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

Abstract

The present invention provides a composition which is capable of forming a coating film that is formed in a specific region of a substrate and suppresses the formation of a film by atomic layer deposition processing. 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. A composition according to the present invention is for forming a coating film that suppresses the formation of a film by atomic layer deposition processing, and contains a solvent and a compound which includes a polyorganosiloxane structure and a specific functional group that bonds or adsorbs to a substrate.

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] As a method for selectively modifying a substrate as described above, Patent Document 1 discloses a surface treatment method for treating a surface including two or more regions, wherein adjacent regions among the two or more regions are made of different materials, and the surface treatment method and agent can selectively modify at least one region with a good reaction rate, thereby achieving good contrast between the regions made of different materials. The surface treatment method and agent are "a surface treatment agent containing a phosphonic acid diester compound (P) represented by general formula (P-1) and an acid."

[0004] Japanese Patent Application Laid-Open No. 2022-100079

[0005] The coating used for selective modification of a substrate as described above is required to suppress the amount of material deposited on the coating when atomic layer deposition (ALD) processing is performed on the coating, i.e., to have excellent ALD inhibition properties.

[0006] The present inventors formed a coating using the composition disclosed in Patent Document 1 and subjected the coating to an ALD process, and found that there was room for further improvement in ALD inhibition. Therefore, an object of the present invention is to provide a composition that can form a coating that is formed in a specific region of a substrate and that inhibits film formation by atomic layer deposition. 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, comprising a compound including a specific functional group that bonds to or adsorbs to a substrate and a polyorganosiloxane structure, and a solvent. [2] The composition according to [1], wherein the specific functional group is a basic functional group or an acidic functional group. [3] The composition according to [1] or [2], 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 according to [2] or [3], wherein the basic functional group is an amino group, a hydrazine group, or a guanidine group. [5] The composition according to any one of [2] to [4], wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group. [6] The composition according to any one of [2] to [5], wherein the basic functional group is a primary amino group. [7] The composition according to [2], wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group. [8] The composition according to [2] or [7], wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group. [9] The composition according to any one of [1] to [8], wherein the compound has a weight-average molecular weight of 1,000 or more.

[10] The composition according to any one of [1] to [9], wherein the polyorganosiloxane structure contains a repeating unit represented by formula (1) described below.

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

[10] , wherein the compound is a compound represented by any one of formula (2), formula (3), and formula (4) described later.

[12] The composition according to

[11] , wherein the weight average molecular weight of the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (4) is all 1,000 or more.

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

[12] , wherein the content of the compound is 5.00 mass% or less with respect to the total mass of the composition.

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

[13] , 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.

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

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

[16] A method for producing a modified substrate, comprising the step of contacting a substrate with the composition 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 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 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 a modified substrate according to

[16] .

[19] A compound represented by formula (5) described below.

[0009] The present invention provides a composition that can form a coating that is formed on a specific region of a substrate and that suppresses film formation by atomic layer deposition. 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, 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, "(meth)acrylic" is a concept that includes either or both of acrylic and methacrylic, "(meth)acrylate" is a concept that includes either or both of acrylate and methacrylate, and "(meth)acryloyl" is a concept that includes either or both of acryloyl and methacryloyl.

[0014] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight-average molecular weight. Furthermore, in this specification, unless otherwise specified, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and polydispersity index (PDI; Poly Dispersity Index) (Mw / Mn) of a specific 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 (Refractive Index Detector)).

[0015] In this specification, pKa is a value calculated using the following software package 1 based on a database of Hammett's substituent constants and known literature values. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs). If pKa cannot be calculated using the above method, a value calculated by molecular orbital calculation is used. As a specific method using molecular orbital calculation, a value obtained using Gaussian 16 based on DFT (density functional theory) is used.

[0016] [Composition] 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 processing, and includes a compound (hereinafter also referred to as "the specific compound") that includes a specific functional group that bonds to or adsorbs to a substrate and a polyorganosiloxane structure, and a solvent.

[0017] Although the reason why the composition having the above configuration can solve the problems 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 specific functional group possessed by the specific compound can bond to or adsorb to the surface of a substrate, such as a metal surface, and form a coating. Furthermore, the polyorganosiloxane structure possessed by the specific compound has high thermal stability, so it can withstand the temperature of the ALD treatment, and furthermore, because it has a relatively low surface energy, it is highly effective in inhibiting film formation by the ALD treatment. Therefore, it is believed that the specific compound having the above structure was able to form a coating that can effectively inhibit film formation by the ALD treatment. Hereinafter, the ability of this composition to form a coating that further inhibits film formation by atomic layer deposition (hereinafter also referred to as an "ALD-inhibiting film") is also referred to as "excellent effects of the present invention."

[0018] [Specific Compound] The composition contains a specific compound. As described above, the specific compound contains a specific functional group that bonds to or adsorbs to a substrate and a polyorganosiloxane structure. In order to achieve better effects of the present invention, the molecular weight (or weight average molecular weight) of the specific compound is preferably 500 or more, more preferably 1000 or more, and even more preferably 2000 or more. The upper limit can be, for example, 5000 or less. When the specific compound has a molecular weight distribution, the polydispersity (Mw / Mn, PDI) is preferably 5.0 or less, more preferably 2.0 or less, even more preferably 1.5 or less, and particularly preferably 1.3 or less. The lower limit is usually 1.0, and preferably 1.05 or more.

[0019] <Specific Functional Group> The specific compound may have a specific functional group in the main chain or in the side chain, but preferably at the end of the main chain or the end of the side chain, and more preferably at the end of the main chain. In this specification, the term "main chain" refers to the longest atomic chain among the atomic chains constituting the specific compound, and the term "side chain" refers to an atomic chain other than the main chain among the atomic chains constituting the specific compound. In this specification, the term "end" refers to an atomic group connected to the end of the main chain or the side chain. The number of specific functional groups contained in the specific compound is not particularly limited as long as it is 1 or more, but is preferably 1 to 100, more preferably 1 to 60, more preferably 1 or 2, and even more preferably 1.

[0020] 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.

[0021] 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.

[0022] Examples of the specific functional group include a basic functional group and an acidic functional group. In addition, examples of the specific functional group include a nitrogen-containing group, a hydroxy group (—OH), a thiol group (—SH), a cyano group (—CN), a phosphonate ester bond-containing group, a sulfonate ester bond-containing group, an ethylenically unsaturated group, a carbon-carbon triple bond, a boronic acid group (—BO ２ H ２ ), an epoxy group, or a disulfide bond-containing group, but these groups are preferably basic functional groups or acidic functional groups.

[0023] When the specific functional group is a 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 preferably 7.0 or more, more preferably 8.0 or more, and even more preferably 9.0 or more. An example of an upper limit is 30.0 or less. 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 preferably 5.0 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. An example of a lower limit is -5.0 or more.

[0024] 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. Ｎeach independently represents a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms). 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.

[0025] Among these, the basic functional group is preferably an amino group or a nitrogen-containing aromatic heterocyclic group. The amino group may be any of a primary amino group, a secondary amino group, and a tertiary amino group, but a primary amino group is preferred. When the amino group is secondary or tertiary, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 12. The nitrogen-containing aromatic heterocyclic group is preferably an aromatic heterocyclic group having 5 or 6 ring atoms, such as an imidazole group or a pyridyl group.

[0026] 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 alkyl group include a carboxyl group (—H), a carboxyl group (—COOH), and a phenolic hydroxyl group, and a phosphonic acid group, a phosphinic acid group, or a sulfo group is preferred.

[0027] When the specific functional group is the specific functional group B, it is preferably a group capable of forming a hydrogen bond, an acid-base interaction, or a covalent bond (e.g., an Si—O bond, an Si—C bond, etc.) with a nonmetal. Examples of the specific functional group B include hydrolyzable silyl groups such as alkoxysilyl groups and chlorosilyl groups, siloxane bond-containing groups, silanol groups, ethylenic double bonds, cyano groups, and thiol groups.

[0028] <Polyorganosiloxane structure> The specific compound contains a polyorganosiloxane structure. When the specific compound contains a polyorganosiloxane structure, not only is the effect of the present invention excellent, but the heat resistance of the ALD inhibitory film formed by the specific compound is also excellent. The polyorganosiloxane structure preferably contains a repeating unit represented by the following formula (1):

[0029]

[0030] In formula (1), each R independently represents a hydrocarbon group. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group being preferred. The aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, and even more preferably 1 or 2. 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, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenyl group.

[0031] When the polyorganosiloxane structure contains a repeating unit represented by formula (1), the degree of polymerization of the repeating unit represented by formula (1) is preferably 2 to 100, more preferably 5 to 50, and even more preferably 10 to 50. The polyorganosiloxane structure may have one or more repeating units represented by formula (1). The content of the repeating units represented by formula (1) is preferably 25% by mass or more, more preferably 60% by mass or more, and even more preferably 80% by mass or more, based on the total repeating units of the polyorganosiloxane structure. The upper limit is not particularly limited and may be 100% by mass.

[0032] The polyorganosiloxane structure may have a repeating unit other than the repeating unit represented by the above formula (1). The other repeating units may be used alone or in combination of two or more. The specific compound may also contain repeating units other than the repeating units contained in the polyorganosiloxane structure. The content of the other repeating units is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, and even more preferably 0 to 5% by mass, based on the total repeating units of the specific compound.

[0033] The specific compound is preferably a compound represented by any one of formulas (2) to (4).

[0034]

[0035] In formula (2), n represents an integer of 2 or more. n is preferably 2 to 100, more preferably 5 to 50, and even more preferably 10 to 50. X １ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group.

[0036] In formula (2), L 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. １ Among these, a divalent linking group selected from a divalent aliphatic hydrocarbon group, a divalent aromatic group, -O-, -CO-, and a linking group formed by combining two or more of these groups is preferred. Examples of the linking group formed by combining two or more of the above groups include a divalent aliphatic hydrocarbon group (hereinafter also referred to as "linking group A") which may have at least one of an etheric oxygen atom and an ester bond (-COO-), and a group represented by -divalent aromatic group-linking group A-.

[0037] 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 number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 10, in terms of achieving better effects of the present invention.

[0038] 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 divalent aromatic group may be either monocyclic or polycyclic. The divalent aromatic group preferably has 4 to 25 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10. Among these, the arylene group is preferably a group represented by any one of the following formulas (2-1) to (2-3): In the formulae, * represents a bonding position.

[0039]

[0040] 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.

[0041] In formula (2), Y １ represents an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a hydrogen atom. １ is preferably an aliphatic hydrocarbon group which may have a substituent, or a hydrogen atom.

[0042] Y １ The aliphatic hydrocarbon group represented by Y may be linear, branched, or cyclic, but is preferably linear. １ Examples of the aliphatic hydrocarbon group represented by Y include an alkyl group, an alkenyl group, and an alkynyl group, and an alkyl group is preferred. １The number of carbon atoms in the aliphatic hydrocarbon group represented by the formula (I) is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 10, in terms of achieving better effects of the present invention.

[0043] Y １ The aromatic group represented by Y may be either an aryl group or a heteroaryl group. １ The aromatic group represented by the formula (I) may be either a monocyclic or polycyclic group. １ The aromatic group represented by the formula (I) preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms. １ Examples of the substituent that the aromatic group represented by the formula (I) 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.

[0044]

[0045] In formula (3), m and k each independently represent an integer of 2 or greater. m is preferably 2 to 100, more preferably 5 to 50, and even more preferably 10 to 50. k is preferably 2 to 50, more preferably 5 to 30, and even more preferably 5 to 20. X ２ each independently represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group.

[0046] In formula (3), L ２ each independently 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. ２ Examples of the divalent linking group represented by the formula include -NR Ｃ and divalent aliphatic hydrocarbon groups which may have an etheric oxygen atom. ２ is a divalent linking group (—CH ２Specific examples of the divalent linking group containing a methylene group bonded to a Si atom include -CH ２ -(methylene group), -methylene group-divalent aliphatic hydrocarbon group-, and -methylene group-divalent aromatic group- are exemplified. Specific examples and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic group include the above-mentioned L １ These are the same as the specific examples and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic group exemplified above.

[0047] In formula (3), Y ２ each independently represents an aliphatic hydrocarbon group which may have a substituent, -L ａ -X ａ , or -OR ａ Represents Y. ２ is often an aliphatic hydrocarbon group. ２ Examples of the aliphatic hydrocarbon group represented by the formula: １ Among these, an aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred.

[0048] Above -L ａ -X ａ In this case, L ａ represents a single bond or a divalent linking group, and X ａ represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo 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. ａ Examples of the divalent linking group represented by the formula include -NR Ｃ - optionally containing a divalent aliphatic hydrocarbon group, and a divalent aliphatic hydrocarbon group which may have an etheric oxygen atom. Specific examples and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic group include the above-mentioned L １These are the same as the specific examples and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic group exemplified above.

[0049] Above - OR ａ In this case, R ａ represents an aliphatic hydrocarbon group which may have a substituent, or a hydrogen atom. ａ The aliphatic hydrocarbon group represented by R may be linear, branched, or cyclic. ａ Examples of the aliphatic hydrocarbon group represented by R include an alkyl group, an alkenyl group, and an alkynyl group. ａ The aliphatic hydrocarbon group represented by the formula (I) may have, for example, 1 to 10 carbon atoms.

[0050]

[0051] In formula (4), l represents an integer of 2 or more. l is preferably 2 to 100, more preferably 5 to 50, and even more preferably 10 to 50. X ３ each independently represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group.

[0052] L ３ each independently 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. ２ Examples of the divalent linking group represented by the formula include -NR Ｃ - optionally containing a divalent aliphatic hydrocarbon group, and a divalent aliphatic hydrocarbon group which may have an etheric oxygen atom. Specific examples and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic group include the above-mentioned L １ These are the same as the specific examples and preferred embodiments of the divalent aliphatic hydrocarbon group and the divalent aromatic group exemplified above.

[0053] The specific compound is also preferably a compound represented by the following formula (5):

[0054]

[0055] In formula (5), r represents an integer of 2 or more. r is preferably 2 to 100, more preferably 5 to 50, and even more preferably 10 to 50. X ４ represents an amino group or a nitrogen-containing aromatic heterocyclic group. ４ is preferably an amino group, more preferably a primary amino group. Specific examples and preferred aspects of the amino group and nitrogen-containing aromatic heterocyclic group are as described above for the specific functional group. Of these, the secondary or tertiary amino group preferably has 1 to 20 carbon atoms, more preferably 1 to 15, and even more preferably 1 to 12. As the nitrogen-containing aromatic heterocyclic group, an aromatic heterocyclic group having 5 or 6 ring atoms, such as an imidazole group or a pyridyl group, is preferred.

[0056] In formula (5), L ４ represents an alkylene group which may have -O- or -COO-. The alkylene group may be linear, branched, or cyclic, but is preferably linear. The number of carbon atoms in the alkylene group is preferably 5 to 30, more preferably 5 to 20, and even more preferably 5 to 10, in terms of achieving better effects of the present invention.

[0057] In formula (5), Y ４ represents an alkyl group. The alkyl group may be linear, branched, or cyclic, but is preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 3 to 20, and even more preferably 4 to 10, in terms of achieving better effects of the present invention.

[0058] The weight average molecular weight of the compounds represented by formulas (2) to (4) is preferably 500 or more, more preferably 1000 or more, and even more preferably 2000 or more. The upper limit is, for example, 5000 or less.

[0059] The specific compound may be a commercially available product. Specific examples of commercially available products include KF-868, KF-865, KF-864, PAM-E, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, X-22-16608-3, X-22-9409, KF-859, KF-393, KF-860, KF-880, KF-8004, KF-8002, KF-8005, KF-867, KF-8021, KF-869, KF-861, KF-857, KF-862, KF-858, and X-22-3939A (all manufactured by Shin-Etsu Chemical Co., Ltd.).

[0060] 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 0.10% 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 less than 100% by mass, and preferably 99.9999% by mass or less.

[0061] [Solvent] The present composition 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.

[0062] 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.

[0063] 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.

[0064] 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.

[0065] 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.

[0066] 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.

[0067] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0068] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0069] 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.

[0070] 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 less than 100% by mass, preferably 99.999% by mass or less, and 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.

[0071] [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.

[0072] [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.

[0073] 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.

[0074] 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.

[0075] [Uses of the composition] The composition is a composition for forming a coating that inhibits film formation by atomic layer deposition, and is preferably used in a substrate modification process in the manufacturing process of a semiconductor device. The above process results in a modified substrate having a coating formed on the substrate surface. The composition is also preferably used in the manufacture of a laminate in which a material is deposited in areas where no coating has been formed by the above process, by subjecting the modified substrate to ALD processing. The methods for manufacturing the modified substrate and the laminate will be described in detail below.

[0076] <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.

[0077] 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 molybdenum 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.

[0078] 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 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.

[0079] The method for forming the non-metallic 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 non-metallic surface B is a surface treatment performed on a region made of 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] 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.

[0085] 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 multi-layer structure.

[0086] <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.

[0087] 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 methods 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.

[0088] 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.

[0089] 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.).

[0090] [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. 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 a 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 a 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 1 to 10 minutes.

[0091] 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.

[0092] 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.

[0093] [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.

[0094] [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.

[0095] 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.

[0096] 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.

[0097] [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.

[0098] 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.

[0099] 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.

[0100] 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, and may be 0.

[0101] [Step 3: Removal of Coating] 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.

[0102] 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 surface of the laminate 1, and physical dry etching, such as sputter etching and ion beam etching. Wet etching can be performed by supplying an etching solution to the laminate 1. 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, or hydrocarbon-based solvents are preferred. Among these, chemical dry etching or wet etching is preferred.

[0103] 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.

[0104] [Preparation of the present composition] [Compound] Compound E-1 was synthesized as follows.

[0105]

[0106] [Synthesis of Intermediate E-1A] Under a nitrogen flow (50 mL / min), X-22-170BX (10.0 g, 3.8 mmol, Shin-Etsu Chemical Co., Ltd.), triphenylphosphine (3.94 g, 15.0 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.), phthalimide (2.21 g, 15.0 mmmmol), and tetrahydrofuran (THF) (32 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 (registered trademark), 3.51 g, 15.0 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) in THF (18 mL). While maintaining the internal temperature of the reaction solution obtained above at 5°C or below, the solution was added dropwise to the reaction solution over 4 hours. After completion of the dropwise addition, the reaction solution was stirred at 25°C for 12 hours. After completion of the reaction, the solvent was distilled off from the reaction solution, ethyl acetate (100 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) and distilled water (100 mL) were added thereto, 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 solvent was distilled off from the resulting organic phase under a reduced pressure of 40 ° C. / 10 hPa. The resulting crude product was purified by silica gel column chromatography to obtain intermediate E-1A.

[0107] [Synthesis of Specific Compound E-1] Under a nitrogen flow (0.1 L / min), intermediate E-1A (8.00 g, 2.9 mmol) and ethanol (40 mL, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a three-necked flask and stirred. Hydrazine monohydrate (0.57 g, 11.5 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to the resulting mixture and heated to reflux for 1 hour. After completion of the reaction, the solvent was distilled off from the reaction solution, and t-butyl methyl ether (100 mL, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) and a 1 M aqueous sodium hydroxide solution (100 mL) were added thereto. 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. Compound E-1 was obtained by distilling off the solvent from the resulting organic phase under a reduced pressure of 40 ° C. / 10 hPa.

[0108] The obtained specific compound E-1 １The H-NMR (Nuclear Magnetic Resonance) data is shown below. １ H-NMR (400MHz, THF-d8): δ (ppm) = 3.20-3.44 (m, 4H), 2.60-2.80 (m, 2H), 1.53-1.65 (m, 2H), 1.30-1.40 ( m, 4H), 0.90 (t, J=7.0Hz, 3H), 0.54-0.63 (m, 4H), 0.50-0.70 (m, 204H).

[0109] Compounds E-2 to E-15 other than Compound E-1 were synthesized according to the synthesis method of Compound E-1, with the raw materials and reaction conditions appropriately adjusted to obtain the compounds shown below.

[0110] The materials used in preparing the compositions of the Examples and Comparative Examples are listed below. Regarding the specific compounds below, the numerical value at the bottom right of each repeating unit represents the degree of polymerization of that repeating unit, and the numerical value below each compound represents the weight-average molecular weight of that compound. The weight-average molecular weight and degree of polymerization of each specific compound were obtained by GPC measurement under the conditions described above. Compounds E-1 to E-15 correspond to compounds represented by formula (2).

[0111] [Specific compound]

[0112]

[0113]

[0114]

[0115] The following specific compounds were used which are commercially available: KF-865 (manufactured by Shin-Etsu Chemical Co., Ltd., compound represented by formula (3)) KF-860 (manufactured by Shin-Etsu Chemical Co., Ltd., compound represented by formula (3)) X-22-3939A (manufactured by Shin-Etsu Chemical Co., Ltd., compound represented by formula (3)) X-22-161A (manufactured by Shin-Etsu Chemical Co., Ltd., compound represented by formula (4)) X-22-9409 (manufactured by Shin-Etsu Chemical Co., Ltd., compound represented by formula (4)) KF-857 (manufactured by Shin-Etsu Chemical Co., Ltd., compound represented by formula (3))

[0116] [Comparative Compounds]

[0117]

[0118] [Solvent] PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether

[0119] [Solution Preparation] Compositions for each of the Examples and Comparative Examples were prepared by mixing specific compounds (synthetic or commercially available products) with solvents to obtain the compositions shown in the following table.

[0120] [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.

[0121] Next, each of the cleaned wafers was immersed in each of the compositions 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 wafer was immersed in IPA to perform a rinse treatment. 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 the rinsing, the wafer was dried by spraying nitrogen gas onto it. A modified substrate was obtained by the above procedure.

[0122] [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 substrate], and for the substrates before treatment by immersion in each composition (unmodified substrates: Comparative Examples CA1 to CE1), the contact angle was measured three times using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.) in an environment of 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 analyzed as 72.9 mN / m.

[0123] [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 modified substrate (wafer with each layer) obtained by [Preparation of Modified Substrate] and on a substrate (unmodified substrate) 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 ALD processing 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 ALD processing, i.e., the better the ALD inhibition. ALD inhibition of D or higher is preferable, with S being most preferable.

[0124] S: The thickness of the ALD film is less than 0.5 nm. A: The thickness of the ALD film is 0.5 nm or more and less than 1.0 nm. B: The thickness of the ALD film is 1.0 nm or more and less than 1.5 nm. C: The thickness of the ALD film is 1.5 nm or more and less than 2.0 nm. D: The thickness of the ALD film is 2.0 nm or more and less than 2.5 nm. E: The thickness of the ALD film is 2.5 nm or more.

[0125] [Results] Tables 1 to 5 show the composition and evaluation results of each composition. 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 after subtracting the content of the specific compound or comparative compound from the total mass of the composition.

[0126] In Tables 1 to 3, the values ​​in the "pKa (conjugate acid)" column indicate the acid dissociation constant of the conjugate acid of a compound obtained by adding a proton to a specific functional group in a specific compound. A "-" column indicates that the acid dissociation constant has not been evaluated. In Tables 4 to 5, the values ​​in the "pKa" column indicate the acid dissociation constant of a specific functional group in a specific compound. As described above, the acid dissociation constants are values ​​calculated using the following software package 1 based on values ​​based on a database of Hammett's substituent constants and publicly known literature values. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs) In addition, Table 1 assumes a W layer as the first surface, Table 2 assumes a Mo layer as the first surface, Table 3 assumes a Ru layer as the first surface, Table 4 assumes a Cu layer as the first surface, and Table 5 assumes a Co layer as the first surface, and all results show results assuming a Si layer (silicon wafer) as the second surface.

[0127]

[0128]

[0129]

[0130]

[0131]

[0132]

[0133] The results in Tables 1 to 5 confirm that the composition of the present invention can form a coating film that has excellent ALD inhibitory properties.

[0134] Furthermore, a comparison between Example A2 and Example A3 confirmed that when the specific functional group is a basic functional group or an acidic functional group, the ALD inhibitory properties are superior. A comparison between Example A3 and Example A4 confirmed that when the specific functional group is a basic functional group and 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 higher, the ALD inhibitory properties are superior. A comparison between Example A4 and Example A5 confirmed that when the specific functional group is a basic functional group and the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group, the ALD inhibitory properties are superior. A comparison between Example A1 and Example A5 confirmed that when the specific functional group is a basic functional group and the basic functional group is a primary amino group, the ALD inhibitory properties are superior. A comparison between Example A1 and Example A6 confirmed that when the weight-average molecular weight of the specific compound is 1000 or higher, the ALD inhibitory properties are superior. Comparison of Examples A1, A7, and A15 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 increase in the pure water contact angle on the modified Si substrate is small compared to Comparative Example CA1 (reference), and the substrate selectivity of ALD inhibition is better.

[0135] Furthermore, a comparison between Example D3 and Example D4 and the like confirmed that when the specific functional group is an acidic functional group and the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is 5.0 or less, the ALD inhibitory property is more excellent. A comparison between Example D4 and Example D5 and the like confirmed that when the specific functional group is an acidic functional group and the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group, the ALD inhibitory property is more excellent.

Claims

1. A composition for forming a coating that inhibits film formation by atomic layer deposition, comprising a compound having a specific functional group that bonds or adsorbs to a substrate and a polyorganosiloxane structure, and a solvent.

2. The composition according to claim 1, wherein the specific functional group is a basic functional group or an acidic functional group.

3. The composition according to claim 2, wherein, when the specific functional group is a 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 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 according to claim 2, wherein the basic functional group is an amino group, a hydrazine group, or a guanidine group.

5. The composition according to claim 2, wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group.

6. The composition of claim 2, wherein the basic functional group is a primary amino group.

7. The composition of claim 2, wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, a sulfo group, or a carboxy group.

8. The composition of claim 2, wherein the acidic functional group is a phosphonic acid group, a phosphinic acid group, or a sulfo group.

9. The composition according to claim 1, wherein the compound has a weight average molecular weight of 1,000 or more.

10. The composition according to claim 1, wherein the polyorganosiloxane structure contains a repeating unit represented by formula (1). In formula (1), each R independently represents a hydrocarbon group.

11. The composition according to claim 1, wherein the compound is a compound represented by any one of formulas (2), (3), and (4). In formula (2), n 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. １ represents a single bond or a divalent linking group. １ represents an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a hydrogen atom. In formula (3), m and k each independently represent an integer of 2 or more. X ２ each independently represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ２ each independently represents a single bond or a divalent linking group. ２ each independently represents an aliphatic hydrocarbon group which may have a substituent; -L ａ -X ａ , or -OR ａ Represents: L ａ represents a single bond or a divalent linking group; X ａ R represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ａ represents an aliphatic hydrocarbon group which may have a substituent, or a hydrogen atom. In formula (4), l represents an integer of 2 or more. X ３ each independently represents a primary amino group, a phosphonic acid group, a phosphinic acid group, or a sulfo group. ３ each independently represents a single bond or a divalent linking group.

12. The composition according to claim 11, wherein the compound represented by formula (2), the compound represented by formula (3), and the compound represented by formula (4) each have a weight average molecular weight of 1,000 or more.

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

14. The composition according to claim 1, wherein the combined amount of the compound and the solvent is 99.90% by mass or more based on the total mass of the composition.

15. The composition according to claim 1, wherein the film obtained by applying the composition 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 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 of which is made of a different material, with the composition 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 an atomic layer deposition process 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 represented by formula (5). In formula (5), r represents an integer of 2 or more. ４ represents an amino group or a nitrogen-containing aromatic heterocyclic group. ４ represents an alkylene group which may have —O— or —COO—. ４ represents an alkyl group.

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