Composition, method for manufacturing modified substrate, method for manufacturing layered body, and method for manufacturing electronic device,

Abstract

The present invention provides a composition that makes it possible to form a film havign exceptional ALD inhibition properties, a method for manufacturing a modified substrate, a method for manufacturing a layered body, and a method for manufacturing an electronic device. A composition according to the present invention is used for forming a film that suppresses film formation by atomic layer deposition processing, wherein the composition contains an organic solvent, and a C8 or lower acyclic compound that has only one phosphonic acid group.

Description

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

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

[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 an 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 capable of forming 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, and a method for producing 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 composition for forming a coating that inhibits film formation by atomic layer deposition, the composition comprising an acyclic compound having only one phosphonic acid group and 8 or less carbon atoms, and an organic solvent. [2] The composition according to [1], wherein the compound is a compound represented by the following formula (1): X-PO ３ H ２(1) In formula (1), X represents a linear or branched aliphatic hydrocarbon group which may have a substituent. However, the number of carbon atoms contained in the linear or branched aliphatic hydrocarbon group which may have a substituent is 8 or less. [3] The composition according to [1] or [2], wherein X in formula (1) represents a linear aliphatic hydrocarbon group which may have a substituent. [4] The composition according to any one of [1] to [3], wherein the compound is propylphosphonic acid. [5] The composition according to any one of [1] to [4], wherein the organic solvent contains a protic polar solvent, and the content of the protic polar solvent is 50 mass % or more relative to the total mass of the organic solvent. [6] A method for producing a modified substrate, comprising the step of contacting a substrate with the composition according to any one of [1] to [5], to form a coating on the substrate. [7] A method for producing a laminate, comprising: Step 1: contacting a substrate having at least two surfaces, a first surface and a second surface, made of different materials, with the composition according to any one of [1] to [5] to form a first coating on the first surface; and Step 2: subjecting the substrate obtained in Step 1 to atomic layer deposition to form a second coating on the second surface. [8] A method for producing a laminate according to [7], wherein the first surface has a group that forms a covalent bond with a phosphonic acid group or a group that forms a hydrogen bond. [9] A method for producing a laminate according to [7] or [8], further comprising a step of heating the substrate obtained in Step 1 at 60°C or higher.

[10] A method for producing a laminate according to any one of [7] to [9], further comprising a step of cleaning the substrate obtained in Step 1.

[11] A method for producing a laminate according to any one of [7] to

[10] , wherein the second surface is made of an insulator.

[12] The method for producing a laminate according to any one of [7] to

[11] , wherein the first surface and the second surface are made of an insulator.

[13] The method for producing a laminate according to any one of [7] to

[12] , wherein the first surface is made of aluminum oxide.

[14] The method for producing a laminate according to any one of [7] to

[13] , wherein the second coating is a metal film, a metal oxide film, a metal nitride film, or a film containing silicon.

[15] A method for producing an electronic device, comprising the method for producing a laminate according to any one of [7] to

[14] .

[0009] According to the present invention, a composition capable of forming a coating film having excellent ALD inhibitory properties can be provided. The present invention also provides a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

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

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

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

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

[0014] [Composition] The composition of the present invention (hereinafter also referred to as "the composition") will be described in detail below. The composition is a composition for forming a coating that inhibits film formation by atomic layer deposition processing, and includes an acyclic compound having only one phosphonic acid group and 8 or less carbon atoms (hereinafter also referred to as "specific compound"), and an organic solvent.

[0015] Although the reason why the composition having the above configuration can solve the problems of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The phosphonic acid group possessed by the specific compound can bind to or adsorb to the surface of a substrate, such as a metal surface or a metal oxide surface, and form a coating that inhibits atomic layer deposition. Furthermore, since the specific compound has 8 or fewer carbon atoms, it has a small molecular size, allowing the coating to be formed more densely and highly effective in inhibiting film formation by ALD. Therefore, it is believed that the specific compound having the above structure enables the formation of a coating that can effectively inhibit film formation by ALD. Hereinafter, the ability of this composition to form a coating that better inhibits film formation by atomic layer deposition (hereinafter also referred to as an "ALD-inhibiting film") is also referred to as "excellent effects of the present invention."

[0016] [Specific Compound] The present composition contains a specific compound. As described above, the specific compound is a phosphonic acid group (—PO ３ H ２ ) and an acyclic compound having 8 or less carbon atoms. In terms of obtaining superior effects of the present invention, the molecular weight of the specific compound is preferably 200 or less, more preferably 150 or less, and even more preferably 130 or less. The lower limit is, for example, 50 or more.

[0017] The specific compound being an "acyclic compound having 8 or less carbon atoms" means that the specific compound has 8 or less carbon atoms and does not have a ring structure. The ring structure includes any of an alicyclic structure, an aliphatic heterocyclic structure, and an aromatic ring structure. The number of carbon atoms contained in the specific compound is not particularly limited as long as it is 8 or less, but is preferably 5 or less, and more preferably 3 or less. The specific compound may have a substituent other than the phosphonic acid group. When the specific compound has a substituent, the number of carbon atoms contained in the substituent is also included in the number of carbon atoms of the specific compound.

[0018] In terms of achieving better effects of the present invention, the specific compound is preferably a compound represented by the following formula (1): X-PO ３ H ２ (1) In formula (1), X represents a linear or branched aliphatic hydrocarbon group which may have a substituent. However, the number of carbon atoms contained in the compound represented by formula (1) is 8 or less. Among these, 5 or less is preferable, and 3 or less is more preferable. Note that, in order to fall within the range of the number of carbon atoms contained in the compound represented by formula (1), the number of carbon atoms contained in the linear or branched aliphatic hydrocarbon group which may have a substituent is 8 or less. For example, when the aliphatic hydrocarbon group does not have a substituent, the number of carbon atoms contained in the aliphatic hydrocarbon group is 8 or less, and when the aliphatic hydrocarbon group has a substituent, the sum of the number of carbon atoms contained in the substituent and the number of carbon atoms contained in the aliphatic hydrocarbon group is 8 or less.

[0019] X is preferably a linear aliphatic hydrocarbon group which may have a substituent. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group, with an alkyl group being preferred. The aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably 1 to 3 carbon atoms. Examples of the substituent which the aliphatic hydrocarbon group may have include the groups exemplified as the substituent W below, but it is preferable that the aliphatic hydrocarbon group has no substituent. Substituent W: a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a hydroxy group, a thiol group, a boronic acid group, a cyano group, a nitro group, an alkoxy group, a silyloxy group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an amino group, an alkylthio group, an acyl group, an alkoxycarbonyl group, and a silyl group.

[0020] Specific examples of the specific compound include alkylphosphonic acids such as methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, t-butylphosphonic acid, isobutylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, n-octylphosphonic acid, and 2-ethylhexylphosphonic acid, amino group-containing alkylphosphonic acids such as (1-amino-2-methylpropyl)phosphonic acid, and vinylphosphonic acid, etc. Among these, methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, (1-amino-2-methylpropyl)phosphonic acid, and n-octylphosphonic acid are preferred, and propylphosphonic acid is more preferred.

[0021] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 0.01 to 100 mmol / L, more preferably 0.01 to 10 mmol / L, and even more preferably 0.01 to 5 mmol / L, relative to the volume of the composition. The total amount of the specific compound and the organic solvent described below is preferably 90.00 mass% or more, more preferably 95.00 mass% or more, and even more preferably 99.90 mass% or more, relative to the total mass of the composition. The upper limit is 100 mass% or less, and preferably 99.9999 mass% or less.

[0022] [Organic Solvent] The present composition contains an organic solvent. 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.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0028] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0029] 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.

[0030] Among these, the organic solvent is preferably an alcohol-based solvent, an ether-based solvent, an ester-based solvent, or a ketone-based solvent, more preferably an aliphatic monoalcohol-based solvent, a glycol monoether-based solvent, a glycol ester-based solvent, a monocarboxylic acid ester-based solvent, an ether-based solvent, or a lactone-based solvent, and even more preferably an aliphatic monoalcohol-based solvent.

[0031] The organic solvent preferably contains a protic polar solvent. When the organic solvent contains a protic polar solvent, the content of the protic polar solvent is preferably 20% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, relative to the total mass of the organic solvent. The upper limit is not particularly limited and may be 100% by mass or less. The organic solvents may be used alone or in combination of two or more. As the protic polar solvent, an alcohol solvent is preferred, a monoalcohol solvent is more preferred, and an aliphatic monoalcohol solvent having 1 to 18 carbon atoms is even more preferred. As the aprotic polar solvent, an ester solvent is preferred, a glycol ester solvent is more preferred, and a glycol monoether carboxylate solvent having 5 to 21 carbon atoms is even more preferred. The content of the organic 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, and more preferably 99.9% by mass or less.

[0032] [Other Components] The present composition may contain other components in addition to the specific compound and the organic solvent. Examples of other components include water.

[0033] [Method for producing the present composition] The method for producing the present composition is not particularly limited, and the composition can be produced, for example, by mixing the above-mentioned components. The order or timing of mixing the components is not particularly limited, and the composition can be produced, for example, by adding the specific compound to a stirrer such as a mixer containing a purified organic solvent and then thoroughly stirring. In order to achieve better effects of the present invention, it is preferable that the raw materials of the present composition (e.g., the organic solvent and the specific compound) have been subjected to a purification treatment.

[0034] The production process of the present composition may include a step selected from the group consisting of a distillation step of distilling raw materials, a dehydration step of dehydrating the present composition, a metal removal step of removing metal components from the present composition, a filtration step of filtering the present composition, and a destaticization step of destaticizing the present composition.

[0035] This composition can be filled into a known container for storage, transportation, and use. As a container, a container with a high degree of cleanliness within the container for semiconductor applications and which suppresses the elution of impurities from the inner wall of the container's storage section into each liquid is preferred. Examples of such containers include various containers commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these. Furthermore, the containers exemplified in paragraphs

[0121] to

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

[0036] [Uses of the composition] As described above, the composition is a composition for forming a coating that inhibits film formation by atomic layer deposition, 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 areas where no coating has been 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 below.

[0037] <Substrate> The substrate is not particularly limited, but preferably has at least one of a metal surface A made of a material containing metal atoms and a non-metal surface B made of a material not containing metal atoms, and more preferably has a metal surface A. The metal surface A is not particularly limited as long as it contains metal atoms.

[0038] 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, and more preferably aluminum atoms, 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, alloys, nitrides, oxides, and silicides, with elemental metals, alloys, or oxides being preferred. Examples of alloys include alloys containing two or more of the metal atoms contained in the metal surface A described above. The method for forming the metal surface A is not particularly limited, and known methods can be used. Examples include CVD, plating, and physical vapor deposition.

[0039] Examples of non-metallic materials constituting the non-metallic surface B include non-metallic elements such as silicon and carbon, non-metallic oxides such as silicon oxide, non-metallic nitrides such as silicon nitride, non-metallic oxynitrides such as silicon oxynitride, and organic materials. The material constituting the non-metallic surface B is preferably a non-metallic material containing silicon atoms, more preferably silicon oxide. Specific examples of silicon oxide include SiO ｙ (wherein y is preferably 0.5 to 2.0, more preferably 1.0 to 2.0), and SiO ｚ C ｗ (wherein z is preferably 0.5 to 2.0, more preferably 1.0 to 2.0, and w is preferably 0.5 to 2.0, more preferably 1.0 to 2.0). ｙ and SiO ｚ C ｗ The material represented by the composition may further contain hydrogen. ｚ C ｗ Examples of the material represented by the composition include Si(OC ２ H ５ ) ４ (tetraethyl orthosilicate, TEOS). Silicon oxides include SiO２ A material represented by the formula (silicon dioxide) or TEOS is preferred.

[0040] 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.

[0041] The substrate preferably has at least two surfaces, a first surface and a second surface, made of different materials. The first surface preferably interacts with the phosphonic acid group of the specific compound, and a coating containing the specific compound is formed upon contact with the composition. The first surface preferably has a group that forms a covalent bond with the phosphonic acid group or a group that forms a hydrogen bond with the phosphonic acid group. The second surface may be made of a material different from the first surface, but is preferably a surface on which the coating does not form upon contact with the composition. Regarding the combination of the first and second surfaces, it is preferable that at least the second surface be made of an insulator, and it is more preferable that both the first and second surfaces be made of insulators. Examples of the insulator include metal oxides, with aluminum oxide being preferred. In particular, when the first surface is made of an insulator, it is preferable that the first surface be made of aluminum oxide.

[0042] A preferred embodiment of the substrate is embodiment 1, in which the first surface is metal surface A. In embodiment 1, the metal atoms contained in metal surface A, which is the first surface, can be, for example, a metal element, an alloy, or a metal oxide, with metal oxide being preferred. Examples of the metal element and alloy include the metal elements and alloys thereof exemplified as the metals contained in metal surface A, with copper element or cobalt element being preferred. Examples of the metal oxide include aluminum oxide, tantalum oxide, iron oxide, and copper oxide.

[0043] 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, metal nitride, or metal oxynitride, more preferably a metal oxide. Furthermore, the non-metal material constituting the non-metal surface B of the second surface is preferably a non-metal material containing silicon atoms, more preferably a silicon oxide.

[0044] A preferred embodiment of the substrate is embodiment 2, in which the first surface is a nonmetallic surface B. In embodiment 2, the second surface is preferably a nonmetallic surface B different from the first surface or a metallic surface A, more preferably a nonmetallic surface B different from the first surface. Regarding the first surface, the nonmetallic material constituting the nonmetallic surface B is preferably a nonmetallic material containing silicon atoms, more preferably a nonmetallic nitride containing silicon atoms or a nonmetallic silicon nitride containing silicon atoms, and even more preferably silicon nitride (SiN) or silicon oxynitride (SiOCN). Furthermore, when the second surface is a nonmetallic surface B different from the first surface, the nonmetallic material constituting the nonmetallic surface B is preferably a nonmetallic material containing silicon atoms different from the first surface, more preferably silicon oxide. In embodiment 2, the metal atoms contained in the second surface, metallic surface A, are preferably a single metal or an alloy.

[0045] The shape of the substrate is not particularly limited, and any shape of a substrate generally used as a semiconductor substrate can be used. The substrate may be a substrate having the above-described surface, and may be a single layer or a multilayer structure. The shape of the first and second surfaces is not particularly limited, and examples thereof include a planar shape, a dotted shape, and a striped shape.

[0046] <Coating> The coating formed on a substrate using the present composition is a coating containing a specific compound contained in the present composition. The coating preferably functions as a mask when depositing a material in an ALD process. That is, when an ALD process is performed on a modified substrate on which a coating using the present composition has been formed in a specific region, the material preferably does not deposit in the region where the coating has been formed, but deposits in the region where the coating has not been formed, forming a film (hereinafter also referred to as an "ALD film"). This results in a laminate in which an ALD film is selectively formed in regions other than the region where the coating has been formed.

[0047] The coating also preferably functions as a mask when forming a metal-containing film by chemical vapor deposition (CVD) other than ALD. That is, in a CVD process, deposition of a film by CVD (hereinafter also referred to as a "CVD film") can be suppressed in the region where the coating is formed, and a CVD film can be deposited in the region where the coating is not formed. This results in a laminate in which a CVD film is selectively formed in the region other than the region where the coating is formed. Examples of CVD other than ALD that can be preferably applied to the modified substrate include known techniques such as thermal CVD and plasma CVD. As raw materials for the CVD film used in the CVD process, raw materials for the ALD film described below can be used.

[0048] The thickness of the coating is preferably 0.1 to 100.0 nm, more preferably 0.5 to 50.0 nm, and even more preferably 3.0 to 30.0 nm.

[0049] In order to obtain superior effects of the present invention, the contact angle of water with the coating is preferably 60° or more, more preferably 80° or more, and even more preferably 90° or more. There is no particular upper limit, and it is often 120° or less. The water contact angle is the average value of three contact angles measured 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.).

[0050] [Method for Producing Modified Substrate] The method for producing a modified substrate of the present invention includes a step of contacting a substrate with the present composition to form a coating on the substrate. This results in a modified substrate having a coating formed on the substrate. The method for producing a modified substrate of the present invention can be suitably used, for example, in the production of electronic devices. The method for contacting a substrate with the present composition is not particularly limited, and known methods can be used. Examples include a method of applying (e.g., spin coating) or spraying the present composition onto a substrate, and a method of immersing a substrate in the present composition. When immersing a substrate in the present composition, the present composition may be subjected to convection. The temperature of the present composition when contacting the substrate with the present composition is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. The time for contacting the substrate with the present composition is also not particularly limited, but is preferably 30 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and even more preferably 5 to 15 minutes.

[0051] After contacting the substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and known methods can be used, such as an oven or a hot plate. The heating temperature is preferably 60 to 400°C, more preferably 100 to 350°C, even more preferably 130 to 300°C, and particularly preferably 150 to 250°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 1 to 30 minutes, and even more preferably 3 to 10 minutes.

[0052] It is also preferable to perform a rinsing treatment after contacting the substrate with the present composition. The rinsing treatment may be performed after the heat treatment. The rinsing treatment can remove at least one of the present composition and impurities adhering to regions on the substrate other than the desired region (e.g., the region that interacts with the phosphonic acid group contained in the specific compound) from the substrate. The rinsing method is not particularly limited, and examples include a method of contacting the substrate with a rinsing liquid. As the contact method, the same method as the method of contacting the present composition with the 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, a known organic solvent can be used, such as the alcohol-based solvents, ether-based solvents, and ester-based solvents described above.

[0053] [Method for Producing a Laminate] The method for producing a laminate of the present invention includes step 1 of contacting a substrate (hereinafter also referred to as a "specific substrate") having at least two surfaces, a first surface and a second surface, each made of a different material, 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 atomic layer deposition to form a second coating on the second surface. This results in a laminate having a second coating (ALD film) on the second surface. The method for producing a laminate of the present invention can be suitably used, for example, in the production of electronic devices.

[0054] [Step 1: Method for producing modified substrate] Step 1 is a step of bringing a specific substrate into contact with the present composition to form a first coating on the first surface. Step 1 results in a modified substrate 1 in which a first coating is formed on the first surface of the specific substrate. The first coating is a coating containing the specific compound contained in the present composition. There are no particular limitations on the method for bringing the specific substrate into contact with the present composition, and the method of bringing the present composition into contact with the substrate in the above-mentioned method for producing a modified substrate can be used.

[0055] The method for producing a laminate of the present invention preferably includes a step (heating step) of heating the specific substrate obtained in step 1. The heating method is not particularly limited, and the heating methods in the method for producing a modified substrate described above can be used, but it is particularly preferable to heat the specific substrate obtained in step 1 at 60°C or higher.

[0056] The method for producing a laminate of the present invention also preferably includes a step of cleaning the specific substrate obtained in step 1 (rinsing step). The rinsing treatment can remove at least one of the composition and impurities adhering to regions other than the first surface (e.g., the second surface) of the specific substrate from the specific substrate. The rinsing method can be the same as the rinsing method used in the method for producing a modified substrate described above. The order in which the heating step and rinsing step are performed is not particularly limited, but it is preferable to perform them in the order of step 1, heating step, and rinsing step.

[0057] [Step 2: ALD Treatment] Step 2 is a step of subjecting the modified substrate 1 obtained in the above step 1 to ALD treatment to form a second coating on the second surface. Step 2 results in a laminate 1 in which a first coating is formed on the first surface and a second coating is 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 in which a first coating is formed on the first surface of a specific substrate in the above step 1, and may be subjected to the above-mentioned heating step, rinsing step, etc. after step 1.

[0058] The ALD process method is not particularly limited, and known methods can be used. For example, a method can be used in which a precursor gas serving as a raw material for the ALD film is supplied to the surface of the modified substrate 1, and then the raw material is decomposed and / or chemically reacted with an oxidizing agent or a reducing agent, etc., to deposit the material, thereby forming an ALD film. The precursor is not particularly limited, and known precursors can be used depending on the type of ALD film to be formed, such as organometallic compounds. Examples of precursors that can be used include alumina, tantalum nitride, and titanium nitride. The oxidizing agent is not particularly limited, and known oxidizing agents used in ALD processes can be used, such as water, oxygen, and ozone.

[0059] The material constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, and the like. The ALD film (second coating) is preferably a metal film, a metal oxide film, a metal nitride film, or a film containing silicon, with a metal oxide film being more preferred. The material of the formed ALD film is 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. In the ALD process, a treatment for modifying the surface of the region where the first coating is not formed may be performed.

[0060] After the ALD process, the thickness of the material deposited on the first coating is preferably as thin as possible, preferably 4.0 nm or less, more preferably 2.0 nm or less, and even more preferably 1.0 nm or less. The lower limit is 0 nm. The ratio of the thickness of the material deposited on the region where the first coating is formed to the thickness of the second coating is preferably 0.75 or less, more preferably 0.50 or less, and even more preferably 0.25 or less. The lower limit of the ratio is 0 or more, and may be 0.

[0061] [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.

[0062] The method for removing the first 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 first coating, and physical dry etching, such as sputter etching and ion beam etching. Wet etching can be performed by supplying an etching solution to the first coating. 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 that can be contained in the composition include organic solvents that are alcohol-based solvents, ester-based solvents, ketone-based solvents, and hydrocarbon-based solvents. Among these, chemical dry etching or wet etching is preferred.

[0063] 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.

[0064] [Preparation of Composition]

[0065] The materials used in preparing the compositions of the Examples and Comparative Examples are listed below. The specific compounds listed below are compounds used in preparing the compositions of the Examples, and the comparative compounds listed below are compounds used in preparing the compositions of the Comparative Examples.

[0066] [Specific compounds] Methylphosphonic acid, Ethylphosphonic acid, Propylphosphonic acid, (1-amino-2-methylpropyl)phosphonic acid, n-Octylphosphonic acid

[0067] [Comparative compounds] Decylphosphonic acid Dodecylphosphonic acid Octadecylphosphonic acid Phenylphosphonic acid 1,8-octanediphosphonic acid

[0068] [Solvents] 4-methyl-2-pentanol (protic polar solvent) PGMEA: propylene glycol monomethyl ether acetate (aprotic polar solvent) Ultrapure water

[0069] [Liquid Preparation] The compositions of each Example and Comparative Example were prepared by mixing the specific compound or comparative compound with a solvent (organic solvent or water) so that the concentration of the specific compound or comparative compound was 1 mmol / L.

[0070] [Preparation of Modified Substrate] A modified substrate was prepared by carrying out the following steps on an aluminum oxide substrate.

[0071] [Film Formation Process] A modified coating was formed on a substrate using the composition of each Example and Comparative Example according to the following procedure. An aluminum oxide substrate was prepared as the substrate. The aluminum oxide substrate was prepared by forming an aluminum oxide layer on one surface of a commercially available silicon wafer (12 inches in diameter) using the ALD method. The ALD conditions were trimethylaluminum as the organometallic source and water as the oxidant, and the ALD treatment temperature was 150°C. The number of ALD cycles was adjusted so that the aluminum oxide layer had a thickness of 30 nm. The aluminum oxide substrate was cut into 2.5 cm square pieces and pretreated by immersing in a container filled with isopropyl alcohol (IPA). The pretreatment was performed while stirring the IPA at a stirring speed of 250 rpm, at an IPA temperature of 25°C, and for 1 minute. The pretreated wafer was dried by spraying nitrogen gas. The pretreated wafer was then immersed in the composition of each Example and Comparative Example to form a modified coating on the substrate. The coating was formed while stirring each composition at a stirring speed of 250 rpm, the temperature of each composition was 25° C., and the immersion time was 10 minutes.

[0072] [Heating Step] Each of the substrates obtained in the above [Film Forming Step] was heated on a hot plate in a nitrogen atmosphere at 180° C. for 5 minutes.

[0073] [Rinse Step] Each substrate obtained in the above [Heating Step] was immersed in IPA for a rinse treatment (cleaning treatment). The rinse treatment was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25°C, and the rinse time was 30 seconds. After rinsing, the wafer was dried by spraying nitrogen gas. By the above procedure, a modified substrate on which a coating containing a specific compound or a comparative compound was formed was obtained.

[0074] [Evaluation] [ALD Inhibition Rate (Deposition Inhibition) Evaluation] An aluminum oxide layer (ALD film) was formed by ALD using an atomic layer deposition system (AD-230LP, manufactured by Samco) on each modified substrate obtained by the above [Preparation of Modified Substrates] and on a substrate immediately after pretreatment (unmodified substrate) that had not been immersed in each composition. Trimethylaluminum was used as the organometallic source, and water was used as the oxidizing agent. The ALD treatment temperature was 150°C. Other conditions were adjusted so that the ALD film formed on the unmodified substrate had a thickness of 5 nm. The thickness of the ALD film on each substrate after ALD treatment was measured using a spectroscopic ellipsometer (M-2000XI, manufactured by J.A. Woollam Japan). Measurements were performed at five points on the substrate, and the average value was used as the film thickness. Measurements were performed over a measurement range of 1.2-2.5 eV and at measurement angles of 70° and 75°. The ALD inhibition rate (%) was calculated from the obtained film thickness using the following formula: ALD inhibition rate (%) = 100 × (T ｐｒｅ -T ＳＡＭ ) / T ｐｒｅ In the above formula, T ｐｒｅ denotes the thickness of the ALD film on the unmodified substrate, and T ＳＡＭ indicates the thickness of the ALD film on each modified substrate obtained by the above-mentioned [Preparation of Modified Substrate]. The higher the ALD inhibition rate, the more difficult it is for a film to be deposited by the ALD treatment, i.e., the better the ALD inhibition property.

[0075] [Results] The composition and evaluation results of each composition are shown in Table 1 below. In the "Solvent" column in Table 1, the entry "4-methyl-2-pentanol / PGMEA (=60 / 40)" indicates that when preparing the composition, 60 mass % of 4-methyl-2-pentanol and 40 mass % of PGMEA were used relative to the total mass of the organic solvent. The same applies to other entries in the "Solvent" column.

[0076]

[0077] The results in Table 1 confirm that the composition of the present invention can form a coating having excellent ALD inhibitory properties. Furthermore, a comparison between Example 5 and other Examples confirms that the effects of the present invention are even better when the specific compound is a compound represented by formula (1) above, where X in formula (1) represents a linear aliphatic hydrocarbon group which may have a substituent. A comparison between Example 2 and other Examples confirms that the effects of the present invention are even better when the specific compound is propylphosphonic acid. A comparison between Example 1 and Examples 6 to 9 confirms that the effects of the present invention are even better when the organic solvent contains a protic polar solvent and the content of the protic polar solvent is 50 mass% or more relative to the total mass of the organic solvent.

Claims

1. A composition for forming a coating that inhibits film formation by atomic layer deposition, comprising an acyclic compound having only one phosphonic acid group and 8 or less carbon atoms, and an organic solvent.

2. The composition according to claim 1, wherein the compound is a compound represented by the following formula (1): X-PO ３ H ２ (1) In formula (1), X represents a linear or branched aliphatic hydrocarbon group which may have a substituent, provided that the number of carbon atoms contained in the compound represented by formula (1) is 8 or less.

3. The composition according to claim 2, wherein in formula (1), X represents a linear aliphatic hydrocarbon group which may have a substituent.

4. The composition of claim 1, wherein said compound is propylphosphonic acid.

5. The composition according to claim 1, wherein the organic solvent comprises a protic polar solvent, and the content of the protic polar solvent is 50 mass % or more based on the total mass of the organic solvent.

6. A method for producing a modified substrate, comprising the step of contacting a substrate with the composition of any one of claims 1 to 5 to form a coating on the substrate.

7. A method for producing a laminate, comprising: step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each surface being made of a different material, with the composition described in any one of claims 1 to 5 to form a first coating on the first surface; and step 2 of subjecting the substrate obtained in step 1 to atomic layer deposition to form a second coating on the second surface.

8. The method for producing a laminate according to claim 7, wherein the first surface has a group that forms a covalent bond with a phosphonic acid group or a group that forms a hydrogen bond.

9. The method for producing a laminate according to claim 7, further comprising the step of heating the substrate obtained in step 1 at 60°C or higher.

10. The method for producing a laminate according to claim 7, further comprising the step of cleaning the substrate obtained in step 1.

11. The method for manufacturing a laminate according to claim 7, wherein the second surface is made of an insulator.

12. The method for manufacturing a laminate according to claim 7, wherein the first surface and the second surface are made of an insulator.

13. The method of manufacturing a laminate according to claim 7, wherein the first surface is composed of aluminum oxide.

14. The method for producing a laminate according to claim 7, wherein the second coating film is a metal film, a metal oxide film, a metal nitride film, or a film containing silicon.

15. A method for manufacturing an electronic device, comprising the method for manufacturing the laminate according to claim 7.

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