Method for manufacturing reactive materials and thin films

Abstract

A reactive material containing a compound represented by the following general formula (1) or (2) is provided. (In Equation (1), R1, R2, R3, and R4 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. Provided, at least one of R1, R2, R3, and R4 represents an electron-withdrawing group.) (In Equation (2), R5 and R6 each independently represent a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. Provided that at least one of R5 and R6 represents an electron-withdrawing group.)

Description

Technology Field

[0001] The present invention relates to a reactive material used to reduce an organometallic compound to a metal, and a method for manufacturing a thin film using the same. Background Technology

[0002] Metallic ruthenium thin films exhibit unique electrical properties and are utilized in various applications. For example, they are known to be used as electrode materials for memory devices, such as DRAMs; resistive films; diamagnetic films used in the recording layers of hard disks; catalyst materials for solid polymer fuel cells; wiring materials for semiconductor devices; and metal gate materials for MOS-FETs.

[0003] Methods for manufacturing thin films include sputtering, ion plating, MOD methods such as coating pyrolysis or sol-gel methods, and chemical vapor deposition. Among these, chemical vapor deposition methods, including CVD and atomic layer deposition (hereinafter referred to as "ALD method"), are mainly used because they have many advantages, such as excellent compositional controllability, step coverage, suitability for mass production, and the ability to perform hybrid integration.

[0004] Various organic ruthenium compounds are known as organic ruthenium compounds used in chemical vapor phase growth methods such as CVD and ALD. For example, Patent Document 1 discloses a method for manufacturing a ruthenium-containing thin film using a ruthenium complex mixture containing two or more types of ruthenium complexes and a reducing gas. Patent Document 2 discloses a method for manufacturing a ruthenium-containing thin film using a raw material for forming a thin film containing a ruthenium compound composed of two six-membered rings that include two carbonyl groups, a ruthenium atom, and a ketoimine group in the ring structure. Patent Document 3 discloses a method for manufacturing a metallic ruthenium thin film comprising a process of depositing a ruthenium compound having cyclohexadiene and benzene rings in the structure onto a gaseous phase, and a process of reacting the ruthenium compound deposited onto the gaseous phase with a reactive gas containing a specific compound. Prior art literature

[0005] Japanese Published Patent Application No. 2014-118605, Japanese Patent No. 6509128, International Publication No. 2020 / 095744 The problem to be solved

[0006] However, in conventional methods for manufacturing metallic ruthenium thin films using the ALD method, there was a problem in that composite thin films containing metallic ruthenium and ruthenium oxide were formed, or metallic ruthenium thin films with a high residual carbon content were formed. Since composite thin films containing ruthenium oxide require reduction to metallic ruthenium by processing at high temperatures, there were cases where the substrate and surrounding components were damaged.

[0007] Accordingly, the present invention aims to provide a method for producing a high-quality metallic ruthenium thin film having low ruthenium oxide content and low residual carbon content, and a reactive material used therein. means of solving the problem

[0008] As a result of repeated careful examination, the inventors discovered that the above problem could be solved by using a reactive material containing a specific compound, and thus completed the present invention.

[0009] That is, the present invention is represented by [1] to [8] below.

[0010] [1] A reactive material containing a compound represented by the following general formula (1) or (2).

[0011] [Chemical Formula 1]

[0012]

[0013] (In Equation (1), R 1 , R 2 , R 3 and R 4 Each represents, independently, a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. The electron-withdrawing group is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a cyano group, an aldehyde group, an acetyl group, a carboxyl group, a carboxymethyl group, a sulfo group, and a sulfomethyl group. provided that R 1 , R 2 , R 3 and R 4 At least one of them represents an electronically absorbing group.)

[0014] [Chemical Formula 2]

[0015]

[0016] (In Equation (2), R 5 and R 6Each represents, independently, a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. The electron-withdrawing group is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a cyano group, an aldehyde group, an acetyl group, a carboxyl group, a carboxymethyl group, a sulfo group, and a sulfomethyl group. provided that R 5 and R 6 At least one of them represents an electronically absorbing group.)

[0017] [2] Reactive material described in [1] used to reduce organometallic compounds to metals.

[0018] [3] A method for manufacturing a thin film, comprising forming a metallic ruthenium thin film using a reactive material described in [1] or [2] in an atomic layer deposition method.

[0019] [4] A process for forming a precursor thin film using a raw material for forming a thin film containing an organic ruthenium compound, and

[0020] A method for manufacturing a thin film as described in [3], having a process of reacting the above precursor thin film with the above reactive material to form a metallic ruthenium thin film.

[0021] [5] A method for manufacturing a thin film as described in [4], wherein the above organic ruthenium compound is selected from the group consisting of an organic ruthenium compound represented by the following general formula (3), an organic ruthenium compound represented by the following general formula (4), and an organic ruthenium compound represented by the following general formula (5).

[0022] [Chemical Formula 3]

[0023]

[0024] (Among equations (3), (4) and (5), L 1...represents a covalent ligand selected from the group consisting of an aminoalkoxy group, an amidinate group, a β-diketonate group, a β-ketoiminate group, a β-dikethyminate group, a group having the structure of a 2,4-pentadienyl group, and a group having the structure of a cyclopentadienyl group, X represents a halogen atom, n represents an integer from 0 to 2, and L 2 represents an electron-donating ligand selected from the group consisting of carbonyl groups, cyano groups, trialkylphosphine compounds, and isocyanide compounds, m represents an integer from 0 to 3, and L 3 represents an electron-donating ligand selected from the group consisting of chain-type diene compounds, cyclic diene compounds, chain-type polyene compounds, and cyclic polyene compounds, y represents 1 or 2, and L 4 represents an electron-donating ligand composed of an arene compound, and z represents 0 or 1.

[0025] [6] A method for manufacturing a thin film as described in [4] or [5], wherein a vaporized raw material for forming a thin film is deposited on the surface of a gas heated to 100 ℃ to 450 ℃ to form the precursor thin film.

[0026] [7] A method for manufacturing a thin film as described in [6], having an additional process of exhausting the un-deposited raw material for forming the thin film from the reaction system after forming the precursor thin film.

[0027] [8] After forming the above metal ruthenium thin film, the process of exhausting the unreacted reactive material from the reaction system is further included.

[0028] A method for manufacturing a thin film as described in [7], which involves repeating the process of forming a precursor thin film, the process of exhausting raw materials for forming a thin film that are not deposited from the reaction system, the process of forming a metal ruthenium thin film, and the process of exhausting unreacted reactive materials from the reaction system. Effects of the invention

[0029] According to the present invention, a method for producing a high-quality metallic ruthenium thin film having low ruthenium oxide content and low residual carbon content, and a reactive material used therein can be provided. Brief explanation of the drawing

[0030] FIG. 1 is a schematic diagram showing an example of an ALD apparatus used in the method for manufacturing a thin film of the present invention. FIG. 2 is a schematic diagram showing another example of an ALD device used in the method for manufacturing a thin film of the present invention. FIG. 3 is a schematic diagram showing another example of an ALD device used in the method for manufacturing a thin film of the present invention. FIG. 4 is a schematic diagram showing another example of an ALD device used in the method for manufacturing a thin film of the present invention. Specific details for implementing the invention

[0031] The present invention is a reactive material containing a compound represented by the general formula (1) or (2) above. Here, a reactive material is a material capable of reducing an organometallic compound to a metal, and more specifically, a material capable of forming a metal film by reacting with a precursor thin film formed from a precursor containing an organometallic compound. The metal of the metal film is a metal derived from the metal species of the precursor. Although the reactive material of the present invention is not limited by the metal species of the precursor, it is preferable to react it with a precursor thin film formed from a precursor containing an organoruthenium compound in order to have good reactivity.

[0032] R in the above general formula (1). 1 , R 2 , R 3 and R 4Examples of hydrocarbon groups having 1 to 4 carbon atoms represented by saturating hydrocarbon groups and unsaturated hydrocarbon groups. Examples of saturated hydrocarbon groups include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl groups. Examples of unsaturated hydrocarbon groups include alkyl groups containing alkenyl groups such as allylmethyl and propenylmethyl groups, and alkyl groups containing alkynyl groups such as ethynylmethyl groups.

[0033] In terms of the ease of forming a metallic ruthenium thin film with low ruthenium oxide content by reacting with an organic ruthenium compound at low temperatures, R in the above general formula (1) 1 , R 2 , R 3 and R 4 It is preferable that at least two of them are electronic suction devices, and it is more preferable that at least three of them are electronic suction devices.

[0034] R in the above general formula (1). 1 , R 2 , R 3 and R 4 The electron-withdrawing group represented by is selected from the group consisting of fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, trifluoromethyl groups, trichloromethyl groups, tribromomethyl groups, triiodomethyl groups, cyano groups, aldehyde groups, acetyl groups, carboxymethyl groups, sulfo groups, and sulfomethyl groups.

[0035] R 1 , R 2 , R 3 and R 4 In the case where two or more are electron-withdrawing groups, the types of electron-withdrawing groups within one molecule may be different, but it is preferable that they be the same. R 1 , R 2 , R 3 and R 4In the case where three of them are electron absorbers, it is preferable that the electron absorbers be halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. R 1 , R 2 , R 3 and R 4 In cases where all of them are electron absorbers, it is preferable for the electron absorbers to be cyano groups, in terms of making it easier to form a metallic ruthenium thin film with less ruthenium oxide.

[0036] R 1 , R 2 , R 3 and R 4 In the case where at least one of them is not an electron absorber, R in terms of the ease of forming a metallic ruthenium thin film with little ruthenium oxide, 1 , R 2 , R 3 and R 4 It is preferable that at least one of them is a hydrogen atom or a methyl group.

[0037] The reactive material of the present invention, in terms of being easy to form a metallic ruthenium thin film with low ruthenium oxide content, is R in the general formula (1) above. 1 , R 2 , R 3 and R 4 It is preferable that at least one of the compounds contains a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, or a trifluoromethyl group, and it is more preferable that the compound contains a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a cyano group.

[0038] Preferred specific examples of the compound represented by the above general formula (1) include, for example, the compounds No. 1 to No. 225 below. However, the present invention is not limited to these compounds. In addition, in the following, “Me” represents a methyl group, “CF3” represents a trifluoromethyl group, “CCl3” represents a trichloromethyl group, “CBr3” represents a tribromomethyl group, “CI3” represents a triiodomethyl group, “CN” represents a cyano group, “CHO” represents an aldehyde group, “COCH3” represents an acetyl group, “COOH” represents a carboxyl group, “COOCH3” represents a carboxymethyl group, “SO3H” represents a sulfo group, and “SO2CH3” represents a sulfomethyl group.

[0039] [Chemical Formula 4]

[0040]

[0041] [Chemical Formula 5]

[0042]

[0043] [Chemical Formula 6]

[0044]

[0045] [Chemical Formula 7]

[0046]

[0047] [Chemical Formula 8]

[0048]

[0049] [Chemical Formula 9]

[0050]

[0051] [Chemical Formula 10]

[0052]

[0053] [Chemical Formula 11]

[0054]

[0055] [Chemical Formula 12]

[0056]

[0057] [Chemical Formula 13]

[0058]

[0059] [Chemical Formula 14]

[0060]

[0061] [Chemical Formula 15]

[0062]

[0063] [Chemical Formula 16]

[0064]

[0065] [Chemical Formula 17]

[0066]

[0067] [Chemical Formula 18]

[0068]

[0069] The compound represented by the above general formula (1) is not particularly limited by its manufacturing method and can be produced by a well-known synthesis method. For example, the compound of No. 135 can be obtained by dibromating malononitrile with bromine and then reductively dimerizing it with copper powder.

[0070] Examples of compounds having two electron-withdrawing groups include No. 7 to No. 12, No. 22 to No. 27, No. 37 to No. 42, No. 52 to No. 57, No. 67 to No. 72, No. 82 to No. 87, No. 97 to No. 102, No. 112 to No. 117, No. 127 to No. 132, No. 142 to No. 147, No. 157 to No. 162, No. 172 to No. 177, No. 187 to No. 192, No. 202 to No. 207, and No. 217 to No. 222.

[0071] Examples of compounds having three or more electron-withdrawing groups include No. 13 to No. 15, No. 28 to No. 30, No. 43 to No. 45, No. 58 to No. 60, No. 73 to No. 75, No. 88 to No. 90, No. 103 to No. 105, No. 118 to No. 120, No. 133 to No. 135, No. 148 to No. 150, No. 163 to No. 165, No. 178 to No. 180, No. 193 to No. 195, No. 208 to No. 210, and No. 223 to No. 225.

[0072] Among these, compounds of No. 43 and No. 135 are preferred in that the effect of the present invention is significantly enhanced.

[0073] Next, we will describe a compound represented by the general formula (2).

[0074] In the above general formula (2), R 5 and R 6 The hydrocarbon group having 1 to 4 carbon atoms represented by is R of the above general formula (1). 1 , R 2 , R 3 and R 4 The same as those listed in can be cited.

[0075] In the above general formula (2), R 5 and R 6 The electron-attracting device represented by is R of the above general formula (1). 1 , R 2 , R 3 and R 4 The same as those listed in can be cited.

[0076] Preferred specific examples of the compound represented by the above general formula (2) include, for example, the compounds of No. 226 to No. 270 below. However, the present invention is not limited to these compounds.

[0077] [Chemical Formula 19]

[0078]

[0079] [Chemical Formula 20]

[0080]

[0081] The compound represented by the above general formula (2) is not particularly limited by its manufacturing method and can be produced by a well-known synthesis method. For example, the compound of No. 232 can be obtained by heating and stirring 1,2-dibromoethane in a mixed solvent of ethanol and water in the presence of sodium hydroxide.

[0082] In the above general formula (2), R 5 and R 6 At least one of them is an electronic absorbing device, and R 5 and R 6 Both sides may contribute electronically. R 5 and R 6 If both sides are electro-absorbing devices, they may have the same electro-absorbing contribution or different electro-absorbing contributions. R 5 and R 6 Examples of compounds in which both of the groups are electron-withdrawing groups include No. 228, No. 231, No. 234, No. 237, No. 240, No. 243, No. 246, No. 249, No. 252, No. 255, No. 258, No. 261, No. 264, No. 267, and No. 270.

[0083] The reactive material of the present invention contains a compound represented by the general formula (1) or the general formula (2), and may be a reactive material composed only of the compound represented by the general formula (1) or a reactive material composed only of the compound represented by the general formula (2), or may be a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2). In addition, the reactive material of the present invention may further include a reactive agent such as water vapor, nitrogen, oxygen, ozone, and hydrogen used in the formation of a thin film.

[0084] In the case where the reactive material of the present invention is a mixture of the compound represented by the general formula (1) and the compound represented by the general formula (2), from the perspective that it is easy to form a metallic ruthenium thin film with low ruthenium oxide content, it is preferable that the compound represented by the general formula (1) has 60 parts by mass or more, 80 parts by mass or more, more preferable that it has 90 parts by mass or more, and most preferable that it has 98 parts by mass or more, with respect to 100 parts by mass of the total of the compound represented by the general formula (1) and the compound represented by the general formula (2). From the perspective that it is easy to form a metallic ruthenium thin film with low ruthenium oxide content, it is preferable that the reactive material of the present invention contains only the compound represented by the general formula (1).

[0085] In terms of making it easy to form a metallic ruthenium thin film with little ruthenium oxide, it is preferable that the sum of the compound represented by the general formula (1) and the compound represented by the general formula (2) be 60 volume% or more with respect to the entire reactive material, more preferable that it be 70 volume% or more, even more preferable that it be 90 volume% or more, even more preferable that it be 98 volume% or more, and most preferable that it be 99 volume% or more.

[0086] Next, a method for manufacturing a thin film according to the present invention will be described. The method for manufacturing a thin film according to the present invention comprises forming a metallic ruthenium thin film using the reactive material described above in an atomic layer deposition method.

[0087] The method for manufacturing a thin film according to the present invention preferably comprises a process of forming a precursor thin film using a raw material for forming a thin film containing an organic ruthenium compound (precursor thin film formation process) and a process of forming a metallic ruthenium thin film by reacting the precursor thin film with the reactive material described above (thin film formation process). It is preferable to have these processes because it is easy to form a high-quality metallic ruthenium thin film that has a low amount of ruthenium oxide and a low amount of residual carbon.

[0088] Hereinafter, the raw material for forming a thin film used in the method for manufacturing a thin film of the present invention will be described.

[0089] <Raw Material for Thin Film Formation>

[0090] The raw material for thin film formation used in the precursor thin film formation process contains an organic ruthenium compound.

[0091] As for the organic ruthenium compound contained in the above-mentioned raw material for forming a thin film, any organic ruthenium compound known as a raw material for forming a thin film can be used without particular limitation, but from the view that the effect of the present invention is significantly enhanced, it is preferable to select from the group consisting of the organic ruthenium compound represented by the following general formula (3), the organic ruthenium compound represented by the following general formula (4), and the organic ruthenium compound represented by the following general formula (5).

[0092] [Chemical Formula 21]

[0093]

[0094] Among the above general formulas (3), (4) and (5), L 1...represents a covalent ligand selected from the group consisting of an aminoalkoxy group, an amidinate group, a β-diketonate group, a β-ketoiminate group, a β-dikethyminate group, a group having the structure of a 2,4-pentadienyl group, and a group having the structure of a cyclopentadienyl group, X represents a halogen atom, n represents an integer from 0 to 2, and L 2 represents an electron-donating ligand selected from the group consisting of carbonyl groups, cyano groups, trialkylphosphine compounds, and isocyanide compounds, m represents an integer from 0 to 3, and L 3 represents an electron-donating ligand selected from the group consisting of chain-type diene compounds, cyclic diene compounds, chain-type polyene compounds, and cyclic polyene compounds, y represents 1 or 2, and L 4 represents an electron-donating ligand composed of an arene compound, and z represents 0 or 1.

[0095] L in the above general formulas (3) and (4) 1As aminoalkoxy groups as covalent ligands represented by, for example, aminomethoxy group, methylaminomethoxy group, dimethylaminomethoxy group, ethylmethylaminomethoxy group, diethylaminomethoxy group, 2-aminoethoxy group, 2-(methylamino)ethoxy group, 2-(dimethylamino)ethoxy group, 2-(ethylmethyl)aminoethoxy group, 2-(diethylamino)ethoxy group, (1-(dimethylamino)propane-2-yl)oxy group, (1-(ethylmethylamino)propane-2-yl)oxy group, (1-(dimethylamino)propane-2-yl)oxy group, (1-(ethylmethylamino)propane-2-yl)oxy group, (1-(dimethylamino)2-methylpropane-2-yl)oxy group, (1-(diethylamino)propane-2-yl)oxy group, (1-(dimethylamino)propane-2-yl)oxy group, Examples include (1-(ethylmethylamino)propane-2-yl)oxy group, (1-(diethylamino)propane-2-yl)oxy group, 3-(dimethylamino)propoxy group, (ethylmethylamino)propoxy group, (diethylamino)propoxy group, (4-(dimethylamino)butane-2-yl)oxy group, (4-(ethylmethylamino)butane-2-yl)oxy group, (4-(diethylamino)butane-2-yl)oxy group, 4-(dimethylamino)-2-methylbutane-2-yl)oxy group, 4-(ethylmethylamino)-2-methylbutane-2-yl)oxy group, 4-(diethylamino)-2-methylbutane-2-yl)oxy group, etc.

[0096] L in the above general formulas (3) and (4) 1 Examples of amidinate groups as covalent ligands represented by are, for instance, N,N'-dimethylacetamidinate group, N,N'-diethylacetamidinate group, N,N'-diisopropylacetamidinate group, N,N'-n-propylacetamidinate group, N,N'-ditert-butylethylpropioamidinate group, N,N'-trifluoromethylbenzamidinate group, N,N'-diphenylbenzamidinate group, N,N'-ditrimethylsilylbenzamidinate group, etc.

[0097] L in the above general formulas (3) and (4) 1Examples of β-diketonate groups as covalent ligands represented by include, for instance, acetylacetonate groups, trifluoroacetylacetonate groups, hexafluoroacetylacetonate groups, dimethylheptanedionate groups, tetramethylheptanedionate groups, heptafluorodimethyloctanedionate groups, tetradecafluorononandionate groups, trifluorodimethylhexanedionate groups, octafluorohexanedionate groups, pentafluorodimethylheptanedionate groups, decafluoroheptanedionate groups, dimethylmethoxyoctanedionate groups, trichloropentanedionate groups, diphenylpropanedionate groups, etc.

[0098] L in the above general formulas (3) and (4) 1 Examples of β-ketoimineates that serve as covalent ligands include, for instance, the β-ketoimineates described in Japanese Patent Publication No. 2002-533910, Japanese Patent Publication No. 2002-302473, Japanese Patent Publication No. 2011-061208, etc.

[0099] L in the above general formulas (3) and (4) 1 Examples of β-diketiminated groups as covalent ligands represented by β-diketiminated groups include, for instance, the β-diketiminated group described in Japanese Patent Publication No. Hei 8-36420, etc.

[0100] L in the above general formulas (3) and (4) 1 Examples of groups having the structure of a 2,4-pentadienyl group as a covalent ligand represented by include, for instance, a hexa-2,4-dienyl group, a 4-methylhexa-2,4-dienyl group, a 2,4-dimethylpenta-2,4-dienyl group, a 2,4-diethylpenta-2,4-dienyl group, a 2,4-diisopropylpenta-2,4-dienyl group, etc.

[0101] L in the above general formulas (3) and (4) 1Examples of groups having the structure of a cyclopentadienyl group as a covalent ligand represented by, for instance, include a cyclopentadienyl group, a methylpentadienyl group, an ethylcyclopentadienyl group, a pentamethylcyclopentadienyl group, etc.

[0102] The halogen atoms represented by X in the above general formula (4) include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.

[0103] L in the above general formulas (4) and (5) 2 Examples of trialkylphosphine compounds that serve as electron-donating ligands include trimethylphosphine, triethylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, etc.

[0104] L in the above general formulas (4) and (5) 2 Isocyanide compounds as electron-donating ligands represented by R 7 Represents a group containing the structure of -N≡C, and R 7 It represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms.

[0105] R 7 Examples of the straight-chain or branched alkyl groups having 1 to 6 carbon atoms represented by the above include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, etc.

[0106] R 7 Examples of the cycloalkyl groups having 3 to 6 carbon atoms represented by the above include cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, etc.

[0107] L in the above general formula (5) 3Examples of chain-type diene compounds that serve as electron-donating ligands include 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 2,3-dimethyl-1,3-pentadiene, 2,4-dimethyl-1,3-pentadiene, 2,4-hexadiene, 3-methyl-1,3-pentadiene, 2-ethyl-1,3-butadiene, 1,3-hexadiene, 1,3-heptadiene, 1,3-octadiene, 1,3-nonadiene, 1,3-decadien, 2-isopropyl-2,3-butadiene, 2-cyclohexyl-1,3-butadiene, etc.

[0108] L in the above general formula (5) 3 Cyclic diene compounds as electron-donating ligands represented by, for example, 1,3-cyclohexadiene, 1,4-cyclohexadiene, 1-methyl-1,3-cyclohexadiene, 2-methyl-1,3-cyclohexadiene, 1-ethyl-1,3-cyclohexadiene, 2-ethyl-1,3-cyclohexadiene, 1-propyl-1,3-cyclohexadiene, 2-propyl-1,3-cyclohexadiene, 1-isopropyl-1,3-cyclohexadiene, 2-isopropyl-1,3-cyclohexadiene, 1-butyl-1,3-cyclohexadiene, 2-butyl-1,3-cyclohexadiene, 1-isobutyl-1,3-cyclohexadiene, 2-Isobutyl-1,3-cyclohexadiene, 1-sec-butyl-1,3-cyclohexadiene, 2-sec-butyl-1,3-cyclohexadiene, 1-tert-butyl-1,3-cyclohexadiene, 2-tert-butyl-1,3-cyclohexadiene, 1-pentyl-1,3-cyclohexadiene, 2-pentyl-1,3-cyclohexadiene, 1-hexyl-1,3-cyclohexadiene, 2-hexyl-1,3-cyclohexadiene, 1-cyclohexyl-1,3-cyclohexadiene, 2-cyclohexyl-1,3-cyclohexadiene, α-phellandrene, α-terpinene, γ-terpinene, norbornadiene, 1,5-cyclooctadiene, Examples include 1,5-dimethyl-1,5-cyclooctadiene.

[0109] In the present invention, a polyene compound refers to a carbon compound having three or more carbon-carbon double bonds in one molecule. L in general formula (5). 3 Chain-type polyene compounds acting as electron-donating ligands represented by [formula] include, for example, 1,3,5-hexatriene, 1,3,5-heptatriene, etc. L in the above general formula (5). 3 Examples of cyclic polyene compounds that serve as electron-donating ligands include cycloheptatriene, cyclooctatriene, cyclooctatetraene, etc.

[0110] L in the above general formula (5) 4 Examples of arene compounds that serve as electron-donating ligands include toluene, benzene, o-xylene, m-xylene, p-xylene, mesitylene, fluorobenzene, o-difluorobenzene, p-difluorobenzene, chlorobenzene, pentafluorobenzene, o-dichlorobenzene, hexafluorobenzene, etc.

[0111] In the view that the effect of the present invention is significantly enhanced, L in the above general formula (3) 1 An organic ruthenium compound having an amidinate group, a β-diketonate group, a β-ketoiminate group, a β-dikethyminate group, a 2,4-pentadienyl group, or a cyclopentadienyl group is preferred, and an organic ruthenium compound having a β-diketonate group, a β-ketoiminate group, or a β-dikethyminate group is more preferred.

[0112] Preferred specific examples of the organic ruthenium compound represented by the above general formula (3) include the compounds of No. 271 to No. 275 below. However, the present invention is not limited to these organic ruthenium compounds.

[0113] [Chemical Formula 22]

[0114]

[0115] In the view that the effect of the present invention is significantly enhanced, L in the above general formula (4) 1 An organic ruthenium compound having an amidanate group, a β-diketonate group, a β-ketoiminate group, a β-dikethyminate group, a 2,4-pentadienyl group, or a cyclopentadienyl group is preferred, an organic ruthenium compound having an amidanate group, a β-diketonate group, a β-dikethyminate group, a 2,4-pentadienyl group, or a cyclopentadienyl group is more preferred, and an organic ruthenium compound having a 2,4-pentadienyl group or a cyclopentadienyl group is even more preferred.

[0116] In terms of the effect of the present invention being significantly enhanced, an organic ruthenium compound in which X in the general formula (4) is a chlorine atom is more preferable.

[0117] In the view that the effect of the present invention is significantly enhanced, L in the above general formula (4) 2 A, an organic ruthenium compound that is a carbonyl group, a cyano group, or a trialkylphosphine compound is preferred, and an organic ruthenium compound that is a carbonyl group or a cyano group is more preferred.

[0118] In view of the effect of the present invention being significant, an organic ruthenium compound in the general formula (4) where n is 0 or 2 is preferred, and an organic ruthenium compound where n is 2 is more preferred.

[0119] In view of the effect of the present invention being significant, an organic ruthenium compound in which m in the general formula (4) is 0 or 2 is preferred, and an organic ruthenium compound in which m is 2 is more preferred.

[0120] Preferred specific examples of the organic ruthenium compound represented by the above general formula (4) include the compounds of No. 276 to No. 305 below. However, the present invention is not limited to these organic ruthenium compounds.

[0121] [Chemical Formula 23]

[0122]

[0123] [Chemical Formula 24]

[0124]

[0125] [Chemical Formula 25]

[0126]

[0127] [Chemical Formula 26]

[0128]

[0129] [Chemical Formula 27]

[0130]

[0131] [Chemical Formula 28]

[0132]

[0133] In the view that the effect of the present invention is significantly enhanced, L in the above general formula (5) 2 A, an organic ruthenium compound that is a carbonyl group, a cyano group, or a trialkylphosphine compound is preferred, and an organic ruthenium compound that is a carbonyl group or a cyano group is more preferred.

[0134] In the view that the effect of the present invention is significantly enhanced, L in the above general formula (5) 3 The organic ruthenium compound that is a chain-type diene compound, a cyclic diene compound, or a cyclic polyene compound is preferred, and the organic ruthenium compound that is a chain-type diene compound or a cyclic diene compound is more preferred.

[0135] In the view that the effect of the present invention is significantly enhanced, L in the above general formula (5) 4 An organic ruthenium compound that is a, toluene, benzene, o-xylene, m-xylene, or p-xylene is preferred, and an organic ruthenium compound that is toluene or benzene is more preferred.

[0136] In view of the effect of the present invention being significant, an organic ruthenium compound in which m in the general formula (5) is 0 or 2 is preferred, and an organic ruthenium compound in which m is 0 is more preferred.

[0137] In view of the effect of the present invention being significant, an organic ruthenium compound in which y in the general formula (5) is 1 or 2 is preferred, and an organic ruthenium compound in which y is 1 is more preferred.

[0138] In view of the effect of the present invention being significant, an organic ruthenium compound in which z in the general formula (5) is 0 or 1 is preferred, and an organic ruthenium compound in which z is 0 is more preferred.

[0139] Preferred specific examples of the organic ruthenium compound represented by the above general formula (5) include the compounds of No. 306 to No. 318 below. However, the present invention is not limited to these organic ruthenium compounds.

[0140] [Chemical Formula 29]

[0141]

[0142] [Chemical Formula 30]

[0143]

[0144] [Chemical Formula 31]

[0145]

[0146] In the method for manufacturing a thin film of the present invention, the structure of the organic ruthenium compound may be used without limitation, and a mixture of organic ruthenium compounds may be used. However, from the perspective of making the effect of the present invention more pronounced, it is preferable to use a raw material for forming a thin film containing an organic ruthenium compound represented by general formula (4) or an organic ruthenium compound represented by general formula (5), it is more preferable to use a raw material for forming a thin film containing an organic ruthenium compound selected from No. 281 to No. 318, and most preferable to use a raw material for forming a thin film containing an organic ruthenium compound selected from No. 303 to No. 309 or No. 316 to No. 318.

[0147] A raw material for forming a thin film containing an organic ruthenium compound only needs to contain the organic ruthenium compound as a precursor for the thin film, and its composition varies depending on the type of thin film intended. For example, when manufacturing a thin film containing only ruthenium atoms as a metal, the raw material for forming the thin film does not contain metal compounds other than ruthenium or metalloid compounds. On the other hand, when manufacturing a thin film containing ruthenium atoms and metals and / or metalloids other than ruthenium atoms, the raw material for forming the thin film may contain, in addition to the organic ruthenium compound, a compound containing the desired metal and / or a compound containing a metalloid (hereinafter, it may also be described as "other precursor").

[0148] In the case of a multi-component ALD method using multiple precursors, other precursors that can be used together with the organic ruthenium compound may include well-known general precursors used as raw materials for forming thin films for the ALD method, without any particular limitations.

[0149] Other precursors mentioned above may include, for example, one or more types selected from the group consisting of compounds used as organic ligands, such as alcohol compounds, glycol compounds, β-diketone compounds, cyclopentadiene compounds, and organic amine compounds, and silicon or metal compounds. In addition, metal species of precursors may include lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, osmium, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, germanium, lead, antimony, bismuth, radium, scandium, ruthenium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.

[0150] Alcohol compounds used as organic ligands for the other precursors mentioned above include, for example, alkyl alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, and tert-pentyl alcohol; Ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1,1-dimethylethanol, 2-ethoxy-1,1-dimethylethanol, 2-isopropoxy-1,1-dimethylethanol, 2-butoxy-1,1-dimethylethanol, 2-(2-methoxyethoxy)-1,1-dimethylethanol, 2-propoxy-1,1-diethylethanol, 2-sec-butoxy-1,1-diethylethanol, 3-methoxy-1,1-dimethylpropanol; Examples include dialkylamino alcohols such as dimethylaminoethanol, ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol, ethylmethylamino-2-pentanol, dimethylamino-2-methyl-2-pentanol, ethylmethylamino-2-methyl-2-pentanol, and diethylamino-2-methyl-2-pentanol.

[0151] Glycol compounds used as organic ligands for the other precursors mentioned above include, for example, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2,4-butanediol, 2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 2,4-hexanediol, 2,4-dimethyl-2,4-pentanediol, etc.

[0152] β-diketone compounds used as organic ligands for the other precursors mentioned above include, for example, acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione, heptane-2,4-dione, 2-methylheptane-3,5-dione, 5-methylheptane-2,4-dione, 6-methylheptane-2,4-dione, 2,2-dimethylheptane-3,5-dione, 2,6-dimethylheptane-3,5-dione, 2,2,6-trimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3,5-dione, octane-2,4-dione, 2,2,6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione, 2,9-dimethylnonane-4,6-dione, Alkyl-substituted β-diketones such as 2-methyl-6-ethyldecane-3,5-dione, 2,2-dimethyl-6-ethyldecane-3,5-dione; fluorine-substituted alkyl β-diketones such as 1,1,1-trifluoropentane-2,4-dione, 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 1,3-diferfluorohexylpropane-1,3-dione; Examples include ether-substituted β-diketones such as 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, and 2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione.

[0153] Examples of cyclopentadiene compounds used as organic ligands for the other precursors mentioned above include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene, etc.

[0154] Organic amine compounds used as organic ligands for the other precursors mentioned above include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, etc.

[0155] The other precursors mentioned above are known in the relevant technical field, and their manufacturing methods are also known. For example, a precursor using an alcohol compound as an organic ligand can be prepared by reacting an inorganic salt of the metal mentioned earlier or its hydrate with an alkali metal alkoxide of the alcohol compound. Here, examples of the inorganic salt of the metal or its hydrate include metal halides, nitrates, etc. Examples of alkali metal alkoxides include sodium alkoxide, lithium alkoxide, potassium alkoxide, etc.

[0156] In the multi-component ALD method described above, there are methods for vaporizing and supplying raw materials for thin film formation independently for each component (hereinafter referred to as the "single source method") and methods for vaporizing and supplying mixed raw materials in which multi-component raw materials are mixed in advance to a desired composition (hereinafter referred to as the "cocktail source method"). In the case of the single source method, for the other precursor mentioned above, it is preferable to use a compound whose thermal and / or oxidative decomposition behavior is similar to that of the organic ruthenium compound included in the raw material for thin film formation. In the case of the cocktail source method, for the other precursor mentioned above, in addition to having a thermal and / or oxidative decomposition behavior similar to that of the organic ruthenium compound included in the raw material for thin film formation, it is preferable to use a compound that does not undergo deterioration due to chemical reactions, etc., when mixed.

[0157] In the case of the cocktail sauce method in a multi-component ALD method, a mixture of an organic ruthenium compound included in the raw material for thin film formation and another precursor, or a mixed solution in which the mixture is dissolved in an organic solvent, can be used as the raw material for thin film formation.

[0158] As for the above-mentioned organic solvent, well-known general organic solvents may be used without particular limitation. Examples of such organic solvents include, for instance, acetic acid esters such as ethyl acetate, butyl acetate, and methoxyethyl acetate; ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, and dioxane; ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and methylcyclohexanone; and hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, and xylene. Examples include hydrocarbons having a cyano group such as 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and 1,4-dicyanobenzene; pyridine, ruthidin, etc. Depending on the solubility of the solute, the relationship between the operating temperature and boiling point and flash point, these organic solvents may be used alone or in a mixture of two or more types.

[0159] When the above-mentioned raw material for forming a thin film contains an organic solvent, it is preferable to adjust the total amount of precursor in the raw material for forming a thin film to 0.01 mol / liter to 2.0 mol / liter, and more preferable to adjust it to 0.05 mol / liter to 1.0 mol / liter, from the perspective that it becomes easier to form a high-quality metallic ruthenium thin film with a low residual carbon content.

[0160] Here, the total amount of precursor refers to the amount of the organic ruthenium compound when the raw material for thin film formation does not contain any precursors other than the organic ruthenium compound. When the raw material for thin film formation contains other precursors in addition to the organic ruthenium compound, it refers to the total amount of the organic ruthenium compound and the other precursors.

[0161] In addition, in the method for manufacturing a thin film according to the present invention, the raw material for forming the thin film may contain a nucleating reagent as needed to improve the stability of the organic ruthenium compound and other precursors. As such nucleating reagents, for example, ethylene glycol ethers such as glyme, diglyme, triglyme, tetraglyme, etc.; crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, dibenzo-24-crown-8, etc.; polyamines such as ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, triethoxytriethyleneamine, etc.; cyclic polyamines such as cyclam, cyclene, etc.; pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, Examples include heterocyclic compounds such as N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, and oxathioran; β-keto esters such as methyl acetoacetate, ethyl acetoacetate, and 2-methoxyethyl acetoacetate; or β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and dipivaloylmethane. From the perspective of ease of adjusting stability, the amount of these nucleating reagents used is preferably in the range of 0.1 mol to 10 mol per 1 mol of the total amount of precursor, and more preferably in the range of 1 mol to 4 mol.

[0162] It is desirable that the raw material for forming the thin film minimizes the inclusion of impurity metal element components, impurity halogen components such as impurity chlorine, and impurity organic components other than the constituent components. Regarding the impurity metal element components, it is preferable that the concentration per element be 100 ppb or less, more preferably 10 ppb or less, and regarding the total amount, it is preferable that the concentration be 1 ppm or less, more preferably 100 ppb or less. In particular, when used as a gate insulating film, gate film, or barrier layer for an LSI, it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements, which affect the electrical characteristics of the resulting thin film. Regarding the impurity halogen components, it is preferable that the concentration be 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. Regarding the total amount of impurity organic components, it is preferable that the concentration be 500 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less. In addition, since moisture causes particle generation in the raw materials for thin film formation or during thin film formation, it is desirable to remove as much moisture as possible from the precursor, organic solvent, and nucleating reagent in advance of use to reduce the moisture content of each. The moisture content of each of the precursor, organic solvent, and nucleating reagent is preferably 10 ppm or less, and more preferably 1 ppm or less. In the method for manufacturing a thin film according to the present invention, by reducing the impurity metal element component, impurity halogen component, impurity organic component, and moisture in the raw materials for thin film formation to the above values ​​or less, it becomes easier to form a high-quality metallic ruthenium thin film with a low residual carbon content.

[0163] In addition, it is desirable that the raw material for forming the thin film contains as few particles as possible in order to reduce or prevent particle contamination of the thin film being formed. Specifically, from the perspective of making it easier to obtain a uniform thin film, it is desirable that the number of particles larger than 0.3 μm in the liquid phase particle detector is 100 or less per 1 ml of the raw material for forming the thin film, and it is more desirable that the number of particles larger than 0.2 μm is 100 or less per 1 ml of the raw material for forming the thin film.

[0164] In the method for manufacturing a thin film according to the present invention, it is preferable to carry out a precursor thin film formation process and a thin film formation process within a film formation chamber (hereinafter, it may also be described as a "deposition reaction unit") in which a gas is installed.

[0165] In addition, the method for manufacturing a thin film according to the present invention preferably includes a process (exhausting process 1) for exhausting the un-deposited raw material for forming a thin film from the deposition chamber after the precursor thin film formation process.

[0166] The method for manufacturing a thin film according to the present invention preferably further comprises a process (exhausting process 2) for exhausting unreacted reactive material from the film formation chamber after the thin film formation process.

[0167] It is desirable to repeat the precursor thin film formation process, exhaust process 1, thin film formation process, and exhaust process 2 in order to make it easier to form a high-quality metallic ruthenium thin film with low ruthenium oxide content and low residual carbon content.

[0168] Hereinafter, each process of the method for manufacturing a thin film of the present invention will be described.

[0169] <Precursor Thin Film Formation Process>

[0170] The precursor thin film formation process is a process of forming a precursor thin film using a raw material for forming a thin film containing an organic ruthenium compound.

[0171] In the present process, the method for forming a precursor thin film using a raw material for thin film formation is any method capable of forming a precursor thin film of a desired thickness, and for example, a method of depositing a raw material gas obtained by vaporizing a raw material for thin film formation containing an organic ruthenium compound on the surface of a gas. More specifically, the raw material gas obtained by vaporizing the raw material for thin film formation is introduced into a deposition chamber equipped with a gas, and the raw material gas is deposited on the surface of the gas to form a precursor thin film.

[0172] As a method for introducing a raw material gas obtained by vaporizing a raw material for forming a thin film into a deposition chamber equipped with a gas, there is a gas transport method in which, as shown in FIGS. 1 and 3, the raw material for forming a thin film is vaporized into a raw material gas by heating and / or depressurizing the raw material container in which the raw material for forming a thin film is stored, and the raw material gas is introduced into a deposition chamber equipped with a gas together with a carrier gas such as argon, nitrogen, or helium as necessary; and a liquid transport method in which, as shown in FIGS. 2 and 4, the raw material for forming a thin film is transported to a vaporization chamber in a liquid or solution state, and the raw material for forming a thin film is vaporized into a raw material gas by heating and / or depressurizing the vaporization chamber, and the raw material gas is introduced into a deposition chamber equipped with a gas. In the case of the gas transport method, the organic ruthenium compound itself can be used as the raw material for forming a thin film. In the case of the liquid transport method, the organic ruthenium compound itself or a solution in which the organic ruthenium compound is dissolved in an organic solvent can be used as the raw material for forming a thin film. The raw materials for forming these thin films may additionally include nucleating reagents, etc.

[0173] In addition, in addition to the gas transport method and liquid transport method mentioned above, methods used in the precursor thin film formation process include the aforementioned single source method and cocktail source method as multi-component ALD methods containing multiple precursors; however, regardless of which introduction method is used, it is preferable to vaporize the raw material for thin film formation in the range of 50°C to 200°C from the perspective of handling ease. Also, when vaporizing the raw material for thin film formation in a raw material container or vaporization chamber to form a raw material gas, it is preferable that the pressure in the raw material container or vaporization chamber be 1 Pa to 10,000 Pa from the perspective of making it easy to vaporize the raw material for thin film formation.

[0174] The material of the gas installed in the above-mentioned membrane chamber may include, for example, silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass; and metals such as metallic cobalt and metallic ruthenium. The shape of the gas may be plate-like, spherical, fibrous, or flake-like. The surface of the gas may be flat or may have a three-dimensional structure such as a trench structure.

[0175] A precursor thin film can be formed on the surface of a gas by introducing a source gas into a film deposition chamber and depositing the source gas onto the surface of the gas. When forming a precursor thin film by depositing the source gas onto the surface of the gas, the gas may be heated, or the inside of the film deposition chamber may be heated. The conditions for forming the precursor thin film are not particularly limited, and, for example, the deposition temperature (gas temperature), the pressure inside the film deposition chamber, etc., can be appropriately determined according to the type of raw material for forming the thin film. From the perspective that a uniform precursor thin film is easily obtained, the precursor thin film formation process is preferably carried out with the gas heated to 100°C or higher, more preferably with the gas heated to 100°C to 450°C, and most preferably with the gas heated to 150°C to 300°C. The pressure inside the film-forming chamber is not particularly limited, but from the perspective that a uniform precursor film is easily obtained, it is preferable to be 1 Pa to 10,000 Pa, and more preferable to be 10 Pa to 1,000 Pa.

[0176] <Exhaust Process 1>

[0177] Exhaust process 1 is a process of exhausting the raw material for thin film formation that has not been deposited on the surface of the gas from the deposition chamber. In exhaust process 1, it is ideal to completely exhaust the raw material for thin film formation (raw material gas) that has not been deposited on the surface of the gas from the deposition chamber, but it is not strictly necessary to exhaust it completely. Examples of exhaust methods include purging the inside of the deposition chamber with an inert gas such as helium, nitrogen, or argon, exhausting by depressurizing the inside of the deposition chamber, and methods combining these. When depressurizing the inside of the deposition chamber, the degree of depressurization is preferably in the range of 0.01 Pa to 300 Pa, and more preferably in the range of 0.01 Pa to 100 Pa, from the perspective that exhausting the raw material gas is promoted.

[0178] <Thin Film Formation Process>

[0179] The thin film formation process is a process of forming a metallic ruthenium thin film by reacting a precursor thin film with a reactive material. Here, reacting the precursor thin film with the reactive material means reacting an organic ruthenium compound contained in the precursor thin film with a compound represented by general formula (1) or a compound represented by general formula (2) contained in the reactive material.

[0180] In this process, for example, a method of contacting a precursor thin film with a reactive gas obtained by vaporizing a reactive material can be used. By contacting the precursor thin film with the reactive gas, the precursor thin film can be reacted with the reactive gas, and a metallic ruthenium thin film can be formed on the surface of the gas. Specifically, after the exhaust process 1, a reactive gas is introduced into the film formation chamber, and through the action of the reactive gas and the action of heat, an organic ruthenium compound contained in the precursor thin film can be reacted with a compound represented by general formula (1) or a compound represented by general formula (2) contained in the reactive gas to form a metallic ruthenium thin film.

[0181] The reactive material used in the thin film formation process may contain a compound represented by general formula (1) or a compound represented by general formula (2), may contain two or more types of compounds represented by general formula (1) or general formula (2), or may be a mixture of a compound represented by general formula (1) and a compound represented by general formula (2). The reactive gas obtained by vaporizing the reactive material may, if necessary, be mixed with a gas selected from the group consisting of argon, nitrogen, oxygen, and hydrogen. In addition, within a range that does not adversely affect the effects of the present invention, the reactive gas may include oxidizing gases such as oxygen, water vapor, and ozone, or reducing gases such as ammonia, hydrogen, monosilane, and hydrazine. From the viewpoint that the effects of the present invention are significantly enhanced, the reactive material used in the method for manufacturing a thin film of the present invention preferably contains a compound represented by general formula (1), and more preferably contains a compound of No. 43 or No. 135.

[0182] In the view that a high-quality metallic ruthenium thin film with a lower residual carbon content is obtained, when reacting the precursor thin film with a reactive material, the reaction temperature (gas temperature) is preferably 100 ℃ or higher, more preferably 100 ℃ to 450 ℃, more preferably 100 ℃ to 300 ℃, and most preferably 150 ℃ to 300 ℃. In addition, in the view that the reaction between the precursor thin film and the reactive gas is improved, the pressure inside the deposition chamber when the thin film formation process is carried out is preferably 1 Pa to 10,000 Pa, and more preferably 10 Pa to 1,000 Pa.

[0183] <Exhaust Process 2>

[0184] In order to form a high-quality metallic ruthenium thin film with a low residual carbon content, the method for manufacturing a thin film according to the present invention preferably includes an exhaust process 2 for exhausting the reactive material that was not used in the formation of the metallic ruthenium thin film after the thin film formation process. Specifically, it is preferable to include an exhaust process 2 for exhausting the reactive material and byproduct gas after a thin film formation process in which the precursor thin film obtained in the precursor thin film formation process is reacted with a reactive gas obtained by vaporizing the aforementioned reactive material to form a metallic ruthenium thin film on the surface of the gas. More specifically, in the thin film formation process, after forming the metallic ruthenium thin film, the process may be to exhaust the reactive gas that did not react with the surface of the precursor thin film and the byproduct gas generated by reacting the precursor thin film with the reactive gas from the film deposition chamber. In the exhaust process 2, it is ideal for the reactive gas and byproduct gas to be completely exhausted from the film deposition chamber, but it is not necessary to exhaust them completely. The exhaust method and the degree of pressure reduction in the case of pressure reduction may be the same as the exhaust process 1 described above.

[0185] The thin film formation process included in the method for manufacturing a thin film of the present invention is performed at least once, but may be performed two or more times until the metallic ruthenium thin film reaches a desired thickness. That is, the thin film may be formed by performing the thin film formation process two or more times and stacking two or more metallic ruthenium thin films. For example, the method for manufacturing a thin film may make a series of operations of a precursor thin film formation process, an exhaust process 1, a thin film formation process, and an exhaust process 2 into one cycle, and the thickness of the metallic ruthenium thin film can be adjusted by adjusting the number of such cycles.

[0186] Specific examples of the ALD apparatus used in the method for manufacturing a thin film according to the present invention include an apparatus as shown in FIG. 1, which vaporizes a raw material for forming a thin film in a raw material container by heating and / or depressurizing it to form a raw material gas, and supplies the raw material gas to a deposition chamber together with a carrier gas as needed, or an apparatus as shown in FIG. 2, which transports a raw material for forming a thin film in a liquid or solution state to a vaporization chamber, vaporizes it in the vaporization chamber by heating and / or depressurizing it to form a raw material gas, and supplies the raw material gas to a deposition chamber. In addition, the apparatus is not limited to a single-wafer apparatus equipped with a deposition chamber as shown in FIG. 1 and FIG. 2, but may also use an apparatus capable of simultaneously processing multiple sheets using a batch furnace.

[0187] In addition, in the method for manufacturing a thin film according to the present invention, as shown in FIGS. 3 and 4, energy such as plasma, light, or voltage may be applied within the film formation chamber, or a catalyst may be used. The timing of applying the energy and the timing of using the catalyst are not particularly limited, and for example, when introducing a raw material gas into the film formation chamber in the precursor thin film formation process, or when heating when forming the precursor thin film, when introducing a reactive gas into the film formation chamber in the thin film formation process, or when reacting the precursor thin film with the reactive gas, or when exhausting the raw material gas, reactive gas, or byproduct gas within the film formation chamber in exhaust process 1 or exhaust process 2, or between each of the above processes.

[0188] In addition, in the method for manufacturing a thin film according to the present invention, in order to obtain a metallic ruthenium thin film having better electrical properties, an annealing treatment may be performed under an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere after the formation of the metallic ruthenium thin film, and if step filling is required, a reflow process may be formed. In this case, the temperature is preferably 200°C to 1,000°C and more preferably 250°C to 500°C from the viewpoint of suppressing heat-induced damage to the metallic ruthenium thin film or gas.

[0189] The thin film produced by the method of manufacturing a thin film according to the present invention can be formed into a desired type of thin film by coating a substrate such as metal, oxide ceramics, nitride ceramics, or glass by appropriately selecting other precursors, reactive materials, and manufacturing conditions. Since the thin film of the present invention has excellent electrical and optical properties, it can be widely used in the manufacture of, for example, electrode materials for memory devices represented by DRAM devices, wiring materials for semiconductor devices, diamagnetic films used in the recording layer of hard disks, and catalyst materials for solid polymer fuel cells.

[0190] <Others>

[0191] In the present disclosure, the following embodiments may be cited.

[0192] [1] A reactive material containing a compound represented by the following general formula (1) or (2).

[0193] [Chemical Formula 32]

[0194]

[0195] (In Equation (1), R 1 , R 2 , R 3 and R 4Each represents, independently, a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. The electron-withdrawing group is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a cyano group, an aldehyde group, an acetyl group, a carboxyl group, a carboxymethyl group, a sulfo group, and a sulfomethyl group. provided that R 1 , R 2 , R 3 and R 4 At least one of them represents an electronically absorbing group.)

[0196] [Chemical Formula 33]

[0197]

[0198] (In Equation (2), R 5 and R 6 Each represents, independently, a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. The electron-withdrawing group is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a cyano group, an aldehyde group, an acetyl group, a carboxyl group, a carboxymethyl group, a sulfo group, and a sulfomethyl group. provided that R 5 and R 6 At least one of them represents an electronically absorbing group.)

[0199] [2] Reactive material described in [1] used to reduce organometallic compounds to metals.

[0200] [3] A method for manufacturing a thin film, comprising forming a metallic ruthenium thin film using a reactive material described in [1] or [2] in an atomic layer deposition method.

[0201] [4] A process for forming a precursor thin film using a raw material for forming a thin film containing an organic ruthenium compound, and

[0202] A method for manufacturing a thin film as described in [3], having a process of reacting the above precursor thin film with the above reactive material to form a metallic ruthenium thin film.

[0203] [5] A method for manufacturing a thin film as described in [4], wherein the above organic ruthenium compound is selected from the group consisting of an organic ruthenium compound represented by the following general formula (3), an organic ruthenium compound represented by the following general formula (4), and an organic ruthenium compound represented by the following general formula (5).

[0204] [Chemical Formula 34]

[0205]

[0206] (Among equations (3), (4) and (5), L 1 ...represents a covalent ligand selected from the group consisting of an aminoalkoxy group, an amidinate group, a β-diketonate group, a β-ketoiminate group, a β-dikethyminate group, a group having the structure of a 2,4-pentadienyl group, and a group having the structure of a cyclopentadienyl group, X represents a halogen atom, n represents an integer from 0 to 2, and L 2 represents an electron-donating ligand selected from the group consisting of carbonyl groups, cyano groups, trialkylphosphine compounds, and isocyanide compounds, m represents an integer from 0 to 3, and L 3 represents an electron-donating ligand selected from the group consisting of chain-type diene compounds, cyclic diene compounds, chain-type polyene compounds, and cyclic polyene compounds, y represents 1 or 2, and L 4 represents an electron-donating ligand composed of an arene compound, and z represents 0 or 1.

[0207] [6] A method for manufacturing a thin film as described in [4] or [5], wherein a vaporized raw material for forming a thin film is deposited on the surface of a gas heated to 100 ℃ to 450 ℃ to form the precursor thin film.

[0208] [7] A method for manufacturing a thin film as described in [6], having an additional process of exhausting the un-deposited raw material for forming the thin film from the reaction system after forming the precursor thin film.

[0209] [8] After forming the above metal ruthenium thin film, the process of exhausting the unreacted reactive material from the reaction system is further included.

[0210] A method for manufacturing a thin film as described in [7], which involves repeating the process of forming a precursor thin film, the process of exhausting raw materials for forming a thin film that are not deposited from the reaction system, the process of forming a metal ruthenium thin film, and the process of exhausting unreacted reactive materials from the reaction system.

[0211] Examples

[0212] The present invention will be explained in more detail below with reference to examples. However, the present invention is not limited by the following examples.

[0213] [Example 1]

[0214] The organic ruthenium compound of No. 303 was used as a raw material for forming a thin film, and a thin film was fabricated on a silicon wafer in gaseous form using the ALD apparatus shown in Fig. 1 under the following conditions and process. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a metallic ruthenium thin film and that the residual carbon content in the thin film was less than the detection limit of 0.1 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gaseous form was a smooth film with a thickness of 1.6 nm, and the film thickness obtained per cycle was 0.008 nm.

[0215] (condition)

[0216] Manufacturing method: ALD method

[0217] Reaction temperature (gas temperature): 220 ℃

[0218] Reactive gas: Vaporized compound of No. 43

[0219] (process)

[0220] A series of processes consisting of (1) to (4) below was repeated for 200 cycles as one cycle.

[0221] (1) Under conditions of a raw material container temperature of 95 ℃ and a pressure inside the raw material container of 26.67 Pa, a raw material gas obtained by vaporizing the raw material for thin film formation is introduced into a film deposition chamber for 20 seconds, and the raw material gas is deposited on the surface of the gas installed inside the film deposition chamber.

[0222] (2) By purging with argon for 10 seconds, the raw gas that was not deposited is exhausted from the system.

[0223] (3) Introduce a reactive gas into the film-forming chamber and react the precursor film with the reactive gas for 1 second at a pressure of 100 Pa.

[0224] (4) Unreacted reactive gases and byproduct gases are exhausted from the system by argon purging for 10 seconds.

[0225] [Example 2]

[0226] A thin film was prepared in the same order as in Example 1, except that the reactive gas was changed to a vaporized compound of No. 135. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a metallic ruthenium thin film and that the residual carbon content in the thin film was less than the detection limit of 0.1 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gas phase was a smooth film with a thickness of 1.5 nm, and the film thickness obtained per cycle was 0.0075 nm.

[0227] [Comparative Example 1]

[0228] A thin film was prepared in the same order as in Example 1, except that the reactive gas was changed to oxygen. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a mixture of metallic ruthenium and ruthenium oxide, and that the residual carbon content in the thin film was less than the detection limit of 0.1 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gas phase was a smooth film with a thickness of 1.8 nm, and the film thickness obtained per cycle was 0.009 nm.

[0229] [Comparative Example 2]

[0230] A thin film was prepared in the same order as in Example 1, except that the reactive gas was changed to hydrogen and the reaction temperature (gas temperature) was changed to 300°C. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, the thin film was a thin film of metallic ruthenium, and the residual carbon content in the thin film was 4.5 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gas phase was a smooth film with a thickness of 1.5 nm, and the film thickness obtained per cycle was 0.0075 nm.

[0231] [Example 3]

[0232] The organic ruthenium compound No. 306 was used as a raw material for forming a thin film, and a thin film was fabricated on a silicon wafer in gaseous form using the ALD apparatus shown in Fig. 1 under the following conditions and process. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a metallic ruthenium thin film and that the residual carbon content in the thin film was less than the detection limit of 0.1 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gaseous form was a smooth film with a thickness of 1.8 nm, and the film thickness obtained per cycle was 0.009 nm.

[0233] (condition)

[0234] Manufacturing method: ALD method

[0235] Reaction temperature (gas temperature): 230 ℃

[0236] Reactive gas: Vaporized compound of No. 43

[0237] (process)

[0238] A series of processes consisting of (1) to (4) below was repeated for 200 cycles as one cycle.

[0239] (1) A raw material gas obtained by vaporizing a raw material for thin film formation under conditions of a raw material container temperature of 120 ℃ and a pressure inside the raw material container of 26.67 Pa is introduced into a film deposition chamber with a pressure of 26.67 Pa for 20 seconds, and the raw material gas is deposited on the surface of a gas installed inside the film deposition chamber.

[0240] (2) By purging with argon for 10 seconds, the raw gas that was not deposited is exhausted from the system.

[0241] (3) Introduce a reactive gas into the film-forming chamber and react the precursor film with the reactive gas for 1 second at a pressure of 100 Pa.

[0242] (4) Unreacted reactive gases and byproduct gases are exhausted from the system by argon purging for 10 seconds.

[0243] [Example 4]

[0244] A thin film was prepared in the same order as in Example 3, except that the reactive gas was changed to a vaporized compound of No. 135. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a metallic ruthenium thin film and that the residual carbon content in the thin film was less than the detection limit of 0.1 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gas phase was a smooth film with a thickness of 1.6 nm, and the film thickness obtained per cycle was 0.008 nm.

[0245] [Comparative Example 3]

[0246] A thin film was prepared in the same order as in Example 3, except that the reactive gas was changed to oxygen. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a mixture of metallic ruthenium and ruthenium oxide, and that the residual carbon content in the thin film was less than the detection limit of 0.1 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gas phase was a smooth film with a thickness of 1.9 nm, and the film thickness obtained per cycle was 0.0095 nm.

[0247] [Comparative Example 4]

[0248] A thin film was prepared in the same order as in Example 3, except that the reactive gas was changed to hydrogen and the reaction temperature (gas temperature) was changed to 320 ℃. As a result of analyzing the composition of the thin film using X-ray photoelectron spectroscopy, the thin film was a thin film of metallic ruthenium, and the residual carbon content in the thin film was 6.5 atm%. In addition, as a result of measuring the film thickness using X-ray reflectance, the thin film formed in the gas phase was a smooth film with a thickness of 1.3 nm, and the film thickness obtained per cycle was 0.0065 nm.

[0249]

[0250] From the above results, it was confirmed that the method for manufacturing a thin film of the present invention, by using a reactive material containing a specific compound in an atomic layer deposition method, can produce a high-quality metallic ruthenium thin film with a low reaction temperature, low ruthenium oxide content, and low residual carbon content. In addition, it was suggested that high productivity can be achieved in the method for manufacturing a thin film of the present invention because the film thickness obtained per cycle is significantly thick.

Claims

Claim 1 A reactive material containing a compound represented by the following general formula (1) or (2). (In Equation (1), R 1 , R 2 , R 3 and R 4 Each represents, independently, a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. The electron-withdrawing group is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a cyano group, an aldehyde group, an acetyl group, a carboxyl group, a carboxymethyl group, a sulfo group, and a sulfomethyl group. provided that R 1 , R 2 , R 3 and R 4 At least one of them represents an electronically absorbing group.) (In Equation (2), R 5 and R 6 Each represents, independently, a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an electron-withdrawing group. The electron-withdrawing group is selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a triiodomethyl group, a cyano group, an aldehyde group, an acetyl group, a carboxyl group, a carboxymethyl group, a sulfo group, and a sulfomethyl group. provided that R 5 and R 6 At least one of them represents an electronically absorbing group.) Claim 2 In claim 1, a reactive material used to reduce an organometallic compound to a metal. Claim 3 A method for manufacturing a thin film, comprising forming a metallic ruthenium thin film using a reactive material described in claim 1 or 2 in an atomic layer deposition method. Claim 4 A method for manufacturing a thin film according to claim 3, comprising a process of forming a precursor thin film using a raw material for forming a thin film containing an organic ruthenium compound, and a process of reacting the precursor thin film with the reactive material to form a metallic ruthenium thin film. Claim 5 A method for manufacturing a thin film according to claim 4, wherein the organic ruthenium compound is selected from the group consisting of an organic ruthenium compound represented by the following general formula (3), an organic ruthenium compound represented by the following general formula (4), and an organic ruthenium compound represented by the following general formula (5). (Among equations (3), (4) and (5), L 1 ...represents a covalent ligand selected from the group consisting of an aminoalkoxy group, an amidinate group, a β-diketonate group, a β-ketoiminate group, a β-dikethyminate group, a group having the structure of a 2,4-pentadienyl group, and a group having the structure of a cyclopentadienyl group, X represents a halogen atom, n represents an integer from 0 to 2, and L 2 represents an electron-donating ligand selected from the group consisting of carbonyl groups, cyano groups, trialkylphosphine compounds, and isocyanide compounds, m represents an integer from 0 to 3, and L 3 represents an electron-donating ligand selected from the group consisting of chain-type diene compounds, cyclic diene compounds, chain-type polyene compounds, and cyclic polyene compounds, y represents 1 or 2, and L 4 represents an electron-donating ligand composed of an arene compound, and z represents 0 or 1. Claim 6 A method for manufacturing a thin film according to claim 4, wherein the vaporized raw material for forming the thin film is deposited on the surface of a gas heated to 100 ℃ to 450 ℃ to form the precursor thin film. Claim 7 A method for manufacturing a thin film according to claim 6, further comprising a process of exhausting the undeposited raw material for forming the thin film from the reaction system after forming the precursor thin film. Claim 8 A method for manufacturing a thin film according to claim 7, further comprising a process of exhausting unreacted reactive material from the reaction system after forming the metal ruthenium thin film, and repeating the process of forming a precursor thin film, exhausting undeposited raw material for forming a thin film from the reaction system, forming a metal ruthenium thin film, and exhausting unreacted reactive material from the reaction system.

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