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

Abstract

The present invention provides: a composition with which it is possible to form, on a region including silicon atoms and nitrogen atoms in a substrate, a coating film capable of suppressing film formation by an atomic layer deposition process; a composition with which it is possible to form, on a region including silicon atoms and germanium atoms in a substrate, a coating film capable of suppressing film formation by an atomic layer deposition process; a method for producing a modified substrate; a method for producing a laminate; a method for producing an electronic device; and a compound. A composition according to the present invention is for forming, on a region that includes silicon atoms and nitrogen atoms and that is included in a substrate, a coating film that suppresses film formation by an atomic layer deposition process, and said composition includes a component that has a repeating unit having an acidic functional group. In addition, a composition according to the present invention is for forming, on a region that includes silicon atoms and nitrogen atoms and that is included in a substrate, a coating film that suppresses film formation by an atomic layer deposition process, and said composition includes a component that has a repeating unit having an acidic functional group.

Description

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

[0001] The present invention relates to a composition, 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] For example, Patent Document 1 discloses Si—NH ２ A method for producing a substrate and a coating liquid capable of selectively forming a film that exhibits high blocking performance against metal oxide formation by an ALD method or a CVD method on a substrate having a surface layer containing a region containing a terminal structure represented by the formula: ２ and heating the coating film formed by the coating step, wherein the coating liquid contains a compound having an aromatic ring structure and a functional group that reacts with the terminal structure of the first region to form a carbon-nitrogen double bond.

[0004] Japanese Patent Application Laid-Open No. 2023-074176

[0005] The coatings used for selectively modifying substrates as described above are required to suppress the amount of material deposited on the coating when atomic layer deposition (ALD) is performed on the coating, i.e., to have excellent ALD inhibition properties. Furthermore, in recent years, substrates having regions containing silicon atoms and nitrogen atoms have been required to have ALD inhibition properties in the regions. Furthermore, in recent years, substrates having regions containing silicon atoms and germanium atoms have also been required to have ALD inhibition properties. The present inventors formed a coating on a substrate having a region containing silicon atoms and nitrogen atoms using the coating liquid disclosed in Patent Document 1, and then performed ALD on the coating, and found that there was room for further improvement in ALD inhibition properties.

[0006] Therefore, an object of the present invention is to provide a composition capable of forming a coating that can suppress film formation by atomic layer deposition on a region containing silicon atoms and nitrogen atoms in a substrate. Another object of the present invention is to provide a composition capable of forming a coating that can suppress film formation by atomic layer deposition on a region containing silicon atoms and germanium atoms in a substrate. Another object of the present invention is to provide a method for manufacturing a modified substrate, a method for manufacturing a laminate, a method for manufacturing 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 on a region of a substrate containing silicon atoms and nitrogen atoms, the composition comprising a compound having a repeating unit with an acidic functional group. [2] A composition for forming a coating that inhibits film formation by atomic layer deposition on a region of a substrate containing silicon atoms and germanium atoms, the composition comprising a compound having a repeating unit with an acidic functional group. [3] The composition according to [1] or [2], wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. [4] The composition according to any one of [1] to [3], wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group. [5] The composition according to any one of [1] to [4], wherein the acidic functional group is a phosphonic acid group or a phosphinic acid group. [6] The composition according to any one of [1] to [5], wherein the weight-average molecular weight of the compound is 1,000 or more. [7] The composition according to any one of [1] to [6], wherein the compound contains one or more repeating units represented by any one of general formulas (1) to (3) described below. [8] The composition according to [7], wherein the compound contains one or more repeating units represented by any one of general formulas (1) to (3) described above, and wherein the weight-average molecular weight of the compound is 1,000 or more. [9] The composition according to any one of [1] to [8], wherein the compound contains one or more repeating units represented by any one of general formulas (4) to (6) described below.

[10] The composition according to any one of [1] to [9], further comprising a solvent, wherein the total amount of the compound and the solvent is 99.90 mass % or more relative to the total mass of the composition.

[11] The composition according to any one of [1] to

[10] , wherein the water contact angle of a film obtained by applying the composition is 60 degrees or more.

[12] A method for producing a modified substrate, comprising the step of contacting a substrate having a region containing silicon atoms and nitrogen atoms with the composition according to any one of [1] and [3] to

[11] to form a coating on the region.

[13] A method for producing a modified substrate, comprising the step of contacting a substrate having a region containing silicon atoms and germanium atoms with the composition according to any one of [2] to

[11] to form a coating on the region.

[14] A method for producing a laminate, comprising the steps of: Step 1: contacting a substrate having a region X containing silicon atoms and nitrogen atoms and a region Y having a composition different from that of region X with the composition according to any one of [1] and [3] to

[11] to form a first coating on region X; and Step 2: subjecting the substrate obtained in Step 1 to atomic layer deposition to form a second coating on region Y.

[15] A method for producing a laminate, comprising: Step 1A of contacting a substrate having a region P containing silicon atoms and germanium atoms and a region Q having a composition different from that of region P with the composition according to any one of [2] to

[11] to form a first coating on region P; and Step 2A of subjecting the substrate obtained in step 1A to atomic layer deposition to form a second coating on region Q.

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

[12] .

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

[13] .

[18] A compound comprising a repeating unit represented by general formula (4) described later.

[0009] According to the present invention, a composition can be provided that can form a coating that can suppress film formation by atomic layer deposition on a region containing silicon atoms and nitrogen atoms in a substrate. Furthermore, according to the present invention, a composition can be provided that can form a coating that can suppress film formation by atomic layer deposition on a region containing silicon atoms and germanium atoms in a substrate. The present invention also provides a method for producing a modified substrate, a method for producing a laminate, a method for producing an electronic device, and a compound.

[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, (meth)acrylate refers to at least one of acrylate and methacrylate. In addition, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid. In this specification, when two or more types of a component are present, the "content" of that component refers to 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] The composition of the present invention (hereinafter also referred to as "the composition") will be described in detail below. The composition is for forming a coating that inhibits film formation by atomic layer deposition on a region of a substrate containing silicon atoms and nitrogen atoms, and includes a compound having a repeating unit with an acidic functional group (hereinafter also referred to as "specific compound"). Another embodiment of the composition (hereinafter also referred to as "embodiment A") is a composition for forming a coating that inhibits film formation by atomic layer deposition on a region of a substrate containing silicon atoms and germanium atoms, and includes a compound having a repeating unit with an acidic functional group (hereinafter also referred to as "specific compound A").

[0016] Although the reason why the composition having the above-described configuration can solve the problem of the present invention is not entirely clear, the inventors speculate as follows. Note that 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 acidic functional group possessed by the specific compound can bond to or adsorb to a region of a substrate containing silicon atoms and nitrogen atoms, thereby forming a coating. Furthermore, since the specific compound has multiple acidic functional groups, it can bond to or adsorb to the surface of the substrate at multiple points, thereby forming a strong coating. Furthermore, the acidic functional group possessed by the specific compound can also bond to or adsorb to a region containing silicon atoms and germanium atoms in the same manner as above to form a coating. 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 ability to form a coating that can suppress the formation of an ALD film on a region containing silicon atoms and nitrogen atoms in a substrate is also referred to as "the effect of the present invention being superior." Furthermore, the ability to form a coating that can suppress the formation of an ALD film on a region containing silicon atoms and germanium atoms in a substrate is also referred to as "the effect of the present invention being superior."

[0017] [Specific Compound and Specific Compound A] The present composition contains a specific compound. Furthermore, in Aspect A of the present composition, specific compound A is contained. Hereinafter, only the specific compound will be described in detail, but unless otherwise specified, specific aspects and preferred aspects of specific compound A are the same as those of the specific compound described below. As described above, the specific compound is a compound having a repeating unit with an acidic functional group. That is, the specific compound is a polymeric compound having multiple repeating units with an acidic functional group. Here, the polymeric compound refers to a compound having multiple repeating units. In the specific compound, the repeating units may be bonded to each other to form a ring structure. The molecular weight of the specific compound is not particularly limited as long as it is within the above range, but the lower limit is preferably 500 or more, more preferably 1,000 or more. The upper limit is preferably 20,000 or less, more preferably 15,000 or less, and even more preferably 8,000 or less. When the specific compound has a molecular weight distribution, the above molecular weight refers to the weight-average molecular weight.

[0018] The number of acidic functional groups contained in the repeating unit of the specific compound is preferably 1 to 6, more preferably 1 or 2, and even more preferably 1. 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. The lower limit is, for example, −5.0 or more.

[0019] The acidic functional group may be a phosphonic acid group (-PO ３ H ２ ), phosphinic acid group (-PO ２ H ２ ), phosphate group (-PO ４ H ２ ), sulfo group (—SO ３ Examples of the hydroxyl group include a phosphonic acid group, a phosphinic acid group, a sulfo group, and a carboxy group, more preferably a phosphonic acid group, a phosphinic acid group, and a sulfo group, and even more preferably a phosphonic acid group or a phosphinic acid group.

[0020] <Hydrophobic Group> It is preferable that the repeating unit having an acidic functional group further has 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 examples include monovalent to trivalent groups, with divalent groups being preferred.

[0021] The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include alkyl groups, alkenyl groups, and alkynyl groups. The linear or branched aliphatic hydrocarbon group preferably has 4 to 30 carbon atoms, more preferably 6 to 24 carbon atoms, and even more preferably 6 to 18 carbon atoms. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The cyclic aliphatic hydrocarbon group preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and even more preferably 6 to 20 carbon atoms.

[0022] 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.

[0023] 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 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 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.

[0024] 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.

[0025] The specific compound preferably contains one or more repeating units represented by any one of the following general formulas (1) to (3), and more preferably contains one or more repeating units represented by any one of the following general formulas (4) to (6). When the specific compound contains repeating units represented by any one of the general formulas (1) to (3) (general formulas (4) to (6)), the total content of repeating units represented by general formulas (1) to (3) (general formulas (4) to (6)) is preferably 40 mol% or more, more preferably 50 mol% or more, and particularly preferably 90 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. In particular, the specific compound preferably contains only one type of repeating unit represented by any one of the general formulas (1) to (3) (general formulas (4) to (6)). Furthermore, it is also preferable that the specific compound contains one or more repeating units represented by any one of the general formulas (1) to (3), and that the weight-average molecular weight of the compound is 1,000 or more. Each of the repeating units will be described in detail below.

[0026]

[0027] <Repeating unit represented by general formula (1)> In general formula (1), R １ represents a hydrogen atom, a fluorine atom, or a methyl group. １is preferably a hydrogen atom. １ represents a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. １ As L, a phosphonic acid group, a phosphinic acid group, or a sulfo group is preferred, and a phosphonic acid group or a phosphinic acid group is more preferred. １ represents a single bond or a divalent linking group. １ The divalent linking group is preferably a divalent aliphatic hydrocarbon group, a divalent aromatic group, —O—, —CO—, —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. The divalent linking group preferably contains the above-mentioned hydrophobic group. Examples of linking groups formed by combining two or more of the above-mentioned groups include -O-divalent aliphatic hydrocarbon group-, -divalent aromatic group-O-divalent aliphatic hydrocarbon group-, -COO- (ester bond), -CONH- (amide bond), -COO-divalent aromatic group-, -CONH-divalent aromatic group-, -COO-divalent aliphatic hydrocarbon group-, -divalent aliphatic hydrocarbon group-O-divalent aliphatic hydrocarbon group-, and -CONH-divalent aliphatic hydrocarbon group-.

[0028] The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. Examples of the divalent aliphatic hydrocarbon group include alkylene groups, alkenylene groups, and alkynylene groups, with alkylene groups being preferred. The divalent aliphatic hydrocarbon group preferably has 4 to 30 carbon atoms, more preferably 6 to 24, and even more preferably 6 to 18.

[0029] 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.

[0030] 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. L １ Among these, —O-alkylene group having 4 to 30 carbon atoms— is preferred, —O-alkylene group having 6 to 24 carbon atoms— is more preferred, and —O-alkylene group having 6 to 18 carbon atoms— is even more preferred.

[0031] In the above general formula (1), M １ represents a divalent aromatic group. The aromatic ring constituting the divalent aromatic group may be either monocyclic or polycyclic. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but an aromatic hydrocarbon group is preferred. The divalent aromatic group preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. The divalent aromatic group may have a substituent, and examples of the substituent include the aliphatic hydrocarbon groups described above. Specific embodiments and preferred embodiments of the aliphatic hydrocarbon group are as described above for the hydrophobic group. 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 divalent aromatic group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2. Of the divalent aromatic groups, a phenylene group which may have a substituent is preferred, and a phenylene group is more preferred.

[0032] The repeating unit represented by the general formula (1) is preferably a repeating unit represented by the general formula (4). ４ represents a phosphonic acid group or a phosphinic acid group. ４ represents a single bond or a divalent linking group. ４ Specific examples and preferred embodiments of the formula are: １ The specific examples and preferred embodiments are the same as those of the above.

[0033] <Repeating unit represented by formula (2)> In formula (2), X ２ represents a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. ２ As L, a phosphonic acid group, a phosphinic acid group, or a sulfo group is preferred, and a phosphonic acid group or a phosphinic acid group is more preferred. ２ represents a single bond or a divalent linking group. ２ is preferably a divalent linking group. ２ Specific examples and preferred embodiments of the divalent linking group represented by the formula: １ The repeating unit represented by formula (2) is preferably a repeating unit represented by formula (5). In formula (5), X ５ each independently represents a phosphonic acid group or a phosphinic acid group. ５ represents a single bond or a divalent linking group. ５ Specific examples and preferred embodiments of the formula are: １ The specific examples and preferred embodiments are the same as those of the above.

[0034] <Repeating unit represented by formula (3)> In formula (3), X ３ represents a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. ３ As L, a phosphonic acid group, a phosphinic acid group, or a sulfo group is preferred, and a phosphonic acid group or a phosphinic acid group is more preferred. ３ represents a single bond or a divalent linking group. ３ is preferably a divalent linking group. ３ Specific examples and preferred embodiments of the divalent linking group represented by the formula: １ The specific examples and preferred embodiments are the same as those of the divalent linking group represented by the formula: ３ is also preferably a polyalkyleneoxy group having 5 or more carbon atoms (preferably a polyethyleneoxy group).

[0035] In the above general formula (3), M ３represents a trivalent aromatic group. The aromatic ring constituting the trivalent aromatic group may be either monocyclic or polycyclic. The aromatic group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The aromatic group preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. The trivalent aromatic group may have a substituent, and examples thereof include an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom. Specific and preferred embodiments of the aliphatic hydrocarbon group are as described above. 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. Among these, the trivalent aromatic group is preferably a group formed by removing three hydrogen atoms from a benzene ring which may have a substituent, and more preferably a group formed by removing three hydrogen atoms from a benzene ring which may have an alkyl group having 1 to 4 carbon atoms.

[0036] The repeating unit represented by general formula (3) is preferably a repeating unit represented by general formula (6). ６ represents a phosphonic acid group or a phosphinic acid group. ６ represents a single bond or a divalent linking group. ６ Specific examples and preferred embodiments of the formula are: １ The specific examples and preferred embodiments are the same as those of R ６ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Of these, the alkyl group having 1 to 4 carbon atoms is preferably a methyl group or a t-butyl group.

[0037] <Repeating Units Not Containing an Acidic Functional Group> In addition to the repeating units described above, the specific compound may also have a repeating unit not containing an acidic functional group. When the specific compound has a repeating unit not containing an acidic functional group, the content of the repeating unit not containing an acidic functional group is preferably 50 mol% or less, more preferably 25 mol% or less, and even more preferably 5 mol% or less, relative to the total repeating units of the specific compound. The lower limit is not particularly limited, but may be, for example, 0 mol% or more. Examples of repeating units not containing an acidic functional group include repeating units derived from monomers such as aromatic vinyl compounds, (meth)acrylates, and (meth)acrylamide compounds. Among these, repeating units not containing an acidic functional group are preferably repeating units derived from styrene or N-alkylacrylamide compounds. It is also preferable that the repeating unit not containing an acidic functional group has the above-mentioned hydrophobic group.

[0038] Among these, the specific compound is preferably a compound (polymer) containing a repeating unit represented by the above general formula (4). The present invention also includes an invention of a compound containing a repeating unit represented by the general formula (4).

[0039] 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 (hereinafter including Aspect A). 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. Furthermore, when the composition contains a solvent described below, the total amount of the specific compound and the solvent 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.

[0040] [Solvent] The present composition (hereinafter also referred to as Aspect A) preferably contains a solvent. Examples of the solvent include water and organic solvents, and organic solvents are 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.

[0041] 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 (IPA), 2-butanol, isobutyl alcohol, tert-butyl alcohol, isopentyl alcohol, and 4-methyl-2-pentanol (methyl isobutylcarbinol); alicyclic monoalcohol-based solvents having 3 to 18 carbon atoms, such as cyclohexanol; aromatic monoalcohol-based solvents, such as benzyl alcohol; and ketone monoalcohol-based solvents, such as diacetone alcohol. Examples of polyol-based solvents include glycol-based solvents having 2 to 18 carbon atoms, such as ethylene glycol, 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 (TEGBE), 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.

[0042] Examples of ether-based solvents include glycol ether-based solvents such as tetraethylene glycol dimethyl ether (TEGDME), triethylene glycol butyl methyl ether (TEGBME), ethylene glycol dimethyl ether (dimethoxyethane), dipropylene glycol methyl-n-propyl ether, and dipropylene glycol methyl-n-butyl ether; dialkyl ether-based solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dihexyl ether, and cyclohexyl methyl ether; cyclic ether-based solvents such as tetrahydrofuran and tetrahydropyran; anisole; and diphenyl ether.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0047] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0048] 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. The solvent may also preferably contain at least one selected from the group consisting of TEGBE, TEGDME, TEGBME, PGME, diethylene glycol monomethyl ether, triethylene glycol butyl methyl ether, diethylene glycol monoethyl ether, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl-n-butyl ether, triacetin, 1,3-butylene glycol, ethylene glycol, IPA, dimethoxyethane, THF, propylene glycol diacetate, dipropylene glycol methyl ether acetate, diethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanediol diacetate, sulfolane, ethyl lactate, and DMSO.

[0049] 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, relative to 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 composition also preferably contains water. When the composition contains water, the content of water is preferably 0.5% by mass or more, more preferably 5.00% by mass or more, even more preferably 10.00% by mass or more, and particularly preferably 30.00% by mass or more, relative to the total mass of the composition. The upper limit is preferably less than 100% by mass, more preferably 90% by mass or less, and even more preferably 80% 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, relative to the total amount of all solvents. The upper limit is not particularly limited, and may be 100% by mass.

[0050] [Other Components] The present composition (hereinafter also referred to as Aspect A) may contain other components in addition to the specific compound and the solvent. Examples of the other components include polymerization inhibitors. Examples of the polymerization inhibitor include phenolic compounds, quinone compounds, free radical compounds, amine compounds, and phosphine compounds.

[0051] [Method for producing the present composition] The method for producing the present composition (hereinafter, including aspect A) 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, followed by thorough stirring. In order to achieve better effects of the present invention, it is preferable that the raw materials of the present composition (for example, the solvent and the specific compound) have been subjected to a purification treatment.

[0052] The production process of the present composition may include a step selected from the group consisting of a distillation step of distilling raw materials, a dehydration step of dehydrating the present composition, a metal removal step of removing metal components from the present composition, a filtration step of filtering the present composition, and a destaticization step of destaticizing the present composition.

[0053] 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.

[0054] [Uses of the Composition] As described above, the composition is a composition for forming a coating (hereinafter also referred to as a "modifying film") that suppresses film formation by atomic layer deposition (ALD) on a region (hereinafter also referred to as a "substrate") containing silicon atoms and nitrogen atoms (hereinafter also referred to as a "region X"). This composition is often used in the manufacturing process of semiconductor devices. Furthermore, in Aspect A of the composition, the composition is a composition for forming a coating (modifying film) that suppresses film formation by ALD on a region (hereinafter also referred to as a "region P") containing silicon atoms and germanium atoms (hereinafter also referred to as a "substrate A"). This composition is also often used in the manufacturing process of semiconductor devices. Use of the composition (hereinafter also including Aspect A) allows for the formation of a modified substrate in which a modified film is selectively formed on Region X (Region P in the case of Aspect A) of the substrate. The present composition is also preferably used to produce a laminate in which a material is deposited in a region other than region X (region P in the case of embodiment A) by subjecting the modified substrate to an ALD treatment. Methods for producing a modified substrate and a laminate will be described in detail later.

[0055] <Substrate> The substrate has a region (region X) containing silicon atoms and nitrogen atoms. The shape of the substrate is not particularly limited, and any substrate shape commonly used as a semiconductor substrate can be used. The substrate may be a substrate having the above-described surface, and may be a single layer or a multilayer structure. Region X preferably contains a compound containing silicon atoms and nitrogen atoms, and more preferably contains only a compound containing silicon atoms and nitrogen atoms. Examples of compounds containing silicon atoms and nitrogen atoms include silicon nitride (SiN), silicon oxynitride, and silicon oxycarbon nitride, with silicon nitride being preferred.

[0056] <Substrate A> Substrate A has a region (region P) containing silicon atoms and germanium atoms. The shape of the substrate is not particularly limited, and substrate shapes commonly used as semiconductor substrates can be adopted. Furthermore, the substrate may be a substrate having the above-described surface, and may be a single-layer or multi-layer structure. Region P is not particularly limited as long as it is a compound containing silicon atoms and germanium atoms, but is often silicon-germanium (SiGe). In this specification, silicon-germanium refers to a material containing silicon elements (Si elements) and germanium elements (Ge elements), and a material composed essentially of only Si elements and Ge elements is preferred. The term "substantially" as used herein means that the total content of Si elements and Ge elements is 90 atomic % or more relative to the total atoms of the material. A material composed essentially of only Si elements and Ge elements may contain other elements (e.g., carbon element (C element), nitrogen element (N element), oxygen element (O element), boron element (B element), and phosphorus element (P element), etc.) as long as the total content of Si elements and Ge elements is within the above range.

[0057] The total content of Si and Ge elements in SiGe is preferably 90 to 100 mass%, more preferably 99 to 100 mass%, and even more preferably 99.9 to 100 mass%, relative to the total mass of SiGe. In SiGe, the content of Ge elements (Ge / (Si+Ge)) relative to the total content of Si and Ge elements is preferably 95 atomic % or less, more preferably 80 atomic % or less, and even more preferably 70 atomic % or less. The lower limit of the content of Ge elements relative to the total content of Si and Ge elements is preferably 5 atomic % or more, and more preferably 25 atomic % or more.

[0058] The substrate preferably has a region (hereinafter simply referred to as "region Y") whose composition is different from that of the region X. The substrate A also preferably has a region (hereinafter simply referred to as "region Q") whose composition is different from that of the region P. Region Y (hereinafter, region Q in the case of embodiment A) includes a metal surface A made of a material containing metal atoms and a non-metal surface B made of a non-metal material, with the non-metal surface B being preferred. The shape of the region X (or region P) and region Y (or region Q) is not particularly limited, and examples thereof include planar, dotted, and striped shapes.

[0059] 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.

[0060] 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, non-metallic oxynitrides, and organic materials. The material constituting the non-metallic surface B is preferably a non-metallic material containing silicon atoms, more preferably a compound containing silicon atoms but not containing nitrogen atoms, and even more preferably silicon or silicon oxide. Specific examples of silicon oxides 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.

[0061] 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.

[0062] <Coating> The coating obtained by applying the present composition (hereinafter, including Aspect A) is a film containing a specific compound (specific compound A when the present composition is Aspect A). This coating preferably contains a component other than the solvent contained in the present composition (e.g., the specific compound), and functions as a mask that suppresses film formation by atomic layer deposition (ALD). That is, when an ALD process is performed on a modified substrate having a coating formed on region X (or region P) using the present composition, it is preferable that no material is deposited in region X (or region P), but that material is deposited in region Y (or region Q) to form a film (hereinafter also referred to as an "ALD film"). This results in a laminate in which an ALD film is selectively formed in region Y (or region Q).

[0063] 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.

[0064] 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.

[0065] In order to obtain superior effects of the present invention, the water contact angle of the coating is preferably 50 degrees or more, more preferably 60 degrees or more, and even more preferably 70 degrees or more. There is no particular upper limit, and it is often 120 degrees or less. In particular, it is preferable that the water contact angle of a coating formed on silicon nitride is within the above range. 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.).

[0066] [Method for Producing Modified Substrate] The method for producing a modified substrate of the present invention includes a step of contacting a substrate having a region (region X) containing silicon atoms and nitrogen atoms with the present composition to form a coating on region X. This results in a modified substrate having a coating formed on the substrate. The method for producing a modified substrate of the present invention also includes a step of contacting a substrate having a region (region P) containing silicon atoms and germanium atoms with the present composition to form a coating on region P. This results in a modified substrate having a coating formed on the substrate. The method for producing a modified substrate of the present invention (hereinafter also referred to as Aspect A) is suitable for use, for example, in the production of electronic devices (semiconductor devices). The method for contacting a substrate (hereinafter, or substrate A) 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 convected. 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 which the substrate is brought into contact with the composition is not particularly limited, but is preferably 30 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and even more preferably 3 to 15 minutes.

[0067] 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.

[0068] It is also preferable to carry out a rinsing treatment after contacting the substrate with the present composition. The rinsing treatment can remove from the substrate at least one of the present composition and impurities adhering to regions other than the desired region (e.g., region X) on 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 present 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.

[0069] [Method for Producing a Laminate] The method for producing a laminate of the present invention includes step 1 of contacting a substrate (hereinafter also referred to as a "specific substrate") having a region X containing silicon atoms and nitrogen atoms and a region Y having a composition different from that of region X with the present composition to form a first coating on region X, and step 2 of subjecting the substrate obtained in step 1 to atomic layer deposition to form a second coating on region Y. Furthermore, in the above-mentioned embodiment A, the method for producing a laminate of the present invention includes step 1A of contacting a substrate (hereinafter also referred to as a "specific substrate A") having a region P containing silicon atoms and germanium atoms and a region Q having a composition different from that of region P with the present composition to form a first coating on region P, and step 2A of subjecting the substrate obtained in step 1A to atomic layer deposition to form a second coating on region Q. This results in a laminate having a second coating (ALD film) on region Y (hereinafter referred to as region Q in the case of embodiment A). Steps 1 and 2 will be described in detail below, but specific and preferred aspects of step 1 are the same as those of step 1A, and specific and preferred aspects of step 2 are the same as those of step 2A.

[0070] [Step 1: Method for Producing Modified Substrate] Step 1 (hereinafter, Step 1A in the case of Aspect A) is a step of contacting a specific substrate (hereinafter, Specific Substrate A in the case of Aspect A) with the present composition (hereinafter, Composition of Aspect A in the case of Aspect A) to form a first coating on Region X (hereinafter, Region P in the case of Aspect A). Step 1 results in a modified substrate 1 having a first coating formed on Region X of the specific substrate. The first coating is a coating containing the specific compound contained in the present composition. The method for contacting the specific substrate with the present composition is not particularly limited, and the method of contacting the present composition with a substrate in the above-mentioned method for producing a modified substrate can be used. After contacting the specific substrate with the present composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and the heating method in the above-mentioned method for producing a modified substrate can be used.

[0071] It is also preferable to perform a rinse treatment on the modified substrate 1 having the first coating formed on the region X. The rinse treatment can remove at least one of the present composition and impurities adhering to regions other than the region X (e.g., region Y) on the specific substrate from the specific substrate. As the rinse method, the rinse method in the above-described method for producing a modified substrate can be used.

[0072] [Step 2: ALD Treatment] Step 2 (hereinafter, Step 2A in the case of Aspect A) is a step of subjecting the modified substrate obtained in Step 1 to ALD treatment to form a second coating on region Y (hereinafter, Region Q in the case of Aspect A). Step 2 results in a laminate 1 in which a first coating is formed on region X and a second coating is formed on region Y. The second coating is a film formed by ALD treatment (ALD film). Note that the modified substrate 1 may be any substrate in which a first coating has been formed on region X of the specific substrate in Step 1, and may be subjected to the above-mentioned heating treatment, rinsing treatment, etc. after Step 1.

[0073] The ALD treatment 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 TDMAH (tetrakis(dimethylamino)hafnium), alumina, pentakis(dimethylamino)tantalum, and tetrakis(dimethylamino)titanium. The oxidizing agent is not particularly limited, and known oxidizing agents used in ALD treatments can be used, such as water, oxygen, and ozone.

[0074] 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.

[0075] 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.

[0076] [Step 3: Removal of Coating (Removal Treatment)] The method for producing a laminate of the present invention (hereinafter also including Aspect A) may include, after Step 2, Step 3 of removing the first coating formed on region X in Step 1. Step 3 results in a laminate 2 that has no coating on region X and has a second coating on region Y.

[0077] The method for removing the first coating is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof. Known methods can be used for dry etching, such as chemical dry etching, which supplies reactive ions or reactive radicals to the laminate surface, and physical dry etching, such as sputter etching and ion beam etching. Among these, removal by plasma treatment is preferred. For wet etching, a method in which an etching solution is supplied to the laminate can be used. Examples of the etching solution include an etching solution containing an oxidizing agent such as ozone and hydrofluoric acid, and an etching solution 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.

[0078] 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.

[0079] [Synthesis of Specific Compound E-1] Specific compound E-1 was synthesized as follows.

[0080]

[0081] [Synthesis of Intermediate E-1A] Under a nitrogen flow (50 mL / min), 12-bromo-1-dodecanol (30.0 g, 0.11 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), triphenylphosphine (44.5 g, 0.17 mol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4-vinylphenol (17.7 g, 0.15 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and THF (tetrahydrofuran, 375 mL) were placed in a three-neck flask and cooled to 0°C. Next, a solution was prepared separately by dissolving bis(2-methoxyethyl) azodicarboxylate (DMEAD®, 39.7 g, 0.17 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in THF (188 mL). The solution was added dropwise to the reaction solution obtained above over 4 hours while maintaining the internal temperature of the reaction solution at 5°C or below. After the dropwise addition was completed, the reaction solution was stirred at 25 ° C. for 1 hour. Next, the solvent was distilled off from the reaction solution under a reduced pressure of 40 ° C. / 10 hPa. After distillation, ethyl acetate (500 mL, 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. The solution was then left to stand, the lower phase (aqueous phase) was removed, and distilled water (400 mL) was added to the upper phase (organic phase) and stirred. Further, the solution was left to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. The solvent was distilled off from the resulting organic phase under a reduced pressure of 40 ° C. / 10 hPa to obtain a 40% by weight ethyl acetate solution. The resulting 40% by weight ethyl acetate solution was added to methanol (260 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) and cooled to 0 ° C. The mixture was stirred for 30 minutes while kept at 0°C, and the precipitated crystals were washed with methanol and then dried with air at 40°C for 12 hours to obtain intermediate E-1A.

[0082] [Synthesis of Intermediate E-1B] Intermediate E-1A (28.0 g, 0.08 mol), triisopropyl phosphite (47.6 g, 0.23 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (280 mg, 1.63 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were placed in a three-neck flask, and the resulting mixture was stirred for 4 hours at 135° C. Next, the excess triisopropyl phosphite was distilled off from the resulting reaction solution under reduced pressure of 70° C. / 5 hPa, and the resulting crude product was purified by silica gel column chromatography to obtain Intermediate E-1B.

[0083] [Synthesis of Intermediate E-1C] Intermediate E-1B (5.0 g, 11.0 mmol), MEK (methyl ethyl ketone, 20 mL), and V-65 (2,2'-Azobis(2,4-dimethylvaleronitrile), 0.27 g, 1.1 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask, and the resulting mixture was stirred at 80°C for 4 hours. The resulting reaction solution was added dropwise to DIPE (diisopropyl ether, 200 mL) and cooled to 0°C. The mixture was stirred for 30 minutes while maintaining the temperature at 0°C, and then the supernatant liquid of the precipitated oil was removed, washed with DIPE, and dried under reduced pressure at 60°C for 12 hours to obtain Intermediate E-1C.

[0084] [Synthesis of Specific Compound E-1] Intermediate E-1C (2.2 g, 4.9 mmol) and dichloromethane (22 mL) were placed in a three-necked flask and cooled to 0°C. Bromotrimethylsilane (TMSBr, 3.72 g, 24.3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the resulting mixture and stirred at 0°C for 24 hours. Then, methanol (150 mL) was added to the resulting reaction solution and stirred at 25°C for an additional 1 hour. The resulting solution was concentrated, DIPE was added, and the mixture was stirred at 25°C for 1 hour. The supernatant liquid of the precipitated oil was removed, washed with DIPE, and then dried under reduced pressure at 60°C for 12 hours to obtain Specific Compound E-1. １ The H-NMR (Nuclear Magnetic Resonance) data is shown below. １H-NMR (400MHz, THF-d8): δ (ppm) = 5.80-7.20 (br, 4H), 3.45-4.10 (br, 2H), 1.44-1.79 (br, 8H), 1.00-1.44 (br, 17H), 0.60-0.95 (br, 2H).

[0085] Specific compounds E-5 and E-14 to E-18 were synthesized according to the synthesis method of specific compound E-1, with appropriate adjustment of raw materials, reaction conditions, etc. Specific compounds other than these were synthesized using known synthesis methods, or commercially available products were used as needed.

[0086] 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-20) or comparative compound (CE-1 to CE-3) indicate the molecular weight of the compound. When the specific compound or comparative compound has a molecular weight distribution, the numerical values ​​are the weight-average molecular weight (Mw) values ​​obtained by GPC measurement under the conditions described above. In addition, in E-10, E-13, and E-19, the repeating units are bonded to each other at the bonding positions indicated by "*" to form a ring structure. For example, specific compound E-13 corresponds to the structure shown below.

[0087]

[0088] [Specific compound]

[0089]

[0090]

[0091] [Comparative Compounds]

[0092]

[0093] [Solvents] PGME: Propylene glycol monomethyl ether, PGMEA: Propylene glycol monomethyl ether acetate, TEGBE: Triethylene glycol monobutyl ether, TEGDME: Tetraethylene glycol dimethyl ether, TEGBME: Triethylene glycol butyl methyl ether, IPA: Isopropyl alcohol, Water (ultrapure water)

[0094] [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.

[0095] [Preparation of Modified Substrate] A commercially available silicon wafer (diameter 12 inches) was prepared as a substrate. On one surface of this silicon wafer, a silicon nitride (SiN) layer, a silicon-germanium (Si:Ge=40:60 (element ratio), SiGe) layer, and a silicon oxide (SiO ２ ) layers are formed on the SiN layer wafer, the SiGe layer wafer, and the SiO ２ The SiN layer was formed by the ALD method, and the SiGe layer and the SiO ２ The layers were formed by CVD. The film formation conditions were adjusted so that the thickness of each layer was 20 nm. ２ Each layer wafer was cut into 2 cm squares and cleaned by immersion in isopropyl alcohol (IPA). The cleaning was performed while stirring the IPA at 250 rpm, the IPA temperature was 25°C, and the cleaning time was 30 seconds. After cleaning, the wafers were dried by spraying nitrogen gas onto them to prepare unmodified substrates.

[0096] Next, each wafer (unmodified substrate) after the cleaning was immersed in each composition to perform a modification treatment. The immersion was performed while stirring the composition at a stirring speed of 250 rpm, with the composition temperature at 25°C and the immersion time at 10 minutes. After the 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, with the IPA temperature at 25°C and the rinsing time at 30 seconds. After rinsing, the wafer was dried by spraying nitrogen gas. Using the above procedure, each modified substrate was obtained.

[0097] [Evaluation] [Evaluation of pure water contact angle after substrate modification] Each modified substrate (SiN layer wafer, SiGe layer wafer, and SiO ２For each of the substrates (layer wafers) before immersion in each composition (unmodified substrates), and the substrates before treatment (unmodified substrates), the contact angle was measured three times at 23°C using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.) 500 milliseconds after a water droplet made contact with 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.

[0098] [Evaluation of ALD Inhibition (Deposition Inhibition)] A hafnium oxide (HfOx) layer (ALD film) was formed by ALD using an atomic layer deposition apparatus (AD-230LP, manufactured by Samco) on the modified SiN layer wafers and SiGe layer wafers obtained by [Preparation of Modified Substrates], and on the substrates (unmodified substrates: Comparative Examples CA4 and CB4) before immersion in each composition. TDMAH (tetrakis(dimethylamino)hafnium) was used as the organometallic source, and water was used as the oxidizing 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, ALD films were formed on the modified substrates under conditions such that the thickness of the ALD film on the SiN layer wafers and SiGe layer wafers before immersion in the compositions 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 D or higher is preferable, with S being most preferable.

[0099] (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.

[0100] [Results] The composition and evaluation results of each composition are shown in Tables 1 and 2. In Table 1, the region X is a SiN layer, the region Y is a SiO ２ In Table 2, the region P is a SiGe layer, and the region Q is a SiO ２ The results assuming layers are shown.

[0101] 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 "amount (parts by mass)" of water in the "solvent" column represents the content (unit: parts by mass) of ultrapure water when the total mass of the composition is 100 parts by mass. In the tables, the content of solvent is the remainder after subtracting the content of the specific compound or comparative compound from the total mass of the composition. However, when the composition contains water, the content of water is also subtracted.

[0102]

[0103]

[0104]

[0105]

[0106] The results in Table 1 confirm that the composition of the present invention can form a coating that can suppress the formation of an ALD film on a region containing silicon atoms and nitrogen atoms in a substrate (excellent ALD inhibitory properties). Furthermore, the results in Table 2 confirm that the composition of the present invention can form a coating that can suppress the formation of an ALD film on a region containing silicon atoms and germanium atoms in a substrate (excellent ALD inhibitory properties). Furthermore, a comparison between Examples A2 and A3 confirms that when the acidic functional group possessed by the specific compound 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 Examples A3 and A4 confirms that when the acidic functional group possessed by the specific compound is a phosphonic acid group, a phosphinic acid group, or a sulfo group, the ALD inhibitory properties are more excellent. Comparisons of Examples A1 and A11-A12, etc., confirmed that when the content of the specific compound is 5.00 mass% or less relative to the total mass of the composition, the ALD-inhibiting film is selectively formed in regions of the substrate containing silicon atoms and nitrogen atoms, relative to regions containing silicon atoms but not nitrogen atoms, based on the contact angle values. Comparisons of Examples A18 and A19, etc. confirmed that when the acidic functional group possessed by the specific compound is a phosphonic acid group or a phosphinic acid group, the ALD inhibitory properties are superior. Comparisons of Examples A5 and A20, etc. confirmed that when the weight-average molecular weight of the specific compound is 1,000 or more, the ALD inhibitory properties are superior. Comparisons of Examples A1 with A6 and A7, etc. confirmed that when the specific compound contains one or more repeating units represented by any of general formulas (1) to (3), the ALD inhibitory properties are superior. Comparison of Examples A10 to A20 and the like confirmed that the ALD inhibitory properties were superior when the specific compound contained one or more repeating units represented by any one of general formulas (4) to (6). Comparison of Examples A20 to A24 and the like confirmed that the ALD inhibitory properties were superior when the content of the specific compound was 0.001 mass% or more relative to the total mass of the composition.

Claims

1. A composition for forming a coating that inhibits film formation by atomic layer deposition on a region of a substrate containing silicon atoms and nitrogen atoms, the composition comprising a compound having a repeating unit with an acidic functional group.

2. A composition for forming a coating that inhibits film formation by atomic layer deposition on a region of a substrate containing silicon atoms and germanium atoms, the composition comprising a compound having a repeating unit with an acidic functional group.

3. The composition according to claim 1 or 2, wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group.

4. The composition according to claim 1 or 2, wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group.

5. The composition according to claim 1 or 2, wherein the acidic functional group is a phosphonic acid group or a phosphinic acid group.

6. The composition according to claim 1 or 2, wherein the weight-average molecular weight of the compound is 1,000 or more.

7. The composition according to claim 1 or 2, wherein the compound contains one or more repeating units represented by any one of general formulas (1) to (3). In general formula (1), X １ represents a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. １ represents a single bond or a divalent linking group. １ represents a divalent aromatic group. １ represents a hydrogen atom, a fluorine atom, or a methyl group. ２ represents a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. ２ represents a single bond or a divalent linking group. ３ represents a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. ３ represents a single bond or a divalent linking group. ３ represents a trivalent aromatic group.

8. The composition according to claim 7, wherein the compound contains one or more repeating units represented by any one of general formulas (1) to (3), and the weight-average molecular weight of the compound is 1,000 or more.

9. The composition according to claim 1 or 2, wherein the compound contains one or more repeating units represented by any one of general formulas (4) to (6). In general formula (4), X ４ represents a phosphonic acid group or a phosphinic acid group. ４ represents a single bond or a divalent linking group. ５ represents a phosphonic acid group or a phosphinic acid group. ５ represents a single bond or a divalent linking group. ６ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ６ represents a phosphonic acid group or a phosphinic acid group. ６ represents a single bond or a divalent linking group.

10. The composition according to claim 1 or 2, further comprising a solvent, wherein the total amount of the compound and the solvent is 99.90% by mass or more based on the total mass of the composition.

11. The composition according to claim 1 or 2, wherein the film obtained by applying the composition has a water contact angle of 60 degrees or more.

12. A method for producing a modified substrate, comprising the step of contacting a substrate having a region containing silicon atoms and nitrogen atoms with the composition of claim 1 to form a coating on said region.

13. A method for producing a modified substrate, comprising the step of contacting a substrate having a region containing silicon atoms and germanium atoms with the composition of claim 2 to form a coating on said region.

14. A method for manufacturing a laminate, comprising: step 1 of contacting a substrate having a region X containing silicon atoms and nitrogen atoms and a region Y having a different composition from region X with the composition of claim 1 to form a first coating on region X; and step 2 of subjecting the substrate obtained in step 1 to atomic layer deposition to form a second coating on region Y.

15. A method for manufacturing a laminate, comprising: step 1A of contacting a substrate having a region P containing silicon atoms and germanium atoms and a region Q having a different composition from region P with the composition described in claim 2 to form a first coating on region P; and step 2A of subjecting the substrate obtained in step 1A to atomic layer deposition to form a second coating on region Q.

16. A method for producing an electronic device, comprising the method for producing the modified substrate according to claim 12.

17. A method for producing an electronic device, comprising the method for producing the modified substrate according to claim 13.

18. A compound containing a repeating unit represented by general formula (4). In general formula (4), X ４ represents a phosphonic acid group or a phosphinic acid group. ４ each independently represents a divalent linking group.

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