Method for manufacturing modified substrate, method for manufacturing electronic device, and kit

Abstract

The present invention provides a method for manufacturing a modified substrate, the method enabling the manufacture of a modified substrate in which an ALD coating film is formed in a predetermined region with good selectivity by performing ALD processing. Also provided are a method for manufacturing an electronic device and a kit. This method for manufacturing a modified substrate involves: a step X1 for forming a first coating film on a first surface of a substrate having at least two surfaces, i.e. the first surface and a second surface, wherein the first surface and the second surface are formed from different materials; a step Y1 for forming, on the first coating film, a second coating film that forms an ion bond with the first coating film; and a step Z1 for subjecting the substrate obtained in the step Y1 to atomic layer deposition treatment to form a third coating film on the second surface.

Description

Modified substrate manufacturing method, electronic device manufacturing method, and kit

[0001] The present invention relates to a method for producing a modified substrate, a method for producing an electronic device, and a kit.

[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 present inventors attempted to use the technology described in Patent Document 1 to modify one of the regions (e.g., the metal region) of a substrate having multiple regions (e.g., a metal region and an insulator region) made of different materials on its surface to form a film (modified film), and then perform ALD processing to form an ALD coating on the other region where the modified film was not formed. As a result, the modified film was formed even in the region where the ALD coating was desired to be formed, and selective formation of the ALD coating was not possible. In other words, the modified film could not be formed with good selectivity in the desired region, making it difficult to form an ALD coating with good selectivity.

[0006] Therefore, an object of the present invention is to provide a method for manufacturing a modified substrate, which can perform an ALD treatment to manufacture a modified substrate on which an ALD coating is formed with good selectivity in a predetermined region. Another object of the present invention is to provide a method and kit for manufacturing an electronic device.

[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 method for manufacturing a modified substrate, comprising: a step X1 of forming a first coating on a first surface of a substrate having at least two surfaces, a first surface and a second surface, each made of a different material; a step Y1 of forming a second coating on the first surface, the second coating forming an ionic bond with the first coating; and a step Z1 of subjecting the substrate obtained in step Y1 to atomic layer deposition to form a third coating on the second surface. [2] A method for manufacturing a modified substrate, comprising: a substrate having at least two surfaces, a first surface and a second surface, each made of a different material, and a first coating A disposed on the first surface and containing a compound having a basic functional group or a compound having an acidic functional group; a step Y2 of forming a second coating A on the first coating A, the second coating A forming an ionic bond with the first coating A; and a step Z2 of subjecting the substrate obtained in step Y2 to atomic layer deposition to form a third coating on the second surface. [3] The method for producing a modified substrate according to [1], wherein the first coating comprises a compound having a basic functional group or a compound having an acidic functional group. [4] The method for producing a modified substrate according to [3], wherein the first coating comprises the compound having the basic functional group, and the compound has a nitrogen atom. [5] The method for producing a modified substrate according to [3] or [4], wherein the compound having a basic functional group is a compound having two or more nitrogen atoms. [6] The method for producing a modified substrate according to any one of [3] to [5], wherein the compound having a basic functional group is a nitrogen-containing heterocyclic compound. [7] The method for producing a modified substrate according to [1], wherein the second coating comprises a compound having a basic functional group or a compound having an acidic functional group. [8] The method for producing a modified substrate according to [7], wherein the second coating comprises the compound having the acidic functional group. [9] The method for producing a modified substrate according to [7] or [8], wherein the acidic functional group is a carboxy group or a phosphonic acid group.

[10] The method for producing a modified substrate according to any one of [7] to [9], wherein the compound having an acidic functional group is a compound having a linear aliphatic hydrocarbon group having 12 to 45 carbon atoms.

[11] The method for producing a modified substrate according to any one of [1] to

[10] , wherein the first surface is a metal surface.

[12] A method for producing a modified substrate according to any one of [1] to

[11] , wherein the first surface is a metal surface composed of at least one of cobalt and copper.

[13] A method for producing a modified substrate according to any one of [1] to

[12] , wherein the second surface is an insulator surface.

[14] A method for producing a modified substrate according to any one of [1] to

[13] , wherein the second surface is an alumina surface.

[15] A method for producing an electronic device, comprising the method for producing a modified substrate according to any one of [1] to

[14] .

[16] A kit for forming a coating that inhibits film formation by atomic layer deposition, comprising: a first coating-forming composition containing a first compound having one of a basic functional group and an acidic functional group; and a second coating-forming composition containing a second compound having the other of the basic functional group and the acidic functional group.

[17] A kit for forming a coating that inhibits film formation by atomic layer deposition, comprising: a substrate having at least two surfaces, a first surface and a second surface, each surface being made of a different material; and a coating-forming composition having a first coating A disposed on the first surface and including a first compound having one of a basic functional group and an acidic functional group; and a coating-forming composition including a second compound having the other of the basic functional group and the acidic functional group.

[18] The kit according to

[16] or

[17] , wherein the first compound includes a compound having a basic functional group, and the compound having the basic functional group has a nitrogen atom.

[19] The kit according to

[18] , wherein the compound having a basic functional group is a compound having two or more nitrogen atoms.

[20] The kit according to

[18] or

[19] , wherein the compound having a basic functional group is a nitrogen-containing heterocyclic compound.

[21] The kit according to any one of

[16] to

[20] , wherein the acidic functional group is a carboxy group or a phosphonic acid group.

[0009] According to the present invention, a method for manufacturing a modified substrate, which can be produced by performing an ALD treatment and forming an ALD coating on a predetermined region with good selectivity, can be provided. Also, a method for manufacturing an electronic device and a kit can be provided.

[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] [Method for Producing Modified Substrate] The method for producing a modified substrate of the present invention (hereinafter also referred to as "the present production method") will be described in detail below. A first embodiment of the present production method is a method for producing a modified substrate, comprising: a step X1 of forming a first coating on a first surface of a substrate having at least two surfaces, a first surface and a second surface, each surface being made of a different material; a step Y1 of forming a second coating on the first coating, the second coating forming an ionic bond with the first coating; and a step Z1 of performing atomic layer deposition on the substrate obtained in the step Y1 to form a third coating on the second surface.

[0014] A second embodiment of the present manufacturing method is a method for manufacturing a modified substrate, the method including: a coated substrate having a substrate having at least two surfaces, a first surface and a second surface, each of which is made of a different material; and a first coating A disposed on the first surface and containing a compound having a basic functional group or a compound having an acidic functional group; a step Y2 of forming a second coating A on the first coating A in the coated substrate, the second coating A forming an ionic bond with the first coating A; and a step Z2 of performing atomic layer deposition on the substrate obtained in the step Y2 to form a third coating on the second surface.

[0015] Although the mechanism by which the present production method having the above configuration can solve the problems of the present invention is not entirely clear, the present inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effects are obtained. In other words, even if the effects are obtained by a mechanism other than the one described below, it is still included in the scope of the present invention.

[0016] Although the detailed mechanism of this production method is unknown, it is presumed that by forming both the first coating (or first coating A) and the second coating (or second coating A), it was possible to form the third coating with good selectivity in the second region even in cases where it would be difficult to form the third coating (ALD coating) with good selectivity in the second region using only one of the coatings. Furthermore, it is believed that the formation of an ionic bond between the first coating (or first coating A) and the second coating (or second coating A) resulted in excellent ALD inhibition, allowing the third coating to be formed with good selectivity in the second region. Hereinafter, the ability to produce a modified substrate on which an ALD coating is formed with good selectivity in a predetermined region by performing an ALD process is also referred to as "excellent effects of the present invention."

[0017] [First embodiment] The first embodiment of the present production method is a method for producing a modified substrate, including the above-mentioned steps X1 to Z1. Each step will be described in detail below.

[0018] <Step X1> As described above, step X1 is a step of forming a first coating on a first surface of a substrate (hereinafter also referred to as a "specific substrate") having at least two surfaces, a first surface and a second surface, made of different materials. By performing this step, the first coating is preferentially formed on the first surface. In other words, in this step, a coating is more likely to be formed on the first surface than on the second surface. In this step, it is preferable that a coating is not formed on the second surface. The first coating and the specific substrate will be described in detail below.

[0019] (First Coating) The first coating forms an ionic bond with the second coating in step Y1 and functions as a mask when a third coating is formed by ALD in step Z1. This allows the third coating to be formed on the second surface. In order to form an ionic bond with the second coating, the first coating preferably contains a compound having a basic functional group or an acidic functional group (hereinafter, these are also collectively referred to as "specific group").

[0020] In particular, the first coating preferably contains a compound having a basic functional group. Examples of the basic functional group include a group containing a nitrogen atom, such as a nitrogen-containing heterocyclic group, an amino group, or a hydrazine group (H ２N-NH-*. * indicates the bonding position.) and guanidine group (H ２ N-C(=NH)-NH-*. * represents the bond position.

[0021] The acidic functional group may be, for example, a carboxyl group (—COOH), a phosphonic acid group (—PO ３ H ２ ), sulfo group (—SO ３ H), a phenolic hydroxyl group, and a phosphate group (-PO ４ H ２ ) are listed.

[0022] The amino group may be primary, secondary, or tertiary, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.

[0023] Examples of the nitrogen-containing heterocyclic group include nitrogen-containing aromatic heterocyclic groups such as triazole group, benzotriazole group, pyridyl group, oxazolyl group, thiazolyl group, triazine group, pyrrole group, imidazole group, pyrazole group, and benzimidazole 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.

[0024] The compound having a basic functional group is preferably a compound having a nitrogen atom. When the basic functional group is a group containing a nitrogen atom, the compound having a basic functional group containing a nitrogen atom corresponds to a compound having a nitrogen atom. The compound having a basic functional group may be a compound having two or more nitrogen atoms, and the number of nitrogen atoms in the compound is preferably 2 to 6, more preferably 2 to 4, and even more preferably 2 or 3.

[0025] The compound having a basic functional group is preferably a nitrogen-containing heterocyclic compound, more preferably a nitrogen-containing aromatic heterocyclic compound. Examples of the nitrogen-containing aromatic heterocyclic compound include triazole compounds, pyrrole compounds, pyrazole compounds, imidazole compounds, tetrazole compounds, pyridine compounds, pyrazine compounds, pyridazine compounds, pyrimidine compounds, indolizine compounds, indole compounds, isoindole compounds, indazole compounds, purine compounds, quinolizine compounds, quinoline compounds, isoquinoline compounds, naphthyridine compounds, phthalazine compounds, quinoxaline compounds, quinazoline compounds, cinnoline compounds, butylidine compounds, thiazole compounds, isothiazole compounds, thiadiazole compounds, oxazole compounds, isoxazole compounds, and furazan compounds.Of these, triazole compounds are preferred, and examples of the triazole compounds include 1,2,3-triazole, 1,2,4-triazole, 1-methyl-1,2,4-triazole, methyl-1H-1,2,4-triazole-3-carboxylate, 1,2,4-triazole-3-carboxylic acid, methyl 1,2,4-triazole-3-carboxylate, 1H-1,2,4-triazole-3-thiol, 3,5-diamino-1H-1,2,4-triazole, 3-amino-1, 2,4-triazole-5-thiol, 3-amino-1H-1,2,4-triazole, 3-amino-5-benzyl-4H-1,2,4-triazole, 3-amino-5-methyl-4H-1,2,4-triazole, 3-nitro-1,2,4-triazole, 3-bromo-5-nitro-1,2,4-triazole, 4-(1,2,4-triazol-1-yl)phenol, 4-amino-1,2,4-triazole, 4-amino-3,5-dipropyl-4H-1,2,4-triazo 4-amino-3,5-dimethyl-4H-1,2,4-triazole, 4-amino-3,5-dipeptyl-4H-1,2,4-triazole, 5-methyl-1,2,4-triazole-3,4-diamine, 1H-benzotriazole (1,2,3-benzotriazole), 1-hydroxybenzotriazole, 1-aminobenzotriazole, 1-carboxybenzotriazole, 5-chloro-1H-benzotriazole, 5-nitro-1H-benzotriazole, 5-calcium benzotriazole, 5-methyl-1,2,4-triazole-3,4-diamine, 1H-benzotriazole (1,2,3-benzotriazole), 1-hydroxybenzotriazole, 1-aminobenzotriazole, 1-carboxybenzotriazole, 5-chloro-1H-benzotriazole, 5-nitro-1H-benzotriazole, 5-methyl ..., 5-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 5-methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, 1-methyl-1H-benzotriazole, carboxy-1H-benzotriazole, 5-methyl-1H-benzotriazole, 5,6-dimethyl-1H-benzotriazole, 1-(1',2'-dicarboxyethyl)benzotriazole, 1-[N,N-bis(hydroxyethyl)aminomethyl]benzotriazole, 1-[N,N-bis(hydroxyethyl)aminomethyl]-5-methylbenzotriazole, and 1-[N,N-bis(hydroxyethyl)aminomethyl]-4-methylbenzotriazole.

[0026] (Specific Substrate) In the specific substrate, the first surface is the surface on which the first coating is formed, and the second surface is not particularly limited as long as it is a surface composed of a material other than the material constituting the first surface. The materials constituting the first surface and the second surface are not particularly limited, but it is preferable that at least one of the first surface and the second surface is a metal surface A composed of a metal material or a non-metal surface B composed of a non-metal material, and it is more preferable that at least one of the first surface and the second surface is a metal surface A, and it is even more preferable that the first surface is a metal surface A and the second surface is a non-metal surface B. In this specification, the term "metal material" refers to a material that contains metal atoms and exhibits metallic properties, and the term "non-metal material" refers to a material other than a metal material.

[0027] The metal atoms contained in the metal surface A are not particularly limited, but are preferably copper atoms, cobalt atoms, tungsten atoms, ruthenium atoms, titanium atoms, tantalum atoms, molybdenum atoms, germanium atoms, zirconium atoms, aluminum atoms, tin atoms, nickel atoms, palladium atoms, indium atoms, zinc atoms, gold atoms, silver atoms, or platinum atoms, more preferably copper atoms, cobalt atoms, tungsten atoms, ruthenium atoms, or tantalum atoms, and even more preferably copper atoms or cobalt atoms. The form of the metal atoms in the metal surface A is not particularly limited, but examples include elemental metals and alloys. Examples of alloys include alloys containing two or more of the metal atoms contained in the metal surface A. The method for forming the metal surface A is not particularly limited, and known methods can be used. Examples include physical vapor deposition (PVD), chemical vapor deposition (CVD), and plating.

[0028] The non-metallic material constituting the non-metallic surface B is not particularly limited, and examples thereof include insulators. Examples of insulators include oxides such as alumina, silicon oxide, and silicon oxycarbide, nitrides such as aluminum nitride and silicon nitride, oxynitrides such as silicon oxynitride, non-metallic elements such as silicon and carbon, and organic substances. The insulator may also be a low-dielectric material (low-k material). Examples of low-dielectric materials include silicon oxide, silicon oxycarbide, silicon nitride, silicon oxycarbonitride, and silicon carbonitride. The material constituting the non-metallic surface B is preferably a metal oxide or an insulating material containing silicon atoms, and more preferably alumina or silicon oxide. Specific examples of silicon oxide include SiO ｙ (wherein y is preferably 0.5 to 2.0, more preferably 1.0 to 2.0), and SiO ｚ C ｗ (wherein z is preferably 0.5 to 2.0, more preferably 1.0 to 2.0, and w is preferably 0.5 to 2.0, more preferably 1.0 to 2.0). ｙ and SiO ｚ C ｗ The material represented by the composition may further contain hydrogen. ｚ C ｗ Examples of the material represented by the composition include Si(OC ２ H ５ ) ４ (tetraethyl orthosilicate, TEOS). Silicon oxides include SiO ２ A material represented by the formula (silicon dioxide) or TEOS is preferred.

[0029] The method for forming the non-metallic surface B is not particularly limited, and examples thereof include CVD, PVD, 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.

[0030] A preferred embodiment of the specific substrate is embodiment 1, in which the first surface is a metal surface A. Among these, the first surface is preferably a metal surface made of at least one of cobalt and copper.

[0031] In addition, in Aspect 1, the second surface is preferably a non-metallic surface B. In Aspect 1, the non-metallic material constituting the non-metallic surface B constituting the second surface is preferably a metal oxide. Examples of metal oxides include aluminum oxide, tantalum oxide, iron oxide, and copper oxide. The second surface is preferably an insulating surface, and more preferably an alumina surface.

[0032] The shape of the specific substrate is not particularly limited, and can be any shape commonly used as a semiconductor substrate. The specific substrate may be a substrate having the above-described surface, and may be a single-layer or multi-layer structure. The shapes of the first and second surfaces are not particularly limited, and examples thereof include planar, dotted, and striped shapes.

[0033] In step X1, the method for forming the first coating on the first surface of the specific substrate is not particularly limited, and examples thereof include a method of contacting the specific substrate with a composition (hereinafter also referred to as the "first coating composition") containing a component (e.g., a compound having a specific group) contained in the first coating. The method for contacting the first coating composition with the specific substrate 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 during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. The contact time is not particularly limited, but is preferably 10 seconds to 20 minutes, more preferably 30 seconds to 5 minutes.

[0034] In the step X1, it is also preferable to perform a rinsing treatment after the above-described treatment. The rinsing treatment can remove the composition and impurities adhering to regions of the specific substrate other than the first surface. The rinsing method is not particularly limited, and examples include a method of contacting the specific substrate with a rinsing liquid. As the contacting method, the same method as the method of contacting the first coating-forming composition with the specific substrate can be used. The temperature of the rinsing liquid during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. As the rinsing liquid, water or a known organic solvent can be used; for example, a solvent that can be contained in the first coating-forming composition described below can be used as the rinsing liquid.

[0035] The first coating composition will be described in detail below.

[0036] (First Coating Forming Composition) Compound for Forming the First Coating (First Compound) The first coating forming composition contains a compound for forming the first coating (hereinafter also referred to as "first compound"). As the first compound, a compound having the above-mentioned specific group is preferred, and a compound having the above-mentioned basic functional group is more preferred. The molecular weight of the first compound is preferably 50 to 1,000, more preferably 50 to 500, and even more preferably 50 to 150.

[0037] The content of the first compound is preferably 0.001 to 10% by mass, more preferably 0.005 to 5.00% by mass, and even more preferably 0.01 to 1.00% by mass, relative to the total mass of the composition for forming the first coating film. Two or more types of first compounds may be used in combination. When two or more types of first compounds are used in combination, the total content thereof is preferably within the above range.

[0038] Solvent The first coating film-forming composition preferably contains a solvent. Examples of the solvent include water and organic solvents, with water being preferred. The water is not particularly limited, but examples include distilled water, ion-exchanged water, pure water, and ultrapure water, with ultrapure water being preferred. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and hydrocarbon-based solvents.

[0039] 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 (1-methoxy-2-propanol, 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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.

[0044] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0045] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0046] The content of the solvent is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 97.00% by mass or more, based on the total mass of the first coating-forming composition. The upper limit is 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. The total amount of the first compound and the solvent is preferably 95.00 to 100% by mass, more preferably 99.00 to 100% by mass, and even more preferably 99.90 to 100% by mass, based on the total mass of the first coating-forming composition. When the total amount of the first compound and the solvent is within the above range, the amount of components other than the first compound and the solvent is minimal, resulting in minimal impurities in the composition, allowing for efficient formation of a film composed of the first 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 thereof be within the above range.

[0047] Other Components The first coating film-forming composition may contain other components in addition to the first compound and the solvent described above, but it is preferable that it does not contain any other components.

[0048] (Method for producing the composition for forming the first coating film) The method for producing the composition for forming the first coating film 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 first compound to a stirrer such as a mixing mixer containing a purified solvent and then stirring thoroughly. When the composition contains other components other than the first compound, the other components may be added simultaneously with the first compound or at different times. In the production process for producing the composition, the steps described below may be carried out.

[0049] (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").

[0050] (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.

[0051] (Static Elimination Step) The method for producing the composition may further include a static elimination step of eliminating static electricity from the composition.

[0052] <Step Y1> Next, step Y1 will be described in detail. Step Y1 is a step of forming a second coating on the first coating obtained in step X1, the second coating forming an ionic bond with the first coating.

[0053] (Second Coating) The second coating preferably contains a compound having a basic functional group or a compound having an acidic functional group, and more preferably contains a compound having an acidic functional group, in order to form an ionic bond with the first coating.

[0054] Examples of the basic functional group of the compound having a basic functional group that may be contained in the second coating include groups similar to the basic functional group that may be contained in the compound that may be contained in the first coating described above. Examples of the acidic functional group of the compound having an acidic functional group that may be contained in the second coating include groups similar to the acidic functional group that may be contained in the compound that may be contained in the first coating described above. An ionic bond is formed between the first coating and the second coating. Therefore, for example, if the first coating contains a compound having a basic functional group, the second coating preferably contains a compound having an acidic functional group. Also, if the first coating contains a compound having an acidic functional group, the second coating preferably contains a compound having a basic functional group. As described above, if one of the first coating and the second coating contains a compound having a basic functional group and the other contains a compound having an acidic functional group, an ionic bond is formed between the two compounds, resulting in the formation of an ionic bond between the first coating and the second coating. It is preferable that the second coating contain a compound having an acidic functional group. The acidic functional group is preferably a carboxy group, a phosphonic acid group, or a sulfo group, and more preferably a carboxy group or a phosphonic acid group.

[0055] The compound contained in the second coating for forming the second coating (hereinafter also referred to as the "second compound") preferably further has a hydrophobic group in addition to the basic functional group or the acidic functional group. The hydrophobic group is not particularly limited, and examples thereof include an aliphatic hydrocarbon group which may have an etheric oxygen atom, an aromatic ring group, and a group formed by combining these. Among these, an aliphatic hydrocarbon group which may have an etheric oxygen atom is preferred, and a linear aliphatic hydrocarbon group which may have an etheric oxygen atom is more preferred.

[0056] The aliphatic hydrocarbon group may be linear, branched, or cyclic, with linear being preferred. The valence of the aliphatic hydrocarbon group is not particularly limited, but is often monovalent. Examples of monovalent aliphatic hydrocarbon groups include alkyl groups, alkenyl groups, and alkynyl groups, with alkyl groups being preferred. The number of carbon atoms in the aliphatic hydrocarbon group is not particularly limited, but from the viewpoint of improving the stability of the second coating on the first surface, it is preferably 1 to 45, more preferably 8 to 45, even more preferably 12 to 45, and particularly preferably 12 to 18.

[0057] The aromatic ring group may be either an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group. The aromatic ring group may be either a monocyclic or polycyclic group. The number of carbon atoms in the aromatic ring group is preferably 5 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0058] In step Y1, the method for forming the second coating is not particularly limited, and examples thereof include a method of contacting a composition containing components (such as the second compound) contained in the second coating (hereinafter also referred to as the "second coating-forming composition") with the specific substrate on which the first coating is disposed. The method for contacting the second coating-forming composition with the specific substrate on which the first coating is formed is not particularly limited, and known methods can be used. For example, a method similar to the method for contacting the first coating-forming composition with the specific substrate can be used. The temperature of the composition during contact is not particularly limited, but is preferably 0 to 50°C, and more preferably 10 to 30°C. The contact time is not particularly limited, but is preferably 1 to 30 minutes, and more preferably 5 to 15 minutes.

[0059] In the above-mentioned step Y1, it is also preferable to perform a rinsing treatment after the above-mentioned treatment. The rinsing treatment can remove the composition and impurities adhering to areas on the specific substrate other than the first coating. The rinsing method is not particularly limited, and examples include a method of contacting a rinsing liquid with the specific substrate on which the second coating is disposed. As the contacting method, a method similar to the method of contacting the first coating-forming composition with the specific substrate can be used. The temperature of the rinsing liquid during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. As the rinsing liquid, water or a known organic solvent can be used; for example, a solvent that can be contained in the second coating-forming composition described below can be used as the rinsing liquid.

[0060] The second coating film-forming composition will be described in detail below.

[0061] (Composition for forming second coating film) Second compound The composition for forming the second coating film contains the compound (second compound) for forming the second coating film described above. As the second compound, the compound having a basic functional group or a compound having an acidic functional group described above is preferred, and a compound having an acidic functional group is more preferred. The second compound may also have a hydrophobic group.

[0062] As the second compound, a compound represented by formula (S1) is particularly preferred. １ -Y １ Formula (S1) In formula (S1), X １ represents a carboxy group or a phosphonic acid group. １ Among these, a carboxy group is preferred.

[0063] In formula (S1), Y １ represents a monovalent aliphatic hydrocarbon group which may have an etheric oxygen atom. １ As the alkyl group, an alkyl group which may have an etheric oxygen atom is preferred, and an alkyl group having 12 to 45 carbon atoms which may have an etheric oxygen atom is more preferred.

[0064] Specific examples of the compound represented by formula (S1) include higher fatty acids, more specifically stearic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, behenic acid, oleic acid, undecylenic acid, tall acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), and docosahexaenoic acid (DHA).

[0065] The molecular weight of the second compound is preferably 50 to 1,000, more preferably 150 to 700, and even more preferably 150 to 500.

[0066] The content of the second compound is preferably 0.001 to 10% by mass, more preferably 0.001 to 5.00% by mass, and even more preferably 0.01 to 0.99% by mass, relative to the total mass of the composition for forming the second coating film. Two or more types of second compounds may be used in combination. When two or more types of second compounds are used in combination, the total content thereof is preferably within the above range.

[0067] Solvent The second coating film-forming composition preferably contains a solvent. Examples of the solvent include water and organic solvents, with organic solvents being preferred. Water is not particularly limited, but examples include distilled water, ion-exchanged water, pure water, and ultrapure water, with ultrapure water being preferred. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and hydrocarbon-based solvents. Specific examples of the solvents exemplified above include the solvents exemplified for the solvents that may be contained in the first coating film-forming composition.

[0068] Among these, the solvent preferably contains a glycol monoether-based solvent, a glycol ester-based solvent, a lactone-based solvent, or an alcohol-based solvent, and more preferably contains at least one solvent selected from the group consisting of PGMEA, PGME, methyl isobutyl carbinol, isopropyl alcohol, cyclohexanone, ethyl lactate, EtOH, and γ-butyrolactone.

[0069] The content of the solvent is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 97.00% by mass or more, based on the total mass of the composition for forming a second coating film. The upper limit is preferably 99.999% by mass or less, more preferably 99.99% by mass or less. The total amount of the second compound and the solvent is preferably 95.00 to 100% by mass, more preferably 99.00 to 100% by mass, and even more preferably 99.90 to 100% by mass, based on the total mass of the composition for forming a second coating film. When the total amount of the second compound and the solvent is within the above range, the amount of components other than the second compound and the solvent is minimal, resulting in minimal impurities in the composition, allowing for efficient formation of a film composed of the second 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 be within the above range.

[0070] Other Components The composition for forming the second coating film may contain other components in addition to the second compound and the solvent described above, but it is preferable that it does not contain any other components.

[0071] (Method for producing the composition for forming the second coating film) The method for producing the composition for forming the second coating film 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 second compound to a stirrer such as a mixer containing a purified solvent and then thoroughly stirring. When the composition contains other components other than the second compound, the other components may be added simultaneously with the second compound or at different times. In the production process for producing the composition, at least one of the metal removal process, filtration process, and static elimination process described above may be performed.

[0072] <Step Z1> Next, step Z1 will be described in detail. Step Z1 is a step of performing atomic layer deposition on the substrate obtained in step Y1 to form a third coating on the second surface. The third coating is a film formed by ALD (ALD film). Step Z1 may also include a treatment for modifying the second surface.

[0073] The ALD treatment method is not particularly limited, and known methods can be used, but thermal ALD is preferred. A specific procedure for the ALD treatment includes, for example, supplying a precursor gas, which is the raw material for the ALD film, to the substrate obtained in step Y1, and then decomposing and / or chemically reacting the raw material with an oxidizing agent or the like to deposit the material, thereby forming an ALD film. 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. 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 known oxidizing agents used in ALD treatment can be used, such as water, oxygen, and ozone.

[0074] The materials constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, etc. The materials of the formed ALD film are not particularly limited, and examples thereof 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.

[0075] [Second Embodiment] The second embodiment of the present production method is a method for producing a modified substrate, which includes the above-mentioned steps Y2 to Z2. Each step will be described in detail below.

[0076] <Step Y2> Step Y2 is a step of forming a second coating A on a first coating A in a coated substrate having at least two surfaces, a first surface and a second surface, each made of a different material, and a first coating A disposed on the first surface and containing a compound having a basic functional group or an acidic functional group, the second coating A forming an ionic bond with the first coating A. In the coated substrate, the "first coating A" corresponds to the first coating in Step X1, which contains a compound having a basic functional group or a compound having an acidic functional group. Specific and preferred aspects of the compound are the same as those of the first compound described for Step X1. The method for preparing the coated substrate is not particularly limited, and examples include a method for preparing a substrate by performing Step X1 and a method for preparing a commercially available coated substrate.

[0077] (Second Coating A) The second coating A is a coating that forms an ionic bond with the first coating A. Specific and preferred aspects of the second coating A are the same as those of the second coating in step Y1. Furthermore, in step Y2, the second coating A can be formed by a method similar to the method of contacting the second coating composition with the specific substrate on which the first coating has been formed.

[0078] <Step Z2> Next, step Z2 will be described in detail. Step Z2 is a step of performing atomic layer deposition on the substrate obtained in step Z2 to form a third coating on the second surface. Step Z2 can be performed in the same manner as step Z1.

[0079] <Other Steps> This production method (first embodiment or second embodiment of the production method for a modified substrate) may include other steps in addition to the above-described steps X1 to Z1 and steps Y2 to Z2. Examples of such other steps include step W, which is performed after step Z1 (or step Z2), to remove at least one of the first coating (or first coating A) and the second coating (or second coating A). Step W provides a substrate that has no coating on its first surface and a third coating (ALD film) on its second surface.

[0080] The method for removing the coating is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof. Known dry etching methods can be used, such as chemical dry etching, which supplies reactive ions or reactive radicals to the substrate surface obtained in step Z1 (or step Z2), and physical dry etching such as sputter etching and ion beam etching. Wet etching can be performed by supplying an etching solution to the substrate obtained in step Z1 (or step Z2). Examples of etching solutions include etching solutions containing oxidizing agents such as ozone and hydrofluoric acid, and etching solutions containing an organic solvent. Examples of organic solvents include organic solvents that can be contained in the first coating-forming composition, 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.

[0081] [Method for Manufacturing an Electronic Device] The present manufacturing method (the first or second embodiment of the method for manufacturing a modified substrate) 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 the method for manufacturing a modified substrate described above. In the method for manufacturing an electronic device, the present manufacturing method may be performed before or after other steps other than steps X1 to Z1 and steps Y2 to Z2. Furthermore, other steps may be incorporated into the implementation of the present manufacturing method, or the present manufacturing method may be incorporated into other steps. Examples of the other steps include steps 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 steps, exposure steps, removal steps, heat treatment steps, cleaning steps, and inspection steps.

[0082] This manufacturing method may be performed at any stage of a back end of the line (BEOL), a middle end of the line (MOL), or a front end of the line (FEOL).

[0083] [Kit] The present invention also includes a kit. A first embodiment of the kit of the present invention is a kit for forming a coating that inhibits film formation by atomic layer deposition, comprising a first coating-forming composition (hereinafter also referred to as "composition A") containing a first compound having one of a basic functional group and an acidic functional group, and a second coating-forming composition (hereinafter also referred to as "composition B") containing a second compound having the other of the basic functional group and the acidic functional group. A second embodiment of the kit of the present invention is a kit for forming a coating that inhibits film formation by atomic layer deposition, comprising a substrate having at least two surfaces, a first surface and a second surface, each made of a different material; a first coating A disposed on the first surface and containing a first compound having one of a basic functional group and an acidic functional group; and a coating-forming composition (hereinafter also referred to as "composition B'") containing a second compound having the other of the basic functional group and the acidic functional group. Each embodiment is described in detail below.

[0084] [First Embodiment] A first embodiment of the kit of the present invention is a kit including the above-mentioned Composition A and Composition B. Composition A is a coating-forming composition containing a first compound having one of a basic functional group and an acidic functional group. Specific and preferred aspects of Composition A are the same as those of the first coating-forming composition in Step X1 above. In particular, Composition A preferably contains a compound having a basic functional group. The compound having a basic functional group preferably contains a nitrogen atom, and is preferably a compound having two or more nitrogen atoms. The compound having a basic functional group is more preferably a nitrogen-containing heterocyclic compound. Composition B is a coating-forming composition containing a second compound having the other of the basic functional group and the acidic functional group. Specific and preferred aspects of Composition B are the same as those of the second coating-forming composition in Step Y1 above. In particular, Composition B preferably contains a compound having an acidic functional group. The compound having an acidic functional group is preferably a compound having a carboxy group or a phosphonic acid group, and is also preferably a compound having a linear aliphatic hydrocarbon group having 12 to 45 carbon atoms.

[0085] [Second Embodiment] A second embodiment of the kit of the present invention is a kit comprising the above-described coated substrate and composition B'. The substrate is synonymous with the coated substrate detailed in step Y2 above, and composition B' is synonymous with composition B in the kit of the first embodiment. Specific and preferred aspects of the substrate are the same as those of the coated substrate in step Y2 above, and specific and preferred aspects of composition B' are the same as those of composition B in the kit of the first embodiment.

[0086] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be modified 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. In the following evaluations, handling of containers, preparation of compositions, filling, storage, and analytical measurements were all carried out in a clean room meeting ISO Class 2 or lower. Furthermore, containers used for preparation, filling, storage, etc. of the compositions were washed with the solvent used in the preparation or the prepared composition before use.

[0087] [Preparation of the present compositions] The compositions used in each of the examples and comparative examples (compositions A1 to A2, and compositions B1 to B3) were prepared by mixing the specific compound or comparative compound with a solvent to obtain the compositions shown below. Note that all of the various components used in the examples were classified as semiconductor grade or equivalent high purity grade.

[0088] (Composition A1) ・1,2,3-Benzotriazole: 0.1 wt% ・H ２ O: 99.9wt% (composition A2) ・1,2,3-Triazole: 0.1wt% ・H ２ O: 99.9wt% (composition B1) ・Stearic acid: 0.01wt% ・1-Methoxy-2-propanol: 99.99wt% (composition B2) ・Undecanoic acid: 0.01wt%・1-Methoxy-2-propanol: 99.99wt% (composition B3) ・Octadecyl Phosphonic acid: 0.01wt% ・1-Methoxy-2-propanol: 99.99wt%

[0089] [Preparation of Modified Substrate] A modified substrate was prepared according to the following procedure.

[0090] <Wafer Preparation> First, a commercially available silicon wafer (diameter 12 inches) was prepared as a substrate. A copper (Cu) layer, a cobalt (Co) layer, and an aluminum oxide (Al) layer were formed on one surface of the silicon wafer. ２ O ３ By forming a Cu layer wafer, a Co layer wafer, an Al layer, and a silicon oxycarbide (low-k) layer, respectively, ２ O ３ A Cu layer wafer and a low-k layer wafer (hereinafter, these are also collectively referred to as "layered wafers") were prepared. The Cu layer and the Co layer were formed by sputtering, and the Al ２ O ３ The layer was formed by atomic layer deposition (ALD). Furthermore, a commercially available wafer with a low-k layer was used, in which black diamond (a low-k material manufactured by Applied Materials) was disposed on silicon. The deposition conditions were adjusted so that the thickness of each layer was 20 nm. The wafer with the layer was cut into 2 cm squares and cleaned by immersion in isopropyl alcohol (IPA). The cleaning was performed while stirring the IPA at a stirring speed of 250 rpm, with the IPA temperature at 25°C and the cleaning time being 30 seconds. After cleaning, each wafer was dried using a nitrogen stream to prepare the wafer for surface treatment.

[0091] <Step 1> Next, each prepared wafer was surface-treated by immersing it in one of the compositions (Composition A1 or Composition A2) shown in Table 1. The immersion treatment was carried out at a temperature of 25°C for one minute while stirring the composition at a stirring speed of 250 rpm. After immersion, each wafer was rinsed with ion-exchanged distilled water and then dried under a nitrogen stream to obtain a substrate subjected to Step 1. The rinsing treatment was carried out at a temperature of 25°C for 30 seconds while stirring the composition at a stirring speed of 250 rpm.

[0092] <Step 2> The following Step 2 was carried out on the substrate obtained in Step 1. The procedure was as follows: in the surface treatment, Compositions B1 to B3 were used instead of Composition A1 or Composition A2, and the immersion time was 10 minutes, and in the rinsing treatment, ion-exchanged distilled water was changed to IPA. Step 2 was carried out in the same manner as in Step 1 above, to produce a modified substrate.

[0093] [Evaluation] [Evaluation of Pure Water Contact Angle After Substrate Modification] For each modified substrate obtained by [Preparation of Modified Substrate] and each wafer prepared in <Wafer Preparation> before performing steps 1 and 2, a droplet of pure water (2.4 μL) was dropped onto the substrate, and the contact angle was measured three times at 23° C. using a contact angle meter (Dropmaster 700, manufactured by Kyowa Interface Science Co., Ltd.) one second after the drop. The average value was taken as the contact angle (°). The surface tension of pure water was assumed to be 72.9 mN / m for the analysis. The ALD inhibitory properties were evaluated based on the obtained water contact angle values ​​according to the following evaluation criteria. Compared with a blank substrate (Comparative Example 1) that had not undergone any surface treatment, the greater the increase in water contact angle, the more difficult it is to deposit a film by ALD treatment, i.e., the better the ALD inhibitory properties.

[0094] (Evaluation criteria (Cu layer)) A: Water contact angle is 70° or more B: Water contact angle is less than 70°

[0095] (Evaluation criteria (Co layer)) A: Water contact angle of 70° or more B: Water contact angle of less than 70°

[0096] (Evaluation criteria (Al ２ O ３ A: Water contact angle is 55° or less B: Water contact angle is more than 55°

[0097] (Evaluation criteria (low-k layer)) A: Water contact angle is 85° or less B: Water contact angle is more than 85°

[0098] [ALD Inhibition Evaluation] The ALD inhibition of the modified substrate was evaluated by the following procedure. Aluminum oxide (Al) was deposited by ALD on the Cu layer wafer and Co layer wafer after the modification treatment obtained by [Preparation of modified substrate], and the Cu layer wafer and Co layer wafer prepared in <Wafer preparation> before carrying out steps 1 and 2.２ O ３ The ALD film formation test was carried out under the following conditions.

[0099] (ALD conditions) Atomic layer deposition (ALD) apparatus: AD-230LP (manufactured by SUMCO Corporation) Chamber temperature: 300° C. Precursor: trimethylaluminum and H ２ Number of cycles: 50

[0100] After the ALD process, the thickness (Å) of the ALD film on each wafer was measured using an X-ray fluorescence (XRF) analyzer. Measurements were performed at five points on the substrate, and the average value was taken as the film thickness. The ALD inhibitory properties were 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 process, i.e., the better the ALD inhibitory properties.

[0101] (Evaluation criteria (Cu layer)) A: Film thickness is 30 Å or less B: Film thickness is more than 30 Å

[0102] (Evaluation criteria (Co layer)) A: Film thickness is 18 Å or less B: Film thickness is more than 18 Å

[0103] Table 1 shows the compositions used in steps 1 and 2 of each example and comparative example, as well as the evaluation results of the water contact angle. Table 2 shows the compositions used in steps 1 and 2 of each example and comparative example, as well as the evaluation results of the ALD inhibition. In Table 1, the first surface is a surface consisting of at least one of a Cu layer and a Co layer, and the second surface is a surface consisting of an Al layer. ２ O ３ The results are shown assuming the use of a surface made of at least one of a layer wafer and a low-k layer.

[0104]

[0105]

[0106] As shown in Table 1, the first surface is a surface made of at least one of a Cu layer and a Co layer, and the second surface is an Al layer. ２ O ３In the examples, when the surface is made of at least one of a layer wafer and a low-k layer, the increase in contact angle is large on the first surface, and small on the surface in Table 2. That is, the first and second coatings are easily formed on the first surface, and the first and second coatings are not easily formed on the second surface. Therefore, when this manufacturing method is carried out using a substrate having a first surface and a second surface, the first and second coatings are formed on the first surface, and an ALD film is not easily formed on the first surface, and an ALD film is easily formed on the second surface. Furthermore, in the evaluation of the above [ALD inhibition evaluation], the Al film after the modification treatment obtained by [Preparation of modified substrate] exhibited a high degree of resistance to ALD. ２ O ３ When ALD films were formed on the layer wafer and low-k layer wafer in the same manner as on the Cu layer wafer and Co layer wafer, it was confirmed that the thickness of the ALD film was greater than that of the Cu layer and Co layer.

Claims

1. A method for manufacturing a modified substrate, comprising: a step X1 of forming a first coating on a first surface of a substrate having at least two surfaces, the first surface and the second surface being made of different materials; a step Y1 of forming a second coating on the first coating, the second coating forming an ionic bond with the first coating; and a step Z1 of performing an atomic layer deposition process on the substrate obtained in the step Y1 to form a third coating on the second surface.

2. A method for producing a modified substrate, comprising: a step Y2 of forming a second coating A on a coated substrate having a substrate having at least two surfaces, a first surface and a second surface, the first surface and the second surface being made of different materials; and a first coating A disposed on the first surface and containing a compound having a basic functional group or a compound having an acidic functional group, the second coating A forming an ionic bond with the first coating A; and a step Z2 of performing an atomic layer deposition process on the substrate obtained in the step Y2 to form a third coating on the second surface.

3. The method for producing a modified substrate according to claim 1, wherein the first coating contains a compound having a basic functional group or a compound having an acidic functional group.

4. The method for producing a modified substrate according to claim 1, wherein the first coating contains a compound having a basic functional group, and the compound has a nitrogen atom.

5. The method for producing a modified substrate according to claim 4, wherein the compound having a basic functional group is a compound having two or more nitrogen atoms.

6. The method for producing a modified substrate according to claim 4, wherein the compound having a basic functional group is a nitrogen-containing heterocyclic compound.

7. The method for producing a modified substrate according to claim 1, wherein the second coating film contains a compound having a basic functional group or a compound having an acidic functional group.

8. The method for producing a modified substrate according to claim 7, wherein the second coating film contains a compound having an acidic functional group.

9. The method for producing a modified substrate according to claim 7, wherein the acidic functional group is a carboxy group or a phosphonic acid group.

10. The method for producing a modified substrate according to claim 7, wherein the compound having an acidic functional group is a compound having a linear aliphatic hydrocarbon group having 12 to 45 carbon atoms.

11. The method for producing a modified substrate according to any one of claims 1 to 10, wherein the first surface is a metal surface.

12. The method for producing a modified substrate according to any one of claims 1 to 10, wherein the first surface is a metal surface composed of at least one of cobalt and copper.

13. The method for producing a modified substrate according to any one of claims 1 to 10, wherein the second surface is an insulating surface.

14. The method for producing a modified substrate according to any one of claims 1 to 10, wherein the second surface is an alumina surface.

15. A method for producing an electronic device, comprising the method for producing a modified substrate according to any one of claims 1 to 10.

16. A kit for forming a coating that inhibits film formation by atomic layer deposition, comprising: a first coating-forming composition containing a first compound having one of a basic functional group and an acidic functional group; and a second coating-forming composition containing a second compound having the other of the basic functional group and the acidic functional group.

17. A kit for forming a coating that inhibits film formation by an atomic layer deposition process, comprising: a substrate having at least two surfaces, a first surface and a second surface, each surface being made of a different material; and a coated substrate having a first coating A disposed on the first surface and including a first compound having one of a basic functional group and an acidic functional group; and a coating-forming composition including a second compound having the other of the basic functional group and the acidic functional group.

18. The kit according to claim 16 or 17, wherein the first compound comprises a compound having a basic functional group, and the compound having a basic functional group has a nitrogen atom.

19. The kit according to claim 18, wherein the compound having a basic functional group is a compound having two or more nitrogen atoms.

20. The kit according to claim 18, wherein the compound having a basic functional group is a nitrogen-containing heterocyclic compound.

21. The kit according to claim 16 or 17, wherein the acidic functional group is a carboxy group or a phosphonic acid group.

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