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 substrate, which includes a step for applying a composition to the surface of the substrate, a composition containing water and a compound (A) having a nitrogen-containing heterocyclic ring and a monovalent organic group having 4 or more carbon atoms is used as the composition.

Description

TECHNICAL FIELD

[0001] [CROSS-REFERENCE TO RELATED APPLICATIONS]

[0002] This application claims priority based on Japanese Patent Application No. 2023-029874 filed on February 28, 2023, the entire contents of which are incorporated herein by reference.

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

[0004] In a semiconductor manufacturing process, in order to cover and protect a part of the area of a substrate surface, an organic film is sometimes formed in a part of the area, and each treatment such as formation of a metal layer or etching is performed on the substrate after formation of the organic film. When an organic film for protecting a part of the area of a substrate surface is formed on the substrate surface, with further miniaturization of semiconductor elements, it is required to be able to form a film with high selectivity to the area of the substrate surface that is intended to be protected (for example, refer to Patent Literature 1).

[0005] In Patent Literature 1, it is disclosed that, on the surface of a substrate having a first region containing a metal in a surface layer, a composition containing a first polymer having a group containing a first functional group that bonds to the metal contained in the first region at the end of a main chain or a side chain and a solvent is applied, and a coating film formed by the application of the composition is heated, whereby the first region is selectively surface-modified by the first polymer. In addition, in Patent Literature 1, as a solvent used in the preparation of the composition, a solvent capable of dissolving or dispersing the first polymer, such as an alcohol-based solvent, an ether-based solvent, a ketone-based solvent, an amide-based solvent, a hydrocarbon-based solvent, and the like, is disclosed.

[0006] PRIOR ART DOCUMENTS

[0007] PATENT LITERATURE

[0008] Patent Literature 1: International Publication No. 2018 / 043304 SUMMARY

[0009] PROBLEMS TO BE SOLVED BY THE INVENTION

[0010] In the composition for selective modification of a substrate surface, if the main component of the solvent can be water, it is expected that the reduction of environmental load can be achieved, or the handling property of the composition can be made more favorable. However, in the composition containing water, there is a tendency that the storage stability of the composition easily decreases due to the precipitation of the components contained in the composition, or the like. In particular, in the case where the hydrophobicity is imparted to the substrate surface by the selective modification of the substrate surface, a material having high hydrophobicity can be used as the film-forming material. Therefore, there is a concern that the storage stability of the composition easily decreases due to the insufficient solubility of the film-forming material in water.

[0011] In addition, from the viewpoint of achieving the stabilization of the quality of the article in the semiconductor manufacturing process, or the viewpoint of suppressing the reduction of the yield of the article, or the like, it is required to selectively protect the region to be protected when a part of the region of the substrate surface is protected. Furthermore, it is required to perform the high-density modification to the region to be protected, thereby making the impurities less likely to adhere to the protected region (i.e., high blocking performance).

[0012] The present disclosure was completed in view of the problems described above, and the main object thereof is to provide a method for selective modification of a substrate surface and a composition, in which the storage stability of the composition for selective modification of a substrate surface is high, and the substrate surface can be modified with high selectivity and high density.

[0013] Technical means for solving the problems

[0014] To solve the problems described above, the following means is provided according to the present disclosure.

[0015] [1] A method for selective modification of a substrate surface, comprising a step of applying a composition to a surface of a substrate, the composition containing a compound (A) having a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons, and water.

[0016] [2] A method for manufacturing a surface-treated substrate, comprising a step of selectively modifying a surface of a substrate by applying a composition to the surface of the substrate, the composition containing a compound (A) having a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons, and water.

[0017] [3] A composition for selective modification of a substrate surface, the composition containing a compound (A) having a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons, and water.

[0018] Effects of the invention

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

[0020] Hereinafter, matters relating to the embodiments are described in detail. Further, in the present specification, a numerical range recited using "~" is intended to include the numerical values recited before and after the "~" as lower limit values and upper limit values. As long as each component is not particularly mentioned, one kind can be used alone or two or more kinds can be used in combination.

[0021] Method for selectively modifying surface of substrate and composition

[0022] The method for selectively modifying surface of substrate of the present disclosure (hereinafter, also simply referred to as "selective modification method") includes a step of applying a composition (hereinafter, also referred to as "surface modification composition") to the surface of a substrate. The surface modification composition is an aqueous liquid composition containing a compound (A) having a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons, and water as a solvent component. Hereinafter, the surface modification composition is first described, and then the method for selectively modifying surface of substrate using the surface modification composition is described.

[0023] < Surface modification composition >

[0024] The surface modification composition is used as a surface treatment liquid for surface modification of a substrate by forming a film on the surface of the substrate. The region where the film is formed by the surface modification composition is imparted with hydrophobicity. The film formed by the surface modification composition is typically a self-assembled monolayer (SAM) formed by adsorption of the compound (A) on the surface of the substrate. Hereinafter, each component contained in the surface modification composition, and a component optionally arbitrarily formulated (hereinafter, also referred to as "other component") is described.

[0025] • Compound (A)

[0026] The compound (A) has a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons (hereinafter, also referred to as "monovalent organic group R 1 "). It is considered that by using the compound (A) as a monolayer-forming material, due to the nitrogen-containing heterocycle moiety, adsorption ability to the substrate (particularly, the metal region) is exhibited, and due to the monovalent organic group R 1 moiety, hydrophobicity is exhibited. Thereby, excellent hydrophobicity can be imparted to the surface of the substrate. In particular, by having the nitrogen-containing heterocycle, the compound (A) can modify the metal region with high selectivity and high density by interaction with the metal while improving the water solubility of the compound (A). Further, the "interaction" referred to here is, for example, a chemical bond, and covalent bonding, ionic bonding, coordination bonding, etc. can be listed. In the case where the nitrogen atom in the nitrogen-containing heterocycle is coordinated to the metal, the bonding strength between the metal atom and the nitrogen-containing heterocycle can be improved.

[0027] The compound (A) is a compound (low-molecular compound) different from the polymer. The molecular weight of the compound (A) is preferably 1,000 or less, more preferably 800 or less, further preferably 700 or less, and further more preferably 600 or less from the viewpoint of ensuring solubility in water. In addition, the molecular weight of the compound (A) is preferably 120 or more, more preferably 150 or more, and further preferably 200 or more from the viewpoint of obtaining a film having good heat resistance.

[0028] The nitrogen-containing heterocycle possessed by the compound (A) can be an aromatic heterocycle or a non-aromatic heterocycle. In addition, the nitrogen-containing heterocycle possessed by the compound (A) can be a monocyclic ring or a condensed ring. As specific examples of the nitrogen-containing aromatic heterocycle, there can be mentioned a pyrrole ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a benzimidazole ring, a benzotriazole ring, a substituted benzotriazole ring, a carbazole ring, an acridine ring, a pyrazine ring, and the like. As the substituted benzotriazole ring, there can be mentioned a ring having an alkyl group having a carbon number of 1 to 3, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, and the like), a nitro group, or the like as a substituent at the 5-position or the 6-position.

[0029] As specific examples of the nitrogen-containing non-aromatic heterocycle, there can be mentioned a piperidine ring, a piperazine ring, a hexamethylene imine ring, diazabicycloundecene, diazabicyclo[4.3.0]non-5-ene, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and the like. Furthermore, the nitrogen-containing heterocycle possessed by the compound (A) is preferably a heterocycle having only a nitrogen atom as a heteroatom in the ring skeleton.

[0030] In the above, the nitrogen-containing heterocycle possessed by the compound (A) is preferably at least one selected from the group consisting of an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a benzimidazole ring, a benzotriazole ring, a substituted benzotriazole ring, a piperidine ring, a piperazine ring, a hexamethylene imine ring, diazabicycloundecene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and more preferably at least one selected from the group consisting of an imidazole ring, a pyridine ring, a benzimidazole ring, a benzotriazole ring, a substituted benzotriazole ring, a piperidine ring, a piperazine ring, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0031] The compound (A) can also include a nitrogen-containing heterocycle in the form of a salt (i.e., the form in which at least one nitrogen atom included in the ring skeleton of the nitrogen-containing heterocycle is a cation). In the case where the nitrogen-containing heterocycle is in the form of a salt, the counter ion can be any counter ion as long as it is anionic, and is not particularly limited. As specific examples of the counter ion, there can be mentioned a chloride ion, a bromide ion, an iodide ion, a triazole anion, a benzotriazole anion, a 5-methylbenzotriazole anion, and the like.

[0032] from the viewpoint of obtaining a film having excellent hydrophobicity by applying the surface-modifying composition to the surface of the substrate, the monovalent organic group R 1 is preferably a monovalent hydrocarbon group having 4 or more carbon atoms, a monovalent halogenated hydrocarbon group having 4 or more carbon atoms, -R 3 -O-R 6 or -CR 4 (OH)-R 6 (wherein R 3 is an alkanediyl group having 1 to 3 carbon atoms, R 4 is a hydrogen atom or a methyl group, and R 6 is a monovalent hydrocarbon group having 4 or more carbon atoms. The same applies hereinafter). The monovalent organic group R 1 may have, for example, 4 to 40 carbon atoms.

[0033] Here, the "hydrocarbon group" in the present specification includes a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched-chain hydrocarbon group each of which includes only a chain structure and does not include a cyclic structure. The chain hydrocarbon group can be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group which includes only an alicyclic structure as a cyclic structure and does not include an aromatic ring structure. The alicyclic hydrocarbon group need not include only an alicyclic structure, and can include a chain structure in a part thereof. The "aromatic hydrocarbon group" refers to a hydrocarbon group which includes an aromatic ring structure as a cyclic structure. The aromatic hydrocarbon group need not include only an aromatic ring structure, and can include a chain structure or an alicyclic structure in a part thereof.

[0034] Specific examples of the monovalent organic group R 1 include a monovalent chain hydrocarbon group having 4 to 40 carbon atoms, a monovalent alicyclic hydrocarbon group having 4 to 40 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 40 carbon atoms. Specific examples of the monovalent chain hydrocarbon group having 4 to 40 carbon atoms include, for example, alkyl groups such as n-butyl, isobutyl, sec-butyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, eicosyl, docosyl, and the like; alkenyl groups such as propenyl, butenyl, hexenyl, octenyl, decenyl, dodecenyl, and the like; and alkynyl groups such as propynyl, butynyl, and the like.

[0035] Specific examples of the monovalent alicyclic hydrocarbon group having 4 to 40 carbon atoms include, for example, monocyclic alicyclic saturated hydrocarbon groups such as cyclopentyl, cyclohexyl, methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, and the like; monocyclic alicyclic unsaturated hydrocarbon groups such as cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, and the like; polycyclic alicyclic saturated hydrocarbon groups such as norbornyl, adamantyl, tricyclodecyl, and the like; polycyclic alicyclic unsaturated hydrocarbon groups such as norbornenyl, tricyclodecenyl, and the like; and the like.

[0036] As the monovalent aromatic hydrocarbon group having 6 to 40 carbons, for example, there can be mentioned aryl groups such as phenyl, tolyl, xylyl, naphthyl, anthryl, and the like; aralkyl groups such as benzyl, phenethyl, naphthylmethyl, anthrylmethyl, and the like; and the like.

[0037] As the monovalent halogenated hydrocarbon group having 4 or more carbons, there can be mentioned a group in which any hydrogen atom of the group exemplified as the monovalent hydrocarbon group is replaced with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, and the like).

[0038] -R 3 -O-R 6 or -CR 4 (OH)-R 6 Among the groups represented by R 6 , as the monovalent hydrocarbon group represented by R 1 , the same groups as those exemplified as the specific examples of the monovalent hydrocarbon group having 4 or more carbons can be mentioned.

[0039] In terms of being able to impart excellent hydrophobicity to the surface of a substrate, among the monovalent organic groups R 1 , a monovalent hydrocarbon group having 4 or more carbons, -R 3 -O-R 6 or -CR 4 (OH)-R 6 is preferable, a monovalent chain hydrocarbon group having 4 or more carbons, -R 3 -O-R 7 or -CR 4 (OH)-R 7 is more preferable (wherein R 7 is a monovalent chain hydrocarbon group having 4 or more carbons), and a linear or branched alkyl group having 4 or more carbons, -R 3 -O-R 8 or -CR 4 (OH)-R 8 is further preferable (wherein R 8 is a linear or branched alkyl group having 4 or more carbons), and a linear alkyl group having 4 or more carbons, -R 3 -O-R 9 or -CR 4 (OH)-R 9 is further more preferable (wherein R 9 is a linear alkyl group having 4 or more carbons).

[0040] In terms of imparting excellent hydrophobicity to the surface of a substrate, among the monovalent organic groups R 1The carbon number of the monovalent organic group R is preferably 5 or more, more preferably 8 or more, and further preferably 9 or more. In addition, from the viewpoint of improving the solubility of the compound (A) in water or the viewpoint of suppressing a decrease in the adsorbing ability of the compound (A) to a substrate, the carbon number of the monovalent organic group R is preferably 30 or less, more preferably 20 or less, and further preferably 18 or less, and further more preferably 15 or less. 1 The carbon number of the monovalent organic group R is preferably 5 or more, more preferably 8 or more, and further preferably 9 or more. In addition, from the viewpoint of improving the solubility of the compound (A) in water or the viewpoint of suppressing a decrease in the adsorbing ability of the compound (A) to a substrate, the carbon number of the monovalent organic group R is preferably 30 or less, more preferably 20 or less, and further preferably 18 or less, and further more preferably 15 or less.

[0041] In addition, the monovalent organic group R having a carbon number of 4 or more can be present in one molecule in a plurality of number. 1 The compound (A) can further have a monovalent organic group having a carbon number of 1 to 3. As a specific example of the group, an alkyl group (methyl group, ethyl group, propyl group) having a carbon number of 1 to 3, an acetyl group, a formyl group, and the like can be given.

[0042] The compound (A) can have a plurality of number of the monovalent organic group R having a carbon number of 4 or more. 1 The compound (A) can have a plurality of number of the monovalent organic group R having a carbon number of 4 or more. 1 The compound (A) can have a plurality of number of the monovalent organic group R having a carbon number of 4 or more.

[0043] From the viewpoint of improving the coatability of the surface-modifying composition containing water as a solvent or the viewpoint of obtaining a film having a higher density, the compound (A) preferably has a structure in which the monovalent organic group R is bonded to a nitrogen atom constituting the nitrogen-containing heterocycle or the monovalent organic group R is bonded to the nitrogen atom of the nitrogen-containing heterocycle directly or via a divalent linking group. In the latter case, the divalent linking group is preferably an alkanediyl group having a carbon number of 1 to 3, and more preferably a methylene group. 1 The compound (A) preferably has a structure in which the monovalent organic group R is bonded to a nitrogen atom constituting the nitrogen-containing heterocycle or the monovalent organic group R is bonded to the nitrogen atom of the nitrogen-containing heterocycle directly or via a divalent linking group. 1 The compound (A) preferably has a structure in which the monovalent organic group R is bonded to a nitrogen atom constituting the nitrogen-containing heterocycle or the monovalent organic group R is bonded to the nitrogen atom of the nitrogen-containing heterocycle directly or via a divalent linking group. 1 The nitrogen atom to which the monovalent organic group R is bonded can be in the form of a cation.

[0044] From the viewpoint of forming a film having a higher density, the compound (A) is preferably a compound having a structure in which one nitrogen-containing heterocycle is present in one molecule and the monovalent organic group R is bonded to the nitrogen atom of the nitrogen-containing heterocycle directly or via a group having a nitrogen atom. 1 The compound (A) is preferably 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).

[0045] As a specific example of the compound (A), 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) can be given.

[0046] R 1 -X 1 -A 1 ···(1)

[0047] In formula (1), R 1a monovalent hydrocarbon group having 4 to 40 carbons, a halogenated hydrocarbon group having 4 to 40 carbons, -R 3 -O-R 6A or -CR 4 (OH)-R 6A (wherein, R 6A is a monovalent hydrocarbon group having 4 to 40 carbons). X 1 is a single bond or -NR 2 -. R 2 is a hydrogen atom or a methyl group. A 1 is a monovalent group having a nitrogen-containing heterocycle. Wherein, in the case of X 1 being a single bond, R 1 is directly bonded to the nitrogen atom in the nitrogen-containing heterocycle in A 1 , and in the case of X 1 being -NR 2 -, X 1 is directly bonded to the nitrogen-containing heterocycle in A 1 )

[0048] [Chemical Formula 1]

[0049]

[0050] (In formula (2), R 1A is a monovalent hydrocarbon group having 4 to 40 carbons. Y 1 is a single bond or an alkanediyl group having 1 to 3 carbons. R 5 is a hydrogen atom or a methyl group. A 1 is a monovalent group having a nitrogen-containing heterocycle. Wherein, in the case of Y 1 being a single bond, the nitrogen atom to which R 1A is bonded is directly bonded to the nitrogen-containing heterocycle in A 1 , and in the case of Y 1 being an alkanediyl group having 1 to 3 carbons, Y 1 is directly bonded to the nitrogen-containing heterocycle in A 1 . m is 1 or 2, and n is 1 or 2, satisfying m + n ≦ 3)

[0051] [Chemical Formula 2]

[0052]

[0053] (In formula (3), R 1A is a monovalent hydrocarbon group having 4 to 40 carbons. Y 1 is a single bond or an alkanediyl group having 1 to 3 carbons. R 5 is a hydrogen atom or a methyl group. A 1 is a monovalent group having a nitrogen-containing heterocycle. Wherein, in the case of Y 1 being a single bond, the N 1A to which R + is bonded is directly bonded to the nitrogen-containing heterocycle in A 1The nitrogen-containing heterocycle in Y 1 In the case of an alkanediyl group having 1 to 3 carbon atoms, Y 1 Directly bonded to A 1 wherein r is 1 or 2, t is 1 or 2, and satisfies r+t≦4. - is the relative anion)

[0054] In the above formulas (1) to (3), regarding R 1 、R 1A Specific examples and preferred examples of the group represented by include the following: 1 The groups are the same as those described above.

[0055] About A 1 Specific examples and preferred examples of the nitrogen-containing heterocyclic ring may be the same as those described above. 1 The nitrogen-containing heterocyclic ring is bonded with a substituent (wherein, the ... 1 As a different base from A 1 The nitrogen-containing heterocyclic-bonded substituents in the group include alkyl groups having 1 to 3 carbon atoms (methyl, ethyl, and propyl), acetyl, formyl, halogen atoms (fluorine, chlorine, bromine, and iodine), and nitro groups.

[0056] About X - The counter anion of can be the same as the specific examples of the counter ion in the case of containing in the form of a nitrogen-containing heterocyclic salt.

[0057] Specific examples of compound (A) include 1-octylimidazole, 1-nonylimidazole, 1-decylimidazole, 1-undecylimidazole, 1-dodecylimidazole, 1-tridecylimidazole, 1-tetradecylimidazole, 1-pentadecylimidazole, 1-hexadecylimidazole, 1-octylbenzimidazole, 1-nonylbenzimidazole, 1-decylbenzimidazole, 1-undecylbenzimidazole, 1-dodecylbenzimidazole, 1-tridecylbenzimidazole, 1-tetradecylbenzimidazole, 1-pentadecylbenzimidazole, 1-hexadecylbenzimidazole, 1-octyl-4-methylpiperazine, 1-nonyl-4-methylpiperazine, 1-decyl-4-methylpiperazine, 1-undecyl-4-methylpiperazine, 1-dodecyl-4-methylpiperazine, 1-Tridecyl-4-methylpiperazine, 1-tetradecyl-4-methylpiperazine, 1-pentadecyl-4-methylpiperazine, 1-dodecyl-4-ethylpiperazine, 1-tridecyl-4-ethylpiperazine, 1-nonyl-2-methylbenzimidazole, 1-dodecyl-2-methylbenzimidazole, 1-tridecyl-2-methylbenzimidazole, 1-dodecyl-2-ethylbenzimidazole, 1-tridecyl-2-ethylbenzimidazole, 1-dodecyl-6-methylbenzimidazole, 7-undecyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-dodecyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-tridecyl-1,5,7-triazabicyclo[4.4.0] dec-5-ene, 4-undecylamino-1-methylpiperidine, 4-dodecylamino-1-methylpiperidine, 4-tridecylamino-1-methylpiperidine, 2-(dodecylamino)pyridine, 2-(tridecylamino)pyridine, 3-(dodecylamino)pyridine, 3-(tridecylamino)pyridine, 4-(dodecylamino)pyridine, 4-(tridecylamino)pyridine, 1-dodecyl-4-formylimidazole, 1-undecyl-4-formylimidazole, 2-undecylimidazole, 2-dodecylimidazole, 2-tridecylimidazole, 1-undecyl-3-ethylimidazole bromide , 1-dodecyl-3-ethylimidazolium bromide, 1-tridecyl-3-ethylimidazolium bromide, 1-dodecyl-3-ethylimidazolium chloride, 1-tridecyl-3-ethylimidazolium chloride, 1-dodecyl-3-methylimidazolium bromide, 1-tridecyl-3-methylimidazolium bromide, N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N-octyloctan-1-amine, 1-((dodecyloxy)methyl)-1H-benzo[d][1,2,3]triazole, 1-(1H-benzo[d][1,2,3]triazol-1-yl)tridecane-1 -alcohol, N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadec-1-ammonium chloride, 1-dodecyl-1H-benzo[d][1,2,3]triazole N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadec-1-ammonium benzotriazole, N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadec-1-ammonium bromide, N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadec-1-ammonium Methylhexadecane-1-ammonium chloride, N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-di-dodecanemethyl-1-ammonium chloride, N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-di-dodecanemethyl-1-ammonium bromide, N,N-bis((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dodecane-1-ammonium chloride, N,N-bis((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dodecane-1-ammonium bromide, etc.

[0058] In the case where the compound (A) is in the form of a salt, it is preferable to form a monomolecular film on the substrate while removing the component remaining on the substrate using the surface-modifying composition before forming the monomolecular film. By doing so, the process of removing the component remaining on the substrate before forming the monomolecular film and the process of forming the monomolecular film can be performed in one step, and thus the process in the semiconductor manufacturing process can be simplified. From the viewpoint of improving the removal efficiency of the component remaining on the substrate, the compound represented by the formula (3) can be preferably used as the compound (A).

[0059] From the viewpoint of performing high-density modification of the surface of the substrate, the content of the compound (A) in the surface-modifying 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-modifying composition. In addition, from the viewpoint of selectively modifying the surface of the substrate, the content of the compound (A) in the surface-modifying composition is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, and further preferably 0.1% by mass or less, relative to the total amount of the surface-modifying composition.

[0060] • Solvent

[0061] The surface-modifying composition 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 surface-modifying composition is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and still further preferably 20% by mass or more, and still further preferably 40% by mass or more, relative to the total amount of the composition.

[0062] As the solvent component of the surface-modifying composition, water can be used alone, but an organic solvent can also be contained. By using a mixed solvent of water and an organic solvent as the solvent component of the surface-modifying composition, the storage stability of the surface-modifying composition can be improved. 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.

[0063] As specific examples of the organic solvent that can be blended into the surface-modifying composition, as alcohols, for example, linear monoalcohols having a carbon number of 1 to 18 such as methanol, ethanol, propanol, isopropyl alcohol, 4-methyl-2-pentanol, n-hexanol, and the like; alicyclic monoalcohols having a carbon number of 3 to 18 such as cyclohexanol, and the like; polyhydric alcohols having a carbon number of 2 to 18 such as 1,2-propanediol, and the like; polyhydric alcohol partial ethers having a carbon number of 3 to 19 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, diethylene glycol monobutyl ether, and the like.

[0064] As ethers, for example, tetrahydrofuran can be exemplified. As ketones, for example, acetone, methyl ethyl ketone, acetylacetone, diacetone alcohol can be exemplified. As sulfones, for example, sulfolane, dimethyl sulfoxide can be exemplified. As amides, for example, cyclic amides such as N,N'-dimethylimidazolidinone, N-methylpyrrolidone and the like; chain amides such as N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropionamide and the like can be exemplified. As cyclic amines, for example, morpholine, N-(3-aminopropyl)morpholine can be exemplified. As lactams, for example, 1-methyl-2-pyrrolidinone can be exemplified. As esters, for example, monocarboxylic acid esters such as ethyl lactate and the like as chain esters; γ-butyrolactone, δ-valerolactone as cyclic esters can be exemplified.

[0065] In terms of easiness of mixing with water, better coatability of the surface-modifying composition, or in terms of forming a higher density film in the case where the compound (A) is used as a film-forming material, the organic solvent is preferably an alcohol among these, more preferably at least one selected from the group consisting of a chain monool having a carbon number of 1 to 18, a polyol having a carbon number of 2 to 18, and a polyol partial ether having a carbon number of 3 to 19, further preferably a polyol partial ether having a carbon number of 3 to 19. In addition, the carbon number of the at least one compound selected from the group consisting of a chain monool having a carbon number of 1 to 18, a polyol having a carbon number of 2 to 18, and a polyol partial ether having a carbon number of 3 to 19 is preferably 1 to 15, more preferably 1 to 12, further preferably 1 to 10.

[0066] In the case where the surface-modifying composition contains an organic solvent, in terms of minimizing the amount of the organic solvent used, or in terms of forming a higher density film by the compound (A), the content of the organic solvent in the surface-modifying composition is preferably 65% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, further more preferably 40% by mass or less, with respect to the total amount of the surface-modifying composition. In addition, in terms of improving the storage stability of the surface-modifying composition, the content of the organic solvent in the surface-modifying composition is preferably 1% by mass or more, more preferably 2% by mass or more, with respect to the total amount of the surface-modifying composition.

[0067] In terms of minimizing the amount of the organic solvent used, the content of water in the surface-modifying composition is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 45% by mass or more, further more preferably 55% by mass or more, further further preferably 65% by mass or more, further further more preferably 70% by mass or more, with respect to the total amount of water and the organic solvent contained in the surface-modifying composition.

[0068] • Other ingredients

[0069] The surface-modifying composition can contain, in addition to the compound (A) and the solvent component, a component other than the compound (A) and the solvent component (hereinafter also referred to as "other component"). From the viewpoint of improving the storage stability of the surface-modifying composition, the surface-modifying composition preferably contains the compound (A) and water and a pH adjuster together. In addition, the surface-modifying composition can contain a cleaning component as the other component.

[0070] (pH adjuster)

[0071] The pH adjuster is a component for adjusting the hydrogen ion concentration in the surface-modifying composition. The pH adjuster can be any one of inorganic acids, organic acids, inorganic bases, and organic bases, and can also be a salt of these. In addition, a buffer can be used as the pH adjuster to be formulated in the surface-modifying composition.

[0072] As the inorganic acid, phosphoric acid, boric acid, hydrochloric acid, sulfuric acid, nitric acid, and the like can be exemplified; as the organic acid, acetic acid, lactic acid, malonic acid, succinic acid, citric acid, gluconic acid, cis-2-butenedioic acid, N-propylpiperazine-N'-ethanesulfonic acid, and the like can be exemplified; as the inorganic base, ammonia, potassium hydroxide, sodium hydroxide, and the like can be exemplified; as the organic base, monoethanolamine, diethanolamine, triethanolamine, trimethylamine, triethylamine, propylamine, dibutylamine, and the like can be exemplified. As the salt, a compound exhibiting a buffering action as a salt of the above-mentioned acid or base can be exemplified, for example, ammonium chloride, ammonium acetate, sodium citrate, and the like. As the buffer, sodium phosphate buffer, sodium acetate buffer, sodium citrate-phosphate buffer, sodium tartrate buffer, potassium borate buffer, sodium borate buffer, and the like can be exemplified. The organic acid and the organic base as the pH adjuster are preferably a compound having a carbon number of 10 or less, more preferably a compound having a carbon number of 8 or less, and still more preferably a compound having a carbon number of 7 or less.

[0073] From the viewpoint of reducing the metal content in the surface-modifying composition as much as possible, the pH adjuster is preferably an organic acid, an organic base, or ammonia in the above-mentioned, and more preferably a carboxyl group-containing chain compound, a chain monoamine compound, or ammonia. The carboxyl group-containing chain compound is preferably a compound having a carbon number of 8 or less, and more preferably a compound having a carbon number of 2 to 7. The chain monoamine compound is preferably a compound having a carbon number of 6 or less, and more preferably a compound having a carbon number of 2 to 4.

[0074] In the above-mentioned, at least one selected from the group consisting of ammonia, monoethanolamine, diethanolamine, triethanolamine, citric acid, malonic acid, and cis-2-butenedioic acid can be preferably used as the pH adjuster.

[0075] In the case where a pH adjuster is formulated in the surface-modifying composition, the content of the pH adjuster in the surface-modifying composition can be appropriately set depending on the kind of the pH adjuster used, as long as the surface-modifying composition can be adjusted to the desired pH.

[0076] (washing component)

[0077] A washing component can also be formulated in the surface-modifying composition with the aim of removing components (e.g., residues resulting from dry etching for hole formation, etc.) remaining on the substrate before the formation of a monomolecular film on the substrate with the surface-modifying composition. By formulating a washing component together with the compound (A), a monomolecular film containing the compound (A) can be formed on the substrate while removing components remaining on the substrate. Thus, the process of removing components remaining on the substrate before the formation of a monomolecular film and the process of forming a monomolecular film can be performed in one step, and the simplification of the process in the semiconductor manufacturing process can be achieved, which is preferable in terms of the aspect.

[0078] In terms of sufficiently obtaining a washing effect on the surface of the substrate while forming a high-density film on the substrate with the compound (A), the molecular weight of the washing component is preferably less than that of the compound (A). Specifically, the molecular weight of the washing component is preferably 300 or less, more preferably 200 or less, further preferably 100 or less, and still further preferably 80 or less. In addition, the molecular weight of the washing component is preferably 10 or more, and more preferably 15 or more.

[0079] As the washing component, for example, a fluorine-containing compound, hydrogen peroxide, citric acid, ethylene diamine tetraacetic acid (EDTA), or two or more kinds of these can be exemplified. As specific examples of the fluorine-containing compound, for example, hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, hexafluorosilicic acid, etc. can be exemplified. In terms of a high washing effect, as the washing component, a fluorine-containing compound can be preferably used.

[0080] In terms of sufficiently obtaining a washing effect on the substrate, the content of the washing component in the surface-modifying composition is preferably 0.0001% by mass or more, more preferably 0.001% by mass or more, and further preferably 0.005% by mass or more, with respect to the total amount of the surface-modifying composition. In addition, in terms of not hindering the selective modification of the compound (A) to the surface of the substrate, the content of the washing component is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less, with respect to the total amount of the surface-modifying composition.

[0081] As other components which can be added to the surface modification composition, in addition to the above, an antioxidant or the like can be mentioned. The amount of addition of the other components can be appropriately selected within a range not impairing the effects of the present disclosure depending on each component.

[0082] If considering application to a semiconductor manufacturing process, the surface modification composition is preferably low in metal content. Specifically, the total amount of sodium, potassium, and calcium contained in the surface modification composition is preferably 50 ppm or less, more preferably 10 ppm or less, further preferably 1,000 ppb or less, further more preferably 500 ppb or less, further preferably 100 ppb or less. Further, the metal content in the surface modification composition is a value determined by ICP mass analysis (ICP-MS).

[0083] The surface modification composition can be prepared by mixing the compound (A), water, and other components as necessary, and dissolving the compound (A) or the like in water. From the viewpoint of forming a high-density film while ensuring good coatability, the solid content concentration of the surface modification composition (i.e., the proportion of the total mass of the components other than the solvent component in the surface modification composition with respect to the total mass of the surface modification composition) is preferably 0.0001 to 0.30 mass%, more preferably 0.0002 to 0.15 mass%.

[0084] <Selective modification method of substrate surface>

[0085] Next, a selective modification method of a substrate surface performed using the surface modification composition will be described. The selective modification method includes a coating step of coating the surface modification composition on the surface of a substrate.

[0086] • Coating step

[0087] (Substrate)

[0088] As the substrate, a substrate having a first region in a surface layer and a second region different in material from the first region can be preferably used. The first region is preferably different in adsorptivity of the compound (A) from the second region due to the difference in material from the second region. As one example thereof, the first region is a region higher in adsorptivity of the compound (A) than the second region. From the viewpoint of selectively and highly densely modifying the surface of the substrate by the compound (A), it is preferable that the first region be formed of an electrically conductive material and the second region be formed of an insulating material. In addition, the substrate selectively modified by the surface modification composition is preferably one having a first region formed of an electrically conductive material and a second region formed of an insulating material.

[0089] In the case where the first region is a region formed of an electrically conductive material, the first region contains a metal element. As the metal element, for example, 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 can be listed. The metal element contained in the first region can be a metal single body, or an alloy (nickel-copper alloy, cobalt-nickel alloy, gold-silver alloy, etc.), an electrically conductive nitride (tantalum nitride, titanium nitride, etc.), or the like. Among them, the first region preferably contains a metal single body, an alloy, or an electrically conductive nitride, and more preferably contains at least one selected from the group consisting of copper, cobalt, tungsten, tantalum, titanium, and ruthenium.

[0090] In the surface treatment of the substrate with the surface modification composition, the kind of the compound (A) contained in the surface modification composition can also be appropriately selected depending on the kind of the metal contained in the first region. In view of forming a film of high selectivity and high density on the surface of the substrate, in the case where the compound (A) has a nitrogen-containing aromatic heterocycle, the first region preferably contains at least one selected from the group consisting of tungsten, cobalt, copper, molybdenum, and ruthenium, and more preferably contains at least one selected from the group consisting of tungsten, cobalt, and copper. In addition, in the case where the first region contains at least one selected from the group consisting of tungsten, cobalt, copper, molybdenum, and ruthenium, the nitrogen-containing aromatic heterocycle possessed by the compound (A) is preferably an imidazole ring, a pyrazole ring, a triazole ring, a pyridine ring, a benzimidazole ring, or a benzotriazole ring, and more preferably an imidazole ring, a pyridine ring, a benzimidazole ring, or a benzotriazole ring.

[0091] In the case where the compound (A) has a nitrogen-containing non-aromatic heterocycle, the first region preferably contains at least one selected from the group consisting of copper, cobalt, and ruthenium. In addition, in the case where the first region contains at least one selected from the group consisting of copper, cobalt, and ruthenium, the nitrogen-containing non-aromatic heterocycle possessed by the compound (A) is preferably a piperidine ring, a piperazine ring, a hexamethyleneimine ring, diazabicycloundecene, or 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and more preferably a piperidine ring, a piperazine ring, or 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0092] In the case where the second region is a region formed of an insulating material, the second region is formed of, for example, a silicon-containing compound (for example, SiO2, SiOC, Si3N4, SiNx, SiON, SiC, SiOCN, etc.) such as silicon oxide, silicon nitride, silicon oxynitride, silicide, or a metal oxide (for example, aluminum oxide, tantalum oxide, etc.) The second region preferably contains silicon oxide, silicon nitride, silicon oxynitride, silicide, or a metal oxide.

[0093] In particular, in the case where the substrate to which the surface-modifying composition is applied 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, it is preferable to selectively and densely adsorb the compound (A) to the first region among the first and second regions.

[0094] The shape of the coated surface in the substrate is not particularly limited. The coated surface can be, for example, planar, arcuate, concave, convex, or the like. In addition, in the case where the coated surface has a first region and a second region, the configuration of the first and second regions is also not particularly limited. For example, the first and second regions can be arranged in a prescribed direction on a plane in a state of being adjacent to each other. Alternatively, a plurality of regions can be arranged in one of the first and second regions. In addition, one of the first and second regions can constitute a bottom surface of a hole or a groove formed on the substrate, and the other can constitute a side surface thereof.

[0095] Further, on the surface of the substrate to which the film-forming composition is applied, a pretreatment such as plasma treatment using a mixed gas of H2, N2, and H2, an O2 gas, or the like, or a cleaning treatment, a wet modification treatment, or the like of the surface of the substrate can be performed.

[0096] (Application method)

[0097] As a method of applying the surface-modifying composition, for example, a spray method, a roll coating method, a spin coating method, a slit die coating method, a bar coating method, an inkjet method, or the like can be exemplified. Among these, it is preferable to apply the surface-modifying composition to the surface of the substrate by the spin coating method, the slit die coating method, or the bar coating method. The film 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.

[0098] The surface-modifying composition is applied to the surface of the substrate by the application step, whereby a film (specifically, a monomolecular film) formed of the compound (A) is formed on the first region. The surface-modifying composition can be applied to the surface of the substrate, and then the solvent component in the surface-modifying composition can be removed by natural drying, whereby a film can be formed on the first region. In addition, a heating treatment to remove the solvent component from the surface-modifying composition applied to the surface of the substrate can be performed. The heating treatment can 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 can be set to 50°C or higher. The heating time is, for example, 0.5 minutes to 60 minutes. Since the adsorption ability of the compound (A) to metal is high, a film can be formed on the first region even without performing a heating treatment, and simplification of the manufacturing process can be achieved, which is preferable in this respect. The thickness of the film formed on the substrate is, for example, several nm (for example, about 0.5 nm to 20 nm).

[0099] The selective modification method preferably further includes a process (hereinafter, also referred to as "cleaning process") of bringing the surface of the substrate into contact with a rinsing solution after the surface of the substrate is coated with the surface modification composition by the coating process, thereby cleaning the surface of the substrate, thereby removing the component derived from the surface modification composition on the second region. By the cleaning process, in the case where the component derived from the surface modification composition (more specifically, the composition itself or the compound (A), a residual film formed from the composition, or the like) remains on the second region in the form of a residue, the residue can be removed from the second region. Thereby, the region of the surface of the substrate that is desired to be protected can be more highly selectively coated with the film formed from the compound (A), and the surface of the substrate can be selectively protected.

[0100] • Cleaning process

[0101] As the rinsing solution, an organic solvent can be preferably used. As the organic solvent, for example, propylene glycol monomethyl ether acetate, isopropyl alcohol, acetone, methyl ethyl ketone, methyl n-propyl ketone, and a mixed solvent of two or more of these, or the like can be exemplified.

[0102] In removing the component derived from the surface modification composition on the second region by the rinsing solution from the second region, this is performed by bringing the surface of the substrate after the coating process into contact with the rinsing solution. The method of bringing the surface of the substrate into contact with the rinsing solution is not particularly limited, and for example, a spraying method, a spraying method, a dip method, a puddle method, or the like can be applied. In bringing the surface of the substrate into contact with the rinsing solution, for example, a process of supplying and contacting the rinsing solution to the substrate multiple times, or oscillating the rinsing solution or the substrate can be performed. The temperature of the rinsing solution at the time of bringing the surface of the substrate into contact with the rinsing solution is, for example, 5°C to 50°C. The contact time is, for example, 5 seconds to 30 minutes. The amount of use of the rinsing solution can be appropriately set in consideration of the method of contacting the surface of the substrate with the rinsing solution, or the like. The rinsing solution on the substrate can also be removed using a spin coater or the like after bringing the surface of the substrate into contact with the rinsing solution.

[0103] By the method including the coating process and optionally the cleaning process, a substrate subjected to surface treatment by a composition containing the compound (A) and water can be obtained. That is, according to the present disclosure, a method for manufacturing a surface-treated substrate can be provided, which includes a process of selectively modifying the surface of the substrate by coating a composition on the surface of the substrate.

[0104] By the method including the coating process and the cleaning process described above, the surface of the substrate can be subjected to surface modification with high selectivity and high density using a simple process. For the substrate obtained by the coating process and optionally the cleaning process, for example, each process based on the following processes (contact process, metal layer formation process, film removal process) can also be further performed.

[0105] • Contacting process

[0106] The contacting process is a process of contacting the alcohol, the dilute acid, the hydrogen peroxide water, the ozone, the plasma, the ammonia, or the aqueous solution of the ammonium fluoride salt with the surface of the substrate after the film is formed on the first region by the coating process (preferably after the contact with the rinse solution based on the cleaning process). In the manufacturing process of a semiconductor or the like, an oxide film layer is sometimes formed on the surface of the substrate in contact with air (on the second region). Therefore, by providing such a contacting process, the oxide film layer formed on the second region can be removed. As the dilute acid in the contacting process, for example, dilute hydrochloric acid, dilute sulfuric acid, dilute citric acid, dilute oxalic acid, dilute maleic acid, dilute acetic acid, dilute isobutyric acid, dilute 2-ethylhexanoic acid, or the like can be exemplified.

[0107] • Metal layer forming process

[0108] The metal layer forming process is a process of forming a metal layer on the second region after the film is formed on the first region by the coating process (preferably after the contact with the rinse solution based on the cleaning process, more preferably after the contacting process). The first region in the surface of the substrate after the cleaning process is covered with the protective film (monomolecular film) formed by the compound (A). Therefore, when the metal layer is formed by the metal layer forming process, the metal layer can be selectively formed with respect to the first region and the second region of the second region. The method of forming the metal layer is not particularly limited, but from the viewpoint of high selectivity with respect to a fine region for pattern formation, it is preferable to form a metal pattern by a chemical vapor deposition (CVD) method or an atomic layer deposition (ALD) method. The metal layer formed on the second region can be a barrier layer for separating a metal portion from an insulating portion or for suppressing diffusion of metal from the metal portion. The thickness of the metal layer can be appropriately set depending on the use of the substrate or the like, and is, for example, 1 nm to 30 nm.

[0109] • Film removing process

[0110] The film removing 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 removal of the film can be performed by etching. As the method of etching, for example, a known method such as reactive ion etching (RIE), physical etching, or the like can be exemplified. As the reactive ion etching, for example, chemical dry etching using CF4gas or O2gas or the like, utilizing the difference in etching rate of each layer, or the like; chemical wet etching (wet development) using an etching liquid of an organic solvent or hydrofluoric acid or the like can be exemplified. As the physical etching, sputtering etching, ion beam etching, or the like can be exemplified. Among these, the reactive ion etching is preferable, and the chemical dry etching or the chemical wet etching is more preferable.

[0111] As a solvent for chemical wet etching, for example, the following can be mentioned: acetic acid, APM (a mixture of ammonia, hydrogen peroxide water, and water), SPM (a mixture of sulfuric acid and hydrogen peroxide water), 2.38 mass% TMAH aqueous solution, dilute hydrofluoric acid, water, and the like.

[0112] By carrying out the procedures (coating procedure, cleaning procedure, contact procedure, metal layer forming procedure, and film removing procedure), a substrate in which a metal layer is selectively formed on the second region and the surface (for example, a metal surface) of the first region is exposed with respect to the first region can be obtained. Further processing such as plating treatment can also be carried out on the obtained substrate. In the case where plating treatment is carried out, the method of plating is not particularly limited, and known electrolytic plating, non-electrolytic plating, melt plating, vacuum plating, vapor phase plating, and the like can be used. In the case where it is applied to a semiconductor manufacturing procedure, electrolytic plating or non-electrolytic plating among these is preferably used. Furthermore, after the plating treatment, planarization treatment (CMP treatment) of the surface of the substrate and the like can also be carried out as necessary.

[0113] According to the present disclosure described above, the following means is provided.

[0114] [Means 1] A method for selectively modifying a surface of a substrate, comprising a procedure of applying a composition to a surface of a substrate, the composition containing a compound (A) having a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons, and water.

[0115] [Means 2] The method for selectively modifying a surface of a substrate according to [Means 1], wherein the substrate contains a first region and a second region having a material different from the first region, and a film is formed on the first region by applying the composition to a surface of the substrate containing the first region and the second region.

[0116] [Means 3] The method for selectively modifying a surface of a substrate according to [Means 2], wherein the first region is formed of an electrically conductive material, and the second region is formed of an insulating material.

[0117] [Means 4] The method for selectively modifying a surface of a substrate according to [Means 2] or [Means 3], further comprising a procedure of removing a component derived from the composition on the second region by bringing the surface of the substrate into contact with a rinsing solution after the application of the composition.

[0118] [Means 5] The method for selectively modifying a surface of a substrate according to [Means 4], further comprising a procedure of bringing an alcohol, a dilute acid, hydrogen peroxide water, ozone, plasma, ammonia, or an aqueous solution of a fluoboratesalt into contact with the surface of the substrate after the contact with the rinsing solution.

[0119] [Means 6] The method for selectively modifying a substrate surface according to [Means 4] or [Means 5], further comprising a step of forming a metal layer on the second region after the contact with the elution solution.

[0120] [Means 7] The method for selectively modifying a substrate surface according to [Means 6], further comprising a step of removing the film on the first region formed by the composition after the formation of the metal layer.

[0121] [Means 8] The method for selectively modifying a substrate surface according to any one of [Means 1] to [Means 7], wherein the monovalent organic group having a carbon number of 4 or more of the compound (A) is bonded to the nitrogen atom constituting the nitrogen-containing heterocycle, or is bonded to the nitrogen atom constituting the nitrogen-containing heterocycle directly or via a divalent linking group.

[0122] [Means 9] The method for selectively modifying a substrate surface according to any one of [Means 1] to [Means 8], wherein the composition further contains a pH adjustor.

[0123] [Means 10] The method for selectively modifying a substrate surface according to [Means 9], wherein the pH adjustor is an organic acid, an organic base, or ammonia.

[0124] [Means 11] The method for selectively modifying a substrate surface according to [Means 9] or [Means 10], wherein the pH adjustor is a chain compound containing a carboxyl group, a chain monoamine compound, or ammonia.

[0125] [Means 12] The method for selectively modifying a substrate surface according to any one of [Means 1] to [Means 11], wherein the monovalent organic group having a carbon number of 4 or more of the compound (A) is a monovalent hydrocarbon group having a carbon number of 4 or more, a monovalent halogenated hydrocarbon group having a carbon number of 4 or more, -R 3 -O-R 6 or -CR 4 (OH)-R 6 (wherein, R 3 is an alkanediyl group having a carbon number of 1 to 3, R 4 is a hydrogen atom or a methyl group, and R 6 is a monovalent hydrocarbon group having a carbon number of 4 or more).

[0126] [Means 13] The method for selectively modifying a substrate surface according to any one of [Means 1] to [Means 12], wherein the monovalent organic group having a carbon number of 4 or more of the compound (A) is a monovalent chain hydrocarbon group having a carbon number of 4 or more, -R 3 -O-R 7 or -CR 4 (OH)-R 7 (wherein, R 3R is an alkylene group having 1 to 3 carbons, R 4 R is a hydrogen atom or a methyl group, R 7 R is a monovalent chain hydrocarbon group having 4 or more carbons.

[0127] [Means 14] The method for selectively modifying a surface of a substrate according to any one of [Means 1] to [Means 13], wherein the composition further contains an organic solvent, and the content of the organic solvent in the composition is 60 mass% or less relative to the total amount of the composition.

[0128] [Means 15] The method for selectively modifying a surface of a substrate according to [Means 14], 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.

[0129] [Means 16] The method for selectively modifying a surface of a substrate according to any one of [Means 1] to [Means 15], wherein the content of water is 10 mass% or more relative to the total amount of the composition.

[0130] [Means 17] The method for selectively modifying a surface of a substrate according to any one of [Means 1] to [Means 16], wherein the composition further contains a cleaning component.

[0131] [Means 18] The method for selectively modifying a surface of a substrate according to [Means 17], wherein the cleaning component is a fluorine-containing compound.

[0132] [Means 19] A method for manufacturing a surface-treated substrate, comprising a step of selectively modifying a surface of a substrate by applying a composition to the surface of the substrate, the composition containing a compound (A) having a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons, and water.

[0133] [Means 20] A composition for selectively modifying a surface of a substrate, the composition containing a compound (A) having a nitrogen-containing heterocycle and a monovalent organic group having 4 or more carbons, and water.

[0134] [Means 21] The composition according to [Means 20], wherein the monovalent organic group having 4 or more carbons of the compound (A) is bonded to a nitrogen atom constituting the nitrogen-containing heterocycle, or is bonded to the nitrogen atom of the nitrogen-containing heterocycle directly or via a divalent linking group.

[0135] [Means 22] The composition according to [Means 20] or [Means 21], further containing a pH adjustor.

[0136] [Means 23] The composition according to any one of [Means 20] to [Means 22], wherein the monovalent organic group having 4 or more carbons of the compound (A) is a monovalent hydrocarbon group having 4 or more carbons, a monovalent halogenated hydrocarbon group having 4 or more carbons, -R 3 -O-R 6 or -CR 4 (OH)-R 6 (wherein, R 3 is an alkanediyl group having 1 to 3 carbons, R 4 is a hydrogen atom or a methyl group, and R 6 is a monovalent hydrocarbon group having 4 or more carbons).

[0137] [Means 24] The composition according to any one of [Means 20] to [Means 23], further comprising an organic solvent, the content of the organic solvent being 60 mass% or less relative to the total amount of the composition.

[0138] Examples

[0139] Hereinafter, the present disclosure will be specifically described based on examples, but the present disclosure is not limited to these examples. The following shows the measurement method of each physical property value.

[0140] < Synthesis of Compound (A) >

[0141] [Synthesis Example 1] Synthesis of 1-dodecylimidazole (Compound (A-2))

[0142] Into a 100 mL three-necked flask, imidazole 1.70 g (25 mmol), 1-bromododecane 6.3 g (25 mmol), potassium carbonate 6.9 g (50 mmol), and acetone 50 mL were charged, and stirred at 72°C for 7 hours under reflux while blowing nitrogen. After returning to normal temperature, water washing was performed three times with ethyl acetate / pure water. The organic layer was recovered, dehydrated with anhydrous sodium sulfate, and the filtrate was recovered with a crimped filter paper, and concentrated under reduced pressure with an evaporator.

[0143] The solvent was distilled off with an evaporator and an oil pump, and the product was recovered by column chromatography using only ethyl acetate (Rf: 0.2). The solvent was distilled off with an evaporator and an oil pump, and the product was recovered by column chromatography using only ethyl acetate (Rf: 0.2). 1 H-NMR and 13 C-NMR were used to confirm the structure.

[0144] 1 H NMR (CDCI3, 400 MHz); δ 7.45 (s, 1H, imidazole ring), 7.05 (s, 1H, imidazole ring), 6.90 (s, 1H, imidazole ring), 3.96-3.90 (q, 2H, CH2), 2.04-1.75 (m, 2H, CH2), 1.30-1.25 (br, 20H, CH2), 0.90 (t, 3H, CH3).

[0145] 13 C NMR (CDC13, 100 MHz); δ 137.1 (imidazole ring), 129.4 (imidazole ring), 118.8 (imidazole ring), 47.1, 31.9, 31.2, 29.7, 29.6, 29.5, 29.4, 29.1, 26.6, 22.8 (CH2), 14.2 (CH3).

[0146] [Synthesis Example 2 to Synthesis Example 10] Synthesis of Compound (A-1), Compound (A-3) to Compound (A-9), and Compound (A-11)

[0147] 1-dodecyl-3-ethylimidazole bromide (Compound (A-1)) was derived by quaternary chlorination of 1-dodecylimidazole with ethyl bromide.

[0148] 1-dodecylbenzimidazole (Compound (A-3)), 1-dodecyl-4-methylpiperazine (Compound (A-4)), 1-dodecyl-2-methylbenzimidazole (Compound (A-5)), 7-dodecyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (Compound (A-6)), 4-dodecylamino-1-methylpiperidine (Compound (A-7)), 1-dodecyl, 4-(tridecylamino)pyridine (Compound (A-8)), 1-dodecyl-4-formylimidazole (Compound (A-9)) were derived from SN2 reaction of alkyl halide corresponding to the target.

[0149] 3,3,4,4,5,5,6,6,7,7,8,8,11,11,12,12,13,13,14,14,15,15,16,16,16-pentacosafluoro-9-hexadecen-1-ylphosphonic acid (Compound (A-11)) was synthesized with reference to Japanese Patent No. 2022-00497.

[0150] 2-undecylimidazole (Compound (A-10)) and 2-methylimidazole (Compound (A-12)) were obtained from Tokyo Chemical Industry Co., Ltd.

[0151] [Synthesis Example 11] Synthesis of Compound (A-13): N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N-octyloctan-1-amine

[0152] To a 100ml three-necked flask were added benzotriazole 5.96g (50mmol), 37% formaldehyde 4.87g (60mmol), methanol 60g, and stirred for 30 minutes under cooling in an ice bath. To this was slowly added dropwise a mixture of dioctylamine 12.1g (50mmol) and methanol 8.7g over 30 minutes. After the completion of the dropwise addition, the temperature was returned to normal, and stirring was continued for 2 hours.

[0153] After the completion of the reaction, the organic layer was recovered by washing with dichloromethane / ultra-pure water three times, dehydrated with anhydrous sodium sulfate, and the filtrate was recovered and concentrated. The concentrate was purified by column chromatography with ethyl acetate / n-hexane = 1 / 1 vol%. After concentration, 6.2g of a colorless transparent liquid was obtained. The obtained colorless transparent liquid compound was designated as compound (A-13).

[0154] The structure confirmation results obtained by 1 H-NMR and 13 C-NMR were as follows.

[0155] 1 H NMR (400 MHz) δ; 8.07-8.05 (1H, m, Ph), 7.62-7.60 (1H, m, Ph), 7.50-7.46 (1H, m, Ph), 7.38-7.34 (1H m, Ph), 5.49 (2H, s, CH2), 2.64-2.56 (2H, m, CH2), 1.55-1.51 (4H, br, CH2), 1.30-1.26 (20H, br, CH2), 0.89 (6H, m, CH3).

[0156] 13 C NMR (100 MHz) δ; 145.5, 132.8, 119.6, 126.2, 110.0, 75.2, 54.6, 31.9, 29.3, 28.0, 27.3, 22.7, 14.1

[0157] [Synthesis Example 12] Synthesis of Compound (A-14): 1-((Dodecyloxy)methyl)-1H-benzo[d][1,2,3]triazole

[0158]

[0159] [Synthesis Example 12] Synthesis of Compound (A-14): 1-((Dodecyloxy)methyl)-1H-benzo[d][1,2,3]triazole

[0160] To a 100ml three-necked flask were added benzotriazole 5.96g (50mmol), 37% formaldehyde 4.87g (60mmol), methanol 60g, and stirred for 30 minutes under cooling in an ice bath. To this was slowly added dropwise a mixture of dioctylamine 12.1g (50mmol) and methanol 8.7g over 30 minutes. After the completion of the dropwise addition, the temperature was returned to normal, and stirring was continued for 2 hours.

[0161] After the reaction, dichloromethane / ultra-pure water, a small amount of saturated ammonium chloride aqueous solution, and water were added, and washing was performed three times. The organic layer was dried using anhydrous sodium sulfate and then concentrated. The obtained white solid was used as the compound (A-14).

[0162] The structure confirmation results obtained by 1 H-NMR and 13 C-NMR are as follows.

[0163] 1 H NMR (400 MHz) δ; 8.00 (1H, m, Ph), 7.75 (1H, m, Ph), 7.47 (1H, m, Ph), 7.36 (1H, m, Ph), 5.81 (2H, s, CH2), 3.35 (2H, m, CH2), 1.50 (2H, m, CH2), 1.43 (2H, m, CH2), 1.30-1.26 (16H, m, CH2), 0.90 (3H, t, CH3).

[0164] 13 C NMR (400 MHz) δ; 146.2, 132.0, 126.2, 119.6, 110.0, 79.5, 69.8, 31.9, 29.7, 29.6, 29.3, 29.2, 22.7, 14.1.

[0165] [Synthesis Example 4]

[0166]

[0167] [Synthesis Example 13] Synthesis of compound (A-15): 1-(1H-benzo[d][1,2,3]triazol-1-yl)tridecan-1-ol

[0168] Into a 100-ml three-necked flask, benzotriazole 5.96 g (50 mmol), decanal 9.26 g (50 mmol), and diisopropyl ether 30 g were added, and stirred at normal temperature under nitrogen atmosphere. Precipitate was generated during the reaction. After 6 hours, white solid was recovered using a Buchner funnel while washing with diisopropyl ether. After drying, 8.6 g of white solid was obtained. The obtained white solid was used as the compound (A-15).

[0169] The structure confirmation results obtained by 1 H-NMR and 13 C-NMR are as follows.

[0170] 1H NMR (400 MHz) δ 8.00 (1H, m, Ph), 7.75 (1H, m, Ph), 7.47 (1H, m, Ph), 7.36 (1H, m, Ph), 5.70 (1H, d, CH), 4.52 (1H, br, OH), 1.90 (2H, m, CH2), 1.27-1.25 (18H, m, CH2), 0.88 (3H, t, CH3).

[0171] 13 C NMR (400 MHz) δ 144.7, 133.3, 126.2, 119.6, 93.1, 34.2, 31.9, 29.6, 29.3, 22.7, 20.8, 14.1.

[0172] [Synthesis Example 14] Synthesis of Compound (A-16): N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadecan-1-aminium chloride

[0173]

[0174] [Synthesis Example 14] Synthesis of Compound (A-16): N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadecan-1-aminium chloride

[0175] To a 100 ml tomato type flask, 1-chloromethylbenzotriazole 5.03 g (30 mmol), dimethyl dodecylamine 9.70 g (33 mmol), acetonitrile were stirred at 85°C for 6 hours. After cooling to room temperature, methanol 150 ml and hexane 200 ml were added and liquid-liquid washing was performed three times. The target was obtained by recovering and concentrating the methanol layer. After drying, 13.3 g was obtained as a white solid. The obtained white solid was set as Compound (A-16).

[0176] The structure confirmation results obtained by1H-NMR and 1 H-NMR and 13 C-NMR were as follows.

[0177] 1 H NMR (400 MHz) δ 8.81 (1H, d, Ph), 8.06 (1H, d, Ph), 7.69-7.66 (1H, m, Ph), 7.47-7.43 (1H, m, Ph), 7.02 (2H, s, CH2), 3.66 (2H, m, CH2), 3.53 (6H, s, CH3), 1.91 (2H, br, CH2), 1.34-1.23 (28H, m, CH2), 0.90 (3H, t, CH3).

[0178] 13C NMR (400 MHz) δ; 145.4, 134.8, 130.5, 125.6, 120.1, 111.6, 70.0, 63.2, 50.6, 48.9, 32.0, 29.7, 29.6, 29.5, 29.4, 29.2, 26.3, 22.8, 22.7, 14.2.

[0179] [Chemical 6]

[0180]

[0181] [Synthesis Example 15] Synthesis of Compound (A-17): 1-Dodecyl-1H-benzo[d][1,2,3]triazole Reference: Chemistry of Materials, 2010, 22, 4034 Synthesis of Compound (A-17).

[0182] [Chemical 7]

[0183]

[0184] [Synthesis Example 16] Synthesis of Compound (A-18): N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadecan-1-aminium benzotriazolate

[0185] To a 100 ml of a tomato type flask, N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dimethylhexadecan-1-aminium chloride 6.02 g (15 mmol), sodium benzotriazolate 2.12 g (15 mmol), dichloromethane 100 ml, DIW (ultra-pure water) 100 ml were added, and stirred at room temperature for 6 hours. After the reaction was completed, water washing was performed three times, and the organic layer was recovered, dried using anhydrous sodium sulfate, and concentrated using an evaporator. The obtained white solid was refined by column chromatography using an eluent of dichloromethane / methanol = 10 / 1 vol%, and the organic solvent was concentrated to obtain a white solid (6.10 g).

[0186] The structure confirmation results obtained by 1 H-NMR and 13 C-NMR were as follows.

[0187] 1H NMR (400 MHz) δ; 8.39 (d, 1H, Ph), 8.02 (d, 1H, Ph), 7.86 (d, 2H, Ph), 7.51 (m, 1H, Ph), 7.41 (m, 1H, Ph), 7.27 (d, 2H, Ph), 6.92 (s, 2H, CH2), 3.31 (br, 8H, CH2, CH3), 1.68 (br, 2H, CH2), 1.67-1.18 (br, 26H, CH2), 0.88 (t, 3H, CH3).

[0188] 13 C NMR (100 MHz) δ; 145.3, 134.7, 130.4, 125.5, 121.8, 120.1, 116.4, 111.1, 69.9, 63.0, 48.8, 32.0, 29.8, 29.6, 29.5, 29.4, 29.3, 29.1, 26.2, 22.7, 22.5, 14.2.

[0189] [Synthesis Example 17] Synthesis of Compound (A-19): N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-didodecylmethyl-1-aminium bromide

[0190]

[0191] [Synthesis Example 17] Synthesis of Compound (A-19): N-((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-didodecylmethyl-1-aminium bromide

[0192] Into a 100 ml pear-shaped flask, 1-hydroxymethylbenzotriazole 4.48 g (30 mmol) and phosphorus tribromide 9.48 g (35 mmol) were added, and stirred at normal temperature for 3 hours in toluene. After removing toluene with an evaporator, 50 ml of cold water was added, and further 2M NaOH aqueous solution was added until pH approached 11. Next, extraction was performed twice with dichloromethane. Dried with anhydrous sodium sulfate, and removed the solvent with an evaporator, and refined by column chromatography with dichloromethane to obtain 1-(bromomethyl)-1H-benzo[d][1,2,3]triazole 5.8 g.

[0193] Next, into a 100 ml pear-shaped flask, 1-(bromomethyl)-1H-benzo[d][1,2,3]triazole 6.36 g (30 mmol), di-dodecylmethylamine 11.0 g (30 mmol), and acetonitrile 30 ml were added, and stirred for 8 hours under heating distillation. After cooling to normal temperature, methanol 150 ml and hexane 200 ml were added, and liquid washing was performed three times. The target was obtained by recovering the methanol layer and concentrating. After drying, 15.1 g of white solid was obtained. This was set as Compound (A-19).

[0194] By1 H-NMR and 13 The structural confirmation results obtained by C-NMR are as follows.

[0195] 1 H NMR (400 MHz) δ; 8.00 (1H, d, Ph), 7.75 (1H, d, Ph), 7.36 (1H, m, Ph), 7.47 (1H, m, Ph), 5.68 (2H, s, CH2), 3.30 (4H, m, CH2), 3.22 (3H, s, CH3), 1.71 (4H, br, CH2), 1.30-1.26 (38H, m, CH2), 0.88 (6H, t, CH3).

[0196] 13 C NMR (400 MHz) δ; 145.5, 132.8, 126.2, 126.1, 119.6, 110.0, 91.3, 60.0, 59.9, 50.6, 47.8, 31.9, 29.6, 29.3, 26.8, 22.7, 14.1.

[0197] [Chemical 9]

[0198]

[0199] [Synthesis Example 18] Synthesis of Compound (A-20): N,N-bis((1H-benzo[d][1,2,3]triazol-1-yl)methyl)-N,N-dodecan-1-aminium bromide

[0200] Into a 100 ml of a flask, 1-hydroxymethylbenzotriazole 4.48 g (30 mmol) and phosphorus tribromide 9.48 g (35 mmol) were added, and stirred in toluene at normal temperature for 3 hours. After removing toluene by an evaporator, 50 ml of cold water was added, and further 2M NaOH aqueous solution was added until pH was close to 11. Next, extraction was performed twice using dichloromethane. Drying was performed using anhydrous sodium sulfate, and the solvent was removed by an evaporator, and purification was performed by column chromatography using dichloromethane to obtain 1-(bromomethyl)-1H-benzo[d][1,2,3]triazole 5.8 g.

[0201] Next, to 100 ml of a tomato type flask, 1-(bromomethyl)-1H- benzo[d][1,2,3]triazole 4.24 g (20 mmol), di-dodecylamine 9.56 g (10 mmol), acetonitrile 30 ml were added, and stirring was performed under heating distillation for 8 hours. After cooling to normal temperature, methanol 150 ml and hexane 200 ml were added, and liquid washing was performed three times. The methanol layer was recovered and concentrated, the flask was immersed in dry ice acetone to perform crystallization, and slurry washing was performed using ethyl acetate. The slurry was recovered using a Buchner funnel and dried, and 9.6 g of a white solid was obtained. This was set as compound (A-20).

[0202] The structure of the compound (A-1) was confirmed by 1 H-NMR and 13 The structure confirmation results obtained by

[0203] 1 H NMR (400 MHz) δ; 7.96 (d, 2H, Ph), 7.67 (d, 2H, Ph), 7.39-7.36 (m, 4H, Ph), 4.80 (s, 4H, CH2), 2.4 (br, 2H, CH2), 2.34 (br, 2H, CH2), 1.36-1.26 (br, 40, CH2), 0.89 (t, 6H, CH3).

[0204] 13 C NMR (100 MHz) δ; 145.5, 132.8, 126.2, 119.6, 110.0, 88.0, 61.0, 50.0, 32.1, 31.9, 30.8, 29.6, 29.3, 27.6, 25.2, 22.7, 21.0, 14.1.

[0205] [Chemical 10]

[0206]

[0207] The following shows the structural formulas of compounds (A-1) to (A-20).

[0208] [Chemical 11]

[0209]

[0210] [Chemical 12]

[0211]

[0212] Preparation of a composition for surface modification

[0213] Each component used for the preparation of a composition for surface modification is as follows.

[0214] • Low molecular compound

[0215] A-1 to A-20: Compound (A-1) to Compound (A-20)

[0216] A-21: Emal 0 (manufactured by Kokyo Co., Ltd., anionic surfactant, sodium lauryl sulfate)

[0217] • (B) pH adjuster

[0218] B-1: Monoethanolamine

[0219] B-2: 25% aqueous ammonia solution

[0220] B-3: Citric acid

[0221] B-4: Malonic acid

[0222] B-5: cis-2-butenedioic acid

[0223] B-6: Potassium hydroxide

[0224] B-7: N-Propylpiperazine-N'-ethanesulfonic acid

[0225] [Chemical 13]

[0226]

[0227] • (C) Solvent

[0228] C-1: Water

[0229] C-2: Diethylene glycol mono-n-butyl ether

[0230] C-3: Diethylene glycol monomethyl ether

[0231] C-4: 2-Methoxy-1-propanol

[0232] C-5: Ethylene glycol mono-n-butyl ether

[0233] C-6: Sulfolane

[0234] C-7: γ-Butyrolactone

[0235] [Chemical 14]

[0236]

[0237] • (D) Cleaning ingredient

[0238] Mol-1; Hydrofluoric acid

[0239] Mol-2; Ammonium fluoride

[0240] Mol-3; Tetramethylammonium fluoride

[0241] Mol-4; hexafluorosilicic acid

[0242] Mol-5; hydrogen peroxide

[0243] 1. Preparation of a composition for surface modification (1)

[0244] [Example 1]

[0245] To 0.05 g of compound (A-1) was added 99.95 g of solvent (C-1) and, after stirring, filtration was performed using a high-density polyethylene filter having a pore size of 0.45 μm, thereby preparing a composition (SM-1) having a solid content concentration of 0.050%.

[0246] [Examples 2 to 26 and Comparative Examples 1 to 4]

[0247] Using each component shown in Tables 1 and 2 in the kind and blending amount shown, the same operation as in Example 1 was performed, thereby respectively preparing compositions (SM-2) to (SM-26) and compositions (SR-1) to (SR-4), except that. Further, the blending amount of compound (B-2) indicates the blending amount of aqueous ammonia solution.

[0248]

[0249]

[0250] 2. Evaluation (1)

[0251] Using the compositions (SM-1) to (SM-26) and compositions (SR-1) to (SR-4) prepared in the above 1., the following evaluation was performed. The results of these are shown in Tables 3 and 4.

[0252] Evaluation of solubility

[0253] The solubility of each composition obtained in the above 1. was visually observed, and in the case where permeation was observed, it was set to "good (O)", and in the case where at least either of blur and dissolution residue was confirmed, it was set to "poor (X)".

[0254] Evaluation of coatability

[0255] The coatability of each composition was evaluated using the substrates shown below.

[0256] W: 8-inch tungsten substrate, Cu: 8-inch copper substrate, Co: 8-inch cobalt substrate, Ru: 8-inch ruthenium substrate, AI2O3: 8-inch alumina substrate, SiN: 8-inch silicon nitride substrate, low-k; low dielectric silicon oxide substrate

[0257] These substrates were obtained from Advantec Corporation.

[0258] Each of the compositions prepared in 1. was spin-coated on each of the various substrates cut to 3 cm x 3 cm using a spin coater (Mikasa Corporation's "MS-B300") under conditions of 1,500 rpm for 20 seconds (coating step). Subsequently, the coated substrate was baked at 150°C for 180 seconds. Thereafter, the substrate was cleaned using propylene glycol monomethyl ether acetate as a rinsing liquid (first removal step, hereinafter also referred to as "cleaning step"). In the cleaning step, the components in the composition were removed by the rinsing liquid without being adsorbed on the surface of the substrate, and thus no film was formed on the substrate. The coated surface of the substrate was observed using an optical microscope, and the presence or absence of voids and film breakage on the film surface was confirmed. Those having no voids and film breakage were rated "good (O)", those having no film breakage but having voids were rated "fair (D)", and those having both voids and film breakage were rated "poor (X)".

[0259] < Evaluation of Contact Angle >

[0260] Each of the compositions prepared in 1. was spin-coated on each of the various substrates for evaluation of coatability cut to 3 cm x 3 cm using a spin coater (Mikasa Corporation's "MS-B300") under conditions of 1,500 rpm for 20 seconds. Thereafter, the substrate was cleaned using isopropyl alcohol. For the cleaned substrate, the static contact angle of the coated surface was measured using a contact angle meter (Kyowa Interface Science Co., Ltd.'s "Drop master DM-501"). It can be said that a film was selectively formed on a substrate on which the static contact angle was greatly increased with respect to the static contact angle of the substrate before surface treatment with the surface-modifying composition (Reference Example 1).

[0261] < Evaluation of Storage Stability >

[0262] Each of the surface-modifying compositions prepared in 1. was placed in a vial, and stored at 50°C for 2 weeks. The amount of change in viscosity before and after the storage stability test was expressed as Δη, and the case where the amount of change Δη was less than 1 Pa s was rated "good (O)", the case where the amount of change Δη was 1 Pa s or more and less than 3 Pa s was rated "fair (D)", and the case where the amount of change Δη was 3 Pa s or more was rated "poor (X)".

[0263] < Evaluation of Resistance to Metal Corrosion (Evaluation Based on Etching Rate) >

[0264] Each of the wafers with a 100-nm-thick ruthenium film and the wafers with a 200-nm-thick molybdenum film was cut into a 30-mm x 10-mm piece, and wafer pieces for etching rate evaluation (hereinafter, also referred to as "evaluation wafer pieces") were prepared. Each of the compositions prepared in the above-mentioned 1 was warmed to 60°C, and the evaluation wafer pieces were immersed in each of the compositions for 5 minutes. Thereafter, the evaluation wafer pieces were taken out, washed with running water, and the thicknesses of the ruthenium film and the molybdenum film were measured. As to the thicknesses of the ruthenium film and the molybdenum film, the resistance values were measured by a resistivity measuring machine (manufactured by KLA-Tencor Corporation, model "RS-100") and by a direct current 4-probe method, and the thicknesses were calculated from the obtained resistance values (hereinafter, referred to as "sheet resistance values". Unit: Ω / sq), the volume resistivities of ruthenium or molybdenum, and the following mathematical formulae.

[0265] Thickness of ruthenium film (nm) = [volume resistivity of ruthenium film (Ω-m) ÷ sheet resistance value (Ω / sq)] x 10 9

[0266] Thickness of molybdenum film (nm) = [volume resistivity of molybdenum film (Ω-m) ÷ sheet resistance value (Ω / sq)] x 10 9

[0267] From the amount of change in the thickness of the ruthenium film or the molybdenum film before and after immersion in the surface modification composition, the etching rate was calculated by the following mathematical formula.

[0268] Etching rate of ruthenium film (nm / min) = (thickness of ruthenium film before etching (nm) - thickness of ruthenium film after etching (nm)) / etching time (min)

[0269] Etching rate of molybdenum film (nm / min) = (thickness of molybdenum film before etching (nm) - thickness of molybdenum film after etching (nm)) / etching time (min)

[0270] The evaluation criteria for the etching rate of the ruthenium film were as follows. It can be said that the smaller the etching rate of the ruthenium film, the better the metal corrosion resistance of the surface modification composition.

[0271] (Evaluation Criteria)

[0272] A: In the case where the etching rate is less than 1.5 nm / min, it was judged to be very good.

[0273] B: In the case where the etching rate is 1.5 nm / min or more and less than 3 nm / min, it is practical, and thus judged to be good.

[0274] C: In the case where the etching rate is 3 nm / min or more, the etching rate is large and it is difficult to be practical, and thus judged to be poor.

[0275] The evaluation criteria for the etching rate of the molybdenum film are as follows. It can be said that the smaller the etching rate of the molybdenum film, the better the metal corrosion resistance of the surface modification composition.

[0276] (Evaluation Criteria)

[0277] A: In the case where the etching rate is not more than 20 nm / min, it is judged to be very good.

[0278] B: In the case where the etching rate is more than 20 nm / min, the etching rate is large and it is difficult to be practical, and thus it is judged to be poor.

[0279] < Evaluation of Dry Etching Residue Removal Performance (Evaluation Based on Etching Rate) >

[0280] A reactive ion etching device (RIE-10NR) was used to perform dry etching treatment on a LowK film substrate, and a treated body was obtained. The obtained treated body was cut into 3.5 cm x 3.5 cm, and was immersed in each of the compositions prepared in the above-mentioned 1. for 1 minute, respectively. Thereafter, the wafer sheet (treated body) was taken out, and was cleaned with water and isopropyl alcohol. The F component in the surface of the cleaned treated body was quantified by X-ray photoelectron analysis (manufactured by Ulvac, model "Quantum 2000"), and the proportion of the quantitative value of the F component in the surface-treated substrate when the quantitative value of the F component in the substrate not immersed in each composition was taken as a reference value was calculated as the cleaning efficiency (%).

[0281] (Evaluation Criteria)

[0282] A: The cleaning efficiency was 98% or more (good)

[0283] B: The cleaning efficiency was less than 98% and was 90% or more (OK)

[0284] C: The cleaning efficiency was less than 90% (poor)

[0285] (Dry Etching Conditions)

[0286] Gas flow rate: Ar / C4F8 / N2 = 100 sccm / 50 sccm / 33 sccm

[0287] Plasma power: 170 W / 40 MHz (high frequency), 80 W / 13 MHz (low frequency)

[0288] Pressure: 50 mTorr

[0289] Formulation time: 100 seconds

[0290] < Evaluation of Metal Oxide Blocking Performance (Evaluation of ALD Resistance) >

[0291] For a substrate (let it be "surface-treated substrate") on which a tungsten substrate (W substrate) was surface-coated with each of the surface-modifying compositions prepared in the above-mentioned 1, in order to evaluate the degree of inhibition of ALD on oxide layer formation, metal oxide blocking evaluation was performed. As a control, a W substrate which was not surface-treated with each of the surface-modifying compositions (let it be "untreated substrate") was subjected to ALD in the same manner as the surface-treated substrate. As for ALD, a Cambridge Nanotech FIJI within Stanford University was used, and was performed under the conditions shown below. As a precursor, trimethylaluminum was used, and water was used as a co-catalyst. The ALD cycle was fixed at 47 cycles.

[0292] (ALD conditions)

[0293] Kind of film: ALD AI2O3

[0294] Chamber: Cambridge Nanotech Fiji

[0295] Stage temperature: 200°C

[0296] Treatment time: 0.3 seconds trimethylaluminum / 15 seconds purge / 0.06 seconds water / 23 seconds purge

[0297] Thickness on W substrate: 5.4 nm (polarizing analysis method)

[0298] Loading: The stage was cooled for 5 minutes before loading

[0299] Queue time: Within 3 hours after removal

[0300] The Al component in the substrate surface of the W substrate after ALD (surface-treated substrate and untreated substrate) was quantified by X-ray photoelectron analysis (ESCA). As for ESCA, a "Quantum 2000" by Ulvac (K.K.) was used, and the Al component other than the film component and the substrate component was quantified with Al2p (72 eV-78 eV) from a condition of 100 μmφ. Thereafter, the quantified value of the Al component of the untreated substrate was taken as a reference value, and the quantified value of the Al component of the surface-treated substrate was calculated as to what extent it was reduced from the reference value as a blocking rate (%). It can be said that the greater the value of the blocking rate, the more the film formed on the W substrate with the surface-modifying composition is formed by the components (low molecular compounds in Table 1) in the surface-modifying composition being adsorbed on the W substrate surface at a high density, and has a high blocking performance for the metal oxide formed by ALD. A case where the blocking rate is 98% or more was taken as "good (O)", a case where it is less than 98% but 90% or more was taken as "acceptable (Δ)", and a case where it is less than 90% was taken as "poor (X)".

[0301] Measurement of metal content

[0302] The metal content of sodium, potassium, and calcium was measured using a NexION5000 ICP mass spectrometer (manufactured by Perkin Elmer) with dilution of each composition 20 times with diethylene glycol butyl ether / ultra-pure water = 80 / 20 (mass parts). With respect to the evaluation, in the case where the total amount of sodium, potassium, and calcium was less than 100 ppb, it was set to "good (O)", in the case where it was 100 ppb or more and less than 10 ppm, it was set to "possible (Δ)", and in the case where it exceeded 10 ppm, it was set to "not possible (X)".

[0303] [Table 3]

[0304]

[0305]

[0306] From the results, in the surface modification compositions of Examples 1 to 26 using Compound (A) as the film forming material and containing water, the solubility of Compound (A) in water was good, and the coatability and storage stability were also good. In addition, by using the surface modification compositions of Examples 1 to 26, a film can be formed with high selectivity and high density with respect to a metal surface. Furthermore, the film formed from the surface modification compositions of Examples 1 to 26 exhibited good resistance to metal corrosion. In addition, in the case where Compound (A-1) to Compound (A-9) were used as the film forming material, the coatability and resistance to ALD were also better than in the case where Compound (A-10) was used. Therefore, it can be said that the monovalent organic group R 1 In the case where it is bonded to a nitrogen atom constituting a nitrogen-containing heterocycle or a nitrogen atom bonded to a nitrogen-containing heterocycle, the coatability of the composition can be made better, and a film of higher density can be formed. In addition, by further formulating a pH adjuster, a surface modification composition with further improved storage stability can be obtained (Examples 2 to 15, Examples 17 to 26).

[0307] In contrast, the surface modification composition of Comparative Example 1 using only an organic solvent as a solvent is compared with Example 16 comprising water, and the result is poor coatability and ALD resistance. In addition, the evaluation of the surface modification composition of Comparative Example 2 using compound (A-11) instead of compound (A) is low in solubility in water and poor in storage stability. In addition, the selective modification of the metal surface, metal corrosion resistance and metal oxide blocking performance are also insufficient. The selective modification of the metal surface and the metal oxide blocking performance in the surface modification composition of Comparative Example 3 using compound (A-12) are poorer than Examples 1 to 26, and the selective modification of the metal surface, metal corrosion resistance and metal oxide blocking performance in the surface modification composition of Comparative Example 4 using compound (A-21) are also poorer than Examples 1 to 26.

[0308] 3. Preparation of surface modification composition (2)

[0309] [Example 27]

[0310] To 0.03 g of compound (A-16) was added 99.95 g of solvent (C-1) and stirred, and then 0.01 g of compound (Mol-1) and 0.01 g of compound (B-1) were added. After stirring, the mixture was filtered using a high-density polyethylene filter with pores of 0.45 μm to prepare a composition (SM-27) with a solid content concentration of 0.05%.

[0311] [Example 28 to Example 38]

[0312] The same procedures as in Example 27 were carried out except that the components shown in Table 5 were used in their respective types and amounts, thereby preparing compositions (SM-28) to (SM-38).

[0313] [Table 5]

[0314]

[0315] 2. Evaluation (2)

[0316] The same evaluations as in Examples 1 to 26 and Comparative Examples 1 to 4 were performed using the compositions (SM-27) to (SM-38) prepared in 3. The results are shown in Table 6.

[0317] [Table 6]

[0318]

[0319] As shown in Table 6, for the surface-modifying compositions of Examples 27 to 38 which use Compound (A) as a film-forming material and contain water, the solubility of Compound (A) in water is also good, and the coatability and storage stability are also good. In addition, by using the surface-modifying compositions of Examples 27 to 38, a film can be formed with high selectivity and high density with respect to a metal surface. Furthermore, the film formed from the surface-modifying compositions of Examples 27 to 38 exhibits good resistance to metal corrosion, and exhibits good residue removal performance.

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 nitrogen-containing heterocyclic ring and a monovalent organic group having 4 or more carbon atoms, and water.

2. The method for selectively modifying a substrate surface according to claim 1, wherein the substrate comprises a first region and a second region having a material different from that of the first region, The composition is applied to the surface of a substrate including the first region and the second region, thereby forming a film on the first region.

3. The method for selectively modifying a 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 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.

5. The method for selectively modifying a substrate surface according to claim 4, further comprising the step of contacting the substrate surface after contact with the eluent with an alcohol, dilute acid, hydrogen peroxide solution, ozone, plasma, ammonia or ammonium fluoride salt solution. 6 . The method for selectively modifying a substrate surface according to claim 4 , further comprising forming a metal layer on the second region after contacting with the eluent. 7 . The method for selectively modifying a substrate surface according to claim 6 , further comprising a step of removing the film formed from the composition on the first region after forming the metal layer.

8. The method for selectively modifying a substrate surface according to claim 1 or 2, wherein the monovalent organic group having more than 4 carbon atoms in the compound (A) is bonded to a nitrogen atom constituting the nitrogen-containing heterocycle, or is bonded to a nitrogen atom directly or via a divalent linking group in the nitrogen-containing heterocycle.

9. The method for selectively modifying a substrate surface according to claim 1 or 2, wherein the composition further comprises a pH adjuster. 10 . The method for selectively modifying a substrate surface according to claim 9 , wherein the pH adjuster is an organic acid, an organic base or ammonia. 11 . The method for selectively modifying a substrate surface according to claim 9 , wherein the pH adjuster is a carboxyl group-containing chain compound, a chain monoamine compound, or ammonia.

12. The method for selectively modifying the surface of a substrate according to claim 1 or 2, wherein the monovalent organic group having 4 or more carbon atoms in the compound (A) is a monovalent hydrocarbon group having 4 or more carbon atoms, a monovalent halogenated hydrocarbon group having 4 or more carbon atoms, or -R 3 -OR 6 or -CR 4 (OH)-R 6 (in, R 3 is an alkanediyl group having 1 to 3 carbon atoms, R 4 is a hydrogen atom or a methyl group, R 6 is a monovalent hydrocarbon group having 4 or more carbon atoms).

13. The selective modification method for a substrate surface according to claim 1 or 2, wherein the monovalent organic group having 4 or more carbon atoms in the compound (A) is a monovalent chain hydrocarbon group having 4 or more carbon atoms, -R 3 -OR 7 or -CR 4 (OH)-R 7 (in, R 3 is an alkanediyl group having 1 to 3 carbon atoms, R 4 is a hydrogen atom or a methyl group, R 7 is a monovalent chain hydrocarbon group having 4 or more carbon atoms).

14. The selective modification method for substrate surface according to claim 1 or 2, wherein the composition further contains 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. 15 . The method for selectively modifying a substrate surface according to claim 14 , 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. 16 . The method for selectively modifying a substrate surface according to claim 1 , wherein the content of water is 10% by mass or more relative to the total amount of the composition.

17. The method for selectively modifying the surface of a substrate according to claim 1 or 2, wherein the composition further contains a cleaning component.

18. The method for selectively modifying a substrate surface according to claim 17, wherein the cleaning component is a fluorine-containing compound.

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 nitrogen-containing heterocyclic ring and a monovalent organic group having 4 or more carbon atoms, and water.

20. A composition for selectively modifying a substrate surface, comprising: Compound (A) having a nitrogen-containing heterocyclic ring and a monovalent organic group having 4 or more carbon atoms; and water.

21. The composition according to claim 20, wherein the monovalent organic group having 4 or more carbon atoms in the compound (A) is bonded to a nitrogen atom constituting the nitrogen-containing heterocyclic ring, or is bonded to a nitrogen atom bonded to the nitrogen-containing heterocyclic ring directly or via a divalent linking group.

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

23. The composition according to claim 20 or 21, wherein the monovalent organic group having 4 or more carbon atoms in the compound (A) is a monovalent hydrocarbon group having 4 or more carbon atoms, a monovalent halogenated hydrocarbon group having 4 or more carbon atoms, or -R 3 -OR 6 or -CR 4 (OH)-R 6 (in, R 3 is an alkanediyl group having 1 to 3 carbon atoms, R 4 is a hydrogen atom or a methyl group, R 6 is a monovalent hydrocarbon group having 4 or more carbon atoms).

24. 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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