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

Abstract

In a method for selectively modifying the surface of a base material, which includes a step for applying a composition to the surface of the base material, a composition containing water and a compound (A) having a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms is used as the composition.

Description

Technical Field

[0001] [Cross-reference to related applications]

[0002] This application claims the benefit of priority based on Japanese Patent Application No. 2023-53728, filed on March 29, 2023, the entirety of which is incorporated herein by reference.

[0003] The present disclosure relates to a method for selectively modifying a substrate surface, a method for manufacturing a surface-treated substrate, and a composition. Background Art

[0004] In semiconductor manufacturing processes, an organic film is sometimes formed on a portion of a substrate surface to cover and protect the portion. After the organic film is formed, the substrate is subjected to various processes such as metal layer formation or etching. When an organic film is formed on a substrate surface to protect a portion of the substrate surface, with the further miniaturization of semiconductor devices, there is a demand for highly selective film formation on the desired area of ​​the substrate surface (see, for example, Patent Document 1).

[0005] Patent Document 1 discloses that a composition comprising a first polymer having a first functional group that bonds to the metal contained in the first region at a terminal of a main chain or a side chain and a solvent is applied to the surface of a substrate having a first region containing a metal on its surface layer, and the coating film formed by applying the composition is heated, thereby selectively modifying the surface of the first region with the first polymer. Patent Document 1 also discloses that solvents capable of dissolving or dispersing the first polymer, such as alcoholic solvents, etheric solvents, ketone-based solvents, amide-based solvents, and hydrocarbon-based solvents, are used in preparing the composition.

[0006] Prior art literature

[0007] Patent Literature

[0008] Patent Document 1: International Publication No. 2018 / 043304 Summary of the Invention

[0009] Problems to be solved by the invention

[0010] In the composition used for selective modification of the substrate surface, if the main component of the solvent can be set to water, it is expected that the environmental load can be reduced or the handleability of the composition can be made better. However, in the composition containing water, precipitation of the components contained in the composition is likely to occur, and there is a tendency for the storage stability of the composition to be easily reduced. In particular, when the substrate surface is imparted with water repellency by selectively modifying the substrate surface, a highly hydrophobic material can be used as the film-forming material. Therefore, there is a possibility that the storage stability of the composition is easily reduced due to insufficient solubility of the film-forming material in water.

[0011] Furthermore, to stabilize the quality of products during semiconductor manufacturing processes or to prevent a decrease in product yield, it is necessary to selectively protect the desired area when protecting a portion of the substrate surface. Furthermore, it is necessary to modify the desired area with high density to prevent impurities from adhering to the protected area (i.e., to achieve high barrier properties).

[0012] The present disclosure has been made in view of the above-mentioned problems, and its main object is to provide a method and composition for selectively modifying a substrate surface, which has high storage stability of a composition used for selectively modifying a substrate surface and can modify the substrate surface with high selectivity and high density.

[0013] Technical means to solve the problem

[0014] In order to solve the above-mentioned problems, the present disclosure provides the following means.

[0015] [1] A method for selectively modifying a substrate surface, comprising applying a composition comprising a compound (A) having a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms, and water, to the surface of the substrate.

[0016] [2] A method for producing a surface-treated substrate, comprising applying a composition to the surface of a substrate to selectively modify the surface of the substrate, wherein the composition contains a compound (A) having a carboxylate anion portion and a monovalent organic group having 8 or more carbon atoms, and water.

[0017] [3] A composition for selectively modifying a substrate surface, the composition comprising: a compound (A) having a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms; and water.

[0018] Effects of the Invention

[0019] According to the present disclosure, a composition used for selective modification of a substrate surface has high storage stability and can modify the substrate surface with high selectivity and high density. DETAILED DESCRIPTION

[0020] Hereinafter, matters related to the embodiment will be described in detail. In addition, in this specification, the numerical range described using "to" means that the numerical values ​​described before and after "to" are included as the lower limit and the upper limit. Unless otherwise specified, each component may be used alone or in combination of two or more.

[0021] Method and composition for selective modification of substrate surface

[0022] The method for selectively modifying a substrate surface disclosed herein (hereinafter referred to as the "selective modification method") includes applying a composition (hereinafter also referred to as the "surface modification composition") to the surface of a substrate. The surface modification composition is an aqueous liquid composition containing a compound (A) having a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms, and water as a solvent. Below, the surface modification composition is first described, followed by a method for selectively modifying a substrate surface using the surface modification composition.

[0023] <Surface Modification Composition>

[0024] The surface modification composition is used as a surface treatment liquid to form a film on the surface of a substrate to modify the substrate's surface. The area where the surface modification composition forms the film is rendered hydrophobic. Typically, the film formed by the surface modification composition is a self-assembled monolayer (SAM) formed by adsorption of compound (A) on the substrate surface. The following describes the various components contained in the surface modification composition and the optional components (hereinafter referred to as "other components") that may be added as needed.

[0025] Compound (A)

[0026] The compound (A) has a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms (hereinafter also referred to as "monovalent organic group R 1 ”). It is believed that by using compound (A) as a monomolecular film forming material, the carboxylate anion portion exhibits adsorption ability to the substrate (especially the metal region), and the monovalent organic group R 1 And exhibit water repellency. Thus, excellent water repellency can be imparted to the surface of the substrate. In particular, compound (A) can improve the water solubility of compound (A) by having a carboxylate anion portion, while modifying the metal region of the substrate with high selectivity and high density through interaction with the metal. In addition, the "interaction" mentioned here is, for example, a chemical bond, which can be listed as: covalent bonding, ionic bonding, coordination bonding, etc. When the carboxylate anion portion is coordinated with the metal, the bonding force between the metal atom and the carboxylate anion can be increased.

[0027] Compound (A) is a compound different from a polymer (a low molecular weight compound). From the perspective of ensuring solubility in water, the molecular weight of 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. Furthermore, from the perspective of obtaining a film with good heat resistance, the molecular weight of compound (A) is preferably 155 or more, more preferably 180 or more, and even more preferably 200 or more.

[0028] The compound (A) may have one or more carboxylate anion moieties, and the number thereof is not particularly limited. From the perspective of enhancing adsorption to a substrate (particularly a metal region), the compound (A) preferably has two or more carboxylate anion moieties. In addition, in order to ensure adsorption to a substrate, the number of carboxylate anion moieties possessed by the compound (A) is preferably six or less, more preferably four or less.

[0029] The carboxylate anion moiety of the compound (A) can form a salt with a basic cation such as ammonium ion. When the carboxylate anion moiety forms a salt, the counterion may be a cationic counterion.

[0030] Specific examples of cations that form a salt with the carboxylate anion portion include metal ions such as lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion, magnesium ion, calcium ion, strontium ion, and barium ion; and organic cations such as ammonium ion, 2-ethanolammonium ion, 1-butanolammonium-4-ion, diethanolammonium ion, triethanolammonium ion, propylammonium ion, butylammonium ion, diisopropylammonium ion, dibutylammonium ion, ethylenediammonium ion, 2,2-imidodi(ethylammonium ion), N,N'-di(2-ammonioethyl)ethylenediammonium ion, N,N-bis(2-aminoethyl)methylammonium ion, N,N-bis(3-aminopropyl)methylammonium ion, tetramethylammonium ion, tetraethylammonium ion, and tetrabutylammonium ion.

[0031] From the viewpoint of enhancing the adsorption property to the metal region, the carboxylate anion portion of the compound (A) preferably forms a carboxyl group with a hydrogen ion or forms a salt with an organic cation.

[0032] The carboxylate anion portion possessed by compound (A) may be bonded to an aliphatic carbon or to an aromatic carbon. From the viewpoint of improving solubility in aqueous solution and storage stability, it is preferred that at least a portion of the carboxylate anion portion possessed by compound (A) is bonded to an aliphatic carbon, and it is preferred that all the carboxylate anion portions possessed by compound (A) are bonded to an aliphatic carbon. In the case where compound (A) has two or more carboxylate anion portions, compound (A) is preferably a structure having two or more carboxylate anion portions bonded to a chain hydrocarbon, and more preferably a structure having two or more carboxylate anion portions bonded to a saturated chain hydrocarbon. The chain hydrocarbon to which the carboxylate anion portion is bonded may be straight chain or branched.

[0033] As the monovalent organic group R possessed by the compound (A) 1 , and the like include: a monovalent hydrocarbon group, a monovalent group in which any hydrogen atom possessed by a monovalent hydrocarbon group is substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a phosphono group, a sulfonyl group, an acetyl group or a formyl group, etc. From the viewpoint of making the film formed from the surface modification composition exhibit excellent water repellency, the monovalent organic group R 1 It is preferred that the - ).

[0034] From the viewpoint of obtaining a film with excellent water repellency by applying the surface modification composition to the surface of a substrate, the monovalent organic group R 1 It is preferably a monovalent hydrocarbon group or a halogenated hydrocarbon group having 8 or more carbon atoms. 1 The carbon number of alkyl is, for example, 8 to 40.

[0035] Here, in this specification, the so-called "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. The so-called "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that does not contain a cyclic structure but only contains a chain structure. The chain hydrocarbon group may be saturated or unsaturated. The so-called "alicyclic hydrocarbon group" refers to a hydrocarbon group that only contains an alicyclic hydrocarbon structure as a ring structure and does not contain an aromatic ring structure. The alicyclic hydrocarbon group does not need to contain only an alicyclic hydrocarbon structure, and also includes a group having a chain structure in a part thereof. The so-called "aromatic hydrocarbon group" refers to a hydrocarbon group that contains an aromatic ring structure as a ring structure. Among them, it is not necessary to contain only an aromatic ring structure, and a chain structure or an alicyclic hydrocarbon structure may also be contained in a part thereof.

[0036] About monovalent organic radical R 1 Specific examples of the monovalent hydrocarbon group include a monovalent chain hydrocarbon group having 8 to 40 carbon atoms, a monovalent alicyclic hydrocarbon group having 8 to 40 carbon atoms, and a monovalent aromatic hydrocarbon group having 8 to 40 carbon atoms.

[0037] About Organic R 1Specific examples of the monovalent hydrocarbon group include, as monovalent chain hydrocarbon groups having 8 to 40 carbon atoms, straight-chain or branched alkyl groups such as n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, sec-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-pentacosyl, and n-tetracontyl; straight-chain or branched alkenyl groups such as octenyl, decenyl, isodecenyl, dodecenyl, n-tetradecenyl, n-hexadecenyl, n-octadecenyl, n-eicosyl, and n-pentacosenyl; and straight-chain or branched alkynyl groups such as octynyl, decynyl, isodecenyl, dodecynyl, n-tetradecynyl, n-hexadecynyl, n-octadecynyl, n-eicosyl, and n-pentacosenyl.

[0038] Examples of the monovalent alicyclic hydrocarbon group having 8 to 40 carbon atoms include monocyclic alicyclic saturated hydrocarbon groups such as propylcyclopentyl, trimethylcyclopentyl, propylcyclohexyl, ethylcyclohexyl, dimethylcyclohexyl, propylcycloheptyl, ethylcycloheptyl, and methylcycloheptyl; monocyclic alicyclic unsaturated hydrocarbon groups such as propylcyclopentenyl, ethylcyclohexenyl, methylcycloheptenyl, and methylcyclooctenyl; polycyclic alicyclic saturated hydrocarbon groups such as methylnorbornyl, adamantyl, and tricyclodecanyl; and polycyclic alicyclic unsaturated hydrocarbon groups such as methylnorbornyl and tricyclodecanyl.

[0039] Examples of the monovalent aromatic hydrocarbon group having 8 to 40 carbon atoms include aryl groups such as dimethylphenyl, ethylphenyl, naphthyl, and anthracenyl; and aralkyl groups such as phenethyl, naphthylmethyl, and anthracenylmethyl.

[0040] As a monovalent organic radical R 1 Specific examples of the monovalent halogenated hydrocarbon group include groups in which arbitrary hydrogen atoms possessed by the groups exemplified as the monovalent hydrocarbon group are substituted with halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.).

[0041] In terms of improving the solubility of the compound (A) in water and imparting excellent water repellency to the substrate surface, the monovalent organic group R 1 Preferably, it is a monovalent hydrocarbon group, more preferably a monovalent chain hydrocarbon group, further preferably a linear or branched alkyl group, further more preferably a linear alkyl group. From the viewpoint of imparting excellent water repellency to the substrate surface, the monovalent organic group R 1 The number of carbon atoms in R is preferably 8 or more, more preferably 10 or more, and further preferably 12 or more. In addition, from the viewpoint of improving the solubility of the compound (A) in water or suppressing the decrease in the adsorption ability of the compound (A) to the substrate, the monovalent organic group R 1 The carbon number of is preferably 30 or less, more preferably 20 or less, further preferably 18 or less, further more preferably 15 or less.

[0042] Compound (A) has one or more carboxylate anion moieties and a monovalent organic group R 1 In terms of making the coating property of the surface modification composition containing water as a solvent more excellent and obtaining a film with a higher density, the compound (A) is preferably a carboxylate anion portion that forms a carboxyl group with a hydrogen ion or a salt with an organic cation, and the monovalent organic group R 1 From the perspective of forming a higher density film by compound (A), compound (A) is more preferably a carboxylate anion bonded to an aliphatic carbon and forming a carboxyl group with a hydrogen ion or a salt with an organic cation, and the monovalent organic group R 1 The compound (A) is preferably a carboxylate anion bonded to an aliphatic carbon and forming a salt with an organic cation, and the monovalent organic group R 1 For hydrocarbon groups.

[0043] Preferred specific examples of the compound (A) include compounds represented by the following formula (0).

[0044] [Chemistry 1]

[0045]

[0046] (In formula (0), R 1 is a monovalent organic group with a carbon number of 8 or more; X + is a hydrogen ion, an organic cation or a metal cation; n is an integer greater than 1; when n is 1, R 2 is a single bond, and when n is 2 or more, R 2 is a (n+1) valent saturated chain hydrocarbon group having 1 to 4 carbon atoms)

[0047] In the formula (0), R 1 is the monovalent organic group R 1 The corresponding basis. About R 1 Specific examples and preferred examples of the group represented by include the following: 1 The base described is the same base.

[0048] About X + Specific examples of the organic cations and metal cations represented by X include the same cations as those described above as specific examples of cations that form salts with the carboxylate anion portion. + It is preferably a hydrogen ion or an organic cation, and more preferably an organic cation.

[0049] n is preferably 1 to 6, more preferably 1 to 4, further preferably 1 or 2, and further more preferably 2.

[0050] When n is 2 or more, the two or more carboxylate anion moieties of compound (A) may be bonded to R 2 The same aliphatic carbon atoms in the saturated chain hydrocarbon groups may be bonded to different aliphatic carbon atoms.

[0051] More preferred specific examples of the compound (A) include a compound represented by the following formula (1) and a compound represented by the following formula (2).

[0052] [Chemistry 2]

[0053] R 1 -COO - X + …(1)

[0054] (In formula (1), R 1 is a monovalent organic group with a carbon number of 8 or more; X + is a hydrogen ion, an organic cation, or a metal cation)

[0055] [Chemistry 3]

[0056]

[0057] (In formula (2), R 1 is a monovalent organic group with a carbon number of 8 or more; X + is a hydrogen ion, an organic cation or a metal cation; R 2 is a trivalent saturated chain hydrocarbon group having 1 to 4 carbon atoms)

[0058] In the above formula (1) and formula (2), regarding R 1 Specific examples and preferred examples of the group represented by include the following: 1 The base described is the same base.

[0059] About X + Specific examples of the organic cations and metal cations represented by X include the same cations as those described above as specific examples of cations that form salts with the carboxylate anion portion. + It is preferably a hydrogen ion or an organic cation, and more preferably an organic cation.

[0060] Specific examples of the compound (A) include nonanoic acid, decanoic acid, tetradecanoic acid, hexadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid, heptacosanoic acid, 11-mercaptoundecanoic acid, 16-mercaptohexadecanoic acid, 10-aminoundecanoic acid, 18-aminononadecanoic acid, isononanoic acid, 2-propylhexanoic acid, 3,5,5-trimethylhexanoic acid, neodecanoic acid, 2,2,3,5-tetramethylhexanoic acid, 2,4-dimethyl-2-isopropylpentanoic acid, cyclohexanoic acid, 2,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, 2,2-diethylhexanoic acid, 1,4-dimethyl-5-(3-methyl-2-butenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,3-dimethyl-2-(3-methyl-2-butenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,2,3- Monocarboxylic acids such as trimethyl-5-(1-methyl-2-propenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,4,5-trimethyl-2-(2-methyl-2-propenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,4,5-trimethyl-2-(2-methyl-1-propenyl)-3-cyclohexen-1-yl-carboxylic acid, 1,5,6-trimethyl-3-(2-methyl-1-propenyl)-4-cyclohexen-1-yl-carboxylic acid, 1-methyl-4-(4-methyl-3-pentenyl)-4-cyclohexen-1-yl-carboxylic acid, 1-methyl-3-(4-methyl-3-pentenyl)-3-cyclohexen-1-yl-carboxylic acid, and 2-methoxycarbonyl-3-(2-methyl-1-propenyl)-5,6-dimethyl-4-cyclohexen-1-yl-carboxylic acid;

[0061] Dicarboxylic acids such as octylsuccinic acid, decylsuccinic acid, octadecylsuccinic acid, triacontanylsuccinic acid, 1-decenylsuccinic acid, 1-octadecenylsuccinic acid, 10,10,10-trifluorodecylsuccinic acid, 18,18,18-trifluorooctadecylsuccinic acid, sodium octadecylsuccinate, potassium octadecylsuccinate, ammonium octadecylsuccinate, tetramethylammonium octadecylsuccinate, tetrabutylammonium octadecylsuccinate, ethanolamine octadecylsuccinate, and triethanolamine octadecylsuccinate;

[0062] 2-Hydroxy-1,2,3-undecantricarboxylic acid, 2-Hydroxy-1,2,3-tridecyltricarboxylic acid, 2-Hydroxy-1,2,3-heneicosyltricarboxylic acid, 2-Hydroxy-1,2,3-triacontyltricarboxylic acid, 2-Hydroxy-4,5-tridecenyl-1,2,3-undecantricarboxylic acid, 2-Hydroxy-4,5-eicosenyl-1,2,3-undecantricarboxylic acid, 13,13,13-trifluoro-2-hydroxy-1,2,3-tridecyltricarboxylic acid, 21,21,21-trifluoro- Tricarboxylic acids such as 2-hydroxy-1,2,3-heneicosanetricarboxylic acid, sodium 2-hydroxy-1,2,3-tridecyltricarboxylate, potassium 2-hydroxy-1,2,3-tridecyltricarboxylate, ammonium 2-hydroxy-1,2,3-tridecyltricarboxylate, tetramethylammonium 2-hydroxy-1,2,3-tridecyltricarboxylate, tetrabutylammonium 2-hydroxy-1,2,3-tridecyltricarboxylate, ethanolamine 2-hydroxy-1,2,3-tridecyltricarboxylate, and triethanolamine 2-hydroxy-1,2,3-tridecyltricarboxylate.

[0063] From the perspective of high-density modification of the substrate surface, the content of compound (A) in the surface modification composition is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, relative to the total amount of the surface modification composition. Furthermore, from the perspective of highly selective modification of the substrate surface, the content of compound (A) in the surface modification composition is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less, relative to the total amount of the surface modification composition.

[0064] Solvent

[0065] The surface-modifying composition is an aqueous composition containing water as a solvent component. Water can be used alone as the solvent component of the surface-modifying composition, but an organic solvent may also be contained. Using a mixed solvent of water and an organic solvent as the solvent component of the surface-modifying composition can improve the storage stability of the surface-modifying composition. The organic solvent is preferably at least one selected from the group consisting of alcohols, ethers, ketones, sulfones, amides, cyclic amines, lactams, and esters.

[0066] Specific examples of organic solvents that can be formulated into the surface modification composition include, as alcohols, 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; polyols having 2 to 18 carbon atoms, such as 1,2-propylene glycol; and polyol partial ethers 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.

[0067] Examples of ethers include tetrahydrofuran. Examples of ketones include acetone, methyl ethyl ketone, acetonylacetone, 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 chain 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 monocarboxylic acid esters such as ethyl lactate as chain esters; and cyclic esters such as γ-butyrolactone and δ-valerolactone.

[0068] Among these, the organic solvent is preferably an alcohol, more preferably at least one selected from the group consisting of linear monoalcohols having 1 to 18 carbon atoms, polyols having 2 to 18 carbon atoms, and partial ethers of polyols having 3 to 19 carbon atoms, and even more preferably a partial ether of polyols having 3 to 19 carbon atoms, because it easily mixes with water and can improve the coating properties of the surface modification composition, or because it can form a higher density film when compound (A) is used as a film-forming material. Furthermore, the at least one compound selected from the group consisting of linear monoalcohols having 1 to 18 carbon atoms, polyols having 2 to 18 carbon atoms, and partial ethers of polyols having 3 to 19 carbon atoms preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and even more preferably 1 to 10 carbon atoms.

[0069] When the surface modification composition contains an organic solvent, from the perspective of minimizing the amount of the organic solvent used or forming a higher density film using compound (A), the content of the organic solvent in the surface modification composition is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and further more preferably 40% by mass or less, relative to the total amount of the surface modification composition. In addition, from the perspective of improving the storage stability of the surface modification composition, the content of the organic solvent in the surface modification composition is preferably 1% by mass or more, more preferably 2% by mass or more, relative to the total amount of the surface modification composition.

[0070] The water content in the surface-modifying composition is, for example, 1% by mass or greater, preferably 10% by mass or greater, more preferably 15% by mass or greater, and even more preferably 25% by mass or greater, relative to the total amount of the composition. Furthermore, from the perspective of minimizing the amount of organic solvent used, the water content is preferably 30% by mass or greater, more preferably 35% by mass or greater, even more preferably 45% by mass or greater, even more preferably 55% by mass or greater, particularly preferably 65% ​​by mass or greater, and even more preferably 70% by mass or greater, relative to the total amount of water and the organic solvent contained in the surface-modifying composition.

[0071] Other ingredients

[0072] In addition to the compound (A) and the solvent component, the surface modification composition may also contain a component different from the compound (A) and the solvent component (hereinafter also referred to as "other component"). In order to improve the storage stability of the surface modification composition, the surface modification composition preferably contains the compound (A) and water together with a pH adjuster. In addition, the surface modification composition may also contain a cleaning component as another component.

[0073] (pH adjuster)

[0074] A pH adjuster is a component used to adjust the hydrogen ion concentration in a surface modification composition. The pH adjuster can be any of an inorganic acid, an organic acid with 8 or fewer carbon atoms, an inorganic base, and an organic base, or a salt thereof. A buffer solution can also be used as a pH adjuster in a surface modification composition.

[0075] Specific examples of pH adjusters include inorganic acids such as phosphoric acid, sulfuric acid, nitric acid, boric acid, and hydrochloric acid; organic acids having 8 or fewer carbon atoms such as acetic acid, lactic acid, malonic acid, oxalic acid, succinic acid, citric acid, gluconic acid, maleic 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, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and tetrabutylammonium hydroxide. Salts include compounds that exhibit a buffering effect as salts of the aforementioned acids or bases, such as ammonium chloride, ammonium acetate, and sodium citrate. Buffer solutions 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 8 or less carbon atoms, more preferably 6 or less carbon atoms, and even more preferably 5 or less carbon atoms.

[0076] From the perspective of minimizing the metal content in the surface modification composition, the pH adjuster is preferably an organic acid, ammonia, or an organic base having 8 or fewer carbon atoms, more preferably a carboxyl group-containing chain compound, a chain monoamine compound, or ammonia. The carboxyl group-containing chain compound preferably has 8 or fewer carbon atoms, more preferably 2 to 7 carbon atoms. The chain monoamine compound preferably has 8 or fewer carbon atoms, more preferably 2 to 6 carbon atoms.

[0077] As the pH adjuster, at least one selected from the group consisting of ammonia, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, ethylbutylammonium hydroxide, citric acid, malonic acid, maleic acid, oxalic acid, acetic acid, phosphoric acid, sulfuric acid, nitric acid, boric acid, and succinic acid can be preferably used.

[0078] When a pH adjuster is added to the surface modification composition, the content of the pH adjuster in the surface modification composition may be appropriately set depending on the type of pH adjuster used, as long as the surface modification composition can be adjusted to a desired pH.

[0079] When a surface modification composition contains a carboxyl group-containing compound having 8 or less carbon atoms as a pH adjuster, the content of the carboxyl group-containing compound having 8 or less carbon atoms is preferably set to 0.01% by mass or less, more preferably 0.008% by mass or less, and even more preferably 0.005% by mass or less, relative to the total amount of the composition, in order to suppress a decrease in the coating properties of the composition and the selective modification properties of the substrate surface.

[0080] When forming a film on a metal substrate, the pH of the surface-modifying composition is preferably 13.0 or less from the perspective of suppressing corrosion of the substrate surface caused by the surface-modifying composition (i.e., obtaining a composition with high metal corrosion resistance). The pH of the surface-modifying composition is more preferably 12.0 or less, even more preferably 11.0 or less, and even more preferably 10.0 or less. Furthermore, the pH of the surface-modifying composition is preferably 6.0 or greater, more preferably 7.0 or greater. In this specification, the pH of a composition is a value measured at 25°C and 1 atm.

[0081] (Cleaning ingredients)

[0082] For the purpose of removing the components remaining on the substrate (for example, residues caused by dry etching for hole formation) before the surface modification composition is formed on the substrate, a cleaning component can also be prepared in the surface modification composition. By preparing the cleaning component together with the compound (A), a monomolecular film comprising the compound (A) can be formed on the substrate while removing the components remaining on the substrate. Thus, the process of removing the components remaining on the substrate before forming the monomolecular film and the process of forming the monomolecular film can be implemented in one process, which can simplify the process in the semiconductor manufacturing process, and is preferred in this respect.

[0083] From the perspective of achieving a sufficient cleaning effect on the substrate surface while forming a high-density film on the substrate with compound (A), the molecular weight of the cleaning component is preferably smaller than the molecular weight of 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. Furthermore, the molecular weight of the cleaning component is preferably 10 or more, more preferably 15 or more.

[0084] Examples of cleaning components include fluorine-containing compounds, hydrogen peroxide, citric acid, ethylenediaminetetraacetic acid (EDTA), or two or more thereof. Specific examples of fluorine-containing compounds include hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, and hexafluorosilicic acid. Fluorine-containing compounds are preferred as cleaning components due to their high cleaning effectiveness.

[0085] From the perspective of achieving a sufficient cleaning effect on the substrate, the content of the cleaning component in the surface modification 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, relative to the total amount of the surface modification composition. Furthermore, from the perspective of not hindering 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, relative to the total amount of the surface modification composition.

[0086] As other components that can be added to the surface modification composition, in addition to the above, antioxidants etc. can be mentioned. The amount of other components added can be appropriately selected according to each component within a range that does not impair the effects of the present disclosure.

[0087] (Metal content)

[0088] Considering applications in semiconductor manufacturing processes, surface modification compositions preferably have a low metal content. Specifically, the combined amount of sodium, potassium, and calcium contained in the surface modification composition is preferably 1,000 ppm or less, more preferably less than 500 ppm, and even more preferably less than 1 ppm. Furthermore, the metal content in the surface modification composition is measured using inductively coupled plasma-mass spectroscopy (ICP-MS).

[0089] The surface modification composition can be prepared by mixing compound (A), water, and other components as needed, and dissolving compound (A) in water. From the perspective of ensuring good coating properties while forming a high-density film and ensuring resistance to atomic layer deposition (ALD), the solid content concentration of the surface modification composition (i.e., the ratio of the total mass of the components other than the solvent component in the surface modification composition to the total mass of the surface modification composition) is preferably 0.04% by mass to 1.50% by mass, and more preferably 0.08% by mass to 1.00% by mass.

[0090] <Selective modification method for substrate surface>

[0091] Next, a method for selectively modifying a substrate surface using the surface modification composition will be described. The selective modification method includes a coating step of applying the surface modification composition to the surface of the substrate.

[0092] Coating process

[0093] (Base material)

[0094] As a substrate, a substrate having a first region and a second region of a material different from the first region can be preferably used on the surface. The first region is preferably different from the second region in material, and the adsorption of compound (A) is different from that of the second region. As an example, the first region is a region where the adsorption of compound (A) is higher than that of the second region. From the perspective of selectively and densely modifying the surface of the substrate by compound (A), it is preferred that the first region is formed of a conductive material and the second region is formed of an insulating material. In addition, the substrate selectively modified by the surface modification composition preferably has a first region formed of a conductive material and a second region formed of an insulating material.

[0095] When the first region is 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 single metal, an alloy (such as nickel-copper alloy, cobalt-nickel alloy, gold-silver alloy), or a conductive nitride (such as tantalum nitride or titanium nitride). The first region preferably contains a single metal, an alloy, or a conductive nitride, and more preferably contains at least one selected from the group consisting of copper, cobalt, tungsten, tantalum, titanium, and ruthenium.

[0096] When the second region is formed of an insulating material, the second region is formed, for example, of a silicon-containing compound such as silicon oxide, silicon nitride, silicon oxynitride, or silicide (for example, SiO 2 , SiOC, Si 3 N 4 , SiN x , SiON, SiC, SiOCN, etc.), or a metal oxide (for example, aluminum oxide, tantalum oxide, etc.). The second region preferably includes silicon oxide, silicon nitride, silicon oxynitride, silicide, or a metal oxide.

[0097] In particular, when the substrate to be coated with the surface modification composition has a region containing at least one selected from the group consisting of copper, cobalt, tungsten, tantalum, titanium, molybdenum and ruthenium as the first region, and has a region containing silicon oxide, silicon nitride, silicon oxynitride or metal oxide as the second region, the compound (A) can be adsorbed to the first region of the first and second regions with high selectivity and high density, which is preferred from this point of view.

[0098] The shape of the coating surface in the substrate is not particularly limited. The coating surface may be, for example, planar, arc-shaped, concave, or protruding. In addition, when the coating surface has a first region and a second region, the configuration of the first region and the second region is not particularly limited. For example, the first region and the second region may be arranged along a prescribed direction on the plane in a state where the first region and the second region are adjacent. Alternatively, a plurality of other regions may be arranged in one of the first and second regions. In addition, one of the first and second regions may constitute the bottom surface of the hole or groove formed on the substrate, and the other may constitute its side surface.

[0099] In addition, the surface of the substrate coated with the film-forming composition may be subjected to pretreatment such as plasma treatment using H2, a mixed gas of N2 and H2, or O2 gas, or cleaning or wet modification of the substrate surface.

[0100] (Coating method)

[0101] Examples of methods for applying the surface modification composition include spraying, roller coating, spin coating, slot die coating, rod coating, and inkjet coating. Of these, the surface modification composition is preferably applied to the substrate surface by spin coating, slot die coating, or rod coating. The thickness of the coating formed on the substrate can be appropriately set so that the thickness of the film ultimately formed on the substrate is the desired thickness.

[0102] The surface modification composition is applied to the surface of the substrate by a coating process, thereby forming a film (specifically, a monomolecular film) formed by the compound (A) on the first region. The surface modification composition can also be applied to the surface of the substrate, and then the solvent component in the surface modification composition is removed by natural drying, thereby forming a film on the first region. In addition, a heat treatment can be performed to remove the solvent component from the surface modification composition applied to the surface of the substrate. The heat treatment can be performed using a heating device such as an oven or a hot plate. The heating temperature is, for example, above 40°C, and can also be set to above 50°C. The heating time is, for example, 0.5 minutes to 60 minutes. The compound (A) has a high adsorption capacity for metals, and a film can be formed in the first region even without heat treatment, which can simplify the manufacturing process and is preferred in terms of the above aspect. The thickness of the film formed on the substrate is, for example, a few nm (for example, about 0.5 nm to 20 nm).

[0103] The selective modification method preferably further comprises the step of contacting the substrate surface with a rinse solution after applying the surface modification composition in the coating step to clean the substrate surface and thereby remove components derived from the surface modification composition on the second region (hereinafter also referred to as the "cleaning step"). This cleaning step allows for the removal of any components derived from the surface modification composition (more specifically, the composition itself, compound (A), a residual film formed from the composition, etc.) as residues on the second region. This allows the film formed by compound (A) to more selectively coat the desired region of the substrate surface, thereby more selectively protecting the substrate surface.

[0104] Cleaning process

[0105] An organic solvent can be preferably used as the eluent. Examples of the organic solvent include propylene glycol monomethyl ether acetate, isopropyl alcohol, acetone, methyl ethyl ketone, methyl-n-propyl ketone, and mixed solvents of two or more thereof.

[0106] When the components of the surface modification composition on the second area are removed from the second area by the eluent, the surface of the substrate after the coating process is brought into contact with the eluent. The method for bringing the substrate surface into contact with the eluent is not particularly limited, and for example, a spray method, a spray method, an immersion (dip) method, a puddle method, etc. can be applied. When the substrate surface is brought into contact with the eluent, for example, the eluent can be supplied to the substrate and contacted multiple times, or the eluent or the substrate can be oscillated. The temperature of the eluent when the substrate surface is brought into contact with the eluent is, for example, 5°C to 50°C. The contact time is, for example, 5 seconds to 30 minutes. The amount of eluent used can be appropriately set in consideration of the contact method between the substrate surface and the eluent. After the substrate surface is brought into contact with the eluent, the eluent on the substrate can be removed using a spin coater or the like.

[0107] By using a method comprising the coating step and optionally a washing step, a substrate surface-treated with a composition containing compound (A) and water can be obtained. Specifically, the present disclosure provides a method for producing a surface-treated substrate, comprising applying a composition to the surface of a substrate to selectively modify the surface of the substrate.

[0108] The method including the coating step described above can be used to modify the surface of the substrate with high selectivity and density using a simple process. The substrate obtained by the coating step and the optional cleaning step can be further subjected to the following steps (contact step, metal layer formation step, film removal step), for example.

[0109] Contact process

[0110] The contact process is a process of contacting the substrate with alcohol, dilute acid, hydrogen peroxide solution, ozone, plasma, ammonia or ammonium fluoride salt solution after forming a film on the first area by the coating process (preferably the substrate surface after contact with the eluent in the cleaning process). In the manufacturing process of semiconductors, etc., an oxide film layer is sometimes formed on the contact surface of the substrate surface with air (on the second area) due to contact between the substrate surface and the air. Therefore, by providing such a contact process, the oxide film layer formed on the second area can be removed. Examples of the dilute acid mentioned above 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.

[0111] Metal layer formation process

[0112] The metal layer forming process is a process of forming a metal layer on the second area after a film is formed on the first area by a coating process (preferably after contact with a rinsing liquid based on a cleaning process, more preferably after a contact process). The first area on the surface of the substrate after the cleaning process is covered with a protective film (mono-molecular film) formed by compound (A). Therefore, when the metal layer is formed by the metal layer forming process, the metal layer can be selectively formed relative to the first area and the second area in the second area. The method for forming the metal layer is not particularly limited, but from the perspective of highly selective pattern formation relative to a fine area, it is preferred to form a metal pattern by chemical vapor deposition (CVD) or atomic layer deposition (ALD). The metal layer formed on the second area can be a barrier layer for separating the metal part from the insulating part or inhibiting the diffusion of metal from the metal part. The thickness of the metal layer can be appropriately set according to the purpose of the substrate, for example, 1 nm to 30 nm.

[0113] · Film removal process

[0114] The film removal process is a process of removing the film formed on the first region after the metal layer is formed on the second region by the metal layer forming process. The film removal can be performed by etching. As the etching method, for example, known methods such as reactive ion etching (RIE) and physical etching can be listed. As reactive ion etching, chemical dry etching using CF4 gas or O2 gas, etc., which utilizes the difference in etching rate of each layer; chemical wet etching (wet development) using an etching solution such as an organic solvent or a liquid such as hydrofluoric acid, etc. can be listed. As physical etching, sputter etching, ion beam etching, etc. can be listed. Among these, reactive ion etching is preferred, and chemical dry etching or chemical wet etching is more preferred.

[0115] Examples of solvents used in chemical wet etching include acetic acid, ammonia hydrogen peroxide mixture (APM) (a mixture of ammonia, hydrogen peroxide solution, and water), sulfuric acid hydrogen peroxide mixture (SPM) (a mixture of sulfuric acid and hydrogen peroxide solution), a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution, dilute hydrofluoric acid, and water.

[0116] By implementing the above-described processes (coating process, cleaning process, contact process, metal layer forming process and film removal process), a substrate in which a metal layer is selectively formed on the second region and the surface (e.g., metal surface) of the first region is exposed with respect to the first region can be obtained. The obtained substrate can also be further subjected to various treatments such as plating treatment. When the plating treatment is performed, the plating method is not particularly limited, and known electrolytic plating, electroless plating, molten plating, vacuum plating, vapor phase plating, etc. can be used. When applied to a semiconductor manufacturing process, it is preferred to utilize electrolytic plating or electroless plating among these. In addition, after the plating treatment, a flattening treatment (chemical mechanical polishing (CMP) treatment) of the substrate surface can be performed as needed.

[0117] The present disclosure described above can provide the following means.

[0118] [Means 1] A method for selectively modifying a substrate surface, comprising applying a composition comprising a compound (A) having a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms, and water, to the surface of the substrate.

[0119] [Means 2] A method for selectively modifying the surface of a substrate according to [Means 1], wherein the substrate comprises a first region and a second region made of a material different from that of the first region, and a film is formed on the first region by applying the composition to the surface of the substrate comprising the first region and the second region.

[0120] [Means 3] The method for selectively modifying a substrate surface according to [Means 2], wherein the first region is formed of a conductive material and the second region is formed of an insulating material.

[0121] [Means 4] The method for selectively modifying the surface of a substrate according to [Means 2] or [Means 3], further comprising the step of forming a metal layer on the second region after forming a film on the first region.

[0122] [Means 5] The method for selectively modifying the surface of a substrate according to [Means 4] further includes the following step: a step of bringing alcohol, dilute acid, hydrogen peroxide solution, ozone, plasma, ammonia or ammonium fluoride salt aqueous solution into contact with the surface of the substrate after forming a film on the first area and before forming the metal layer.

[0123] [Means 6] The method for selectively modifying the surface of a substrate according to [Means 4] or [Means 5] further includes the following step: after forming the metal layer, removing the film formed by the composition on the first area.

[0124] [Means 7] The method for selectively modifying the surface of a substrate according to any one of [Means 4] to [Means 6] further includes the following step: a step of removing components derived from the composition on the second area by bringing the surface of the substrate into contact with a rinse solution after applying the composition and before forming the metal layer.

[0125] [Means 8] The method for selectively modifying the surface of a substrate according to any one of [Means 1] to [Means 7], wherein the composition further contains a pH adjuster.

[0126] [Means 9] The method for selectively modifying the surface of a substrate according to [Means 8], wherein the pH adjuster is an organic acid having 8 or less carbon atoms, an organic base, or ammonia.

[0127] [Means 10] The method for selectively modifying the surface of a substrate according to [Means 8] or [Means 9], wherein the pH adjuster is a carboxyl group-containing chain compound having 8 or less carbon atoms, a chain monoamine compound, or ammonia.

[0128] [Means 11] The method for selectively modifying the surface of a substrate according to any one of [Means 1] to [Means 10], wherein the monovalent organic group having 8 or more carbon atoms in the compound (A) is a monovalent hydrocarbon group or a halogenated hydrocarbon group.

[0129] [Means 12] The method for selectively modifying the surface of a substrate according to any one of [Means 1] to [Means 11], wherein the monovalent organic group having 8 or more carbon atoms in the compound (A) is a monovalent chain hydrocarbon group.

[0130] [Means 13] The method for selectively modifying the surface of a substrate according to any one of [Means 1] to [Means 12], wherein the compound (A) has two or more carboxylate anion moieties.

[0131] [Means 14] The method for selectively modifying the surface of a substrate according to any one of [Means 1] to [Means 13], wherein the content of water is 10% by mass or more relative to the total amount of the composition.

[0132] [Method 15]

[0133] The method for producing a substrate according to any one of [Means 1] to [Means 15], wherein the composition further contains a cleaning component.

[0134] [Means 16] The method for producing a substrate according to [Means 15], wherein the cleaning component is a fluorine-containing compound.

[0135] [Means 17] A method for selectively modifying the surface of a substrate according to any one of [Means 1] to [Means 16], wherein the composition further contains an organic solvent, and the content of the organic solvent in the composition is 60% by mass or less relative to the total amount of the composition.

[0136] [Means 18] The method for selectively modifying the surface of a substrate according to [Means 17], 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.

[0137] [Means 19] A method for producing a surface-treated substrate, comprising the step of applying a composition to the surface of a substrate to selectively modify the surface of the substrate, wherein the composition contains a compound (A) having a carboxylate anion portion and a monovalent organic group having 8 or more carbon atoms, and water.

[0138] [Means 20] A composition for selectively modifying a substrate surface, comprising: a compound (A) having a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms; and water.

[0139] [Means 21] The composition according to [Means 20], wherein the compound (A) has two or more carboxylate anion moieties.

[0140] [Means 22] The composition according to [Means 20] or [Means 21], wherein the monovalent organic group having 8 or more carbon atoms in the compound (A) is a monovalent hydrocarbon group or a halogenated hydrocarbon group.

[0141] [Means 23] The composition according to any one of [Means 20] to [Means 22], further comprising a pH adjuster.

[0142] [Means 24] The composition according to any one of [Means 20] to [Means 23], wherein the water content is 10% by mass or more relative to the total amount of the composition.

[0143] [Means 25] The composition according to any one of [Means 20] to [Means 24], further comprising an organic solvent, wherein the content of the organic solvent is 60% by mass or less relative to the total amount of the composition.

[0144] [Example]

[0145] Hereinafter, the present invention will be described in detail based on examples, but the present invention is not limited to these examples. The measurement methods of various physical property values ​​are shown below.

[0146] 1. Preparation of composition (surface modification composition)

[0147] Example 1

[0148] 336.90 g of distilled water and 150.00 g of butoxyethanol were added to 0.20 g of octylsuccinic acid and stirred, and then 0.05 g of maleic acid and 0.13 g of potassium hydroxide were added. The pH was adjusted to 8.0, and then filtered through a high-density polyethylene filter having pores of 0.45 μm to prepare a composition (SM-1) having a solid content concentration of 1.0% of compound (A).

[0149] [Examples 2 to 45 and Comparative Examples 1 to 5]

[0150] The same procedures as in Example 1 were carried out except that the components shown in Tables 1 and 2 were used in the same manner as in Example 1 to prepare compositions (SM-2) to (SM-45) and compositions (SR-1) to (SR-5).

[0151] In addition, each component used for preparation of the surface modification composition is as follows.

[0152] Low molecular weight compounds

[0153] A-1: Octylsuccinic acid

[0154] A-2: Decylsuccinic acid

[0155] A-3: Octadecyl succinic acid

[0156] A-4: Triacontanyl succinate

[0157] A-5: Nonanoic acid

[0158] A-6: Undecanoic acid

[0159] A-7: Nonadecanoic acid

[0160] A-8: Tri-undecanoic acid

[0161] A-9: 1-Decenylsuccinic acid

[0162] A-10: 1-octadecenylsuccinic acid

[0163] A-11: 10,10,10-trifluorodecylsuccinic acid

[0164] A-12: 18,18,18-Trifluorooctadecylsuccinic acid

[0165] A-13: Sodium octadecylsuccinate

[0166] A-14: Potassium octadecylsuccinate

[0167] A-15: Octadecyl ammonium succinate

[0168] A-16: Tetramethylammonium octadecylsuccinate

[0169] A-17: Tetrabutylammonium octadecylsuccinate

[0170] A-18: Octadecylethanolamine succinate

[0171] A-19: Triethanolamine octadecylsuccinate

[0172] a-1: Octadecane

[0173] a-2: Benzotriazole

[0174] a-3: Kao Akpo (KAOAKYPO) RLM-45NV (manufactured by Kao Corporation)

[0175] ·Solvent

[0176] SOL-1: Butoxyethanol

[0177] SOL-2: triethylene glycol dimethyl ether

[0178] SOL-3: Diethylene glycol monobutyl ether

[0179] SOL-4: Sulfolane

[0180] SOL-5: Dimethylformamide

[0181] SOL-6: Dimethyl sulfoxide

[0182] SOL-7: Isopropyl alcohol

[0183] SOL-8: 1,3-dimethyl-2-imidazolidinone

[0184] pH adjuster

[0185] Ada-1: Maleic acid

[0186] Ada-2: Malonic acid

[0187] Ada-3: Citric acid

[0188] Ada-4: Oxalic acid

[0189] Ada-5: Acetic acid

[0190] Ada-6: Phosphate

[0191] Ada-7: sulfuric acid

[0192] Ada-8: nitric acid

[0193] Ada-9: Boric acid

[0194] Ada-10: Succinic acid

[0195] Ada-11: Hydrochloric acid

[0196] Adb-1: Potassium hydroxide

[0197] Adb-2: Ammonia

[0198] Adb-3:2-ethanolamine

[0199] Adb-4: Diethanolamine

[0200] Adb-5: triethanolamine

[0201] Adb-6: Propylamine

[0202] Adb-7: dibutylamine

[0203] Adb-8: Tetramethylammonium hydroxide

[0204] Adb-9: Tetraethylammonium hydroxide

[0205] Adb-10: Tetrabutylammonium hydroxide

[0206] Cleansing ingredients

[0207] Mοl-1: hydrofluoric acid

[0208] Mοl-2: ammonium fluoride

[0209] Mοl-3: Tetramethylammonium fluoride

[0210] Mοl-4: Hexafluorosilicic acid

[0211] Mοl-5: Hydrogen peroxide

[0212] [Table 1]

[0213]

[0214] [Table 2]

[0215]

[0216] 2. Evaluation

[0217] The following evaluations were performed using the compositions (SM-1) to (SM-45) and (SR-1) to (SR-5) prepared in 1. The results are shown in Table 2.

[0218] <Solubility Evaluation>

[0219] The solubility of each composition obtained in 1. was evaluated by visual observation.

[0220] (Evaluation Criteria)

[0221] A (good): Permeable.

[0222] B (acceptable): Either turbidity or dissolved residue was observed.

[0223] C (poor): Both turbidity and dissolved residue were observed.

[0224] <Evaluation of storage stability>

[0225] 10 g of each composition prepared in 1. above was placed in a vial and stored at 50°C for two weeks. The change in viscosity before and after storage was expressed as Δη, and storage stability was evaluated by measuring this change. A smaller change in viscosity Δη indicates that the composition can be applied under the same application conditions without day-to-day variability, indicating good storage stability.

[0226] (Evaluation Criteria)

[0227] A (good): Δη is less than 1 Pa·s.

[0228] B (acceptable): Δη is 1 Pa·s or more and less than 3 Pa·s.

[0229] C (poor): Δη is 3 Pa·s or more.

[0230] <Evaluation of hydrophobicity (evaluation of selective modification)>

[0231] A wafer with a 20nm copper film, a wafer with a 20nm aluminum oxide film, a wafer with a 30nm tantalum nitride film, a wafer with a 20nm carbon-doped tungsten film (WdC), a wafer with a 1000nm silicon oxide film (p-tetraethylorthosilane (TEOS) film), and a wafer substrate with a 500nm low-k dielectric silicon oxide film (Low K) were cut into 3cm x 3cm pieces and immersed in each composition prepared in 1. for 1 minute. The wafers were then removed and rinsed with water and isopropyl alcohol to obtain treated objects. Water was dropped onto the treated objects, and the static contact angle of the film-formed surface was measured using a contact angle meter (Dropmaster DM-501, manufactured by Kyowa Interface Science Co., Ltd.).

[0232] (Evaluation criteria for copper films)

[0233] A substrate whose static contact angle after surface treatment with the composition significantly increases relative to its static contact angle before treatment with the composition is selectively modified by the low-molecular compound in the composition, forming a film on the substrate. Ideally, the copper film (Cu) is in a modified state (i.e., coated with the film), so evaluation is performed based on the following criteria.

[0234] A (good): The contact angle is 90 degrees or greater. The film is formed on the substrate at a high density and is practically usable, so it is judged as "good".

[0235] B (Acceptable): The contact angle is 70 degrees or more and less than 90 degrees. A film is formed on the substrate and is used in practical applications, so it is judged as "Acceptable".

[0236] C (poor): The contact angle was less than 70 degrees. No film was formed on the substrate or the film was formed at a low density, which was not practical and was therefore judged as "poor".

[0237] (Evaluation criteria for aluminum oxide films, tantalum nitride films, carbon-doped tungsten films, silicon oxide films, and low-dielectric silicon oxide)

[0238] Aluminum oxide film (AlO x ), tantalum nitride film (TiN), carbon-doped tungsten film (WdC), silicon oxide film (TEOS), and low-dielectric silicon oxide film (Low K) are ideally in an unmodified state (i.e., not covered by a film), so they are evaluated based on the following criteria.

[0239] A (good): The contact angle was less than 40 degrees. Since no film was formed on the substrate and the film was used for practical use, it was judged as "good".

[0240] B (Acceptable): The contact angle is 40 degrees or more and less than 70 degrees. A film is partially formed on the substrate and is practically usable, so it is judged as "Acceptable".

[0241] C (poor): The contact angle was 70 degrees or more. A film was uniformly formed on the substrate, but it was not practically usable and was therefore judged as "poor".

[0242] When the evaluations of various substrates were “good” or “acceptable” (that is, there was no evaluation of “unacceptable”), it can be said that the substrates were selectively surface-modified.

[0243] <Evaluation of Metal Corrosion Resistance (Evaluation Based on Etching Rate)>

[0244] The various substrates used in the hydrophobicity evaluation are cut into 3.5cm × 3.5cm and immersed in each composition prepared in 1. for 10 minutes. Afterwards, the wafer is taken out and the processed body is obtained by cleaning with water and isopropyl alcohol. The thickness of the film of the processed body is measured using a fluorescent X-ray analyzer (manufactured by Rigaku Co., Ltd., model "AZX400") and a spectroscopic ellipsometer (manufactured by Semilab Semiconductor Physics Laboratory Co., Ltd., model "SE-2000"), and the etching rate is calculated according to the thickness of the film before and after immersion in each composition.

[0245] (Evaluation Criteria)

[0246] A (good): The etching rate was less than 0.1 nm / min. Excessive corrosion was suppressed, and thus the result was judged as "good".

[0247] B (Acceptable): The etching rate is 0.1 nm / min or higher and less than 0.5 nm / min. Corrosion can be suppressed and the etching can be used in practical applications, so it is judged as "Acceptable".

[0248] C (poor): The etching rate is 0.5 nm / min or more. The corrosion is so severe that it cannot be used for practical purposes, and is therefore judged as "poor".

[0249] <Evaluation of coating properties>

[0250] An 8-inch copper substrate was used to evaluate the coating properties of each composition. The substrate was cut into 3 cm × 3 cm, and each composition prepared in 1 was spin-coated at 1,500 rpm for 20 seconds using a spin coater ("MS-B300" from Mikasa Co., Ltd.) (coating process). The coated substrate was then calcined at 150°C for 180 seconds. Thereafter, propylene glycol monomethyl ether acetate was used as a rinse solution to clean the substrate (cleaning process). In the cleaning process, when the components in the composition are not adsorbed on the surface of the substrate, the components remaining in the composition on the substrate are removed by the rinse solution, and no film is formed on the substrate. In the evaluation of coating properties, the coated surface of the substrate was observed using an optical microscope to confirm the presence of voids and film breakage on the film surface and perform the evaluation.

[0251] (Evaluation Criteria)

[0252] A (good): No voids or broken membranes.

[0253] B (OK): No membrane rupture but gaps are present.

[0254] C (bad): There are both voids and membrane rupture.

[0255] <Evaluation of Dry Etching Residue Removal Performance (Evaluation Based on Etching Rate)>

[0256] A reactive ion etching apparatus (RIE-10NR) was used to dry-etch the Low K film substrate to obtain a processed body. The processed body obtained was cut into 3.5 cm × 3.5 cm and immersed in each composition prepared in 1. for 1 minute. Afterwards, the wafer (processed body) was taken out and cleaned with water and isopropyl alcohol. The F component in the surface of the cleaned processed body was quantified by X-ray photoelectron analysis (manufactured by ULVAC, model "Quantum 2000"), and the ratio of the quantitative value of the F component in the surface-treated substrate to the quantitative value of the F component in the substrate not immersed in each composition was calculated as the cleaning efficiency (%).

[0257] (Evaluation Criteria)

[0258] A (good): The cleaning efficiency is 98% or more.

[0259] B (acceptable): The cleaning efficiency is less than 98% and 90% or more.

[0260] C (poor): The cleaning efficiency is less than 90%.

[0261] (Dry etching conditions)

[0262] Gas flow rate: Ar / C4F8 / N2=100sccm / 50sccm / 33sccm

[0263] Plasma power: 170W / 40MHz (high frequency), 80W / 13MHz (low frequency)

[0264] Pressure: 50mTorr

[0265] Recipe Time: 100 seconds

[0266] <Evaluation of Metal Oxide Blocking Performance (Evaluation of ALD Resistance)>

[0267] For a substrate (surface-treated substrate) in which a copper film wafer was surface-coated using each composition prepared in 1., an ALD treatment was performed under the following conditions using Cambridge Nanotech FIJI within Stanford University, thereby obtaining an ALD-treated body of the surface-treated substrate. As a control, an ALD was performed in the same manner as for the surface-treated substrate using a copper film wafer that was not surface-treated using each composition (untreated substrate), thereby obtaining an ALD-treated body of the untreated substrate. The Ti component in the substrate surface of the ALD-treated body (surface-treated substrate and untreated substrate) was quantified by X-ray photoelectron analysis (manufactured by Ulvac Co., Ltd., model "Quantum 2000"). The ratio of the quantitative value of the Ti component in the surface-treated substrate to the quantitative value of the Ti component in the untreated substrate was calculated as the blocking rate (%). The film formed on the substrate by the composition is formed by the components in the composition (low molecular weight compounds in Table 1 and Table 2) being adsorbed on the surface of the substrate at a high density. It can be said that the larger the blocking rate value, the higher the blocking performance for ALD-based metal oxide formation.

[0268] (Evaluation Criteria)

[0269] A (good): The blocking rate is 98% or more.

[0270] B (acceptable): The blocking rate is less than 98% and 90% or more.

[0271] C (poor): The blocking rate is less than 90%.

[0272] (ALD conditions)

[0273] Film type: ALD Al2O3

[0274] Stage temperature: 200°C

[0275] Recipe Time: 0.3 sec (trimethylaluminum) / 15 sec (rinse) / 0.06 sec (water) / 23 sec (rinse)

[0276] <Determination of Metal Content>

[0277] Each composition prepared in 1. was diluted 20-fold with butyl diglycol / ultrapure water = 80 / 20 (parts by mass), and the sodium, potassium, and calcium contents were measured using an ICP mass spectrometer (Perkin Elmer, model "NexION 5000").

[0278] (Evaluation Criteria)

[0279] A (good): The total content of sodium, potassium, and calcium is less than 1 ppm. This is particularly practical and is therefore judged as "good."

[0280] B (Acceptable): The total content of sodium, potassium, and calcium is 1 ppm or more and less than 500 ppm. It is considered acceptable for practical use.

[0281] C (poor): The total content of sodium, potassium, and calcium was 500 ppm or more. This was judged as "poor" because it was not practically applicable.

[0282] <Evaluation of film thickness>

[0283] The various substrates used in the hydrophobicity evaluation are cut into 1.0cm × 1.0cm and immersed in each composition prepared in 1. for 1 minute. Afterwards, the wafer is taken out and cleaned with water and isopropyl alcohol. Using a focused ion beam processing device (manufactured by FEI Co., Ltd. of Japan, model "Helios (Helios) 650"), thinning is performed after the hafnium oxide protective layer is supported, thereby obtaining a processed body. Transmission electron microscope (manufactured by FEI Co., Ltd. of Japan, model "Talos (Talos) F200X") is used to observe the obtained processed body, and the thickness of the film of the processed body is measured according to the annular dark field image.

[0284] (Evaluation Criteria)

[0285] A (good): The film thickness is 0.5 nm or more and less than 2.0 nm.

[0286] B (acceptable): The film thickness is 2.0 nm or more and less than 25.0 nm.

[0287] C (poor): The film thickness is 25.0 nm or more.

[0288] [Table 3]

[0289]

[0290]

[0291] According to the results, the surface modification compositions of Examples 1 to 45 using compound (A) as a film-forming material and containing water have good or acceptable evaluation results for water solubility, coating properties and storage stability. In addition, by using the compositions of Examples 1 to 45, films can be formed with high selectivity and high density relative to the metal surface. Furthermore, the films formed by the compositions of Examples 1 to 45 show good metal corrosion resistance. In addition, compared with Examples 13 and 14 in which the carboxylate anion portion of the compound (A) as a film-forming material forms a carboxyl group with a hydrogen ion or forms a salt with an organic cation, the metal content in the composition is less than that of Examples 13 and 14 in which the compound (A) forms a salt with a metal cation. In addition, the coating properties, selective modification properties, metal corrosion resistance and ALD resistance are better. Based on these contents, it can be said that when the carboxylate anion portion in the compound (A) forms a carboxyl group with a hydrogen ion or forms a salt with an organic cation, the coating properties of the composition can be made better, and a film can be formed more selectively and at a higher density. In addition, Examples 39 to 42 in which a cleaning component was blended into the composition showed good residue removal performance on the Low K film substrate after dry etching.

[0292] In contrast, the composition of Comparative Example 1, which uses only an organic solvent as a solvent, has poor coating properties, selective modification properties, ALD resistance, and film thickness compared to the examples. In addition, the composition of Comparative Example 2, in which octadecane is used instead of compound (A), has poor coating properties, and any evaluation of the selective modification properties of the metal surface, metal corrosion resistance, ALD resistance, and film thickness is poor. In addition, the composition of Comparative Example 3, which does not contain compound (A), has poor coating properties, and any evaluation of the selective modification properties of the metal surface, metal corrosion resistance, ALD resistance, and film thickness is poor. In addition, the composition of Comparative Example 4, in which benzotriazole is used instead of compound (A), has poor ALD resistance and film thickness. In addition, in Comparative Example 5, in which a commercially available surfactant is used instead of compound (A), not only is the ALD resistance poor, but the metal content is also high.

Claims

1. A method for selectively modifying a substrate surface, comprising applying a composition to the surface of the substrate, The composition contains a compound (A) having a carboxylate anion portion and a monovalent organic group having 8 or more carbon atoms, and water.

2. The selective modification method for substrate surface according to claim 1, wherein The substrate includes a first region and a second region made of a material different from that of the first region. The composition is applied to a surface of a substrate including the first region and the second region to form a film on the first region.

3. The selective modification method for substrate surface according to claim 2, wherein: The first region is formed of a conductive material, The second region is formed of an insulating material. 4 . The method for selectively modifying a substrate surface according to claim 2 , further comprising the step of forming a metal layer on the second region after forming a film on the first region.

5. The method for selectively modifying a substrate surface according to claim 4, further comprising the step of bringing an alcohol, dilute acid, hydrogen peroxide solution, ozone, plasma, ammonia or an aqueous solution of ammonium fluoride salt into contact with the substrate surface after the film is formed on the first region and before the metal layer is formed. 6 . The method for selectively modifying a substrate surface according to claim 4 , further comprising the step of removing the film formed of the composition on the first region after forming the metal layer.

7. The method for selectively modifying a substrate surface according to claim 4, further comprising the step of removing components derived from the composition on the second area by contacting the surface of the substrate with a rinse solution after applying the composition and before forming the metal layer.

8. The selective modification method for substrate surface according to claim 1 or 2, wherein: The composition also contains a pH adjuster.

9. The selective modification method for substrate surface according to claim 8, wherein: The pH adjuster is an organic acid, an organic base or ammonia having 8 or less carbon atoms.

10. The method for selectively modifying a substrate surface according to claim 8, wherein: The pH adjuster is a carboxyl group-containing chain compound having 8 or less carbon atoms, a chain monoamine compound, or ammonia.

11. The selective modification method for substrate surface according to claim 1 or 2, wherein: The monovalent organic group having 8 or more carbon atoms in the compound (A) is a monovalent hydrocarbon group or a halogenated hydrocarbon group.

12. The selective modification method for substrate surface according to claim 1 or 2, wherein: The monovalent organic group having 8 or more carbon atoms in the compound (A) is a monovalent chain hydrocarbon group.

13. The selective modification method for substrate surface according to claim 1 or 2, wherein: The compound (A) has two or more carboxylate anion parts.

14. The selective modification method for substrate surface according to claim 1 or 2, wherein: The content of water is 10% by mass or more relative to the total amount of the composition.

15. The method for producing a substrate according to claim 1 or 2, wherein: The composition also contains a cleansing ingredient.

16. The method for producing a substrate according to claim 15, wherein: The cleaning component is a fluorine-containing compound.

17. The selective modification method for substrate surface according to claim 1 or 2, wherein: The composition further comprises an organic solvent, The content of the organic solvent in the composition is 60% by mass or less relative to the total amount of the composition.

18. The method for selectively modifying a substrate surface according to claim 17, 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.

19. A method for producing a surface-treated substrate, comprising the steps of applying a composition to the surface of a substrate to selectively modify the surface of the substrate, The composition contains a compound (A) having a carboxylate anion portion and a monovalent organic group having 8 or more carbon atoms, and water.

20. A composition for selectively modifying a substrate surface, comprising: Compound (A) having a carboxylate anion moiety and a monovalent organic group having 8 or more carbon atoms; and water.

21. The composition according to claim 20, wherein The compound (A) has two or more carboxylate anion parts.

22. The composition according to claim 20 or 21, wherein The monovalent organic group having 8 or more carbon atoms in the compound (A) is a monovalent hydrocarbon group or a halogenated hydrocarbon group.

23. The composition according to claim 20 or 21, further comprising a pH adjuster.

24. The composition according to claim 20 or 21, wherein The content of water is 10% by mass or more relative to the total amount of the composition.

25. The composition according to claim 20 or 21, further comprising an organic solvent, The content of the organic solvent is 60% by mass or less based on the total amount of the composition.

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