-treated substrate and method for selectively modifying a substrate surface in the present disclosure include a coating step of coating the composition of the present disclosure onto the surface of the substrate. Note that, hereinafter, the "method for producing a surface-treated substrate" will also be simply referred to as the "substrate manufacturing method," and the "method for selectively modifying a substrate surface" will also be simply referred to as the "selective modification method." Furthermore, the "substrate manufacturing method" and the "selective modification method" will collectively be simply referred to as the "method."

[0060] Coating Process (Substrate) As the substrate, a substrate having a first region and a second region made of a different material from the first region on its surface can be preferably used. The first region is preferably made of a different material from the second region, and therefore has a different adsorption property for compound (A) than the second region. For example, the first region has a higher adsorption property for compound (A) than the second region. From the viewpoint of selectively and densely modifying the surface of the substrate with compound (A), the first region is preferably formed of a conductive material, and the second region is preferably formed of an insulating material. Furthermore, the substrate to be selectively modified with the composition preferably has a first region formed of a conductive material and a second region formed of an insulating material.

[0061] When the first region is a region formed of a conductive material, the first region contains a metal element. Examples of the metal element include at least one selected from the group consisting of copper, iron, zinc, cobalt, aluminum, titanium, tin, tungsten, zirconium, tantalum, germanium, molybdenum, ruthenium, gold, silver, platinum, palladium, and nickel. The metal element contained in the first region may be a simple metal, an alloy (nickel-copper alloy, cobalt-nickel alloy, gold-silver alloy, etc.), a conductive nitride (tantalum nitride, titanium nitride, etc.), or the like. Among these, the first region preferably contains a simple metal, an alloy, or a conductive nitride, more preferably at least one selected from the group consisting of copper, cobalt, tungsten, tantalum, titanium, molybdenum, and ruthenium, and even more preferably at least one selected from the group consisting of tungsten, tantalum, titanium, molybdenum, and ruthenium.

[0062] When the second region is formed of an insulating material, the second region may be formed of a silicon-containing compound such as silicon oxide, silicon nitride, silicon oxynitride, or silicide (e.g., SiO ２ , SiOC, Si ３ N ４ The second region is preferably formed of a silicon oxide, a silicon nitride, a silicon oxynitride, a silicide, or a metal oxide (e.g., silicon nitride, silicon oxynitride, silicide, or metal oxide).

[0063] In particular, when the substrate to which the composition is applied has, as the first region, a region containing at least one element selected from the group consisting of tungsten, tantalum, titanium, molybdenum, and ruthenium, and has, as the second region, a region containing silicon oxide, silicon nitride, silicon oxynitride, or a metal oxide, the composition is suitable in that compound (A) can be highly selectively and densely adsorbed to the first region out of the first and second regions.

[0064] The shape of the coated surface of the substrate is not particularly limited. The coated surface may be, for example, flat, arc-shaped, concave, or protruding. Furthermore, when the coated surface has a first region and a second region, the arrangement of the first region and the second region is not particularly limited. For example, the first region and the second region may be arranged adjacent to each other in a predetermined direction on a plane. Alternatively, multiple first and second regions may be arranged within one of the other regions. Furthermore, one of the first and second regions may form the bottom surface of a hole or groove formed in the substrate, and the other may form the side surface thereof.

[0065] The surface of the substrate to which the composition is applied is preferably coated with, for example, H ２ , N ２ and H ２ Mixture of gas with O ２ Pretreatment such as plasma treatment using gas or the like, cleaning treatment of the substrate surface, or wet modification treatment may be performed.

[0066] (Coating method) Examples of methods for coating the composition on the surface of a substrate include spraying, roll coating, spin coating, slit die coating, bar coating, and inkjet coating. Among these, it is preferable to coat the composition on the surface of the substrate by spin coating, slit die coating, or bar coating. The thickness of the coating film formed on the substrate can be appropriately set so that the thickness of the film finally formed on the substrate is the desired thickness.

[0067] By applying the composition to the surface of the substrate in the coating process, a film (specifically, a monomolecular film) of compound (A) is formed on the first region. After applying the composition to the surface of the substrate, the solvent component in the composition may be removed by natural drying, thereby forming a film on the first region. Alternatively, a heat treatment may be performed to remove the solvent component from the composition applied to the surface of the substrate. The heat treatment may be performed using a heating device such as an oven or a hot plate. The heating temperature is, for example, 40°C or higher, and may be 50°C or higher. The heating time is, for example, 0.5 to 60 minutes. Compound (A) has high adsorption ability to metals, and therefore can form a film on the first region without heat treatment, which is advantageous in that it simplifies the manufacturing process. The thickness of the film formed on the substrate is, for example, several nanometers (e.g., approximately 0.5 to 20 nm).

[0068] Preferably, the method of the present disclosure further includes, after the application of the composition in the above-described application step, a step of contacting the surface of the substrate with a rinse liquid and washing the substrate surface to remove components derived from the composition on the second region (hereinafter also referred to as a "washing step"). This washing step can remove components derived from the composition (more specifically, the composition itself, compound (A), a residual film formed by the composition, etc.) that remain as residues on the second region from the second region. This allows the region of the substrate surface to be protected to be more selectively coated and protected with a film formed by compound (A).

[0069] Washing Step: As the rinse solution, water, an organic solvent, or a mixed solvent of water and an organic solvent can be preferably used. Specific examples of organic solvents used as the rinse solution include at least one selected from the group consisting of alcohols, ethers, ketones, sulfones, amides, cyclic amines, lactams, and esters. Further specific examples of rinse solutions include propylene glycol monomethyl ether acetate, isopropyl alcohol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, and mixed solvents of two or more of these.

[0070] The treatment of removing the components derived from the composition on the second region from the second region using a rinse liquid is carried out by contacting the substrate surface after the coating step with the rinse liquid. The method of contacting the substrate surface with the rinse liquid is not particularly limited, and for example, a shower method, a spray method, a dip method, a puddle method, etc. can be applied. When contacting the substrate surface with the rinse liquid, for example, the rinse liquid may be supplied to the substrate and contacted multiple times, or the rinse liquid or the substrate may be shaken. The temperature when contacting the substrate surface with the rinse liquid is, for example, 5 to 50°C. The contact time is, for example, 5 seconds to 30 minutes. The amount of rinse liquid used can be appropriately set taking into consideration the method of contacting the substrate surface with the rinse liquid, etc. After contacting the substrate surface with the rinse liquid, a further treatment of removing the rinse liquid from the substrate may be carried out using a spin coater or the like.

[0071] According to the method including the above-mentioned coating step and optionally including a washing step, a substrate surface-treated with a composition containing compound (A) and water can be obtained. That is, according to the present disclosure, there is provided a method for producing a surface-treated substrate, which includes a step of selectively modifying the surface of the substrate by applying a composition to the surface of the substrate.

[0072] The method including the coating step described above allows the substrate surface to be surface-modified highly selectively and densely by a simple treatment. In the method for producing a substrate according to the present disclosure, the substrate obtained by the coating step and the optionally included washing step may be further subjected to various treatments, for example, the following steps (contact step, metal layer formation step, film removal step).

[0073] Contacting Step The contacting step is a step of contacting the substrate surface with alcohol, dilute acid, hydrogen peroxide solution, ozone, plasma, ammonia, or an aqueous solution of ammonium fluoride salt after a film has been formed on the first region in the coating step (preferably after contact with the rinse liquid in the cleaning step). In the manufacturing process of semiconductors, etc., an oxide film layer may be formed on the surface of the substrate that comes into contact with air (on the second region). Therefore, by providing the contacting step, the oxide film layer formed on the second region can be removed. Among the above, examples of dilute acids include dilute hydrochloric acid, dilute sulfuric acid, dilute citric acid, dilute oxalic acid, dilute maleic acid, dilute acetic acid, dilute isobutyric acid, and dilute 2-ethylhexanoic acid.

[0074] Metal Layer Forming Step The metal layer forming step is a step of forming a metal layer on the second region after forming a film on the first region in the coating step (preferably after contact with a rinse solution in the cleaning step, more preferably after the contact step). The first region of the substrate surface after the cleaning step is covered with a protective film (monomolecular film) formed by compound (A). Therefore, when forming a metal layer in the metal layer forming step, the metal layer can be selectively formed on the second region out of the first region and the second region.

[0075] The method for forming the metal layer is not particularly limited. From the viewpoint of highly selective pattern formation in a fine region, it is preferable to form the metal pattern by chemical vapor deposition (CVD) or atomic layer deposition (ALD). The metal layer formed on the second region may be a barrier layer for separating the metal portion from the insulating portion or for suppressing metal diffusion from the metal portion. The thickness of the metal layer can be appropriately set depending on the application of the substrate, and is, for example, 1 to 30 nm.

[0076] Film Removal Step The film removal step is a step of removing the film formed on the first region after the metal layer is formed on the second region in the metal layer formation step. The film can be removed by, for example, etching. Examples of etching methods include known methods such as reactive ion etching (RIE) and physical etching. Examples of reactive ion etching include CF ４ Ya O２ Examples of the etching method include chemical dry etching, which uses a gas or the like and utilizes the difference in etching rate between layers; and chemical wet etching (wet development), which uses a liquid etching solution such as an organic solvent or hydrofluoric acid. Examples of physical etching include sputter etching and ion beam etching. Of these, reactive ion etching is preferred, and chemical dry etching or chemical wet etching is more preferred.

[0077] Examples of solvents used in chemical wet etching include acetic acid, APM (a mixture of ammonia, hydrogen peroxide, and water), SPM (a mixture of sulfuric acid and hydrogen peroxide), a 2.38% by mass TMAH aqueous solution, diluted hydrofluoric acid, and water.

[0078] By carrying out the above steps (coating step, cleaning step, contact step, metal layer forming step, and film removing step), a metal layer is selectively formed on the second region out of the first and second regions, and a substrate can be produced in which the surface (e.g., the metal surface) of the first region is exposed. The obtained substrate may further be subjected to various treatments such as plating. When plating is performed, the plating method is not particularly limited, and known electroplating, electroless plating, hot-dip plating, vacuum plating, vapor-phase plating, etc. can be used. When the method of the present disclosure is applied to a semiconductor manufacturing process, electroplating or electroless plating is preferred. After plating, if necessary, the substrate surface may be planarized (CMP treatment, etc.).

[0079] The present disclosure described above includes the following aspects. [Aspect 1] A method for producing a surface-treated substrate, comprising a step of selectively modifying the surface of a substrate including a first region and a second region made of a material different from that of the first region by applying a composition to the surface of the substrate, the composition comprising at least one compound (A) selected from the group consisting of compounds represented by formula (1), compounds represented by formula (2), and compounds represented by formula (3), and 1 mass % or more of water relative to the total amount of the composition. [Aspect 2] A method for producing a substrate according to [Aspect 1], comprising applying the composition to the surface of the substrate including the first region and the second region to form a film on the first region. [Aspect 3] A method for producing a substrate according to [Aspect 2], wherein the first region is formed of a conductive material and the second region is formed of an insulating material. [Aspect 4] A method for producing a substrate according to [Aspect 2], further comprising a step of removing components derived from the composition on the second region by contacting the surface of the substrate with a rinse after applying the composition. [Aspect 5] A method for producing a substrate according to Aspect 4, further comprising the step of contacting the substrate surface after contact with the rinse solution with an alcohol, a dilute acid, hydrogen peroxide solution, ozone, plasma, ammonia, or an aqueous solution of ammonium fluoride salt. [Aspect 6] A method for producing a substrate according to Aspect 4 or Aspect 5, further comprising the step of forming a metal layer on the second region after contact with the rinse solution. [Aspect 7] A method for producing a substrate according to Aspect 6, further comprising the step of removing a film formed from the composition on the first region after forming the metal layer. [Aspect 8] A method for producing a substrate according to any of Aspects 1 to 7, wherein the compound (A) has two or more nitrogen atoms. [Aspect 9] A method for producing a substrate according to any of Aspects 1 to 8, wherein the compound (A) has an alkyl group having 9 or more carbon atoms. [Aspect 10] A method for producing a substrate according to any of Aspects 1 to 9, wherein the compound (A) further has a carboxy group. [Aspect 11] The method for producing a substrate according to any one of [Aspects 1] to [Aspect 10], wherein the composition further contains a cleaning component. [Aspect 12] The method for producing a substrate according to [Aspect 11], wherein the cleaning component is a fluorine-containing compound.[Aspect 13] The method for producing a substrate according to any one of Aspects 1 to 12, wherein the composition further contains an organic solvent, and the content of the organic solvent in the composition is 7% by mass or more and 70% by mass or less, based on the total amount of the composition. [Aspect 14] The method for producing a substrate according to Aspect 13, wherein the organic solvent contained in the composition is at least one selected from the group consisting of alcohols, ethers, ketones, sulfones, amides, cyclic amines, lactams, and esters. [Aspect 15] The method for producing a substrate according to any one of Aspects 1 to 14, wherein the composition further contains a pH adjuster. [Aspect 16] The method for producing a substrate according to Aspect 15, wherein the pH adjuster is an organic acid, an organic base, or ammonia. [Aspect 17] The method for producing a substrate according to Aspect 16, wherein the pH adjuster is a carboxyl group-containing chain compound, a chain monoamine compound, or ammonia. [Aspect 18] The method for producing a substrate according to any one of Aspects 1 to 17, wherein the pH of the composition is less than 10.0. [Aspect 19] The amount of the compound (A) in the composition is M. Ａ (mass%), the amount of metal components is M Ｂ (mass%), M Ａ M against Ｂ The ratio (M Ｂ / M Ａ ) is 1.0 x 10 －２ A method for manufacturing a substrate according to any one of Aspects 1 to 18, wherein the method is as follows: Aspect 20: A method for selectively modifying a substrate surface, comprising a step of applying a composition to a surface of a substrate including a first region and a second region made of a material different from that of the first region, the composition containing compound (A) which is at least one type selected from the group consisting of compounds represented by formula (1) above, compounds represented by formula (2) above, and compounds represented by formula (3) above, and 1 mass % or more of water relative to the total amount of the composition. Aspect 21: A semiconductor processing composition, comprising compound (A) which is at least one type selected from the group consisting of compounds represented by formula (1) above, compounds represented by formula (2) above, and compounds represented by formula (3) above, and 1 mass % or more of water relative to the total amount of the composition, and wherein the amount of compound (A) in the composition is M Ａ (mass%), the amount of metal components is M Ｂ(mass%), M Ａ M against Ｂ The ratio (M Ｂ / M Ａ ) is 1.0 x 10 －２ 1. A semiconductor processing composition, comprising:

[0080] The present disclosure will be specifically described below based on examples, but the present disclosure is not limited to these examples. "Parts" and "%" represent "parts by mass" and "% by mass" unless otherwise specified.

[0081] 1. Preparation of Composition [Example 1] 799.58 g of distilled water and 200.00 g of butoxyethanol were added to 0.40 g of dodecylaminoethylaminoethylglycine and stirred. Subsequently, 0.01 g of maleic acid and 0.01 g of potassium hydroxide were added, and the pH was adjusted to 4.0. After that, the mixture was filtered through a high-density polyethylene filter having 0.45 μm pores to prepare a composition (SM-1) containing compound (A) at a solids concentration of 0.040%.

[0082] Examples 2 to 32 and Comparative Examples 1 to 6 Compositions (SM-2) to (SM-32) and compositions (SR-1) to (SR-6) were prepared in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Tables 1 to 3. In Tables 1 to 3, the numerical values ​​for each component represent mass %.

[0083] In Tables 1 to 3, the details of the compounds used in preparing the compositions are as follows: <SAM material> Compound (A) A-1: ​​Nonylamine A-2: Dodecylamine A-3: Octadecylamine A-4: Docosylamine A-5: Oleylamine A-6: N-dodecylethane-1,2-diamine A-7: N-dodecylaminoethylglycine A-8: N1-(2-aminoethyl)-N2-dodecylethane-1,2-diamine A-9: Dodecylaminoethylaminoethylglycine A-10: N-(3-aminopropyl)-n-dodecylpropane-1,3-diamine A-11: Lauryldiethanolamine A-12: 12-fluorododecan-1-amine A-13: Hexadecyltrimethylammonium bromide A-14: Hexadecyltrimethylammonium hydroxide A-15: Benzyldimethyldodecylammonium chloride A-16: Lauryl sulfobetaine A-17: Lauryl amidopropyl betaine Others B-1: Emal 0 (Kao Corporation, anionic surfactant, sodium lauryl sulfate) B-2: Dodecanethiol B-3: Butylamine B-4: 4-n-butylbenzylamine

[0084] <Organic solvents> D-1: Butyl diglycol D-2: Isopropyl alcohol D-3: Butoxyethanol D-4: Sulfolane D-5: Gamma butyrolactone D-6: N,N-dimethylformamide

[0085] <Other additives> ・pH adjusters K-1: Citric acid K-2: Maleic acid K-3: Malonic acid K-4: Acetic acid K-5: Phosphoric acid K-6: Hydrochloric acid K-7: Potassium hydroxide K-8: 2-ethanolamine K-9: Ammonia: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trade name "ammonia water" K-10: Tetramethylammonium hydroxide ・Cleaning ingredients M-1: Hydrofluoric acid M-2: Ammonium fluoride M-3: Tetramethylammonium fluoride M-4: Hexafluorosilicic acid M-5: Hydrogen peroxide

[0086] 2. Evaluation The following evaluations were carried out using compositions (SM-1) to (SM-32) and compositions (SR-1) to (SR-6) prepared in 1. The results are shown in Tables 1 to 3, respectively.

[0087] <Evaluation of Solubility> The solubility of each composition obtained in 1 above was visually observed and evaluated according to the following criteria: (Evaluation criteria) A: Transparency present (good) B: At least one of cloudiness and residual dissolution observed (fair) C: Both cloudiness and residual dissolution observed (poor)

[0088] <Evaluation of storage stability> 10 g of each composition prepared in 1 above was placed in a vial and stored at 50°C for 2 weeks. The change in viscosity before and after the storage stability test was expressed as Δη, and the change Δη was measured and the storage stability was evaluated according to the following criteria. The smaller the change in viscosity Δη, the more easily the composition can be coated under the same coating conditions with no difference between days, and the better the storage stability can be evaluated. (Evaluation criteria) A: Δη is less than 1 Pa s (good) B: Δη is 1 Pa s or more but less than 3 Pa s (passable) C: Δη is 3 Pa s or more (poor)

[0089] <Evaluation of Hydrophobicity (Selective Modification)> Wafer pieces with a 25 nm tungsten film, a 50 nm molybdenum film, a 20 nm aluminum oxide film, a 1,000 nm silicon oxide film (p-TEOS film), and a 500 nm low-dielectric silicon oxide film (Low K) were cut into 3 cm x 3 cm pieces and immersed in each of the compositions prepared in 1 above for 1 minute. The wafer pieces were then removed and washed with water and isopropyl alcohol to obtain substrates for contact angle measurement. Water was dropped onto the substrates, and the static contact angle of the film-formed surface was measured using a contact angle meter ("Drop Master DM-501" manufactured by Kyowa Interface Science Co., Ltd.). Substrates showing a significant increase in static contact angle after surface treatment with the composition compared to the static contact angle of the substrate before surface treatment with the composition were said to have been selectively modified, and a film formed on the substrate. The evaluation criteria for each substrate were as follows:

[0090] (Evaluation Criteria for Tungsten and Molybdenum Films) Since it is desirable that the tungsten and molybdenum films be in a modified state upon contact with the composition, they were evaluated according to the following criteria. A: When the static contact angle after contact with the composition was 90 degrees or more, it was determined that a high-density film was formed on the substrate and that it could be used for practical purposes, and it was therefore judged as "good." B: When the static contact angle after contact with the composition was 70 degrees or more but less than 90 degrees, it was determined that a medium-density film was formed on the substrate and that it could be used for practical purposes, and it was therefore judged as "passable." C: When the static contact angle after contact with the composition was less than 70 degrees, it was determined that no film was formed on the substrate or that only a low-density film was formed, and it could not be used for practical purposes, and it was therefore judged as "poor."

[0091] (Evaluation Criteria for Aluminum Oxide Film, Silicon Oxide Film, and Low-Dielectric Silicon Oxide Film) Since it is desirable that the aluminum oxide film, silicon oxide film, and low-dielectric silicon oxide film remain unmodified even after contact with the composition, they were evaluated according to the following criteria. A: When the static contact angle after contact with the composition is less than 40 degrees, no film is formed on the substrate, and it is evaluated as being suitable for practical use, and it was judged as "good." B: When the static contact angle after contact with the composition is 40 degrees or more but less than 70 degrees, it is evaluated as being suitable for practical use, although a film is partially formed on the substrate, and it was judged as "passable." C: When the static contact angle after contact with the composition is 70 degrees or more, it is evaluated as being uniformly formed on the substrate, and it is not suitable for practical use, and it was judged as "poor." For various substrates, an evaluation of "A" or "B" (i.e., no evaluation of "C") can be said to indicate that the substrate has been selectively surface-modified by the composition.

[0092] <Evaluation of Metal Corrosion Resistance (Evaluation by Etching Rate)> The tungsten film and molybdenum film substrates used for the hydrophobicity evaluation were cut into 3.5 cm x 3.5 cm pieces and immersed in each of the compositions prepared in 1. above for 10 minutes. The wafer pieces were then removed and washed with water and isopropyl alcohol to obtain treated objects. The thickness of the film on the treated object was measured using an X-ray fluorescence analyzer (manufactured by Rigaku Corporation, model "AZX400") and a spectroscopic ellipsometer (manufactured by Semilab Semiconductor Physics Laboratory Co. Ltd., model "SE-2000"), and the etching rate was calculated from the film thickness before and after treatment with each composition. (Evaluation Criteria) A: If the etching rate was less than 0.1 nm / min, corrosion did not occur and the result was judged to be "good." B: When the etching rate was 0.1 nm / min or more but less than 0.5 nm / min, corrosion was small and the film was suitable for practical use, and was therefore judged as "passable." C: When the etching rate was 0.5 nm / min or more, corrosion was so great that the film was not suitable for practical use, and was therefore judged as "poor."

[0093] <Evaluation of Dry Etching Residue Removal Performance (Evaluation by Etching Rate)> A dry etching process was performed on a low K film substrate using a reactive ion etching apparatus (RIE-10NR) to obtain a dry etching target. The obtained target was cut into 3.5 cm x 3.5 cm pieces and immersed in each of the compositions prepared in 1. above for 1 minute. The wafer pieces (targets) were then removed and washed with water and isopropyl alcohol. The fluorine component on the target surface after cleaning was quantified using an X-ray photoelectron analyzer (ULVAC, model "Quantum 2000"), and the ratio of the fluorine component on the surface-treated substrate to the fluorine component on a substrate that was not immersed in each composition was used as a reference value to calculate the cleaning efficiency (%). (Evaluation criteria) A: Cleaning efficiency is 98% or more (good) B: Cleaning efficiency is less than 98% and 90% or more (passable) C: Cleaning efficiency is less than 90% (poor) (Dry etching conditions) Gas flow rate: Ar / C ４ F ８ / N ２=100 / 50 / 33 sccm Plasma power: 170 W / 40 MHz (high frequency), 80 W / 13 MHz (low frequency) Pressure: 50 mTorr Treatment time: 100 seconds

[0094] <Evaluation of Metal Oxide Blocking Performance (Evaluation of ALD Resistance)> A substrate (surface-treated substrate) in which a tungsten-filmed wafer piece was surface-coated with each of the compositions prepared in 1. above was subjected to ALD treatment using Cambridge Nanotech FIJI at Stanford University under the following conditions to obtain a surface-treated substrate. As a control, a tungsten-filmed wafer piece (untreated substrate) that had not been surface-treated with each composition was subjected to ALD treatment in the same manner as the surface-treated substrate to obtain an ALD-treated untreated substrate. The Ti component on the substrate surface of the treated substrate (surface-treated substrate and untreated substrate) was quantified by X-ray photoelectron analysis (Quantum 2000, manufactured by ULVAC, Inc.). The ratio of the quantitative value of the Ti component on the surface-treated substrate to the reference value was calculated as the blocking rate (%). The larger the value of the blocking rate, the more densely the components in the composition (SAM material in the table) are adsorbed to the substrate surface in the film formed on the substrate from that composition, and the higher the blocking performance against metal oxide formation by ALD processing. (Evaluation criteria) A: Blocking rate of 98% or more (good) B: Blocking rate of 90% or more but less than 98% (acceptable) C: Blocking rate of less than 90% (poor)

[0095] <Measurement of Metal Content> Each composition was diluted 20 times with diethylene glycol butyl ether / ultrapure water = 80 / 20 (parts by mass), and the contents of sodium, potassium, and calcium were measured as metal contents using a NexION 5000 ICP mass spectrometer (manufactured by Perkin Elmer). Ａ ) the total content of sodium, potassium and calcium (M Ｂ ) ratio (M Ｂ / M Ａ ) according to the following criteria: Ｂ / M ＡThe smaller the ratio (M), the lower the metal content in the composition, and the better the composition. Ｂ / M Ａ ) is 10 －２ Less than (good) B: Ratio (M Ｂ / M Ａ ) is 10 －２ 10 above －１ Below (acceptable) C: Ratio (M Ｂ / M Ａ ) is 10 －１ Super (not possible)

[0096]

[0097]

[0098]

[0099] As shown in Tables 1 to 3, the compositions of Examples 1 to 32, which used compound (A) as a film-forming material and contained water, exhibited good solubility of compound (A) in water and good storage stability. Furthermore, the results of evaluating the selective modification and ALD resistance using static contact angles revealed that the compositions of Examples 1 to 32 were capable of forming highly selective and dense films on metal surfaces. Furthermore, the compositions of Examples 1 to 32 exhibited good metal corrosion resistance. Furthermore, by incorporating a fluorine-containing compound as a cleaning component together with compound (A) and water, residue removal performance could be imparted to the compositions (Examples 26 to 29).

[0100] In contrast, the composition of Comparative Example 1, which did not contain a film-forming material, was insufficient in selective modification of the metal surface, metal corrosion resistance, and ALD resistance. The composition of Comparative Example 2, which did not contain water, was inferior in storage stability. Furthermore, the compositions of Comparative Examples 3 to 6, which used B-1 to B-4, respectively, instead of compound (A) as the film-forming material, were insufficient in selective modification of the metal surface, metal corrosion resistance, and ALD resistance.

Claims

1. A method for producing a surface-treated substrate, comprising a step of selectively modifying the surface of a substrate, the surface of the substrate including a first region and a second region made of a material different from that of the first region, by applying a composition to the surface of the substrate, the composition comprising at least one compound (A) selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3), and 1 mass % or more of water relative to the total amount of the composition. (In formula (1), formula (2) and formula (3), R １ , R ４ and R ８ are each independently a monovalent chain group having 9 or more carbon atoms. ２ , R ３ , R ５ , R ６ , R ９ and R １０ are each independently a hydrogen atom or a monovalent chain group having one or more carbon atoms. ７ is a hydrogen atom or a monovalent organic group having one or more carbon atoms. － represents an anion. － represents a monovalent anionic group.

2. A method for producing a substrate according to claim 1, comprising applying the composition to a surface of the substrate including the first region and the second region to form a film on the first region.

3. The method for manufacturing a substrate according to claim 2, wherein the first region is formed of a conductive material, and the second region is formed of an insulating material.

4. The method for producing a substrate according to claim 2, further comprising a step of removing components derived from the composition on the second region by contacting the surface of the substrate with a rinsing liquid after application of the composition.

5. The method for producing a substrate according to claim 4, further comprising a step of contacting the surface of the substrate after contact with the rinsing liquid with an alcohol, a dilute acid, a hydrogen peroxide solution, ozone, plasma, ammonia or an aqueous solution of an ammonium fluoride salt.

6. The method for producing a substrate according to claim 4, further comprising the step of forming a metal layer on the second region after contact with the rinsing liquid.

7. The method for producing a substrate according to claim 6, further comprising the step of removing the film on the first region formed by the composition after the formation of the metal layer.

8. The method for producing a substrate according to claim 1, wherein the compound (A) has two or more nitrogen atoms.

9. The method for producing a substrate according to claim 1, wherein the compound (A) has an alkyl group having 9 or more carbon atoms.

10. The method for producing a substrate according to claim 1, wherein the compound (A) further has a carboxy group.

11. The method of producing a substrate according to claim 1, wherein the composition further comprises a cleaning component.

12. The method for producing a substrate according to claim 11, wherein the cleaning component is a fluorine-containing compound.

13. The method for producing a substrate according to claim 1, wherein the composition further contains an organic solvent, and the content of the organic solvent in the composition is 7% by mass or more and 70% by mass or less based on the total amount of the composition.

14. The method for producing a substrate according to claim 13, wherein the organic solvent contained in the composition is at least one selected from the group consisting of alcohols, ethers, ketones, sulfones, amides, cyclic amines, lactams and esters.

15. The method for producing a substrate according to claim 1, wherein the composition further contains a pH adjuster.

16. The method for producing a substrate according to claim 15, wherein the pH adjuster is an organic acid, an organic base, or ammonia.

17. The method for producing a substrate according to claim 15, wherein the pH adjuster is a carboxyl group-containing chain compound, a chain monoamine compound, or ammonia.

18. The method of producing a substrate according to claim 1, wherein the pH of the composition is less than 10.

0.

19. The amount of the compound (A) in the composition is M Ａ (mass%), the amount of metal component is M Ｂ (mass%), M Ａ M for Ｂ The ratio of (M Ｂ / M Ａ ) is 1.0 x 10 －２ The method for producing a substrate according to claim 1 , wherein:

20. A method for selectively modifying a substrate surface, comprising a step of applying a composition to a surface of a substrate including a first region and a second region made of a material different from that of the first region, wherein the composition contains compound (A) which is at least one type selected from the group consisting of compounds represented by the following formula (1), compounds represented by the following formula (2), and compounds represented by the following formula (3), and 1 mass % or more of water relative to the total amount of the composition. (In formula (1), formula (2) and formula (3), R １ , R ４ and R ８ are each independently a monovalent chain group having 9 or more carbon atoms. ２ , R ３ , R ５ , R ６ , R ９ and R １０ are each independently a hydrogen atom or a monovalent chain group having one or more carbon atoms. ７ is a hydrogen atom or a monovalent organic group having one or more carbon atoms. － represents an anion. － represents a monovalent anionic group.

21. A composition for semiconductor processing, comprising at least one compound (A) selected from the group consisting of a compound represented by the following formula (1), a compound represented by the following formula (2), and a compound represented by the following formula (3), and 1 mass % or more of water based on the total amount of the composition, wherein the amount of the compound (A) in the composition is M Ａ (mass%), the amount of metal component is M Ｂ (mass%), M Ａ M for Ｂ The ratio of (M Ｂ / M Ａ ) is 1.0 x 10 －２ 1. A semiconductor processing composition, comprising: (In formula (1), formula (2) and formula (3), R １ , R ４ and R ８ are each independently a monovalent chain group having 9 or more carbon atoms. ２ , R ３ , R ５ , R ６ , R ９ and R １０ are each independently a hydrogen atom or a monovalent chain group having one or more carbon atoms. ７ is a hydrogen atom or a monovalent organic group having one or more carbon atoms. － represents an anion. － represents a monovalent anionic group.

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