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

Abstract

The present invention provides a composition for processing a semiconductor device that makes it possible to form a coating film having excellent ALD inhibition properties. A composition for processing a semiconductor device according to the present invention includes a compound having a specific functional group bonded or adsorbed to a substrate and a carbon-carbon triple bond and a solvent. The specific functional group is a basic functional group or an acidic functional group.

Description

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

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

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

[0003] As a method for selectively modifying a substrate as described above, Patent Document 1 discloses a 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. 2021-014631

[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 ALD treatment, and found that there was room for further improvement in ALD inhibition. Therefore, an object of the present invention is to provide a composition for semiconductor device treatment that can form a coating with excellent ALD inhibition properties. 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 treating a semiconductor device, comprising: a compound having a specific functional group that bonds to or adsorbs to a substrate and a carbon-carbon triple bond; and a solvent, wherein the specific functional group is a basic functional group or an acidic functional group. [2] The composition for treating a semiconductor device according to [1], wherein, when the specific functional group is a basic functional group, the acid dissociation constant of a conjugate acid of the compound obtained by adding a proton to the basic functional group is 7.0 or more; and when the specific functional group is an acidic functional group, the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is 5.0 or less. [3] The composition for treating a semiconductor device according to [1] or [2], wherein the basic functional group is an amino group, a hydrazine group, or a guanidine group. [4] The composition for treating a semiconductor device according to any one of [1] to [3], wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group. [5] The composition for treating a semiconductor device according to any one of [1] to [4], wherein the basic functional group is a primary amino group. [6] The composition for treating a semiconductor device according to any one of [1] to [5], wherein the acidic functional group is a phosphonic acid group, a sulfo group, or a carboxy group. [7] The composition for treating a semiconductor device according to any one of [1] to [6], wherein the acidic functional group is a phosphonic acid group or a sulfo group. [8] The composition for treating a semiconductor device according to any one of [1] to [7], wherein the molecular weight of the compound is 200 or more. [9] The composition for treating a semiconductor device according to any one of [1] to [8], wherein the compound is a compound represented by general formula (1) described below.

[10] The composition for treating a semiconductor device according to [9], wherein the molecular weight of the compound represented by general formula (1) is 200 or more.

[11] The composition for treating semiconductor devices according to [9] or

[10] , wherein the compound represented by the general formula (1) satisfies at least one of the requirements X1 and X2. Requirement X1: L １ is a divalent linking group containing a divalent aliphatic hydrocarbon group having 6 or more carbon atoms. １

[12] The composition for treating semiconductor devices according to any one of [9] to

[11] , wherein the compound represented by the general formula (1) satisfies at least one of requirement Y1 and requirement Y2. Requirement Y1: L １ is a divalent linking group containing a divalent aromatic group which may have a substituent. １ is an aromatic group which may have a substituent.

[13] The composition for treating a semiconductor device according to any one of [9] to

[12] , wherein the compound represented by general formula (1) is a compound represented by general formula (1b) described below.

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

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

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

[14] , wherein the solvent contains an organic solvent and water.

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

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

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

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

[18] A method for producing a modified substrate, comprising the steps of contacting a substrate with the composition for treating semiconductor devices according to any one of [1] to

[17] , and subjecting the substrate that has been contacted with the composition to a heat treatment to form a coating on the substrate.

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

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

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

[18] .

[21] A compound represented by general formula (2) described later.

[22] A compound represented by general formula (3) described later.

[0009] According to the present invention, there is provided a composition for treating semiconductor devices that can form a coating film with excellent ALD inhibitory properties. 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] The following describes the meaning of each description in this specification. 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] Unless otherwise specified, the compounds described herein may contain structural isomers, optical isomers, and isotopes. Furthermore, structural isomers, optical isomers, and isotopes may be present alone or in combination with one another. In this specification, when there are multiple substituents, linking groups, etc. (hereinafter referred to as "substituents, etc.") denoted by specific symbols, or when multiple substituents, etc. are simultaneously specified, this means that the respective substituents, etc. may be the same or different from one another. This also applies to the specification of the number of substituents, etc. In this specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -COO-) may be either "X-O-CO-Z" or "X-CO-O-Z" when Y in a compound represented by "X-Y-Z" is -COO-.

[0013] 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.

[0014] [Composition for treating semiconductor devices] The composition for treating semiconductor devices of the present invention (hereinafter also referred to as "the composition") will be described in detail below. The composition for treating semiconductor devices of the present invention is a composition for treating semiconductor devices, comprising a compound having a specific functional group that bonds to or adsorbs to a substrate and a carbon-carbon triple bond, and a solvent, wherein the specific functional group is a basic functional group or an acidic functional group. The mechanism by which the problem of the present invention can be solved by the composition for treating semiconductor devices of the present invention having the above-mentioned configuration is not necessarily clear, but 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 included in the scope of the present invention.

[0015] Since ALD processing is generally performed in high-temperature environments of several hundred degrees, it is preferable that the coating that inhibits the deposition of materials during ALD processing has excellent heat resistance. Since the present composition contains a specific compound having a carbon-carbon triple bond in its molecule, the carbon-carbon triple bonds can react with each other due to the heat in the ALD process to form a strong coating. Therefore, it is presumed that, because such a strong coating can be formed, the coating formed using the present composition has excellent ALD inhibitory properties. Hereinafter, the ability of the present composition to form a coating with even better ALD inhibitory properties is also referred to as "excellent effects of the present invention."

[0016] [Specific Compound] The present composition contains a compound (hereinafter also referred to as "specific compound") having a specific functional group that bonds to or adsorbs to a substrate and a carbon-carbon triple bond.

[0017] <Specific Functional Group> Specific examples of the interaction between the specific functional group and the substrate include, for example, covalent bonds, coordinate bonds, ionic bonds, hydrogen bonds, acid-base interactions, van der Waals bonds, and metallic bonds. When a coating is formed using the composition on a metal surface A composed of a metal material in a substrate, a coordinate bond or ionic bond is preferred, and a coordinate bond is more preferred. Examples of the metal include transition metals, and copper, cobalt, titanium, tantalum, tungsten, ruthenium, or molybdenum are preferred, cobalt, titanium, tantalum, tungsten, ruthenium, or molybdenum are more preferred, and cobalt, tungsten, ruthenium, or molybdenum are even more preferred. When a coating is formed using the composition on a non-metal surface B composed of a non-metal material in a substrate, a hydrogen bond, acid-base interaction, or covalent bond is preferred, and acid-base interaction or covalent bond is more preferred. Details of the substrate and the surface of the substrate will be described later.

[0018] 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 an "interactive group A") or a group that bonds to or adsorbs onto a non-metal surface B of the substrate (also referred to as an "interactive group B"), and is more preferably an interactive group A.

[0019] The specific compound preferably has a specific functional group at the molecular end, since this allows for the formation of a denser coating and provides better effects of the present invention. The number of specific functional groups that the specific compound has is not particularly limited as long as it is 1 or more, but is preferably 1 to 3, and more preferably 1.

[0020] As described above, the specific functional group is a basic functional group or an acidic functional group. When the specific functional group is a basic functional group, the acid dissociation constant (hereinafter also referred to as "pKa(b)") of the conjugate acid of the specific compound obtained by adding a proton to the basic functional group is preferably 7.0 or more. For example, when the specific compound is compound E-3 shown below, the equilibrium state with respect to pKa(b) is represented by the following dissociation equilibrium formula, and pKa(b) is 8.2.

[0021]

[0022] When the pKa(b) is 7.0 or more, the specific functional group is more likely to be adsorbed or bonded to the substrate (especially a substrate having a tungsten surface or a ruthenium surface), and a coating exhibiting predetermined properties is more likely to be stably formed on the substrate. The pKa(b) is preferably 8.0 or more, more preferably 9.0 or more, and even more preferably 10.0 or more. There is no particular upper limit, but it is preferably 30.0 or less.

[0023] Examples of basic functional groups include nitrogen-containing groups. Among these, amino groups and hydrazine groups (H ２ N-NH-*. * indicates the bond position.) or a guanidine group (H ２ N-C(=NH)-NH-*. * represents a bonding position. ) is preferred, a primary amino group, a secondary amino group, or a tertiary amino group is more preferred, and a primary amino group is even more preferred. In this specification, an amino group contained in a hydrazine group or a guanidine group is not included in the above amino group (primary amino group, secondary amino group, or tertiary amino group). In other words, in this specification, a hydrazine group and a guanidine group are treated as groups separate from an amino group.

[0024] The nitrogen-containing group may be a nitrogen-containing heterocyclic group, and examples thereof include nitrogen-containing aromatic heterocyclic groups such as a pyridyl group, an oxazolyl group, a triazine group, a pyrrole group, a pyrazole group, an imidazole group, a pyrazole group, a triazole group, a benzimidazole group, and a benztriazole group, as well as nitrogen-containing aliphatic heterocyclic groups formed by removing one hydrogen atom from an alicyclic amine such as pyrrolidine, piperidine, morpholine, 1,4-diazabicyclo[2.2.2]octane (DABCO (registered trademark)), 1,8-diazabicyclo[5.4.0]-7-undecene (DBU (registered trademark)), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0025] The basic functional group is preferably a group represented by any one of formulas (S1) to (S3), where * represents a bonding position.

[0026]

[0027] In formula (S1), R Ｔ each independently represents a hydrogen atom or an alkyl group (preferably having 1 to 5 carbon atoms, more preferably having 1 to 3 carbon atoms). Ｔ may be bonded to each other to form a ring. The ring formed is a ring containing a nitrogen atom, and examples thereof include a pyridine ring, a pyrrolidine ring, a piperidine ring, and a piperazine ring.

[0028] When the specific functional group is an acidic functional group, the acid dissociation constant (hereinafter also referred to as "pKa(a)") of the specific compound when a proton dissociates from the acidic functional group is preferably 5.0 or less. For example, when the specific compound is compound E-15 shown below, the equilibrium state with respect to pKa(a) is represented by the following dissociation equilibrium formula, and pKa(a) is 4.8.

[0029]

[0030] When the pKa(a) is 5.0 or less, the specific functional group is more likely to be adsorbed or bonded to a substrate (particularly a substrate having at least one of a copper surface and a cobalt surface), and a coating exhibiting predetermined properties is more likely to be stably formed on the substrate. The pKa(a) is preferably 10.0 or less, more preferably 5.0 or less, and even more preferably 3.0 or less. There is no particular lower limit, but it is preferably -5.0 or more.

[0031] Examples of the acidic functional group include a phosphonic acid group (-PO ３ H ２ ), sulfo group (—SO ３ H), a carboxy group (—COOH), a phenolic hydroxyl group, or a phosphate group (—PO ４ H ２ ) are included. The acidic functional group is preferably a phosphonic acid group, a sulfo group, or a carboxy group, and more preferably a phosphonic acid group or a sulfo group. The acidic group may form a salt in the present composition. Examples of salts of the acidic group include salts with inorganic metal ions such as alkali metal ions and alkaline earth metal ions.

[0032] <Carbon-Carbon Triple Bond> As described above, the specific compound has a carbon-carbon triple bond (hereinafter also referred to as a "C≡C bond"). Preferably, the C≡C bond is one in which a reaction between C≡C bonds proceeds upon heating. When the specific compound has a C≡C bond, after a film made of the specific compound is formed on a substrate, the polymerizable groups are reacted with each other by heat treatment, resulting in a film made of the specific compound that has excellent heat resistance and is highly inhibitory to ALD film formation. Furthermore, because the film has excellent heat resistance, the process window in semiconductor device processing steps can be widened. The C≡C bond may be an intramolecular bond, or the C≡C bond may be present at a molecular terminal. In terms of achieving better effects of the present invention, it is preferable that the specific compound has a carbon-carbon triple bond within the molecule. The number of C≡C bonds in the specific compound is not particularly limited as long as it is one or more, but is preferably 1 to 3, and more preferably 1 or 2.

[0033] In order to obtain a more excellent effect of the present invention, the molecular weight of the specific compound is preferably 50 or more, more preferably 200 or more, and even more preferably 300 or more. There is no particular upper limit, but an example is 1,000 or less.

[0034] Compound Represented by General Formula (1) The specific compound is preferably a compound represented by general formula (1).

[0035]

[0036] In the general formula (1), X represents a primary amino group, a phosphonic 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.

[0037] In general formula (1), L １ represents a single bond or a divalent linking group. １ Examples of the divalent linking group represented by the formula (I) include a divalent aromatic group, a divalent aliphatic hydrocarbon group, —O—, —CO— (carbonyl group), —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 aromatic group, a divalent aliphatic hydrocarbon group, -O-, and a group formed by combining two or more of these groups are preferred. Examples of a group formed by combining two or more of a divalent aromatic group, a divalent aliphatic hydrocarbon group, and -O- include -divalent aliphatic hydrocarbon group-O-divalent aromatic group-, -divalent aliphatic hydrocarbon group-O-divalent aromatic group-O-divalent aromatic group-, and -divalent aromatic group-NH-CO-divalent aliphatic hydrocarbon group-.

[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 a monocyclic or polycyclic group. 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.

[0039] The arylene group may have a structure in which multiple aromatic hydrocarbon rings are bonded via single bonds, such as a biphenyl structure. Among these, the arylene group is preferably a group represented by any one of the following formulas (2-1) to (2-3). In the formulas, * represents the bonding position.

[0040]

[0041] 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 or an alkynylene group being preferred. The number of carbon atoms in the divalent aliphatic hydrocarbon group is preferably 6 to 30, more preferably 8 to 28, and even more preferably 10 to 24, in order to improve the stability of the film made of the specific compound on the substrate. Of these, the number of carbon atoms in the alkynylene group is preferably 2 to 6, and more preferably 2 or 3.

[0042] L １ The divalent aromatic group and the divalent aliphatic hydrocarbon group exemplified as the divalent linking group represented by the formula (I) may have a substituent. The substituent is preferably an alkyl group, an alkynyl group, an alkoxy group, a phenyl group, or an amide group. The number of carbon atoms in the substituent that the divalent aromatic group and the divalent aliphatic hydrocarbon group may have is preferably 1 to 30, more preferably 6 to 30, still more preferably 8 to 28, and particularly preferably 10 to 24.

[0043] In general formula (1), 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.

[0044] 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. １ The number of carbon atoms in the aliphatic hydrocarbon group represented by Y is preferably 6 to 30, more preferably 8 to 28, and even more preferably 10 to 24, in order to improve the stability of the film made of the specific compound on the substrate. １ The substituent that the aliphatic hydrocarbon group represented by the formula (I) may have includes an aromatic group.

[0045] 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 and an alkoxy group. The number of carbon atoms in the alkyl group is preferably 6 to 30, more preferably 8 to 28, and even more preferably 10 to 24. The number of carbon atoms in the alkoxy group is preferably 6 to 30, more preferably 8 to 28, and even more preferably 10 to 24.

[0046] The compound represented by the general formula (1) preferably satisfies at least one of the following requirements X1 and X2.

[0047] (Requirements X1 and X2) Requirement X1: L １ is a divalent linking group containing a divalent aliphatic hydrocarbon group having 6 or more carbon atoms. １ In the above requirement X1, the divalent aliphatic hydrocarbon group having 6 or more carbon atoms is L １Among the divalent aliphatic hydrocarbon groups exemplified as the divalent linking group represented by the formula (I), groups having 6 or more carbon atoms are exemplified. Among the divalent aliphatic hydrocarbon groups having 6 or more carbon atoms, alkylene groups having 6 or more carbon atoms are preferred. The divalent linking group containing a divalent aliphatic hydrocarbon group having 6 or more carbon atoms may contain a divalent aliphatic hydrocarbon group having 6 or more carbon atoms, and among these, a divalent aliphatic hydrocarbon group having 6 or more carbon atoms or -divalent aliphatic hydrocarbon group having 6 or more carbon atoms-O-divalent aromatic group- is preferred, an alkylene group having 6 or more carbon atoms or -alkylene group having 6 or more carbon atoms-O-phenylene group- is more preferred, and an alkylene group having 6 to 30 carbon atoms is even more preferred.

[0048] In the above requirement X2, the aliphatic hydrocarbon group having 6 or more carbon atoms, which may have a substituent, is preferably Y １ Examples of the optionally substituted aliphatic hydrocarbon group having 6 or more carbon atoms include those represented by the following formula: The optionally substituted aliphatic hydrocarbon group having 6 or more carbon atoms is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 28 carbon atoms, and even more preferably an alkyl group having 10 to 24 carbon atoms.

[0049] The compound represented by the general formula (1) preferably satisfies at least one of the following requirements Y1 and Y2.

[0050] (Requirements Y1 and Y2) Requirement Y1: L １ is a divalent linking group containing a divalent aromatic group which may have a substituent. １ In the above requirement Y1, the divalent aromatic group is L １ Examples of the divalent aromatic group that may have a substituent include the divalent aromatic group represented by L １Examples of the divalent linking group include the groups exemplified as the substituent that the divalent aromatic group exemplified as the divalent linking group represented by the formula (I) may have. The divalent linking group containing a divalent aromatic group that may have a substituent may be any divalent aromatic group that may have a substituent, and among them, an arylene group having 6 to 20 carbon atoms or -alkylene group-O-arylene group having 6 to 20 carbon atoms is preferred, and a phenylene group or -alkylene group-O-phenylene group- is more preferred. The alkylene group preferably has 6 to 30 carbon atoms.

[0051] In the above requirement Y2, the aromatic group which may have a substituent is １ The aromatic group represented by the following formula (I) which may have a substituent is as described in detail above.

[0052] Compound Represented by General Formula (1a) In terms of achieving better effects of the present invention, the compound represented by the general formula (1) is preferably a compound represented by general formula (1a).

[0053]

[0054] In the general formula (1a), X represents a primary amino group, a phosphonic acid group, or a sulfo group. １ａ and L ２ａ Each of Y independently represents a single bond or a divalent linking group. １ａ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. k represents an integer of 0 to 2, and n represents an integer of 0 to 3. When n is 1 or more, a plurality of Y １ａ may be the same or different.

[0055] In general formula (1a), L １ａ and L ２ａ each independently represents a single bond or a divalent linking group. １ａ and L ２ａ Examples of the divalent linking group represented by the formula (1) include the group represented by the formula (1) １ Examples of the divalent linking group represented by the formula: １ａAmong these, a divalent aliphatic hydrocarbon group, —O—, or a group formed by combining a divalent aliphatic hydrocarbon group and —O— (for example, a divalent aliphatic hydrocarbon group —O—) is preferred as L. ２ａ Among these, a single bond, a divalent aliphatic hydrocarbon group, or a group formed by combining a divalent aromatic group with -O- (for example, a divalent aromatic group -O-) is preferred. The divalent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. 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 6 to 30 carbon atoms, more preferably 8 to 28, and even more preferably 10 to 18. The divalent aliphatic hydrocarbon group may have a substituent. Examples of the substituent include a phenyl group.

[0056] In general formula (1a), Y １ａ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. １ａ and an aliphatic hydrocarbon group represented by the following formula: １ａ Examples of the aromatic group which may have a substituent include the aromatic group represented by the general formula (1), １ and an aliphatic hydrocarbon group represented by the following formula: １ Examples of the aromatic group which may have a substituent represented by the formula: １ａ Among these, a hydrogen atom or an aliphatic hydrocarbon group which may have a substituent is preferred. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group or an alkynyl group being preferred. The alkyl group preferably has 6 to 30 carbon atoms, more preferably 8 to 28 carbon atoms, and even more preferably 10 to 18 carbon atoms. The alkynyl group preferably has 2 to 6 carbon atoms, and more preferably 2 or 3 carbon atoms.

[0057] The aromatic group is preferably a monocyclic aryl group. The aromatic group preferably has 4 to 25 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 10. The substituent that the aromatic group may have is preferably an alkyl group, more preferably an alkyl group having 1 to 20 carbon atoms, and even more preferably an alkyl group having 1 to 18 carbon atoms.

[0058] In formula (1a), k represents an integer of 0 to 2, and n represents an integer of 0 to 3. k is preferably 0 or 1, and more preferably 0. n is preferably 0 or 1.

[0059] Compound Represented by General Formula (1b) or General Formula (1c) The compound represented by the general formula (1a) is preferably a compound represented by general formula (1b) or a compound represented by general formula (1c).

[0060]

[0061] In the general formula (1b), X represents a primary amino group, a phosphonic acid group, or a sulfo group. １ｂ represents a single bond or a divalent linking group. １ｂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. In general formula (1c), X represents a primary amino group, a phosphonic acid group, or a sulfo group. １ｃ represents a single bond or a divalent linking group. １ｃ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent.

[0062] In general formula (1b), L １ｂ represents a single bond or a divalent linking group. １ｂ Examples of the divalent linking group represented by the formula (1) include the group represented by the formula (1) １ Examples of the divalent linking group represented by the formula: １ｂ A preferred embodiment of the divalent linking group represented by the formula: １ In general formula (1b), the benzene ring and L １ｂThe bonding position is not particularly limited, but it is preferably bonded to the para position relative to the bonding position between the benzene ring and the triple bond.

[0063] In general formula (1b), Y １ｂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. １ｂ and an aliphatic hydrocarbon group represented by the following formula: １ｂ Specific examples of the aromatic group which may have a substituent represented by the formula (1) include the aromatic group represented by the formula (1) １ and an aliphatic hydrocarbon group represented by the following formula: １ In general formula (1b), two Y １ｂ Among these, it is preferable that at least one of them is an aliphatic hydrocarbon group which may have a hydrogen atom or a substituent, and it is more preferable that both of them are aliphatic hydrocarbon groups which may have a hydrogen atom or a substituent. The aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, and an alkyl group or an alkynyl group is preferable. The number of carbon atoms in the alkyl group is preferably 6 to 30, more preferably 8 to 28, and even more preferably 10 to 18. The number of carbon atoms in the alkynyl group is preferably 2 to 6, and more preferably 2 or 3.

[0064] In general formula (1c), L １ｃ represents a single bond or a divalent linking group. １ｃ Examples of the divalent linking group represented by the formula (1) include the group represented by the formula (1) １ Examples of the divalent linking group represented by the formula: １ｃ A preferred embodiment of the divalent linking group represented by the formula: １ In general formula (1c), the benzene ring and L １ｃ The bonding position is not particularly limited, but it is preferably bonded to the para position relative to the bonding position between the benzene ring and the triple bond.

[0065] In general formula (1c), Y １ｃ represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. １ｃ and an aliphatic hydrocarbon group represented by the following formula: １ｃ Specific examples of the aromatic group which may have a substituent represented by the formula (1) include the aromatic group represented by the formula (1) １ and an aliphatic hydrocarbon group represented by the following formula: １ Examples of the aromatic group which may have a substituent represented by the formula: １ｃ Among these, hydrogen atoms or aliphatic hydrocarbon groups which may have a substituent are preferred. The aliphatic hydrocarbon groups may be linear, branched, or cyclic, but linear groups are preferred. Examples of the aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl or alkynyl groups being preferred. The alkyl group preferably has 6 to 30 carbon atoms, more preferably 8 to 28, and even more preferably 10 to 18. The alkynyl group preferably has 2 to 30 carbon atoms, and more preferably 2 to 18.

[0066] In order to obtain a more excellent effect of the present invention, the molecular weight of the compound represented by the general formula (1) is preferably 50 or more, more preferably 200 or more, and even more preferably 300 or more. There is no particular upper limit, but an example thereof is 1,000 or less.

[0067] The content of the specific compound is preferably 0.001 to 10% by mass, more preferably 0.01 to 5.00% by mass, and even more preferably 0.01 to 0.99% by mass, relative to the total mass of the composition. The content of the polymer is preferably 80% by mass or more, more preferably 90% by mass or more, and even more preferably 93% by mass or more, relative to the total mass of all components in the composition excluding the solvent. The upper limit is less than 100% by mass, and preferably 99.9999% by mass or less. Two or more specific compounds may be used in combination. When two or more specific compounds are used in combination, it is preferable that the total content be in the above range.

[0068] [Solvent] The composition contains a solvent. Examples of the solvent include water and an organic solvent. The solvent preferably contains an organic solvent, and more preferably contains an organic solvent and water. When the solvent contains water and an organic solvent, the content of the organic solvent is preferably 70% by mass or more, more preferably 80.0% by mass or more, and even more preferably 90.0% by mass or more, relative to the total mass of the solvent. The upper limit is less than 100% by mass, preferably 99.9% by mass or less, and more preferably 99.0% by mass or less. When the solvent contains water and an organic solvent, the content of water is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, relative to the total mass of the solvent. The upper limit is preferably 30.0% by mass or less, more preferably 20.0% by mass or less, and even more preferably 10.0% by mass or less. 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0075] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0076] 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 a glycol monoether solvent or an alcohol solvent, more preferably contains at least one selected from the group consisting of PGMEA, PGME, methyl isobutyl carbinol, isopropyl alcohol, cyclohexanone, ethyl lactate, EtOH, and γ-butyrolactone, and even more preferably contains at least one selected from the group consisting of PGMEA, PGME, methyl isobutyl carbinol, and isopropyl alcohol.

[0077] 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 less than 100% by mass, preferably 99.999% by mass or less, more preferably 99.9% by mass or less, and even more preferably 99.0% by mass or less. Furthermore, the total amount of the specific compound and the solvent is preferably 95.00% by mass or more, more preferably 99.00% by mass or more, and even more preferably 99.90% by mass or more, relative to the total mass of the composition. The upper limit is not particularly limited and may be, for example, 100% by mass or less. When the total amount of the specific compound and the solvent is within the above range, the amount of components other than the specific compound and the solvent is very small, so that the composition contains few impurities and can efficiently form a film composed of the specific compound on a substrate. Two or more solvents may be used in combination. When two or more solvents are used in combination, it is preferable that the total content is within the above range.

[0078] [Polymerization inhibitor] The composition preferably contains a polymerization inhibitor, which improves the stability of the composition. The polymerization inhibitor is not particularly limited, and any known polymerization inhibitor can be selected, but a radical polymerization inhibitor is preferred.

[0079] The polymerization inhibitor preferably contains at least one compound selected from the group consisting of a phenol-based compound, a quinone-based compound, a free radical-based compound, an amine-based compound, and a phosphine-based compound, and from the viewpoint of polymerization inhibition ability, a free radical-based compound is more preferred.

[0080] Examples of phenolic compounds include 4-methoxyphenol, hydroquinone, 2-tert-butylhydroquinone, 4-tert-butylcatechol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol, 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthol, 2,4-bis(octylthiomethyl)-6-methylphenol, p-nitrosophenol, and α-nitroso-β-naphthol. Examples of quinone compounds include 1,4-benzoquinone, 1,2-benzoquinone, and 1,4-naphthoquinone. Free radical compounds include poly(4-methacryloyloxy-2,2,6,6-tetramethylpiperidine-N-oxyl), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2,6,6-tetramethylpiperidine 1-oxyl, 2,2-diphenyl-1-picrylhydrazyl, and triphenylpherdazyl. Examples of amine compounds include p-phenylenediamine, 4-aminodiphenylamine, N,N-diethylhydroxylamine, N,N'-diphenyl-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, diphenylamine, N-phenyl-β-naphthylamine, 4,4'-dicumyl-diphenylamine, 4,4'-dioctyl-diphenylamine, phenothiazine, 2-methoxyphenothiazine, phenoxazine, N-nitrosodiphenylamine, N-nitrosophenylnaphthylamine, N-nitrosodinaphthylamine, p-nitrosodiphenylamine, N-nitroso-N-phenylhydroxylamine, N-nitroso-N-phenylhydroxylamine aluminum, and cupferron. Each of the compounds exemplified as the amine-based compound may form a metal salt or a metal complex.An example of the phosphine compound is tris(2,4-di-tert-butylphenyl)phosphite.

[0081] Other polymerization inhibitors that may be included include nitrobenzene-based compounds such as nitrobenzene and 4-nitrotoluene, and thiol ethers such as dioctadecyl 3,3'-thiodipropionate, dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate.

[0082] The molecular weight of the polymerization inhibitor is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but is preferably 80 or more.

[0083] The content of the polymerization inhibitor is preferably 0.0001 parts by mass or more, more preferably 0.001 parts by mass or more, still more preferably 0.005 parts by mass or more, and particularly preferably 0.010 parts by mass or more, relative to 100 parts by mass of the specific compound. Furthermore, the content of the polymerization inhibitor is preferably 10.0 parts by mass or less, more preferably 1.000 parts by mass or less, and even more preferably 0.100 parts by mass or less, relative to 100 parts by mass of the specific compound. The composition may contain one type of polymerization inhibitor alone, or two or more types. When two or more types of polymerization inhibitors are contained, it is preferable that the total amount thereof is within the above range.

[0084] [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 in the composition is not particularly limited. For example, the composition can be produced by adding the specific compound to a stirrer such as a mixing mixer containing a purified solvent and then thoroughly stirring. When the composition contains other components other than the specific compound, the other components may be added simultaneously with the specific compound or at different times. In the production process for producing the composition, the steps described below may be carried out.

[0085] (Metal Removal Step) The above production method may include a metal removal step of removing metal components from the above component and / or composition (hereinafter also referred to as "material to be purified").

[0086] (Filtration step) The above production method preferably includes a filtration step of filtering the liquid to remove foreign matter, coarse particles, etc. from the liquid. The filtration method is not particularly limited, and known filtration methods can be used. Among them, filtering using a filter is preferred.

[0087] (Static Elimination Step) The method for producing the composition may further include a static elimination step of eliminating static electricity from the composition.

[0088] [Uses of the composition] The composition is a composition for semiconductor device processing, and is preferably used for modifying a substrate in the manufacturing process of a semiconductor device. The above-mentioned process results in a modified substrate having a coating formed on the substrate surface. The composition is also preferably used for manufacturing a laminate in which a material is deposited in the region where no coating is formed by the above-mentioned process, by subjecting the modified substrate to an ALD process. Methods for manufacturing a modified substrate and a laminate will be described in detail later.

[0089] <Substrate> The substrate is not particularly limited, but preferably has at least two surfaces, a first surface and a second surface, made of different materials. When the substrate has two surfaces, a specific compound can be selectively bonded or adsorbed to one surface, forming a coating that highly inhibits ALD film formation on that surface. The first surface is a surface that adsorbs or bonds to a specific functional group. The second surface may be made of a material different from the first surface, but is preferably a surface that does not form a film when contacted with the composition. In particular, at least one of the first surface and the second surface is preferably a metal surface A made of a metal material (a material containing metal atoms) or a non-metal surface B made of a non-metal material, and more preferably at least one of the first surface and the second surface is a metal surface A.

[0090] 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. Tungsten atoms, ruthenium atoms, molybdenum atoms, tantalum atoms, or cobalt atoms are more preferred, and tungsten atoms, molybdenum atoms, or cobalt atoms are even more preferred. The form of the metal atoms in the metal surface A is not particularly limited, but examples include 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. When the first surface is a metal surface A containing a molybdenum atom, the specific functional group possessed by the specific compound is preferably a basic functional group. 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 can be mentioned.

[0091] 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 ｗExamples 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.

[0092] 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.

[0093] A preferred embodiment of the substrate is embodiment 1, in which the first surface is a metal surface A. In embodiment 1, the metal atoms contained in the first surface, metal surface A, are preferably 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 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.

[0094] 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.

[0095] 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 interactive group possessed by the polymer is the above-described interactive group B. In embodiment 2, the second surface is preferably a metallic surface A. In embodiment 2, the metal atoms contained in the metallic surface A, which is the second surface, 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.

[0096] 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.

[0097] 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.

[0098] <Coating> The coating formed on a substrate using the present composition 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 having a coating formed on a specific region using the present composition, it is preferable that the material does not deposit in the region where the coating is formed, but the material deposits in the region where the coating is not 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 is formed.

[0099] 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.

[0100] The water contact angle of the film obtained by applying the present composition is preferably 60 degrees or more, more preferably 70 degrees or more, and even more preferably 80 degrees or more. There is no particular upper limit, and it is often 120 degrees 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.).

[0101] [Method for Producing Modified Substrate] The method for producing a modified substrate of the present invention includes the steps of contacting a substrate with the composition and heat-treating the substrate that has been contacted with the composition to form a coating on the substrate. This results in a modified substrate having a coating formed on the substrate. The method for contacting the substrate with the composition is not particularly limited, and known methods can be used. Examples include a method of applying (e.g., spin coating) or spraying the composition onto the substrate, and a method of immersing the substrate in the composition. When immersing the substrate in the composition, the composition may be subjected to convection. The temperature of the composition when contacting the substrate with the composition is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C.

[0102] After contacting the substrate with the composition, the substrate is subjected to a heat treatment to promote the reaction between triple bonds in the specific compound. The heating method is not particularly limited, and known methods can be used, including contacting the substrate with a heating element (e.g., heating with an oven or hot plate) and irradiating the substrate with infrared rays. 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 200 to 300°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 1 minute to 30 minutes, and even more preferably 3 minutes to 10 minutes.

[0103] After contacting the substrate with the present composition, it is also preferable to perform a rinsing treatment. The rinsing treatment can remove the present composition and / or impurities adhering to regions on the substrate other than the desired region (e.g., the region that interacts with the specific functional group 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. The contacting method can be the same as the method of contacting the present composition with the substrate. 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. Known organic solvents can be used as the rinsing liquid, such as the alcohol-based solvents, ether-based solvents, and ester-based solvents described above. It is also preferable to use the solvent contained in the present composition as the rinsing liquid.

[0104] [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.

[0105] [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 components other than the solvent (e.g., a specific compound) contained in the present composition. The method for bringing the specific substrate into contact with the present composition is not particularly limited, 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.

[0106] After contacting the specific substrate with the composition, it is also preferable to subject the coating film to a heat treatment. The heating method is not particularly limited, and the heating methods used in the above-mentioned method for producing a modified substrate can be used.

[0107] 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 the composition and / or 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.

[0108] [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.

[0109] The ALD treatment method is not particularly limited, and known methods can be used, but thermal ALD is preferred. When using thermal ALD, a reaction between carbon-carbon triple bonds possessed by the specific compound in the first coating may proceed during the thermal ALD treatment. To enhance the effects of the present invention, the substrate heating temperature in the ALD treatment is preferably 100 to 400°C, more preferably 150 to 400°C, and even more preferably 250 to 350°C. For example, a method of forming an ALD film by supplying a precursor gas serving as a raw material for the ALD film to the surface of the modified substrate 1, and then decomposing and / or chemically reacting the raw material with an oxidizing agent or the like to deposit the material, can be used. 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 compounds described in paragraphs

[0021] to

[0025] of JP 2022-080800 A. The oxidizing agent is not particularly limited, and any known oxidizing agent used in ALD processing can be used, such as water, oxygen, and ozone.

[0110] 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.

[0111] After the ALD process, the thickness of the material deposited on the first coating is preferably as thin as possible, and is 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, and may be 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 0.5 or less, and even more preferably 0.25 or less. The lower limit of the ratio is 0 or more, and may be 0.

[0112] [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.

[0113] 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.

[0114] [Method for Manufacturing an Electronic Device] The above-described method for manufacturing a modified substrate and a method for manufacturing a laminate can be suitably applied to a method for manufacturing an electronic device. The method for manufacturing an electronic device of the present invention preferably includes a method for manufacturing a modified substrate, and more preferably includes a method for manufacturing a laminate. The method for manufacturing a modified substrate may be performed before or after other processes performed on a substrate. Other processes may be incorporated into the method for manufacturing a modified substrate, or the method for manufacturing a modified substrate may be incorporated into other processes. Examples of other processes include processes for forming structures such as metal wiring, gate structures, source structures, drain structures, insulating films, ferromagnetic layers, and nonmagnetic layers (e.g., layer formation, etching, chemical mechanical polishing, and modification), resist formation processes, exposure processes, removal processes, heat treatment processes, cleaning processes, and inspection processes.

[0115] The above processing method may be performed at any stage of a back end process (BEOL: Back end of the line), a middle process (MOL: Middle of the line), or a front end process (FEOL: Front end of the line).

[0116] [Compound] The present invention also includes an invention of a compound. The compound in the present invention is the above-mentioned specific compound. In terms of achieving better effects of the present invention, the specific compound is preferably a compound represented by general formula (2) or a compound represented by general formula (3). The compound represented by general formula (2) will be described in detail below.

[0117]

[0118] In general formula (2), L ２ represents a divalent linking group containing a divalent aromatic group. ２ represents an aliphatic hydrocarbon group having 8 or more carbon atoms which may have a substituent, or an aromatic group which may have a substituent.

[0119] L ２The definition and preferred embodiments of the divalent linking group containing a divalent aromatic group, represented by the formula (I) are as described in detail in Requirement Y1. As the divalent linking group containing a divalent aromatic group, an arylene group having 6 to 20 carbon atoms or -alkylene group-O-arylene group having 6 to 20 carbon atoms- is preferred, and a phenylene group or -alkylene group-O-phenylene group- is more preferred. The alkylene group preferably has 6 to 30 carbon atoms.

[0120] Y ２ Examples of the aliphatic hydrocarbon group having 8 or more carbon atoms, which may have a substituent, include the aliphatic hydrocarbon groups having 6 or more carbon atoms, which are described in detail in Requirement X2, and which have 8 or more carbon atoms. As the aliphatic hydrocarbon group having 8 or more carbon atoms, which may have a substituent, an alkyl group having 8 to 28 carbon atoms is preferred, and an alkyl group having 10 to 24 carbon atoms is more preferred. Y ２ The definition and preferred embodiments of the aromatic group which may have a substituent and is represented by the following formula are as described in detail in Requirement Y2.

[0121] Next, the compound represented by formula (3) will be described in detail.

[0122]

[0123] In general formula (3), L ３ represents a divalent linking group containing a divalent aromatic group. ３ represents an aliphatic hydrocarbon group having 8 or more carbon atoms which may have a substituent, or an aromatic group which may have a substituent.

[0124] L ３ The definition and preferred embodiment of the divalent linking group containing a divalent aromatic group represented by the formula (2) are as follows: ２ The definition and preferred embodiments are the same as those of the divalent linking group containing a divalent aromatic group represented by the formula: ３ The definition and preferred embodiments of the optionally substituted aliphatic hydrocarbon group having 8 or more carbon atoms, and the definition and preferred embodiments of the optionally substituted aromatic group are given in the general formula (2) of Y ２The definition and preferred embodiments of the optionally substituted aliphatic hydrocarbon group having 8 or more carbon atoms, represented by the following formula (I), are the same as the definition and preferred embodiments of the optionally substituted aromatic group.

[0125] 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.

[0126] [Preparation of the present composition] The components used in preparing the composition of the present invention are shown below.

[0127] [Specific Compound E-1] Specific Compound E-1 was synthesized as follows.

[0128]

[0129] <Synthesis of Intermediate E-1A> Palladium acetate (0.32 g, 1.4 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and tetrahydrofuran (THF, 200 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask under a nitrogen flow (30 mL / min) and stirred. Further, 1,1'-bis(diphenylphosphino)ferrocene (Dppf, 1.56 g, 2.8 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), triethylamine (6.84 g, 67.6 mmol, manufactured by Kanto Chemical Co., Inc.), and potassium acetate (0.55 g, 5.6 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added and stirred at 25°C for 0.5 hours. Thereafter, diisopropyl phosphite (5.15 g, 31.0 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 6-bromo-2-naphthyl triflate (10.0 g, 28.2 mol, manufactured by Kanto Chemical Co., Ltd.) were added, and the resulting reaction solution was stirred under heating and reflux for 8 hours. After cooling the reaction solution to 25 ° C, insoluble matter was removed by filtration using a funnel filled with Celite. The solvent was distilled off from the filtrate under a reduced pressure of 40 ° C / 10 hPa, and ethyl acetate (300 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1 M hydrochloric acid (150 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.

[0130] <Synthesis of Intermediate E-1B> Intermediate E-1A (6.50 g, 17.5 mol) and dichloromethane (130 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask and cooled to 0°C. Bromotrimethylsilane (TMSBr, 26.8 g, 175.1 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the resulting mixture and stirred at 0°C for 24 hours. MeOH (150 mL, Mitsubishi Gas Chemical Company, Inc.) was then added to the reaction solution and stirred at 25°C for 12 hours. The resulting solution was concentrated, and diisopropyl ether (50 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) was added and stirred. After allowing the solution to stand, the supernatant was removed, and dichloromethane (130 mL) was added and cooled to 0°C. The precipitated crystals were collected by filtration to obtain Intermediate E-1B.

[0131] <Synthesis of Specific Compound E-1> Under a nitrogen flow (10 mL / min), intermediate E-1B (1.90 g, 6.6 mmol) and dimethylformamide (DMF, 25 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask and stirred. Furthermore, triethylamine (13.40 g, 132.4 mmol), 1-octadecine (2.49 g, 9.9 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), copper iodide (0.13 g, 0.7 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and tetrakis(triphenylphosphine)palladium(0) (Pd(Ph ３ P) ４ , 0.38 g, 0.3 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 80°C for 12 hours. While the reaction solution was still at 80°C, insoluble matter was removed by filtration using a funnel packed with Celite. The filtrate was cooled to 0°C, and MeOH (30 mL) and 1 M hydrochloric acid (30 mL) were added, followed by stirring at 0°C for 0.5 hours. The obtained crystals were collected by filtration and washed again with MeOH (30 mL) to obtain Specific Compound E-1.

[0132] The obtained specific compound E-1 １ The H-NMR (Nuclear Magnetic Resonance) data is shown below. １ H-NMR (400MHz, THF-d8): δ (ppm) = 8.31 (d, J = 15.0Hz, 1H), 7.90 (s, 1H), 7.74-7.85 (m, 3H), 7.44 (dd, J = 1.1Hz, 8.5Hz, 1H), 3.40-4.10 (br, 2H), 2.46 (t, J = 7.0Hz, 2H), 1.64 (m, 2H), 1.51 (m, 2H), 1.20-1.43 (m, 26H), 0.89 (t, J = 7.0Hz, 3H).

[0133] [Specific Compound E-7] Compound E-7 was synthesized as follows.

[0134]

[0135] <Synthesis of Intermediate E-7A> Under a nitrogen flow (50 mL / min), 12-bromo-1-dodecanol (15.0 g, 56.6 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), triphenylphosphine (22.3 g, 84.8 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 4-iodophenol (16.2 g, 73.5 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and THF (188 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), 19.9 g, 84.8 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) in THF (94 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 1 hour. Next, the solvent was distilled off from the reaction solution under a reduced pressure of 40 ° C. / 10 hPa, and after distillation, ethyl acetate (500 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 1 M aqueous sodium hydroxide solution (250 mL) were added, and the resulting solution was transferred to a separatory funnel and stirred. Then, the solution was allowed to stand, the lower phase (aqueous phase) was removed, and distilled water (400 mL) was added to the upper phase (organic phase) and stirred. After that, the solution was allowed to stand, the lower phase (aqueous phase) was removed, and the upper phase (organic phase) was recovered. Under a reduced pressure of 40 ° C. / 10 hPa, the solvent was distilled off from the resulting organic phase to obtain a 40% by weight ethyl acetate solution. Methanol (260 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the resulting 40% by weight ethyl acetate solution 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-7A.

[0136] <Synthesis of Intermediate E-7B> Intermediate E-7A (12.7 g, 27.2 mmol) and triisopropyl phosphite (14.2 g, 68.2 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 reaction solution under reduced pressure at 70° C. / 5 hPa, and the resulting crude product was purified by silica gel column chromatography to obtain Intermediate E-7B.

[0137] <Synthesis of Intermediate E-7C> Intermediate E-7B (18.3 g, 33.1 mol) and dichloromethane (150 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask and cooled to 0°C. Bromotrimethylsilane (TMSBr, 15.2 g, 99.3 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.) was added to the resulting mixture and stirred at 0°C for 4 hours, after which methanol (150 mL) was added to the reaction solution and stirred at 25°C for 1 hour. The resulting solution was concentrated, diisopropyl ether was added, and the mixture was stirred at 25°C for 1 hour. The precipitated crystals were filtered off, washed with diisopropyl ether, and then dried with air at 40°C for 12 hours to obtain Intermediate E-7C.

[0138] <Synthesis of Specific Compound E-7> Under a nitrogen flow (10 mL / min), intermediate E-7C (3.0 g, 5.4 mmol) and DMF (40 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a three-neck flask and stirred. Furthermore, triethylamine (11.0 g, 108.6 mmol), 1-octadecine (2.0 g, 8.1 mmol, Tokyo Chemical Industry Co., Ltd.), copper iodide (0.1 g, 0.5 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.), and tetrakis(triphenylphosphine)palladium(0) (0.31 g, 0.3 mmol, Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 80°C for 12 hours. While the reaction solution was still at 40°C, insoluble matter was removed by filtration using a funnel packed with Celite. The filtrate was cooled to 0°C and stirred for 0.5 hours. After the crystals were precipitated, the obtained crystals and 1 M hydrochloric acid (40 mL) were added to a recovery flask and stirred for 1 hour at 25° C. The crystals were separated by filtration and recrystallized from THF (30 mL) to obtain Specific Compound E-7.

[0139] The obtained specific compound E-7 １ The H-NMR data is shown below. １ H-NMR (400 MHz, THF-d8): δ (ppm) = 7.23 (d, J = 8.7 Hz, 2H), 6.79 (d, J = 8.7 Hz, 2H), 3.93 (t, J = 6.4 Hz, 2H), 2.35 (t, J = 6.9Hz, 2H), 1.66-1.84 (m, 2H), 1.51-1.65 (m, 6H), 1.40-1.50 (m, 4H), 1.20-1.40 (m, 38H), 0.89 (t, J=6.5Hz, 2H).

[0140] [Specific Compound E-18] Specific Compound E-18 was synthesized as follows.

[0141]

[0142] <Synthesis of Intermediate E-18A> Under a nitrogen flow (0.1 L / min), 12-bromo-1-dodecanol (50.0 g, 0.19 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), DMF (250 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and potassium phthalimide (38.4 g, 0.21 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added to a three-neck flask, and the resulting mixture was stirred at 50°C for 3 hours. The resulting reaction solution was cooled to 25°C, and insoluble matter was removed by filtration. The filtered product was washed with DMF (50 mL) to obtain filtrate A. Distilled water (900 mL) was added to a beaker and stirred at 25°C, and the filtrate A was added dropwise. The resulting crystals were filtered, washed twice with distilled water (200 mL), and then dried with air at 40°C for 24 hours to obtain intermediate E-18A.

[0143] <Synthesis of Intermediate E-18B> Under a nitrogen flow (10 mL / min), 6-bromo-2-naphthol (50.0 g, 0.22 mol, Fujifilm Wako Pure Chemical Industries, Ltd.) and DMF (670 mL, Fujifilm Wako Pure Chemical Industries, Ltd.) were added to a three-neck flask and stirred. Furthermore, triethylamine (453.6 g, 4.48 mol), 1-octadecine (84.2 g, 0.34 mmol, Tokyo Chemical Industry Co., Ltd.), copper iodide (4.3 g, 0.02 mmol, Fujifilm Wako Pure Chemical Industries, Ltd.), and tetrakis(triphenylphosphine)palladium(0) (13.0 g, 0.01 mmol, Tokyo Chemical Industry Co., Ltd.) were added, and the mixture was stirred at 80°C for 12 hours. After completion of the reaction, the reaction solution was cooled to 25°C, and insoluble matter was removed by filtration using a funnel packed with Celite. The resulting filtrate was concentrated to give a crude product, which was purified by silica gel chromatography to give intermediate E-18B.

[0144] <Synthesis of Intermediate E-18C> Under a nitrogen flow (50 mL / min), E-18A (5.8 g, 17.5 mmol), triphenylphosphine (6.88 g, 26.2 mol, FUJIFILM Wako Pure Chemical Industries, Ltd.), E-18B (7.56 g, 19.2 mmol), and THF (87 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), 6.15 g, 26.2 mmol, FUJIFILM Wako Pure Chemical Industries, Ltd.) in THF (29 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 1 hour. The resulting crystals were collected by filtration, washed with a slurry of methanol, and then dried with air at 40° C. for 12 hours to obtain intermediate E-18C.

[0145] <Synthesis of Specific Compound E-18> Under a nitrogen flow (0.1 L / min), intermediate E-18C (4.72 g, 6.6 mmol) and ethanol (63 mL, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask and stirred. Hydrazine monohydrate (1.34 g, 26.7 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to the resulting mixture, and the mixture was heated to reflux for 1 hour. Thereafter, the resulting reaction solution was cooled to 20°C, and the resulting crystals were collected by filtration, slurry-washed with a 1 M aqueous sodium hydroxide solution, and then washed with water. Thereafter, the mixture was dried with a blower at 40°C for 12 hours, thereby obtaining Specific Compound E-18.

[0146] The specific compound E-18 obtained １ The H-NMR data is shown below. １H-NMR (400MHz, THF-d8): δ (ppm) = 7.77 (s, 1H), 7.66 (d, J = 9.0Hz, 1H), 7.62 (d, J = 8.6H z, 1H), 7.33 (dd, J = 1.6, 8.4Hz, 1H), 7.16 (d, J = 2.4Hz, 1H), 7.10 (dd, J = 2.5, 8.9Hz, 1H ), 4.07 (t, J=6.5Hz, 2H), 2.59 (t, J=6.6Hz, 2H), 2.42 (t, J=6.9Hz, 2H), 1.78-1.87 (m, 2H), 1.57-1.66 (m, 2H), 1.45-1.56 (m, 4H), 1.20-1.45 (m, 40H), 0.88 (t, J=6.7Hz, 3H).

[0147] [Specific Compounds and Comparative Compounds] The structures of the specific compounds and comparative compounds used in preparing the compositions of the Examples and Comparative Examples are shown below. Specific compounds other than E-1, E-7, and E-18 were synthesized in the same manner as in the synthesis procedures for E-1, E-7, or E-18 described above. The numerical values ​​below the structural formula of each specific compound indicate the molecular weight of the specific compound.

[0148]

[0149]

[0150]

[0151] [Polymerization inhibitor] TEMPO: 2,2,6,6-tetramethylpiperidine 1-oxyl BHT: 2,6-di-tert-butyl-p-cresol

[0152] [Solvent] PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether MIBC: Methyl isobutyl carbinol IPA: Isopropyl alcohol H ２ O: Pure water

[0153] [Liquid Preparation] The compositions of each of the Examples and Comparative Examples were prepared by mixing the specific compound or comparative compound, a solvent, and, if necessary, a polymerization inhibitor to obtain the compositions shown in Tables 1 to 3.

[0154] [Preparation of Modified Substrates] As substrates, a W-layer wafer in which a W (tungsten) layer was formed by CVD on one surface of a commercially available silicon wafer (diameter 12 inches), a Co-layer wafer in which a Co (cobalt) layer was formed by sputtering, and a Mo-layer wafer in which a Mo (molybdenum) layer was formed by CVD were prepared. The film formation conditions were adjusted so that the thicknesses of the W layer, Co layer, and Mo layer were each 20 nm. The silicon wafer, W-layer wafer, Co-layer wafer, and Mo-layer wafer were cut into 2 cm squares and cleaned by immersion in isopropyl alcohol (IPA). 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 wafers were dried by spraying nitrogen gas.

[0155] 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.

[0156] [Evaluation] [Evaluation of contact angle with pure water after substrate modification] For each modified substrate obtained in [Preparation of modified substrate] and for the substrate (unmodified substrate) before treatment by immersion in each composition, the contact angle was measured three times using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.) at 23°C, 500 milliseconds after a water droplet contacted the surface of the measurement object, and the average value was taken as the contact angle (deg.). The surface tension of pure water was assumed to be 72.9 mN / m for the analysis.

[0157] [Evaluation of ALD Inhibition] Aluminum oxide (Al) was deposited by the ALD method using an atomic layer deposition apparatus (AD-230LP, manufactured by Samco) on the W layer wafer, Co layer wafer, or Mo layer wafer after the modification treatment obtained in [Preparation of Modified Substrate], and on the W layer wafer, Co layer wafer, or Mo layer wafer (unmodified substrate) before the treatment by immersion in each composition.２ O ３ ) layer (ALD film). Trimethylaluminum was used as the organometallic source and water as the oxidizing agent, and the ALD treatment temperature was 200°C. Other conditions were adjusted so that the ALD film formed on the unmodified substrate would have a thickness of 5 nm. The thickness of the ALD film for each sample after the ALD treatment 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. ALD inhibition was evaluated from the obtained film thickness according to the following evaluation criteria. The smaller the film thickness, the more difficult it is for a film to deposit by the ALD treatment, i.e., the better the ALD inhibition. ALD inhibition of D or higher is preferred.

[0158] 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.

[0159] Tables 1 to 3 show the composition and evaluation results of each composition. Table 1 shows the results of evaluating the selectivity of Co-layer wafers relative to silicon wafers, Table 2 shows the results of evaluating the selectivity of W-layer wafers relative to silicon wafers, and Table 3 shows the results of evaluating the selectivity of Mo-layer wafers relative to silicon wafers. In Table 1, the value in the "pKa" column indicates the acid dissociation constant of the specific functional group in the specific compound. In Tables 2 and 3, the value in the "pKa" column indicates the acid dissociation constant of the conjugate acid of a compound obtained by adding a proton to the specific functional group in the specific compound. However, for Example C1, the acid dissociation constant of the specific functional group in the specific compound is shown. In the tables, the content of the solvent is the remainder when the total mass of all components of the composition is 100 parts by mass, excluding the total mass of all components other than the solvent (specific compound or comparative compound, solvent, and polymerization inhibitor).

[0160]

[0161]

[0162]

[0163]

[0164] As shown in Tables 1 to 3, it was confirmed that the composition for semiconductor device processing of the present invention is capable of forming a coating with excellent ALD inhibitory properties. Comparisons between Examples A2 and A3, etc., confirmed that the effects of the present invention are superior when the specific functional group of the specific compound 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. Comparisons between Examples A2 and A3, etc., confirmed that the effects of the present invention are superior when the specific functional group of the specific compound is an acidic functional group and the acidic functional group is a phosphonic acid group or a sulfo group. Comparisons between Examples A4 and A5, etc., confirmed that the effects of the present invention are superior when the molecular weight of the specific compound is 200 or more. Comparisons between Examples A5 to A9 and Examples B4 to B8, etc., confirmed that the effects of the present invention are superior when the specific compound is a compound represented by general formula (1) and satisfies at least one of the above-mentioned requirements Y1 and Y2. Comparison of Examples B1 and B2 confirmed that the effects of the present invention are superior when the specific functional group of the specific compound 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. Comparison of Examples B5 to B9 confirmed that the effects of the present invention are superior when the specific functional group of the specific compound is a basic functional group and the basic functional group is a primary amino group. Comparison of Examples C1 to C3 confirmed that when the specific functional group of the specific compound is a basic functional group, ALD inhibition against the molybdenum surface is superior when the substrate has a molybdenum surface. Comparison of Examples C3 to C9 confirmed that the effects of the present invention are superior when the semiconductor device treatment composition of the present invention contains an organic solvent and water.

Claims

1. A composition for semiconductor device processing, comprising a compound having a specific functional group that bonds to or is adsorbed to a substrate and a carbon-carbon triple bond, and a solvent, wherein the specific functional group is a basic functional group or an acidic functional group.

2. A composition for treating semiconductor devices as described in claim 1, 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.

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

4. The composition for treating a semiconductor device according to claim 3, wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group.

5. The composition for treating a semiconductor device according to claim 4, wherein said basic functional group is a primary amino group.

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

7. The composition for treating a semiconductor device according to claim 6, wherein the acidic functional group is a phosphonic acid group or a sulfo group.

8. The composition for treating a semiconductor device according to claim 1, wherein the compound has a molecular weight of 200 or more.

9. The composition for treating a semiconductor device according to claim 1, wherein the compound is a compound represented by general formula (1). In the general formula (1), X represents a primary amino group, a phosphonic 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.

10. The composition for treating semiconductor devices according to claim 9, wherein the compound represented by general formula (1) has a molecular weight of 200 or more.

11. The composition for treating a semiconductor device according to claim 9, wherein the compound represented by the general formula (1) satisfies at least one of the requirements X1 and X2. Requirement X1: L １ is a divalent linking group containing a divalent aliphatic hydrocarbon group having 6 or more carbon atoms. １ is an aliphatic hydrocarbon group having 6 or more carbon atoms which may have a substituent.

12. The composition for treating a semiconductor device according to claim 9, wherein the compound represented by the general formula (1) satisfies at least one of requirement Y1 and requirement Y2. Requirement Y1: L １ is a divalent linking group containing a divalent aromatic group which may have a substituent. １ is an aromatic group which may have a substituent.

13. The composition for treating a semiconductor device according to claim 9, wherein the compound represented by general formula (1) is a compound represented by general formula (1b). In the general formula (1b), X represents a primary amino group, a phosphonic acid group, or a sulfo group. １ｂ represents a single bond or a divalent linking group. １ｂ each independently represents a hydrogen atom, an aliphatic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent.

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

15. The composition for processing a semiconductor device of claim 1, wherein the solvent comprises an organic solvent and water.

16. The composition for treating a semiconductor device according to claim 1, wherein the total amount of the compound and the solvent is 99.90 mass % or more based on the total mass of the composition for treating a semiconductor device.

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

18. A method for producing a modified substrate, comprising the steps of: contacting a substrate with a composition for treating a semiconductor device according to any one of claims 1 to 17; and subjecting the substrate that has been contacted with the composition to a heat treatment to form a coating on the substrate.

19. 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 a composition for treating a semiconductor device according to any one of claims 1 to 17 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.

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

21. A compound represented by general formula (2). In general formula (2), L ２ represents a divalent linking group containing a divalent aromatic group. ２ represents an aliphatic hydrocarbon group having 8 or more carbon atoms which may have a substituent, or an aromatic group which may have a substituent.

22. A compound represented by general formula (3). In general formula (3), L ３ represents a divalent linking group containing a divalent aromatic group. ３ represents an aliphatic hydrocarbon group having 8 or more carbon atoms which may have a substituent, or an aromatic group which may have a substituent.

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