Composition for processing semiconductor device, method for manufacturing modified substrate, method for manufacturing laminate, method for manufacturing electronic device, and compound

Abstract

The present invention provides: a composition for processing a semiconductor device, the composition having excellent ALD-inhibiting properties and being capable of forming a film that is easily removed by removal processing after ALD processing; a method for manufacturing a modified substrate; a method for manufacturing a laminate; a method for manufacturing an electronic device; and a compound. This composition for processing a semiconductor device is a composition for forming a film that suppresses film formation caused by atomic layer deposition processing, and contains a compound that has at least two specific functional groups bonded or adsorbed to a substrate and has a molecular weight of at least 450 and less than 5,000, wherein the specific functional groups are each a basic functional group or an acidic functional group.

Description

Composition for treating semiconductor devices, method for manufacturing modified substrates, method for manufacturing laminates, method for manufacturing electronic devices, compound

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

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

[0003] As a method for selectively modifying a substrate as described above, Patent Document 1 discloses a substrate processing method capable of selectively forming a self-assembled monolayer as a protective film while suppressing etching of a metal film on the substrate, which method is described as "a substrate processing method for processing a substrate having, on its surface, a metal film-forming region where a metal film 1 is formed and a metal film-non-forming region where no metal film 1 is formed, the substrate processing method including: a dissolved oxygen concentration reduction step of reducing the dissolved oxygen concentration of a processing solution containing a material for forming a self-assembled monolayer 4; and a self-assembled monolayer formation step of bringing the processing solution after the dissolved oxygen concentration reduction step into contact with at least the surface of the substrate, thereby forming a self-assembled monolayer 4 on the metal film 1 in the metal film-forming region while suppressing oxidation of the metal film 1."

[0004] Japanese Patent Application Laid-Open No. 2023-142942

[0005] The coating used for selectively modifying a substrate as described above is required to suppress the amount of material deposited on the coating when subjected to atomic layer deposition (ALD) processing, i.e., to have excellent ALD inhibition properties. The present inventors formed a coating using the composition disclosed in Patent Document 1 and subjected the coating to ALD processing, and found that there is room for further improvement in ALD inhibition properties. Furthermore, it is also desired that the coating be easily removed by removal processing (particularly plasma removal processing) in the ALD processing.

[0006] Therefore, an object of the present invention is to provide a composition for semiconductor device treatment that has excellent ALD inhibitory properties and can form a coating that is easily removed in a removal treatment after ALD treatment. Another object of the present invention is to provide a method for producing a modified substrate, a method for producing a laminate, a method for producing an electronic device, and a compound.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A composition for forming a coating that inhibits film formation by atomic layer deposition, the composition for semiconductor device treatment comprising a compound having two or more specific functional groups that bond to or adsorb to a substrate and having a molecular weight of 450 or more and less than 5,000, wherein the specific functional groups are basic functional groups or acidic functional groups. [2] The composition for semiconductor device treatment according to [1], wherein the composition contains a solvent. [3] The composition for semiconductor device treatment according to [1] or [2], wherein, when the specific functional group is a basic functional group, the acid dissociation constant of a conjugate acid of the compound obtained by adding a proton to the basic functional group is 7.0 or more, and when the specific functional group is an acidic functional group, the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is 5.0 or less. [4] The composition for treating a semiconductor device according to any one of [1] to [3], wherein the specific functional group is the basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group. [5] The composition for treating a semiconductor device according to any one of [1] to [4], wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group. [6] The composition for treating a semiconductor device according to any one of [1] to [5], wherein the basic functional group is a primary amino group. [7] The composition for treating a semiconductor device according to [1], wherein the specific functional group is the acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. [8] The composition for treating a semiconductor device according to [7], wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group. [9] The composition for treating a semiconductor device according to any one of [1] to [8], wherein the compound has four or more of the specific functional groups.

[10] The composition for treating a semiconductor device according to any one of [1] to [9], wherein the compound has a molecular weight of less than 2500.

[11] The composition for treating a semiconductor device according to any one of [1] to [3], wherein the compound is a compound represented by formula (1) described below and has a molecular weight of 450 or more and less than 5000, or a compound having two or more repeating units represented by formula (2) described below and has a molecular weight of 450 or more and less than 5000.

[12] The composition for treating a semiconductor device according to any one of [1] to [3], wherein the compound is a compound represented by any one of formulas (1-1) to (1-5) described below and has a molecular weight of 450 or more and less than 5,000, or a compound having two or more repeating units represented by formula (1-6) described below and has a molecular weight of 450 or more and less than 5,000.

[13] The composition for treating a semiconductor device according to any one of [1] to

[12] , wherein the content of the compound is 5.00 mass% or less, based on the total mass of the composition for treating a semiconductor device.

[14] The composition for treating a semiconductor device according to any one of [2] to

[13] , wherein the total amount of the compound and the solvent is 99.90 mass% or more, based on the total mass of the composition for treating a semiconductor device.

[15] The composition for treating a semiconductor device according to any one of [1] to

[14] , wherein a film obtained by applying the composition for treating a semiconductor device has a water contact angle of 60 degrees or more.

[16] A method for producing a modified substrate, comprising the step of contacting a substrate with the composition for treating a semiconductor device according to any one of [1] to

[15] to form a coating on the substrate.

[17] A method for producing a laminate, comprising: Step 1: contacting a substrate having at least two surfaces, a first surface and a second surface, each made of a different material, with the composition for treating a semiconductor device according to any one of [1] to

[15] to form a first coating on the first surface; and Step 2: subjecting the substrate obtained in Step 1 to an atomic layer deposition treatment to form a second coating on the second surface.

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

[16] .

[19] A compound having two or more repeating units represented by formula (3) described below, and having a molecular weight of 450 or more and less than 5,000.

[0009] According to the present invention, there is provided a composition for semiconductor device treatment that has excellent ALD inhibitory properties and can form a coating that is easily removed in a removal treatment after the ALD treatment. The present invention also provides a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

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

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, "ppm" means "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９ ) and "ppt" stands for "parts-per-trillion (10 －１２ In this specification, when two or more types of a component are present, the "content" of the component means the total content of those two or more components.

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

[0013] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight-average molecular weight. Furthermore, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI) (Mw / Mn) of a compound are defined as polystyrene-equivalent values ​​measured by GPC (Gel Permeation Chromatography) using a GPC apparatus (HLC-8120GPC, manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: 40° C., flow rate: 1.0 mL / min, detector: differential refractive index detector).

[0014] Known methods and software can be used to calculate the acid dissociation constant (pKa), but in the present invention, unless otherwise specified, the structure is drawn using ChemDraw Professional (version 20.1.1.1) manufactured by PerkinElmer, and the value is calculated based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V20.1.1 for Solaris (1994-2007 ACD / Labs) Note that if the pKa cannot be calculated by the above method, a value determined by molecular orbital calculation is used. As a specific method using molecular orbital calculation, values ​​obtained using Gaussian 16 based on DFT (density functional theory) are adopted.

[0015] [Composition for semiconductor device treatment] The composition of the present invention (hereinafter also referred to as "the composition") will be described in detail below. The composition is a composition for forming a coating that inhibits film formation by atomic layer deposition treatment, and contains a compound (hereinafter also referred to as "the specific compound") that has two or more specific functional groups that bond to or adsorb to a substrate and has a molecular weight of 450 or more but less than 5,000, wherein the specific functional groups are basic functional groups or acidic functional groups.

[0016] Although the reason why the composition having the above-described structure can solve the problem of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The specific functional group possessed by the specific compound can bind to or adsorb to a surface of a substrate, such as a metal surface, to form a coating. Furthermore, since the specific compound has multiple specific functional groups, it can bind to or adsorb to the surface of the substrate at multiple points, thereby forming a strong coating. Furthermore, since the molecular weight of the specific compound is within a predetermined range, it can form a coating that is easily removed in a removal process after the ALD process while maintaining the effect of inhibiting film formation by the ALD process. Specifically, when the molecular weight is 450 or more, it is possible to suppress the volatilization of the specific compound during the ALD process. As described above, it is speculated that the problem of the present invention can be solved by the specific compound having the above-described structure. Hereinafter, the achievement of at least one of the effects of being more excellent in ALD inhibition and being able to more easily remove the coating (composition) in the removal treatment after the ALD treatment is also referred to as "the effect of the present invention being more excellent."

[0017] [Specific Compound] The composition contains a specific compound. As described above, the specific compound is a compound having two or more specific functional groups that bond to or adsorb to a substrate and a molecular weight of 450 or more and less than 5,000. The molecular weight of the specific compound is not particularly limited as long as it is within the above range, but the upper limit is preferably less than 4,000, more preferably less than 3,000, and even more preferably less than 2,500. The lower limit is preferably 500 or more, more preferably 1,000 or more. When the specific compound has a molecular weight distribution, the molecular weight refers to the weight average molecular weight. The specific functional group will be described in detail below.

[0018] <Specific Functional Group> The specific compound has two or more specific functional groups that bond to or adsorb to the substrate. The number of specific functional groups that the specific compound has is not particularly limited as long as it is two or more, but it is preferably three or more, and more preferably four or more. Specific examples of the bonding or adsorption between the specific functional group and the substrate include, for example, covalent bonding, coordinate bonding, ionic bonding, hydrogen bonding, acid-base interaction, van der Waals bonding, and metallic bonding. When the composition is used to form a coating on a metal surface A of a substrate composed of a material containing metal atoms, coordinate bonding or ionic bonding is preferred, and coordinate bonding is more preferred. When the composition is used to form a coating on a non-metal surface B of a substrate composed of a non-metal material, hydrogen bonding, acid-base interaction, or covalent bonding is preferred. Details of the substrate and the surface of the substrate will be described later.

[0019] The specific functional group is preferably either a group that bonds to or adsorbs onto a metal surface A of the substrate (also referred to as "specific functional group A") or a group that bonds to or adsorbs onto a non-metal surface B of the substrate (also referred to as "specific functional group B"), and is more preferably the specific functional group A. The specific functional group A is preferably a functional group that can form a coordinate bond with a metal.

[0020] As described above, the specific functional group is a basic functional group or an acidic functional group. When the specific functional group is a basic functional group, the acid dissociation constant of the conjugate acid of the specific compound obtained by adding a proton to the basic functional group is preferably 7.0 or more, more preferably 8.0 or more, and even more preferably 9.0 or more. An example of the upper limit is 30.0 or less. When the specific functional group is an acidic functional group, the acid dissociation constant of the specific compound when a proton dissociates from the acidic functional group is preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. An example of the lower limit is -5.0 or more.

[0021] Examples of the basic functional group include a nitrogen-containing group. Examples of the nitrogen-containing group include an amino group (—NR Ｎ ２ ), quaternary ammonium group (-N ＋ R Ｎ ３ ), a hydrazine group, a guanidine group, and a nitrogen-containing heterocyclic group. Ｎ each independently represents a hydrogen atom or an organic group (a group containing at least one carbon atom). Examples of the nitrogen-containing heterocyclic group include nitrogen-containing aromatic heterocyclic groups such as a pyrrole group, an imidazole group, a pyrazole group, an oxazolyl group, a triazole group, a benzimidazole group, a benztriazole group, a pyridyl group, and a triazine group, and nitrogen-containing aliphatic heterocyclic groups such as a pyrrolidinyl group, a piperidinyl group, and a piperazinyl group, and aromatic heterocyclic groups having 5 or 6 ring atoms such as an imidazole group and a pyridyl group are preferred.

[0022] The basic functional group is preferably an amino group, a hydrazine group, or a guanidine group, more preferably a primary amino group, a secondary amino group, or a tertiary amino group, and even more preferably a primary amino group. When the amino group is a secondary amino group or a tertiary amino group, the number of carbon atoms contained in the secondary amino group or the tertiary amino group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0023] The acidic functional group may be a phosphonic acid group (-PO３ H ２ ), phosphinic acid group (-PO ２ H ２ ), phosphate group (-PO ４ H ２ ), sulfo group (—SO ３ Examples of the alkyl group include aryl, aryl groups (preferably aryl, ...

[0024] <Hydrophobic Group> The specific compound preferably further contains a hydrophobic group. Examples of the hydrophobic group include an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, and a group formed by combining these. The valence of the hydrophobic group is not particularly limited, and may be, for example, monovalent to trivalent. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms in the linear or branched aliphatic hydrocarbon group is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 18. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 6 to 30, more preferably 7 to 30, and even more preferably 8 to 20.

[0025] Examples of substituents that the aliphatic hydrocarbon group may have include halogen atoms. The aliphatic hydrocarbon group may also have an oxygen atom between carbon atoms. That is, the aliphatic hydrocarbon group may have an etheric oxygen atom between carbon atoms.

[0026] The aromatic ring constituting the aromatic group may be either monocyclic or polycyclic. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The aromatic group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms. Examples of substituents that the aromatic group may have include the aliphatic hydrocarbon groups described above. Specific and preferred embodiments of the aliphatic hydrocarbon group are as described above. As the aliphatic hydrocarbon group that the aromatic group may have, an aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferred, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is more preferred, and an alkyl group having 1 to 20 carbon atoms is even more preferred. The number of substituents that the aromatic group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0027] Examples of groups formed by combining an optionally substituted aliphatic hydrocarbon group and an optionally substituted aromatic group include a divalent aliphatic hydrocarbon group-aromatic group, or an aromatic group having an aliphatic hydrocarbon group as a substituent. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but linear or branched is preferred. Examples of divalent aliphatic hydrocarbon groups include alkylene groups, alkenylene groups, and alkynylene groups, with alkylene groups being preferred. The divalent aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Specific examples and preferred embodiments of the aromatic group are as described above. Specific examples and preferred embodiments of the aliphatic hydrocarbon group as a substituent are also as described above.

[0028] The specific compound is preferably a compound represented by formula (1) and having a molecular weight of 450 or more and less than 5,000, or a compound having two or more repeating units represented by formula (2) and having a molecular weight of 450 or more and less than 5,000. It is more preferably a compound represented by any of formulas (1-1) to (1-5) and having a molecular weight of 450 or more and less than 5,000, or a compound having two or more repeating units represented by formula (1-6) and having a molecular weight of 450 or more and less than 5,000. The compounds represented by formula (1), the compounds having two or more repeating units represented by formula (2), the compounds represented by formulas (1-1) to (1-5), and the compounds having two or more repeating units represented by formula (1-6) all have a molecular weight of 450 or more and less than 5,000, and the preferred ranges of these molecular weights are the same as the preferred ranges of the molecular weight of the specific compound described above. Formulas (1) and (2) are described in detail below.

[0029]

[0030] In formula (1), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. １ represents a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic hydrocarbon group, a divalent aromatic group, —O— (an etheric oxygen atom), —CO— (a carbonyl group), and —NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) and groups formed by combining two or more of these groups. Examples of linking groups formed by combining two or more of the above groups include -O-divalent aliphatic hydrocarbon group-, -divalent aromatic ring group-O-divalent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aromatic ring group-, -CONH-divalent aromatic ring group-, -COO-divalent aliphatic hydrocarbon group-, and -CONH-divalent aliphatic hydrocarbon group-.

[0031] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, with an alkylene group being preferred. The divalent aliphatic hydrocarbon group preferably has 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 18 carbon atoms.

[0032] The divalent aromatic group may be either a divalent aromatic hydrocarbon group (arylene group) or a divalent aromatic heterocyclic group (heteroarylene group), with an arylene group being preferred. The aromatic ring constituting the divalent aromatic group may be either a monocyclic or polycyclic ring. The number of carbon atoms in the divalent aromatic group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0033] The divalent aliphatic hydrocarbon group and the divalent aromatic group may have a substituent. Examples of the substituent that the divalent aliphatic hydrocarbon group may have include a halogen atom. Examples of the substituent that the divalent aromatic group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

[0034] In the above formula (1), M １ represents an n-valent linking group. Furthermore, n represents an integer of 2 or more. n is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4. Furthermore, examples of the n-valent linking group include an n-valent aliphatic hydrocarbon group, an n-valent aromatic group, -O- (ether oxygen atom), -CO- (carbonyl group), and -NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; -N< (nitrogen atom), and groups formed by combining two or more of these groups.

[0035] The n-valent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, with an alkylene group being preferred. The n-valent aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.

[0036] The n-valent aromatic group may be either an n-valent aromatic hydrocarbon group or a divalent aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The aromatic ring constituting the n-valent aromatic group may be either a monocyclic or polycyclic ring. The number of carbon atoms in the n-valent aromatic group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0037] The n-valent aliphatic hydrocarbon group and the n-valent aromatic group may have a substituent. Examples of the substituent that the n-valent aliphatic hydrocarbon group may have include a halogen atom. Examples of the substituent that the n-valent aromatic group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

[0038] In the above formula (2), X represents a primary amino group, a tertiary amino group, a hydrazine group, an imidazole group, a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. ２ represents a trivalent linking group. The trivalent linking group includes the above-mentioned M １ Among the examples of n-valent linking groups represented by the formula (2), a linking group where n=3 is exemplified. Among them, a trivalent aliphatic hydrocarbon group or a group formed by combining a trivalent aromatic group and a divalent aliphatic hydrocarbon group is preferred. ２ represents a single bond or an (m+1)-valent linking group, and m represents an integer of 1 or more. ２ is a single bond, m represents 1. m is preferably 1 to 3, and more preferably 1 or 2. Furthermore, examples of the (m+1)-valent linking group include an (m+1)-valent aliphatic hydrocarbon group which may contain an oxygen atom, or an (m+1)-valent aromatic group.

[0039] When the specific compound has a repeating unit represented by formula (2), the content of the repeating unit represented by formula (2) is preferably 50 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and particularly preferably 95 mol% or more, based on the total repeating units of the specific compound. There is no particular upper limit, but it may be, for example, 100 mol% or less.

[0040] Next, the formulas (1-1) to (1-6) will be described in detail.

[0041]

[0042] In formula (1-1), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ３ represents an alkylene group having 5 or more carbon atoms which may contain one or more divalent linking groups selected from —O— and —CO—. ３ As L, -O-alkylene group having 5 to 30 carbon atoms- is preferred, -O-alkylene group having 6 to 20 carbon atoms- is more preferred, and -O-alkylene group having 6 to 20 carbon atoms- is even more preferred. ３ It is also preferable that M is a polyalkyleneoxy group having 5 or more carbon atoms (preferably a polyethyleneoxy group). ３ represents a p-valent aromatic hydrocarbon group which may have a substituent. The number of carbon atoms in the p-valent aromatic hydrocarbon group which may have a substituent is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10. The aromatic hydrocarbon constituting the aromatic hydrocarbon group is preferably a benzene ring, a naphthalene ring, or a triptycene ring. Examples of the substituent that the p-valent aromatic hydrocarbon group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. p represents an integer of 2 or more. p is preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4.

[0043] In formula (1-2), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ４represents a single bond or an alkylene group having 2 or less carbon atoms. R represents an alkyl group having 5 or more carbon atoms, which may have a substituent and may contain -O-, -CONH-, -COO- or -C≡C-. -O-, -CONH-, -COO- and -C≡C- may be contained between carbon atoms of the alkyl group or may be contained at the terminal of the alkyl group, and are preferably contained at the terminal of the alkyl group. The number of carbon atoms in the alkyl group is preferably 5 to 30, more preferably 6 to 20, and even more preferably 6 to 18. Examples of the substituent that the alkyl group may have include a halogen atom. R １ As M, an alkyl group having 5 or more carbon atoms which may have a substituent, an —O-alkyl group having 5 or more carbon atoms which may have a substituent, a —CONH-alkyl group having 5 or more carbon atoms which may have a substituent, a —COO-alkyl group having 5 or more carbon atoms which may have a substituent, or a —C≡C-alkyl group having 5 or more carbon atoms which may have a substituent is preferred. ４ represents a (q+r)-valent linking group. The (q+r)-valent linking group includes the above-mentioned M １ Among the examples of n-valent linking groups represented by the formula (I), examples include linking groups where n = q + r. Among them, trivalent linking groups or tetravalent linking groups are preferred as the (q + r)-valent linking group, in terms of more excellent effects of the present invention. As the trivalent linking group and tetravalent linking group, a trivalent aromatic group, a tetravalent aromatic group, >N-divalent aromatic group-, >N-alkylene group-O-divalent aromatic group-, or -N< (nitrogen atom) is preferred. q represents an integer of 2 or more. q is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 to 3. r represents 1 or 2. q + r is preferably 3 or 4.

[0044] In formula (1-3), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ５represents a (k+1)-valent hydrocarbon group having 5 or more carbon atoms, which may contain one or more divalent linking groups selected from -O- and -CO-, and which may have at least one of a carboxy group, a hydroxy group, and a mercapto group. Examples of hydrocarbon groups include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these, with aliphatic hydrocarbon groups being preferred. The aliphatic hydrocarbon group may be linear, branched, or cyclic, with linear or branched being preferred. The aliphatic hydrocarbon group preferably has 5 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 18 carbon atoms. The aromatic hydrocarbon group may be either monocyclic or polycyclic. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms. Ar represents an aromatic ring which may have a substituent. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. The number of carbon atoms in the aromatic ring is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 15. Examples of substituents that the aromatic ring may have include an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and a halogen atom. Of these, a benzene ring that may have a substituent is preferred as the aromatic ring. w represents an integer of 0 to 2, preferably 1 or 2. k represents an integer of 1 or more, preferably 1 or 2.

[0045] In formula (1-4), X represents a primary amino group, a tertiary amino group, a hydrazine group, an imidazole group, a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. Ar represents an aromatic ring which may have a substituent. Specific examples and preferred embodiments of the aromatic ring which may have a substituent are the same as the specific examples and preferred embodiments of the aromatic ring which may have a substituent represented by Ar in formula (1-3). L ２ represents a single bond or an (m+1)-valent linking group. The (m+1)-valent linking group includes the above-mentioned M １ Among the examples of n-valent linking groups represented by the formula (I), a linking group where n=m+1 can be mentioned. As the (m+1)-valent linking group, a divalent linking group or a trivalent linking group is preferred. As the divalent linking group, L １Specific examples and preferred embodiments of the divalent linking group represented by the formula (I) include, among which an alkylene group which may contain -O-, -CONH-, or -COO- is preferred. -O-, -CONH-, or -COO- may be contained between carbon atoms of the alkylene group or may be contained at the terminal of the alkylene group, and it is preferred that it is contained at the terminal of the alkylene group. The number of carbon atoms in the alkylene group is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 18. Among these, -O-alkylene group- or polyalkyleneoxy group is preferred as the divalent linking group. The number of carbon atoms contained in the polyalkyleneoxy group is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 18. As the trivalent linking group, -O-CO-trivalent aromatic group< is preferred. m represents an integer of 1 or more. However, L ２ When m is a single bond, m represents 1. m is preferably 1 to 6, more preferably 1 or 2, and still more preferably 1. v represents an integer of 4 or more, preferably 4 to 10, more preferably 4 to 6, and still more preferably 4.

[0046] In formula (1-5), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ６ represents a single bond or a divalent linking group. １ Specific examples and preferred embodiments of the divalent linking group represented by the formula (I) include an alkylene group which may contain -O-, -CONH-, or -COO-, and -O-, -CONH-, or -COO- may be contained between carbon atoms of the alkylene group, or may be contained at the terminal of the alkylene group, and it is preferable that it is contained at the terminal of the alkylene group. The number of carbon atoms in the alkylene group is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 18. Of the divalent linking groups, -O-alkylene group- or a polyalkyleneoxy group is particularly preferable. The number of carbon atoms contained in the polyalkyleneoxy group is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 18.

[0047] In the above formula (1-5), Y represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. Examples of the substituent which the aliphatic hydrocarbon group may have include a halogen atom. The linear or branched aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10, and even more preferably 1 to 6. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 15, and even more preferably 3 to 10.

[0048] In formula (1-6), L ７ represents a single bond or a divalent linking group. １ Specific examples and preferred embodiments of the divalent linking group represented by X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. R represents a hydrogen atom or an alkyl group. The alkyl group represented by R preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.

[0049] Among these, the specific compound is preferably a compound having two or more repeating units represented by formula (3) and having a molecular weight of 450 or more and less than 5000. The molecular weight of the compound represented by formula (3) is 450 or more and less than 5000, and the preferred range of this molecular weight is the same as the preferred range of the molecular weight of the specific compound described above.

[0050]

[0051] In formula (3), L ａ represents a divalent linking group having 5 or more atoms excluding hydrogen atoms. The "number of atoms excluding hydrogen atoms" represents the number of atoms excluding hydrogen atoms contained in the divalent linking group. For example, when the divalent linking group is -CH ２ -CH ２In the case of -, the number of atoms is 2 (two carbon atoms). The number of atoms excluding hydrogen atoms contained in the divalent linking group is 5 or more, and from the viewpoint of more excellent effects of the present invention, it is preferably 5 to 40, and more preferably 8 to 18. As the divalent linking group, L in formula (1) １ Among the groups exemplified as divalent linking groups represented by the formula (I), those having 5 or more atoms can be mentioned, and among these, divalent aliphatic hydrocarbon groups having 5 or more atoms are preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 5 to 30, more preferably 6 to 20, and even more preferably 6 to 18. R ａ represents an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a hydrogen atom. Specific examples and preferred embodiments of the aliphatic hydrocarbon group which may have a substituent and the aromatic group which may have a substituent are the same as the specific examples and preferred embodiments of the aliphatic hydrocarbon group which may have a substituent and the aromatic group which may have a substituent given as examples of the hydrophobic group.

[0052] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 10.00% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less, based on the total mass of the composition. The lower limit is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. The total amount of the specific compound and the solvent described below is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 99.90% by mass or more, based on the total mass of the composition. The upper limit is 100% by mass or less, and preferably 99.9999% by mass or less.

[0053] [Solvent] The present composition preferably contains a solvent. Examples of the solvent include water and organic solvents, with organic solvents being preferred. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and hydrocarbon-based solvents.

[0054] Examples of alcohol-based solvents include monoalcohol-based solvents, polyol-based solvents, and glycol monoether-based solvents. Examples of monoalcohol-based solvents include aliphatic monoalcohol-based solvents having 1 to 18 carbon atoms, such as methanol, ethanol (EtOH), 1-propanol, 2-propanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, isopentyl alcohol, and 4-methyl-2-pentanol (methyl isobutyl carbinol); alicyclic monoalcohol-based solvents having 3 to 18 carbon atoms, such as cyclohexanol; aromatic monoalcohol-based solvents, such as benzyl alcohol; and ketone monoalcohol-based solvents, such as diacetone alcohol. Examples of polyol-based solvents include glycol-based solvents having 2 to 18 carbon atoms, such as ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol. Examples of glycol monoether solvents include glycol monoether solvents having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.The alcohol solvent preferably has 1 to 19 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms.

[0055] Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dihexyl ether, and cyclohexyl methyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; anisole; and diphenyl ether.

[0056] Examples of ester solvents include glycol ester solvents, monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate, lactone solvents such as γ-butyrolactone (GBL) and δ-valerolactone, and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. Examples of glycol ester solvents include glycol dicarboxylate solvents having 6 to 22 carbon atoms such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, tetraethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, and methoxybutyl acetate, as well as propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the ester-based solvent include glycol monoether carboxylate solvents having 5 to 21 carbon atoms, such as ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, tetraethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate. The number of carbon atoms in the ester-based solvent is preferably 3 to 22, and more preferably 4 to 12.

[0057] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane and n-hexane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbon solvents such as toluene and xylene.

[0058] Examples of ketone solvents include chain ketone solvents such as methyl isobutyl ketone, acetone, methyl ethyl ketone, diethyl ketone, methyl-n-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-ketone, diisobutyl ketone, and trimethylnonane; cyclic ketone solvents such as cyclohexanone, cyclopentanone, cycloheptanone, and methylcyclohexanone; and acetophenone.

[0059] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0060] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0061] The solvent is preferably an alcohol solvent, an ether solvent, an ester solvent, or a ketone solvent, more preferably an aliphatic monoalcohol solvent, a glycol monoether solvent, a glycol ester solvent, a monocarboxylic acid ester solvent, an ether solvent, or a lactone solvent, and even more preferably a glycol monoether solvent or a glycol ester solvent. Among these, the solvent preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, methyl isobutyl carbinol, EtOH, and γ-butyrolactone, and more preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, and methyl isobutyl carbinol.

[0062] The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 97.00% by mass or more, based on the total mass of the composition. The upper limit is preferably less than 100% by mass, more preferably 99.999% by mass or less, and even more preferably 99.9% by mass or less. The content of one solvent in the composition is preferably 90% by mass or more, more preferably 99% by mass or more, and even more preferably 99.9% by mass or more, based on the total amount of all solvents. The upper limit is not particularly limited and may be 100% by mass.

[0063] [Other Components] The composition may contain other components in addition to the specific compound and the solvent. Examples of the other components include a polymerization inhibitor. Examples of the polymerization inhibitor include a phenolic compound, a quinone compound, a free radical compound, an amine compound, and a phosphine compound.

[0064] [Method for producing the present composition] The method for producing the present composition is not particularly limited, and the composition can be produced, for example, by mixing the above-mentioned components. The order or timing of mixing the components is not particularly limited, and the composition can be produced, for example, by adding the specific compound to a stirrer such as a mixer containing a purified solvent and then thoroughly stirring. In order to achieve better effects of the present invention, it is preferable that the raw materials of the present composition (e.g., the solvent and the specific compound) have been subjected to a purification treatment.

[0065] The production process of the present composition may include a step selected from the group consisting of a distillation step of distilling raw materials, a dehydration step of dehydrating the present composition, a metal removal step of removing metal components from the present composition, a filtration step of filtering the present composition, and a static elimination step of destaticizing the present composition.

[0066] This composition can be filled into a known container for storage, transportation, and use. As a container, a container with a high degree of cleanliness within the container for semiconductor applications and which suppresses the elution of impurities from the inner wall of the container's storage section into each liquid is preferred. Examples of such containers include various containers commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these. Furthermore, the containers exemplified in paragraphs

[0121] to

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

[0067] [Uses of the Composition] The composition is a composition for semiconductor device processing, and is preferably used for modifying a substrate in the manufacturing process of a semiconductor device. In the above process, the composition is used to form a coating that inhibits film formation by atomic layer deposition, thereby obtaining a modified substrate having a coating formed on the substrate surface. The composition is also preferably used for manufacturing a laminate in which a material is deposited in areas where no coating has been formed by ALD processing of the modified substrate. Methods for manufacturing a modified substrate and a laminate will be described in detail below.

[0068] <Substrate> The substrate is not particularly limited, but preferably has at least one of a metal surface A made of a material containing metal atoms and a non-metal surface B made of a non-metal material, and more preferably has a metal surface A.

[0069] The metal atoms contained in the metal surface A are not particularly limited, but are preferably tungsten atoms, copper atoms, ruthenium atoms, cobalt atoms, titanium atoms, tantalum atoms, molybdenum atoms, germanium atoms, zirconium atoms, aluminum atoms, tin atoms, nickel atoms, palladium atoms, indium atoms, zinc atoms, gold atoms, silver atoms, or platinum atoms, more preferably tungsten atoms, ruthenium atoms, molybdenum atoms, copper atoms, or cobalt atoms, and even more preferably tungsten atoms or copper atoms. The form of the metal atoms in the metal surface A is not particularly limited, but includes elemental metals, alloys, nitrides, oxides, and silicides, with elemental metals or alloys being preferred. Examples of alloys include alloys containing two or more of the metal atoms contained in the metal surface A described above. The method for forming the metal surface A is not particularly limited, and known methods can be used. For example, CVD, plating, and physical vapor deposition methods can be used.

[0070] Examples of non-metallic materials constituting the non-metallic surface B include insulators, such as non-metallic elements such as silicon and carbon, non-metallic oxides such as silicon oxide, non-metallic nitrides such as silicon nitride, non-metallic oxynitrides such as silicon oxynitride, and organic materials. The material constituting the non-metallic surface B is preferably a non-metallic material containing silicon atoms, more preferably silicon or silicon oxide. Specific examples of silicon oxide include SiO ｙ (wherein y is preferably 0.5 to 2.0, more preferably 1.0 to 2.0), and SiO ｚ C ｗ (wherein z is preferably 0.5 to 2.0, more preferably 1.0 to 2.0, and w is preferably 0.5 to 2.0, more preferably 1.0 to 2.0). ｙ and SiO ｚ C ｗ The material represented by the composition may further contain hydrogen. ｚ C ｗ Examples of the material represented by the composition include Si(OC ２ H ５ ) ４(tetraethyl orthosilicate, TEOS). Silicon oxides include SiO ２ A material represented by the formula (silicon dioxide) or TEOS is preferred.

[0071] The method for forming the nonmetallic surface B is not particularly limited, and examples thereof include CVD, physical vapor deposition, plasma irradiation, and application of a precursor compound. It is also preferable that the nonmetallic surface B is a surface treatment performed on a region made of silicon or silicon oxide. Examples of the treatment include contact with a treatment liquid such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride water), plasma treatment, corona treatment, and ozone treatment.

[0072] It is also preferable that the substrate has at least two types of surfaces, a first surface and a second surface, which are made of different materials. The first surface is a surface that interacts with a specific functional group of the specific compound. The second surface may be made of a material different from the first surface, but is preferably a surface on which a coating does not form when it comes into contact with the composition. In particular, it is preferable that at least one of the first surface and the second surface is a metal surface A or a non-metal surface B, and it is more preferable that at least one of the first surface and the second surface is a metal surface A.

[0073] A preferred embodiment of the substrate is embodiment 1, in which the first surface is a metal surface A. In embodiment 1, the specific functional group possessed by the specific compound is the specific functional group A described above. In embodiment 1, the metal atoms contained in the metal surface A, which is the first surface, are preferably contained in the form of a metal element, an alloy, a conductive metal nitride, or a metal silicide, and more preferably a metal element or an alloy. Examples of the metal element and alloy include the metal elements and alloys thereof exemplified as the metals contained in the metal surface A. Examples of the conductive metal nitride include tantalum nitride, titanium nitride, iron nitride, and aluminum nitride. Examples of the metal silicide include iron silicide, molybdenum silicide, and tungsten silicide.

[0074] In Aspect 1, the second surface is preferably a metal surface A or a non-metal surface B different from the first surface, more preferably a non-metal surface B. In Aspect 1, the metal atoms contained in the metal surface A constituting the second surface are preferably in the form of a metal oxide, a metal nitride, or a metal oxynitride, more preferably a metal oxide. Examples of metal oxides include aluminum oxide, tantalum oxide, iron oxide, and copper oxide.

[0075] A preferred embodiment of the substrate also includes embodiment 2, in which the first surface is a non-metallic surface B. In embodiment 2, the specific functional group possessed by the specific compound is the above-described specific functional group B. In embodiment 2, the second surface is preferably a metallic surface A. In embodiment 2, the metal atoms contained in the second surface, that is, the metallic surface A, are preferably contained in the form of an elemental metal, an alloy, a conductive metal nitride, or a metal silicide, and more preferably in the form of an elemental metal or an alloy.

[0076] The shape of the first surface and the second surface is not particularly limited, and examples thereof include a planar shape, a dotted shape, and a striped shape.

[0077] The shape of the substrate is not particularly limited, and any shape of substrate generally used as a semiconductor substrate can be used. The substrate may be a substrate having the above-described surface, and may be a single layer or a multilayer structure.

[0078] <Coating> The coating formed on a substrate using the present composition is a coating containing components other than the solvent contained in the composition (e.g., a specific compound). The coating preferably functions as a mask when depositing a material in an ALD process. That is, when an ALD process is performed on a modified substrate on which a coating using the present composition has been formed on a specific region, the material preferably does not deposit in the region where the coating has been formed, but deposits in the region where the coating has not been formed, forming a film (hereinafter also referred to as an "ALD film"). This results in a laminate in which an ALD film is selectively formed in regions other than the region where the coating has been formed.

[0079] The coating also preferably functions as a mask when forming a metal-containing film by chemical vapor deposition (CVD) other than ALD. That is, in a CVD process, deposition of a film by CVD (hereinafter also referred to as a "CVD film") can be suppressed in the region where the coating is formed, and a CVD film can be deposited in the region where the coating is not formed. This results in a laminate in which a CVD film is selectively formed in the region other than the region where the coating is formed. Examples of CVD other than ALD that can be preferably applied to the modified substrate include known techniques such as thermal CVD and plasma CVD. As raw materials for the CVD film used in the CVD process, raw materials for the ALD film described below can be used.

[0080] The thickness of the coating is preferably 0.1 to 100.0 nm, more preferably 0.5 to 50.0 nm, and even more preferably 3.0 to 30.0 nm.

[0081] In order to obtain superior effects of the present invention, the water contact angle of the coating is preferably 60° or more, more preferably 80° or more, and even more preferably 90° or more. There is no particular upper limit, and it is often 120° or less. The water contact angle is the average value of three measurements of the contact angle 500 milliseconds after a water droplet contacts the surface of the measurement object using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.).

[0082] [Method for Producing a Modified Substrate] The method for producing a modified substrate of the present invention includes a step of contacting a substrate with the present composition to form a coating on the substrate. This results in a modified substrate having a coating formed on the substrate. The method for producing a modified substrate of the present invention can be suitably used, for example, in the production of electronic devices (semiconductor devices). The method for contacting a substrate with the present composition is not particularly limited, and known methods can be used. Examples include a method of applying (e.g., spin coating) or spraying the present composition onto a substrate, and a method of immersing a substrate in the present composition. When immersing a substrate in the present composition, the present composition may be subjected to convection. The temperature of the present composition when contacting the substrate with the present composition is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. The time for contacting the substrate with the present composition is also not particularly limited, but is preferably 30 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and even more preferably 5 to 15 minutes.

[0083] After contacting the substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and known methods can be used, such as an oven or a hot plate. The heating temperature is preferably 50 to 400°C, more preferably 100 to 350°C, even more preferably 130 to 300°C, and particularly preferably 150 to 250°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 1 to 30 minutes, and even more preferably 3 to 10 minutes.

[0084] After contacting the substrate with the composition, it is also preferable to perform a rinsing treatment. The rinsing treatment can remove at least one of the composition and impurities adhering to regions on the substrate other than the desired region (e.g., the region that interacts with the specific functional group contained in the specific compound) from the substrate. The rinsing method is not particularly limited, and examples include a method of contacting the substrate with a rinsing liquid. As the contacting method, the same method as the method of contacting the substrate with the composition can be used. The temperature of the rinsing liquid during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. As the rinsing liquid, a known organic solvent can be used, such as the alcohol-based solvents, ether-based solvents, and ester-based solvents described above.

[0085] [Method for Producing Laminate] The method for producing a laminate of the present invention includes step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each made of a different material (hereinafter also referred to as a "specific substrate") with the present composition to form a first coating on the first surface, and step 2 of subjecting the substrate obtained in step 1 to an ALD treatment to form a second coating on the second surface. This results in a laminate having a second coating (ALD film) on the second surface.

[0086] [Step 1: Method for producing modified substrate] Step 1 is a step of bringing a specific substrate into contact with the present composition to form a first coating on the first surface. Step 1 results in a modified substrate 1 in which a first coating is formed on the first surface of the specific substrate. The first coating is a coating containing the specific compound contained in the present composition. There are no particular limitations on the method for bringing the specific substrate into contact with the present composition, and the method of bringing the present composition into contact with the substrate in the above-mentioned method for producing a modified substrate can be used.

[0087] After contacting the specific substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and the heating methods in the above-mentioned method for producing a modified substrate can be used.

[0088] It is also preferable to perform a rinse treatment on the modified substrate 1 having the first coating formed on the first surface. The rinse treatment can remove at least one of the composition and impurities adhering to regions other than the first surface (e.g., the second surface) of the specific substrate from the specific substrate. The rinse method can be the same as the rinse method in the method for producing a modified substrate described above.

[0089] [Step 2: ALD Treatment] Step 2 is a step of subjecting the modified substrate 1 obtained in step 1 to ALD treatment to form a second coating on the second surface. Step 2 results in a laminate 1 having a first coating formed on the first surface and a second coating formed on the second surface. The second coating is a film formed by ALD treatment (ALD film). Note that the modified substrate 1 may be any substrate having a first coating formed on the first surface of the specific substrate in step 1, and may be subjected to the above-mentioned heating treatment, rinsing treatment, etc. after step 1.

[0090] The ALD process method is not particularly limited, and known methods can be used. For example, a method can be used in which a precursor gas serving as a raw material for the ALD film is supplied to the surface of the modified substrate 1, and then the raw material is decomposed and / or chemically reacted with an oxidizing agent or a reducing agent, etc., to deposit the material, thereby forming an ALD film. The precursor is not particularly limited, and known precursors can be used depending on the type of ALD film to be formed, such as organometallic compounds. Examples of precursors that can be used include alumina, tantalum nitride, and titanium nitride. The oxidizing agent is not particularly limited, and known oxidizing agents used in ALD processes can be used, such as water, oxygen, and ozone.

[0091] The materials constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, etc. The materials of the formed ALD film are not particularly limited, and include metals, metal oxides, and metal nitrides. Examples of metals include aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, lanthanum, cerium, hafnium, tantalum, tungsten, platinum, and bismuth. Examples of metal oxides include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide. Examples of metal nitrides include titanium nitride and tantalum nitride. In the ALD process, a treatment for modifying the surface of the region where the first coating is not formed may be performed.

[0092] After the ALD process, the thickness of the material deposited on the first coating is preferably as thin as possible, preferably 4.0 nm or less, more preferably 2.0 nm or less, and even more preferably 1.0 nm or less. The lower limit is 0 nm. The ratio of the thickness of the material deposited on the region where the first coating is formed to the thickness of the second coating is preferably 0.75 or less, more preferably 0.50 or less, and even more preferably 0.25 or less. The lower limit of the ratio is 0 or more.

[0093] [Step 3: Removal of Coating (Removal Treatment)] The method for producing a laminate of the present invention may include, after step 2, step 3 of removing the first coating formed on the first surface in step 1. Step 3 results in a laminate 2 that has no coating on the first surface and has the second coating on the second surface.

[0094] The method for removing the first coating is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof. As dry etching, known methods can be used, such as chemical dry etching, which supplies reactive ions or reactive radicals to the surface of the laminate 1, and physical dry etching, such as sputter etching and ion beam etching. Among these, removal by plasma treatment is preferred. As wet etching, a method in which an etching solution is supplied to the laminate 1 can be used. Examples of the etching solution include etching solutions containing oxidizing agents such as ozone and hydrofluoric acid, and etching solutions containing an organic solvent. Examples of the organic solvent include the organic solvents contained in the above-mentioned chemical solutions, and alcohol-based solvents, ester-based solvents, ketone-based solvents, and hydrocarbon-based solvents are preferred.

[0095] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. The preparation, filling, storage, etc. of the composition were all carried out in a clean room meeting ISO Class 2 or lower. Furthermore, the containers used for the preparation, filling, storage, etc. of the composition were washed with the solvent used in the preparation or the prepared composition before use.

[0096] [Synthesis of Specific Compound E-1] Specific compound E-1 was synthesized as follows.

[0097]

[0098] [Synthesis of Intermediate E-1A] Under a nitrogen flow (0.1 L / min), 12-bromo-1-dodecanol (50.0 g, 0.19 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), DMF (dimethylformamide, 250 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and potassium phthalimide (38.4 g, 0.21 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a three-neck flask, and the resulting mixture was stirred at 50°C for 3 hours. The resulting reaction solution was cooled to 25°C, and insoluble matter was removed by filtration. The filtered product was washed with DMF (50 mL) to obtain filtrate A. Distilled water (900 mL) was added to a beaker and stirred at 25°C, and the filtrate A was added dropwise. The resulting crystals were collected by filtration, washed twice with distilled water (200 mL), and then dried with air at 40°C for 24 hours to obtain intermediate E-1A.

[0099] [Synthesis of Intermediate E-1B] Under a nitrogen flow (50 mL / min), intermediate E-1A (18.4 g, 55.5 mmol), triphenylphosphine (14.6 g, 55.5 mmol, FUJIFILM Wako Pure Chemical Industries, Ltd.), 4-tert-butylcalix[4]arene (3.0 g, 4.6 mmol, Tokyo Chemical Industry Co., Ltd.), and tetrahydrofuran (THF, 130 mL, FUJIFILM Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask, and the resulting reaction solution was cooled to 0°C. Next, a solution was prepared separately by dissolving bis(2-methoxyethyl) azodicarboxylate (DMEAD®, 13.0 g, 55.5 mmol, FUJIFILM Wako Pure Chemical Industries, Ltd.) in THF (130 mL). The solution was added dropwise to the reaction solution obtained above over 2 hours while maintaining the internal temperature of the reaction solution at 5°C or below. After completion of the dropwise addition, the reaction solution was stirred at 25 ° C. for 1 hour. Next, under a reduced pressure of 40 ° C. / 10 hPa, the solvent was distilled off from the reaction solution, and after distillation, ethyl acetate (500 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1 M aqueous sodium hydroxide solution (250 mL) were added, and the resulting solution was transferred to a separatory funnel and stirred. Thereafter, the solution was allowed to stand, the lower phase (aqueous phase) was removed, and distilled water (250 mL) was added to the upper phase (organic phase) and stirred. Further, the solution was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered, and then the solvent was distilled off from the resulting organic phase under a reduced pressure of 40 ° C. / 10 hPa. The obtained crude product was purified by silica gel column chromatography to obtain intermediate E-1B.

[0100] [Synthesis of Specific Compound E-1] Under a nitrogen flow (0.1 L / min), intermediate E-1B (5.5 g, 4.3 mmol) and ethanol (55 mL, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a three-necked flask and stirred. Hydrazine monohydrate (1.7 g, 34.5 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to the resulting mixture and heated to reflux for 1 hour. Thereafter, the resulting reaction solution was cooled to 0 ° C, and the precipitate was removed by filtration. The solvent was distilled off from the filtrate under a reduced pressure of 40 ° C / 10 hPa, and tert-butyl methyl ether (250 mL, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and 1 M aqueous sodium hydroxide solution (150 mL) were added to the resulting crude product, and the resulting solution was transferred to a separatory funnel and stirred. Thereafter, the solution was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. The obtained organic phase was concentrated to obtain specific compound E-1. １ The H-NMR (Nuclear Magnetic Resonance) data is shown below. １ H-NMR (400MHz, THF-d8): δ (ppm) = 7.03 (s, 2H), 4.33 (d, J = 12.5Hz, 1H), 3.98 (t, J = 6.6Hz, 2H), 3.34 (d, J = 1 2.5Hz, 1H), 2.59 (t, J=6.4Hz, 2H), 2.02-2.19 (m, 2H), 1.72-1.85 (m, 2H), 1.10-1.60 (m, 16H), 1.09 (s, 9H).

[0101] [Synthesis of Specific Compound E-8] Specific Compound E-8 was synthesized in the same manner as in the above [Synthesis of Specific Compound E-1], except that the raw material 4-tert-butylcalix[4]arene was replaced with 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol. １ The H-NMR data is shown below. １ H-NMR (400MHz, CDCl ３): δ (ppm) = 6.95 (dd, J = 1.6 Hz, J = 8.4 Hz, 2H), 6.85 (d, J = 1.6 Hz, 2H), 6.75 (d, J = 8.4Hz, 2H), 6.68 (s, 2H), 3.96 (s, 4H), 3.92 (t, J = 6.4Hz, 4 H), 3.72 (t, J=6.4Hz, 2H), 2.67 (t, J=7.2Hz, 6H), 2.22 (s, 6H), 2.13 (s, 3H), 1.64-1.80 (m, 6H), 1.36-1.50 (m, 18H), 1.22-1.34 (m, 42H).

[0102] [Synthesis of Specific Compound E-19] Specific Compound E-19 was synthesized in the same manner as in the above [Synthesis of Specific Compound E-1], except that the raw material 4-tert-butylcalix[4]arene was changed to 2,2'-methylenebis(4-methylphenol). １ The H-NMR data is shown below. １ H-NMR (400MHz, THF-d8): δ (ppm) = 6.82-6.90 (m, 4H), 6.73 (d, J = 8.0Hz, 2H), 3.91 (t, J = 6.4Hz, 4H), 3.86 (s, 2H), 2.59 (t, J=6.4Hz, 4H), 2.16 (s, 6H), 1.70-1.80 (m, 4H), 1.40-1.50 (m, 4H), 1.24-1.40 (m, 32H).

[0103] Specific compounds other than the above-mentioned specific compounds E-1, E-8, and E-19 were synthesized in accordance with the synthesis method of the above-mentioned specific compound E-1, while appropriately adjusting the raw materials, reaction conditions, and the like so as to obtain each of the specific compounds shown below.

[0104] The materials used in preparing the compositions of the Examples and Comparative Examples are listed below. The numerical values ​​listed for each specific compound (E-1 to E-23, and F-1 to F-14) or comparative compound (CE-1 to CE-4) indicate the molecular weight of each compound. When the specific compound or comparative compound has a molecular weight distribution, the values ​​are the weight-average molecular weight (Mw) values ​​obtained by GPC measurement under the conditions described above. Furthermore, for specific compounds E-1 to E-7, E-9, E-11, and F-1 to F-3, the bond positions marked with "*" are mutually linked structures. For example, specific compound E-1 corresponds to the structure shown below.

[0105]

[0106] [Specific compound]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] [Comparative Compounds]

[0114]

[0115] [Solvent] PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate

[0116] [Liquid Preparation] Compositions of each of the Examples and Comparative Examples were prepared by mixing the specific compound or comparative compound with a solvent so as to obtain the composition shown in the table below.

[0117] [Preparation of modified substrate] A commercially available silicon wafer (diameter 12 inches) was prepared as a substrate. A tungsten (W) layer, a ruthenium (Ru) layer, a molybdenum (Mo) layer, a copper (Cu) layer, and a cobalt (Co) layer were formed on one surface of the silicon wafer, respectively, to prepare a W-layer wafer, a Ru-layer wafer, a Mo-layer wafer, a Cu-layer wafer, and a Co-layer wafer (hereinafter, these are also collectively referred to as "layered wafers"). The W layer, Ru layer, and Mo layer were formed by CVD, and the Cu layer and Co layer were formed by sputtering. The film formation conditions were adjusted so that the thickness of each layer was 20 nm. The silicon wafer and each layered wafer were cut into 2 cm squares and washed by immersion in isopropyl alcohol (IPA). The cleaning was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25° C., and the cleaning time was 30 seconds. After cleaning, the wafer was dried by blowing nitrogen gas onto it, thereby preparing an unmodified substrate.

[0118] Next, each unmodified substrate after cleaning was immersed in each composition to perform a modification treatment on the substrate. The immersion was performed while stirring the composition at a stirring speed of 250 rpm, the composition temperature was 25°C, and the immersion time was 10 minutes. After immersion, each substrate was rinsed by immersing it in IPA. The rinsing treatment was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25°C, and the rinsing time was 30 seconds. After rinsing, the wafer was dried by spraying nitrogen gas. A modified substrate was obtained by the above procedure.

[0119] [Evaluation] [Evaluation of contact angle with pure water after substrate modification] For each of the modified substrates (silicon wafer and wafer with each layer) obtained in [Preparation of modified substrates], and for the substrates (unmodified substrates) before immersion in each composition, the contact angle was measured three times using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.) at 23°C, 500 milliseconds after a water droplet contacted the surface of the measurement object, and the average value was taken as the contact angle (deg.). The surface tension of pure water was assumed to be 72.9 mN / m for the analysis.

[0120] [Evaluation of ALD Inhibition (Deposition Inhibition)] A tantalum nitride (TaN) layer (ALD film) was formed by ALD using an atomic layer deposition system (AD-230LP, manufactured by Samco) on each of the modified substrates (wafers with each layer) obtained by [Preparation of Modified Substrates] and on the substrates (unmodified substrates: Comparative Examples CA3 to CE3) before immersion in each composition. PDMAT (pentakis(dimethylamino)tantalum) was used as the organometallic source and ammonia as the reducing agent, and the ALD treatment temperature was 300°C. Other conditions were adjusted so that the thickness of the ALD film formed on the unmodified substrate would be 5 nm. For example, in Table 1, an ALD film was formed on the modified substrate under conditions such that the thickness of the ALD film formed on the W layer wafer before immersion in the composition would be 5 nm. The thickness of the ALD film of each sample after the ALD process was measured using an X-ray fluorescence (XRF) analyzer (AZX400 manufactured by Rigaku Corporation). Measurements were performed at five points on the substrate, and the average value was taken as the film thickness. From the obtained film thickness, ALD inhibition (deposition inhibition) was evaluated according to the following evaluation criteria. The smaller the film thickness, the more difficult it is for a film to deposit by the ALD process, i.e., the better the ALD inhibition. ALD inhibition of F or higher is preferred, with S being most preferred.

[0121] (Evaluation criteria) S: The thickness of the ALD film is less than 0.3 nm. A: The thickness of the ALD film is 0.3 nm or more and less than 0.5 nm. B: The thickness of the ALD film is 0.5 nm or more and less than 1.0 nm. C: The thickness of the ALD film is 1.0 nm or more and less than 1.3 nm. D: The thickness of the ALD film is 1.3 nm or more and less than 1.7 nm. E: The thickness of the ALD film is 1.7 nm or more and less than 2.0 nm. F: The thickness of the ALD film is 2.0 nm or more and less than 2.5 nm. G: The thickness of the ALD film is 2.5 nm or more.

[0122] [Evaluation of Removability of Composition After Evaluation of ALD Inhibition] After the evaluation of ALD inhibition (deposition inhibition), the composition of the Example or Comparative Example on each modified substrate (wafer with each layer) was removed using a hydrogen plasma exposure device (GIGA 80 Plus, manufactured by PVA TePla). The hydrogen plasma exposure was carried out under the following conditions: ２ / Ar=40:10 sccm, ICP: 350 W, RF: 10 W, 350°C-10 min. The amount of composition remaining on each modified substrate after the hydrogen plasma exposure was measured using an X-ray photoelectron spectroscopy (XPS) device (JPS-9030, manufactured by JEOL Ltd.). Specifically, the carbon content of the unmodified substrate and the modified substrate after hydrogen plasma exposure was measured by the XPS measurement, and the amount of remaining composition was calculated using the following formula: remaining amount of composition (%) = carbon content of modified substrate after hydrogen plasma exposure (%) - carbon content of unmodified substrate (%). The composition removability was evaluated using the obtained remaining amount of composition according to the following evaluation criteria. The smaller the remaining amount of composition, the more the composition has been removed by the hydrogen plasma exposure treatment, i.e., the better the composition removability. A rating of A or higher is preferred, with S being most preferred.

[0123] (Evaluation Criteria) S: The remaining amount of the composition is 5% or less. A: The remaining amount of the composition is 5% or more and less than 10%. B: The remaining amount of the composition is 10% or more.

[0124] [Results] The composition and evaluation results of each composition are shown in Tables 1 to 7. Tables 1 and 6 show results assuming a W layer as the first surface, Table 2 shows a Mo layer as the first surface, Table 3 shows a Ru layer as the first surface, Tables 4 and 7 show a Cu layer as the first surface, and Table 5 shows a Co layer as the first surface, and all results show results assuming a Si layer (silicon wafer) as the second surface.

[0125] In the tables, the "amount (parts by mass)" of the specific compound or comparative compound represents the content (unit: parts by mass) of the specific compound or comparative compound when the total mass of the composition is 100 parts by mass. In the tables, the content of the solvent is the remainder obtained by subtracting the content of the specific compound or comparative compound from the total mass of the composition. In the tables, the value in the "pKa" column represents the acid dissociation constant of the conjugate acid of the specific compound obtained by adding a proton to the basic functional group when the specific functional group is a basic functional group, and the acid dissociation constant of the specific compound when a proton dissociates from the acidic functional group when the specific functional group is an acidic functional group. However, the numerical values ​​in the "pKa" column in Examples A22 to A25 indicate the acid dissociation constant of the conjugate acid of the specific compound obtained by adding a proton to the primary amino group, which is the basic functional group used in each Example, and the numerical values ​​in the "pKa" column in Examples D12 to D15 indicate the acid dissociation constant of the specific compound when a proton dissociates from the phosphonic acid group in Examples D12 and D14, and the acid dissociation constant of the specific compound when a proton dissociates from the carboxy group in Examples D13 and D15. As described above, the acid dissociation constants were calculated using the software package 1 based on values ​​from a database of Hammett's substituent constants and known literature values.

[0126]

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133]

[0134] The results in Tables 1 to 7 confirm that the compositions of the present invention have excellent ALD inhibitory properties and can form coatings that are easily removed by removal treatment after ALD processing. Furthermore, comparisons between Examples A1 and A3 and the like confirmed that, for specific compounds, when the specific functional group is a basic functional group, the ALD inhibitory properties are even better when the acid dissociation constant of the conjugate acid of the specific compound, obtained by adding a proton to the basic functional group, is 7.0 or higher. Comparisons between Examples A4 and A5 and the like confirmed that, for specific compounds, when the specific functional group is a basic functional group and the basic functional group is an amino group, a hydrazine group, or a guanidine group, the ALD inhibitory properties are even better. Comparisons between Examples A5 and A6 and the like confirmed that, for specific compounds, when the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group, the ALD inhibitory properties are even better. Comparisons between Examples A1 and A6, etc., confirmed that when the basic functional group is a primary amino group, the ALD inhibitory properties are superior. Comparisons between Example A1 and Examples A7 and A18, etc., confirmed that when the molecular weight of the specific compound is less than 2500, the composition is more easily removed in the removal treatment after the ALD treatment. Comparisons between Example A1 and Examples A8, A12, and A15 to A17, etc., confirmed that when the specific compound has four or more specific functional groups, the ALD inhibitory properties are superior. Comparisons between Example A1 and Examples A20 and A21, etc., confirmed that when the content of the specific compound is 5.00 mass% or less relative to the total mass of the composition for semiconductor device processing, at least one of the effects of ALD inhibitory properties and removability of the composition in the removal treatment after the ALD treatment is superior.

[0135] Furthermore, a comparison between Example D2 and Example D3 and the like confirmed that, for a specific compound, when the specific functional group is an acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group, the ALD inhibitory properties are more excellent. A comparison between Example D1 and Example D3 and the like confirmed that, when the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group, the ALD inhibitory properties are more excellent.

Claims

1. A composition for forming a coating that inhibits film formation by atomic layer deposition processing, the composition being for semiconductor device processing, comprising a compound having two or more specific functional groups that bond to or adsorb to a substrate and a molecular weight of 450 or more but less than 5,000, wherein the specific functional groups are basic functional groups or acidic functional groups.

2. The composition for processing semiconductor devices of claim 1, wherein said composition includes a solvent.

3. The composition for treating semiconductor devices according to claim 1, wherein, when the specific functional group is the basic functional group, the acid dissociation constant of the conjugate acid of the compound obtained by adding a proton to the basic functional group is 7.0 or more, and when the specific functional group is the acidic functional group, the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is 5.0 or less.

4. The composition for treating a semiconductor device according to claim 1, wherein the specific functional group is the basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group.

5. The composition for treating semiconductor devices according to claim 4, wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group.

6. The composition for treating a semiconductor device according to claim 5, wherein the basic functional group is a primary amino group.

7. The composition for treating a semiconductor device according to claim 1, wherein the specific functional group is the acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group.

8. The composition for treating a semiconductor device according to claim 7, wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group.

9. The composition for treating a semiconductor device according to claim 1, wherein said compound has four or more of said specific functional groups.

10. The composition for semiconductor device processing of claim 1, wherein the compound has a molecular weight of less than 2500.

11. The composition for treating semiconductor devices according to claim 1, wherein the compound is a compound represented by formula (1) and has a molecular weight of 450 or more but less than 5,000, or a compound having two or more repeating units represented by formula (2) and has a molecular weight of 450 or more but less than 5,000. In formula (1), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. １ represents a single bond or a divalent linking group. １ represents an n-valent linking group, and n represents an integer of 2 or more. In formula (2), X represents a primary amino group, a tertiary amino group, a hydrazine group, an imidazole group, a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. M ２ represents a trivalent linking group. ２ represents a single bond or an (m+1)-valent linking group, and m represents an integer of 1 or more. ２ When is a single bond, m represents 1.

12. The composition for treating semiconductor devices according to claim 1, wherein the compound is a compound represented by any one of formulas (1-1) to (1-5) and has a molecular weight of 450 or more and less than 5,000, or a compound having two or more repeating units represented by formula (1-6) and has a molecular weight of 450 or more and less than 5,000. In formula (1-1), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ３ represents an alkylene group having 5 or more carbon atoms which may contain one or more divalent linking groups selected from —O— and —CO—. ３ represents a p-valent aromatic hydrocarbon group which may have a substituent, and p represents an integer of 2 or more. １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ４ represents a single bond or an alkylene group having 2 or less carbon atoms. １ represents an alkyl group having 5 or more carbon atoms, which may have a substituent and may contain —O—, —CONH—, —COO— or —C≡C—. M ４ represents a (q+r)-valent linking group, q represents an integer of 2 or more, and r represents 1 or 2. In formula (1-3), X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ５ represents a (k+1)-valent hydrocarbon group having 5 or more carbon atoms, which may contain one or more divalent linking groups selected from -O- and -CO-, and which may have at least one of a carboxy group, a hydroxy group, and a mercapto group. Ar represents an aromatic ring which may have a substituent. w represents an integer of 0 to 2. k represents an integer of 1 or more. In formula (1-4), X represents a primary amino group, a tertiary amino group, a hydrazine group, an imidazole group, a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. Ar represents an aromatic ring which may have a substituent. L ２ represents a single bond or an (m+1)-valent linking group, and m represents an integer of 1 or more. ２ When X is a single bond, m represents 1. v represents an integer of 4 or more. １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ６ represents a single bond or a divalent linking group. Y represents a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent. In formula (1-6), L ７ represents a single bond or a divalent linking group. １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. R represents a hydrogen atom or an alkyl group.

13. The composition for treating semiconductor devices according to claim 1, wherein the content of said compound is 5.00 mass % or less, based on the total mass of said composition for treating semiconductor devices.

14. The composition for treating semiconductor devices according to claim 2, wherein the total amount of the compound and the solvent is 99.90 mass % or more based on the total mass of the composition for treating semiconductor devices.

15. The composition for treating semiconductor devices according to claim 1, wherein the film obtained by applying the composition for treating semiconductor devices has a water contact angle of 60 degrees or more.

16. A method for producing a modified substrate, comprising the step of contacting a substrate with a composition for treating a semiconductor device according to any one of claims 1 to 15 to form a coating on the substrate.

17. A method for producing a laminate, comprising: step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each surface being made of a different material, with a composition for treating semiconductor devices according to any one of claims 1 to 15 to form a first coating on the first surface; and step 2 of subjecting the substrate obtained in step 1 to atomic layer deposition to form a second coating on the second surface.

18. A method for producing an electronic device, comprising the method for producing the modified substrate according to claim 16.

19. A compound having two or more repeating units represented by formula (3) and having a molecular weight of 450 or more and less than 5,000. In formula (3), L ａ represents a divalent linking group having 5 or more atoms excluding hydrogen atoms. ａ represents an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a hydrogen atom.