Alkoxide compound, raw material for forming thin film, and method for producing thin film

Abstract

The present invention provides: an alkoxide compound represented by general formula (1); a thin film-forming material containing said compound; and a method for manufacturing a thin film. (In the formula, R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1-5 carbon atoms, or a fluorine atom-containing alkyl group having 1-5 carbon atoms, R3 and R4 each independently represent an alkyl group having 1-5 carbon atoms or a fluorine atom-containing alkyl group having 1-5 carbon atoms, R5 represents a hydrogen atom, a group containing a fluorine atom, or an alkyl group having 1-5 carbon atoms, R6 represents a group containing a fluorine atom, M represents a metal atom or a semimetal atom, and n represents the valence of an atom represented by M. However, if M is a copper atom, R3 and R4 each independently represent an alkyl group having 1-2 carbon atoms, and R5 represents a hydrogen atom.)

Description

[Technical field]

[0001] The present invention relates to a novel compound, a thin film-forming material containing the compound, and a method for producing a thin film using the thin film-forming material. [Background technology]

[0002] Thin film materials containing metal elements or semi-metal atoms have excellent electrical and optical properties and are therefore used in components of electronic components such as electrode films, resistive films, and barrier films, components for recording media such as magnetic films, and electrode components for solar cells and the like.

[0003] Examples of methods for manufacturing the above-mentioned thin films include sputtering, ion plating, metal organic decomposition (MOD) methods such as coating pyrolysis and sol-gel methods, chemical vapor deposition, etc. Among these, chemical vapor deposition (hereinafter sometimes simply referred to as "CVD") including atomic layer deposition (ALD) is the most suitable manufacturing process because it has many advantages such as excellent composition controllability and step coverage, suitability for mass production, and the ability to achieve hybrid integration.

[0004] Various compounds have been reported as alkoxide compounds used in chemical vapor deposition. For example, Patent Document 1 discloses an aminoalkoxide-titanium compound, an aminoalkoxide-zirconium compound, and an aminoalkoxide-hafnium compound. Patent Document 2 discloses an aminoalkoxide-copper compound. Patent Document 3 discloses an aminoalkoxide-copper compound, an aminoalkoxide-nickel compound, and an aminoalkoxide-cobalt compound. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2006-312600 A [Patent Document 2] JP 2006-328019 A [Patent Document 3] JP 2018-133569 A Summary of the Invention [Problem to be solved by the invention]

[0006] In a method for forming a thin film by vaporizing a compound, such as a CVD method, the properties required for a compound (precursor) used as a raw material are a high vapor pressure, a low melting point (preferably liquid at room temperature), high thermal stability, and the ability to produce a high-quality thin film with good productivity. A raw material for forming a thin film containing an alkoxide compound is required to have, among other things, a high vapor pressure, high thermal stability, and the ability to produce a high-quality thin film with good productivity when used as a raw material for forming a thin film, but an alkoxide compound that can fully satisfy these requirements has not existed until now.

[0007] Therefore, an object of the present invention is to provide an alkoxide compound which has a higher vapor pressure and higher thermal stability than conventional alkoxide compounds, and which, when used as a thin film forming raw material, enables the production of high-quality thin films with good productivity. [Means for solving the problem]

[0008] As a result of extensive investigations, the present inventors discovered that an alkoxide compound having a ligand with a specific structure can solve the above problems, and thus arrived at the present invention.

[0009] That is, the present invention is an alkoxide compound represented by the following general formula (1).

[0010] [ka]

[0011] (In the formula, R 1 and R2 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorine-containing alkyl group having 1 to 5 carbon atoms; R 3 and R 4 each independently represents an alkyl group having 1 to 5 carbon atoms or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms; R 5 represents a hydrogen atom, a group containing a fluorine atom, or an alkyl group having 1 to 5 carbon atoms; R 6 represents a group containing a fluorine atom, M represents a metal atom or a metalloid atom, and n represents the valence of the atom represented by M. However, when M is a copper atom, R 3 and R 4 each independently represents an alkyl group having 1 to 2 carbon atoms; R 5 represents a hydrogen atom.)

[0012] The present invention also relates to a thin film-forming material containing the above compound.

[0013] The present invention also provides a method for producing a thin film, comprising the steps of: vaporizing the thin film-forming raw material; introducing vapor containing the vaporized alkoxide compound represented by general formula (1) into a treatment atmosphere; and decomposing and / or chemically reacting the compound to form a thin film containing metal atoms or semi-metal atoms on the surface of the substrate.

[0014] The alkoxide compound represented by the following general formula (2) has the same meaning as the alkoxide compound represented by the above general formula (1).

[0015] [ka]

[0016] (In the formula, R 1 and R 2 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorine-containing alkyl group having 1 to 5 carbon atoms; R 3 and R 4each independently represents an alkyl group having 1 to 5 carbon atoms or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms; R 5 represents a hydrogen atom, a group containing a fluorine atom, or an alkyl group having 1 to 5 carbon atoms; R 6 represents a group containing a fluorine atom, M represents a metal atom or a metalloid atom, and n represents the valence of the atom represented by M. 1 ~R 4 In the above formula, the hydrogen atoms of the alkyl group may be partially or completely substituted with fluorine atoms. However, when M is a copper atom, R 3 and R 4 each independently represents an alkyl group having 1 to 2 carbon atoms; R 5 represents a hydrogen atom.) Effect of the Invention

[0017] According to the present invention, it is possible to provide an alkoxide compound that has a higher vapor pressure and higher thermal stability than conventional alkoxide compounds, and when used as a raw material for forming a thin film, can produce a high-quality thin film with good productivity. The compound of the present invention is suitable as a raw material for forming a thin film in a CVD method, and since it has an ALD window, it can be preferably used as a raw material for forming a thin film in an ALD method. [Brief description of the drawings]

[0018] [Figure 1] FIG. 1 is a schematic diagram showing one embodiment of an ALD apparatus used in the thin film production method according to the present invention. [Diagram 2] FIG. 2 is a schematic diagram showing another embodiment of an ALD apparatus used in the thin film production method according to the present invention. [Diagram 3] FIG. 3 is a schematic diagram showing yet another embodiment of an ALD apparatus used in the thin film production method according to the present invention. [Figure 4] FIG. 4 is a schematic diagram showing yet another embodiment of an ALD apparatus used in the thin film production method according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0019] The alkoxide compound of the present invention is represented by the above general formula (1). The alkoxide compound of the present invention is suitable as a precursor in a thin film manufacturing method having a vaporization step, such as the ALD method, which is a type of CVD method.

[0020] In the above general formula (1), R 1 and R 2 R each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms. 3 and R 4 R each independently represents an alkyl group having 1 to 5 carbon atoms or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms. 5 R represents a hydrogen atom, a group containing a fluorine atom, or an alkyl group having 1 to 5 carbon atoms. 6 represents a group containing a fluorine atom, M represents a metal atom or a metalloid atom, and n represents the valence of the atom represented by M. However, when M is a copper atom, R 3 and R 4 each independently represents an alkyl group having 1 to 2 carbon atoms; R 5 represents a hydrogen atom.

[0021] Above, R 1 ~R 5 Specific examples of the "alkyl group having 1 to 5 carbon atoms" in the above formula include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group.

[0022] Above, R 1 ~R 4The "fluorine atom-containing alkyl group having 1 to 5 carbon atoms" in the above refers to an alkyl group in which some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms. Specific examples of the fluorine atom-containing alkyl group include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2,2-pentafluoroethyl group, a 3,3,3-trifluoropropyl group, a 2,2,3,3,3-pentafluoropropyl group, a 1,1,2,2,3,3,3-heptafluoropropyl group, a 4,4,4-trifluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, and a 1,1,2,2,3,3,4,4,4-nonafluorobutyl group.

[0023] Above, R 5 and R 6 The "fluorine atom-containing group" in the formula (I) refers to a fluoro group or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms. Specific examples of the "fluorine atom-containing alkyl group having 1 to 5 carbon atoms" herein include R 1 ~R 4 These are the same as the specific examples of "fluorine atom-containing alkyl group having 1 to 5 carbon atoms" in the above.

[0024] Examples of the metal atom or metalloid atom represented by M include a copper atom, a cobalt atom, a nickel atom, a tin atom, a zinc atom, a yttrium atom, an iron atom, an indium atom, a gallium atom, an aluminum atom, a titanium atom, a germanium atom, a zirconium atom, a hafnium atom, and a silicon atom.

[0025] In the above general formula (1), R 1 ~R 6 and M are appropriately selected depending on the manufacturing method of the thin film to be applied. When used in a manufacturing method of a thin film having a step of vaporizing a compound, R is selected so as to obtain a compound with a high vapor pressure and high thermal stability. 1 ~R 6 It is preferable to select M=0.

[0026] Since the vapor pressure of the compound is large, R in the general formula (1) 1 and R 2 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom. 3 and R 4 R is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. 3 is a methyl group and R 4 It is particularly preferable that R in the general formula (1) is an ethyl group. 5 is preferably a group containing a hydrogen atom or a fluorine atom, more preferably a hydrogen atom. 6 As the fluoroalkyl group, a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a 3,3,3-trifluoropropyl group is preferable, a trifluoromethyl group, a 2,2,2-trifluoroethyl group or a 3,3,3-trifluoropropyl group is more preferable, and a trifluoromethyl group is particularly preferable.

[0027] As M in general formula (1), a copper atom, a cobalt atom, a nickel atom, a tin atom, a zinc atom, a yttrium atom, an iron atom, an indium atom, a gallium atom, an aluminum atom, a titanium atom, a germanium atom, a zirconium atom, a hafnium atom, or a silicon atom is preferred, because high-quality thin films can be produced with good productivity, and a copper atom, a cobalt atom, a nickel atom, or a tin atom is more preferred. In addition, when used in a thin film manufacturing method using the MOD method that does not involve a vaporization process, R 1 ~R 6 and M can be arbitrarily selected depending on the solubility in the solvent used, the thin film forming reaction, and the like.

[0028] Preferred specific examples of the alkoxide compound represented by the above general formula (1) include the following compounds No. 1 to No. 174. In the following compounds No. 1 to No. 174, "Me" represents a methyl group, "Et" represents an ethyl group, and "iPr" represents an isopropyl group.

[0029] [ka]

[0030] [ka]

[0031] [ka]

[0032] [ka]

[0033] [ka]

[0034] [ka]

[0035] [ka]

[0036] [ka]

[0037] [ka]

[0038] [ka]

[0039] [ka]

[0040] The method for producing the alkoxide compound represented by the above general formula (1) is not particularly limited, and the compound is produced by applying a known reaction. For example, the compound can be obtained by reacting a metal methoxide complex having a corresponding structure with an alcohol ligand having a corresponding structure in a toluene solvent, distilling off the solvent, and then purifying the resulting reaction product by distillation or sublimation. From the viewpoint of achieving the desired effects of the present invention, the alkoxide compounds No. 4, No. 40, No. 76, No. 109 and No. 110 are preferred, and the alkoxide compounds No. 4, No. 40, No. 76 and No. 110 are more preferred.

[0041] Examples of alcohol compounds that can be used for the alcohol ligand include 3-(dimethylamino)-1,1,1-trifluoropropan-2-ol, 3-(diethylamino)-1,1,1-trifluoropropan-2-ol, 3-(ethylmethylamino)-1,1,1-trifluoropropan-2-ol, 3-(diisopropylamino)-1,1,1-trifluoropropan-2-ol, 2-((dimethylamino)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol, 2-((diethylamino)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol, 2-((ethylmethylamino)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol, and 2-((diisopropylamino)methyl)-1,1,1,3,3,3-hexafluoropropan-2-ol.

[0042] Next, the thin film forming material of the present invention will be described. The thin film forming material of the present invention contains an alkoxide compound represented by the above general formula (1) as a precursor of the thin film. The form differs depending on the manufacturing process to which the thin film forming material is applied. For example, when manufacturing a thin film containing only metal atoms or metalloid atoms as metals, the thin film forming material of the present invention does not contain metal compounds and metalloid compounds other than the alkoxide compound represented by the above general formula (1). On the other hand, when manufacturing a thin film containing two or more types of metals and / or metalloids, the thin film forming material of the present invention can also contain a compound containing a desired metal and / or a compound containing a metalloid (hereinafter, sometimes referred to as "other precursors"). The thin film forming material of the present invention may further contain an organic solvent and / or a nucleophilic reagent, as described later. As explained above, the physical properties of the alkoxide compound represented by the above general formula (1), which is a precursor, are suitable for the CVD method, so the thin film forming material of the present invention is useful as a chemical vapor deposition material (hereinafter, sometimes referred to as "CVD material"). Among them, since the alkoxide compound represented by the above general formula (1) has an ALD window, the thin film-forming raw material of the present invention is particularly suitable for the ALD method.

[0043] When the thin film forming material of the present invention is a material for chemical vapor deposition, its form is appropriately selected depending on the method of transportation and supply in the CVD method to be used.

[0044] The above-mentioned transport supply method includes a gas transport method in which the CVD raw material is heated and / or depressurized in a container (hereinafter sometimes referred to as a "raw material container") in which the raw material is stored to be vaporized into a raw material gas, and the raw material gas is introduced into a film formation chamber (hereinafter sometimes referred to as a "deposition reaction section") in which a substrate is placed together with a carrier gas such as argon, nitrogen, or helium used as necessary, and a liquid transport method in which the CVD raw material is transported in a liquid or solution state to a vaporization chamber, heated and / or depressurized in the vaporization chamber to be vaporized into a raw material gas, and the raw material gas is introduced into a film formation chamber. In the case of the gas transport method, the alkoxide compound represented by the above general formula (1) itself can be used as a CVD raw material. In the case of the liquid transport method, the alkoxide compound represented by the above general formula (1) itself or a solution in which the compound is dissolved in an organic solvent can be used as a CVD raw material. These CVD raw materials may further contain other precursors, nucleophilic reagents, etc.

[0045] In addition, in the multi-component CVD method, there is a method in which each component of the CVD raw material is vaporized and supplied independently (hereinafter, sometimes referred to as the "single source method"), and a method in which a mixed raw material in which multi-component raw materials are mixed in advance in a desired composition is vaporized and supplied (hereinafter, sometimes referred to as the "cocktail source method"). In the case of the cocktail source method, a mixture of the alkoxide compound represented by the above general formula (1) and other precursors, or a mixed solution in which the mixture is dissolved in an organic solvent, can be used as the CVD raw material. This mixture or mixed solution may further contain a nucleophilic reagent, etc.

[0046] The organic solvent is not particularly limited, and any well-known organic solvent can be used. Examples of the organic solvent include acetates 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; hydrocarbons such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, and xylene; hydrocarbons having a cyano group such as 1-cyanopropane, 1-cyanonobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and 1,4-dicyanobenzene; pyridine, lutidine, and the like. These organic solvents may be used alone or in combination of two or more depending on the solubility of the solute, the relationship between the use temperature and the boiling point, the flash point, and the like.

[0047] When the thin film forming raw material of the present invention is a mixed solution with the above-mentioned organic solvent, the total amount of precursors in the thin film forming raw material is preferably 0.01 mol / L to 2.0 mol / L, and more preferably 0.05 mol / L to 1.0 mol / L.

[0048] Here, the total amount of precursors means the amount of the alkoxide compound represented by the above general formula (1) when the thin film forming raw material of the present invention does not contain any metal compounds and semi-metal compounds other than the alkoxide compound represented by the above general formula (1), and means the total amount of the alkoxide compound represented by the above general formula (1) and the other precursors when the thin film forming raw material of the present invention contains, in addition to the alkoxide compound represented by the above general formula (1), compounds containing other metals and / or compounds containing semi-metals (other precursors).

[0049] In the case of a multi-component CVD method, other precursors used together with the alkoxide compound represented by the above general formula (1) are not particularly limited, and any well-known precursors used as CVD materials can be used.

[0050] Examples of the other precursors include compounds of silicon or metal with one or more 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. Examples of the metal species of the precursor include lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, germanium, tin, lead, antimony, bismuth, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium, and lutetium.

[0051] Examples of the alcohol compounds that can be used as organic ligands for the other precursors include 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; 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-butoxyethanol, and 2-isopropoxy-1,1-dimethylethanol. ether alcohols such as 2-(2-methoxyethoxy)-1,1-dimethylethanol, 2-propoxy-1,1-diethylethanol, 2-s-butoxy-1,1-diethylethanol, and 3-methoxy-1,1-dimethylpropanol; and 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.

[0052] Examples of glycol compounds that can be used as organic ligands for the other precursors include 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, and 2,4-dimethyl-2,4-pentanediol.

[0053] The β-diketone compounds used as organic ligands for the above other precursors include 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, 2-methyl-6- Examples of the alkyl-substituted β-diketones include ethyldecane-3,5-dione and 2,2-dimethyl-6-ethyldecane-3,5-dione; fluorine-substituted alkyl β-diketones include 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 and 1,3-diperfluorohexylpropane-1,3-dione; and ether-substituted β-diketones include 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.

[0054] Examples of the cyclopentadiene compound used as an organic ligand for the other precursors include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, and tetramethylcyclopentadiene.

[0055] Examples of the organic amine compound used as the organic ligand of the other precursors include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, and isopropylmethylamine.

[0056] The above other precursors are known in the art, and their manufacturing methods are also known. As an example of the manufacturing method, when an alcohol compound is used as the organic ligand, the precursor can be manufactured by reacting the inorganic salt of the metal or its hydrate described above with an alkali metal alkoxide of the alcohol compound. Here, examples of the inorganic salt of the metal or its hydrate include metal halides and nitrates, and examples of the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, potassium alkoxide, and the like.

[0057] In the case of the single source method, it is preferable to use, as the other precursor, a compound whose thermal decomposition and / or oxidative decomposition behavior is similar to that of the alkoxide compound represented by the above general formula (1).In the case of the cocktail source method, it is preferable to use, as the other precursor, a compound whose thermal decomposition and / or oxidative decomposition behavior is similar to that of the alkoxide compound represented by the above general formula (1) and which does not undergo changes that impair the desired properties of the precursor due to chemical reactions during mixing, etc.

[0058] Furthermore, the thin film forming raw material of the present invention may contain a nucleophilic reagent, if necessary, to provide stability to the alkoxide compound represented by the above general formula (1) and other precursors. The nucleophilic reagent may be ethylene glycol ethers such as glyme, diglyme, triglyme, and tetraglyme, crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, and dibenzo-24-crown-8, ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine ... Examples of the nucleophilic reagent include polyamines such as ethoxytriethyleneamine, cyclic polyamines such as cyclam and cyclen, heterocyclic compounds such as pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, and oxathiolane, β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, and 2-methoxyethyl acetoacetate, and β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and dipivaloylmethane. The amount of these nucleophilic reagents used is preferably 0.1 mol to 10 mol, and more preferably 1 to 4 mol, per mol of the total amount of the precursor.

[0059] The thin film forming material of the present invention is made to contain as little impurity metal elements, impurity halogens such as impurity chlorine, and impurity organic matter as possible, other than the components constituting the thin film. The impurity metal elements are preferably 100 ppb or less per element, more preferably 10 ppb or less, and the total amount is preferably 1 ppm or less, more preferably 100 ppb or less. In particular, when used as a gate insulating film, gate film, or barrier layer of an LSI, it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements that affect the electrical properties of the resulting thin film. The impurity halogens are preferably 100 ppm or less, more preferably 10 ppm or less, and most preferably 1 ppm or less. The impurity organic matter is preferably 500 ppm or less in total, more preferably 50 ppm or less, and most preferably 10 ppm or less. In addition, moisture is a cause of particle generation in the chemical vapor deposition material and particle generation during thin film formation, so it is preferable to remove moisture as much as possible from the precursor, organic solvent, and nucleophilic reagent before use. The moisture content of each of the precursor, the organic solvent and the nucleophilic reagent is preferably 10 ppm or less, and more preferably 1 ppm or less.

[0060] In addition, the thin film forming material of the present invention is preferably free of particles as much as possible in order to reduce or prevent particle contamination of the thin film to be formed. Specifically, in particle measurement in the liquid phase using a light scattering type liquid-borne particle detector, the number of particles larger than 0.3 μm is preferably 100 or less per 1 mL of liquid phase, more preferably the number of particles larger than 0.2 μm is 1000 or less per 1 mL of liquid phase, and most preferably the number of particles larger than 0.2 μm is 100 or less per 1 mL of liquid phase.

[0061] Next, a method for producing a thin film using the thin film-forming raw material of the present invention will be described. The thin film-producing method of the present invention is a CVD method in which a raw material gas obtained by vaporizing the thin film-forming raw material of the present invention and a reactive gas used as necessary are introduced into a film-forming chamber (treatment atmosphere) in which a substrate is placed, and then precursors in the raw material gas are decomposed and / or chemically reacted on the substrate to grow and deposit a thin film containing metal atoms or semimetal atoms on the substrate surface. There are no particular limitations on the raw material transport supply method, deposition method, production conditions, production equipment, etc., and well-known general conditions and methods can be used.

[0062] Examples of the reactive gas used as necessary include oxidizing gases such as oxygen, ozone, and steam, hydrocarbon compounds such as methane and ethane, reducing gases such as hydrogen, carbon monoxide, and organometallic compounds, organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines, and alkylenediamines, and nitriding gases such as hydrazine and ammonia. These reactive gases may be used alone or in combination of two or more. The alkoxide compound represented by the general formula (1) has a property of reacting well with a reducing gas or an oxidizing gas, and has a property of reacting particularly well with hydrogen, steam, or ozone. Therefore, it is preferable to use a reducing gas or an oxidizing gas as the reactive gas, and it is particularly preferable to use hydrogen, steam, or ozone.

[0063] The above-mentioned transport supply method may include the gas transport method, liquid transport method, single source method, cocktail source method, etc.

[0064] In addition, examples of the above deposition method include thermal CVD, which deposits a thin film by reacting a source gas or a source gas and a reactive gas using only heat, plasma CVD, which uses heat and plasma, photo-CVD, which uses heat and light, photo-plasma CVD, which uses heat, light, and plasma, and ALD, which divides the CVD deposition reaction into elementary processes and deposits in stages at the molecular level.

[0065] Examples of the material of the substrate include silicon, ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide, glass, and metals such as metal cobalt. Examples of the shape of the substrate include plate-like, spherical, fibrous, and scaly shapes. The surface of the substrate may be flat or may have a three-dimensional structure such as a trench structure.

[0066] The above-mentioned production conditions include the reaction temperature (substrate temperature), reaction pressure, deposition rate, etc. The reaction temperature is preferably from room temperature to 500° C., and more preferably from 150° C. to 350° C. The reaction pressure is preferably from 10 Pa to atmospheric pressure in the case of thermal CVD or photo-CVD, and preferably from 10 Pa to 2,000 Pa in the case of using plasma.

[0067] The deposition rate can be controlled by the supply conditions of the raw material (vaporization temperature, vaporization pressure), the reaction temperature, and the reaction pressure. If the deposition rate is high, the properties of the obtained thin film may deteriorate, and if it is low, problems may occur in productivity, so that the deposition rate is preferably 0.01 nm / min to 100 nm / min, and more preferably 1 nm / min to 50 nm / min. In the case of the ALD method, the deposition rate is controlled by the number of cycles so as to obtain a desired film thickness.

[0068] Further, the above-mentioned manufacturing conditions include the temperature and pressure when the thin film forming raw material is vaporized to obtain a raw material gas. The step of vaporizing the thin film forming raw material to obtain a raw material gas may be performed in a raw material container or in a vaporization chamber. In either case, the thin film forming raw material of the present invention is preferably evaporated at 0°C to 150°C. When the thin film forming raw material is vaporized in a raw material container or in a vaporization chamber to obtain a raw material gas, the pressure in the raw material container and the pressure in the vaporization chamber are preferably both 1 Pa to 10,000 Pa.

[0069] The thin film manufacturing method of the present invention employs an ALD method, and may include a raw material introduction step of vaporizing a thin film-forming raw material to form a raw material gas by the above-mentioned transport and supply method and introducing the raw material gas into a film formation chamber, as well as a precursor thin film formation step of forming a precursor thin film on the surface of the substrate using the above-mentioned compound in the raw material gas, an exhaust step of exhausting unreacted compound gas, and a metal- or metalloid-containing thin film formation step of chemically reacting the precursor thin film with a reactive gas to form a thin film containing a metal or metalloid on the surface of the substrate.

[0070] In the following, each step of the ALD method will be described in detail using the case of forming a metal thin film as an example. First, the above-mentioned raw material introduction step is performed. The preferred temperature and pressure when the raw material for forming the thin film is used as the raw material gas are the same as those described in the thin film manufacturing method by the CVD method. Next, the raw material gas introduced into the film formation chamber comes into contact with the surface of the substrate to form a precursor thin film on the substrate surface (precursor thin film formation step). At this time, the substrate or the film formation chamber may be heated to apply heat. The precursor thin film formed in this step is a thin film formed from the alkoxide compound represented by the above general formula (1), or a thin film formed by decomposition and / or reaction of a part of the alkoxide compound represented by the above general formula (1), and has a different composition from the target metal thin film. The substrate temperature when this step is performed is preferably room temperature to 500°C, more preferably 150°C to 350°C. The pressure of the system (inside the film formation chamber) when this step is performed is preferably 1 Pa to 10,000 Pa, more preferably 10 Pa to 1,000 Pa.

[0071] Next, unreacted compound gases and by-produced gases are exhausted from the deposition chamber (exhaust process). Ideally, unreacted compound gases and by-produced gases are completely exhausted from the deposition chamber, but it is not necessary to exhaust them completely. Exhaust methods include a method of purging the system with an inert gas such as nitrogen, helium, or argon, a method of exhausting by reducing the pressure inside the system, and a combination of these methods. When reducing the pressure, the degree of reduction is preferably 0.01 Pa to 300 Pa, and more preferably 0.01 Pa to 100 Pa.

[0072] Next, a reducing gas is introduced into the film-forming chamber as a reactive gas, and a metal thin film is formed from the precursor thin film obtained in the previous precursor thin film forming step by the action of the reducing gas or the action of the reducing gas and heat (metal-containing thin film forming step). The temperature when applying heat in this step is preferably room temperature to 500°C, more preferably 150 to 350°C. The pressure of the system (inside the film-forming chamber) when this step is performed is preferably 1 Pa to 10,000 Pa, more preferably 10 Pa to 1,000 Pa. The alkoxide compound represented by the above general formula (1) has good reactivity with a reducing gas, so that a high-quality metal thin film with a low residual carbon content can be obtained.

[0073] In the thin film manufacturing method of the present invention, when the ALD method is adopted as described above, thin film deposition by a series of operations consisting of the raw material introduction step, precursor thin film formation step, exhaust step, and metal-containing thin film formation step is regarded as one cycle, and this cycle may be repeated several times until a thin film of a required thickness is obtained. In this case, after one cycle, it is preferable to exhaust unreacted compound gas, reactive gas, and by-product gas from the deposition reaction section in the same manner as in the exhaust step, and then perform the next cycle.

[0074] In addition, in forming a metal thin film by the ALD method, energy such as plasma, light, voltage, etc. may be applied, and a catalyst may be used. The timing of applying the energy and the timing of using the catalyst are not particularly limited, and may be, for example, when introducing a compound gas in the raw material introduction step, when heating in the precursor thin film formation step or the metal-containing thin film formation step, when exhausting the system in the exhaust step, when introducing a reducing gas in the metal-containing thin film formation step, or between the above steps.

[0075] In the method for producing a thin film of the present invention, after deposition of the thin film, an annealing treatment may be performed in an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere in order to obtain better electrical properties, and a reflow step may be performed if step filling is required. The temperature in this case is 200°C to 1,000°C, and preferably 250°C to 500°C.

[0076] A well-known ALD apparatus can be used in the thin film manufacturing method of the present invention. Specific examples of ALD apparatus include an apparatus capable of supplying a precursor by bubbling as shown in Figs. 1 and 3, and an apparatus having a vaporization chamber as shown in Figs. 2 and 4. In addition, an apparatus capable of performing plasma treatment on a reactive gas as shown in Figs. 3 and 4 can be used. Note that the present invention is not limited to single-wafer apparatuses equipped with a film-forming chamber (hereinafter referred to as a "deposition reaction section") as shown in Figs. 1 to 4, but an apparatus capable of simultaneously processing multiple wafers using a batch furnace can also be used. These can also be used as CVD apparatuses.

[0077] The thin film produced by using the thin film-forming material of the present invention can be a desired type of thin film such as metal, oxide ceramics, nitride ceramics, glass, etc., by appropriately selecting other precursors, reactive gases, and production conditions. The thin films are known to exhibit electrical properties and optical properties, and are used in various applications. For example, metal thin films, metal oxide thin films, metal Examples of such thin films include nitride thin films, alloy thin films, and metal-containing complex oxide thin films. These thin films are widely used in the manufacture of, for example, electrode materials for memory elements such as DRAM elements, resistive films, diamagnetic films used in the recording layers of hard disks, and catalyst materials for polymer electrolyte fuel cells. EXAMPLES

[0078] The present invention will be described in more detail below with reference to examples, comparative examples and evaluation examples, but the present invention is not limited to the following examples.

[0079] <Production of Alkoxide Compounds> The following Examples 1 to 5 show the results of producing alkoxide compounds.

[0080] [Example 1] Preparation of Compound No. 4 In a 100 ml four-neck flask, dissolve sodium hydride (0.24 g, 10.0 mmol) in dehydrated THF (20 ml) at room temperature. Add 3-(ethylmethylamino)-1,1,1-trifluoropropan-2-ol (1.71 g, 10.0 mmol) to this solution and stir at 85°C for 1 hour, then at room temperature for 17 hours. Add this solution dropwise to hexaamminenickel(II) chloride and stir at 85°C for 3 hours, then at room temperature for 15 hours. Distill off the solvent under slight reduced pressure in an oil bath at 70°C. Add 20 ml of dehydrated hexane and stir at room temperature. Filtrate under an inert atmosphere using a G4 ball filter to obtain a dark brown liquid. Remove the solvent under slight reduced pressure in an oil bath at 60°C. Thereafter, the brown solid remaining in the flask was purified by distillation under reduced pressure (20 to 30 Pa), and 1.55 g (3.88 mmol, yield 78%) of compound No. 4 was obtained as a distillate in the form of brown crystals.

[0081] (Analysis value) (1) Elemental analysis (metal analysis: ICP-AES) C: 36.2% by mass, H: 5.4% by mass, F: 28.5% by mass, N: 7.0% by mass, Ni: 14.9% by mass, O: 8.0% by mass (Theoretical values; C: 36.1% by mass, H: 5.6% by mass, F: 28.6% by mass, N: 7.0% by mass, Ni: 14.7% by mass, O: 8.0% by mass) (2) Structural analysis (single crystal X-ray analysis) Crystal lattice size: 0.28mm x 0.27mm x 0.21mm Crystal system: Monoclinic (2 molecules in asymmetric unit, R1=0.0669, wR2=0.1911) Lattice parameters: a=5.837Å b=8.063Å c=17.49Å β=92.655° V=822Å 3

[0082] [Example 2] Preparation of Compound No. 40 In a 100 ml four-neck flask, add tin bismuth. ( Trimethylsilyl) The amide complex (1.92 g, 4.36 mmol) was dissolved in dehydrated toluene (30 ml) at room temperature. 3-(ethylmethylamino)-1,1,1-trifluoropropan-2-ol (1.49 g, 8.72 mmol) was added to this solution, and the mixture was stirred at room temperature for 22 hours. The solvent was removed by distillation in an oil bath at 100°C under slightly reduced pressure. The purple viscous liquid remaining in the flask was then purified by distillation under reduced pressure (20 to 30 Pa), and 1.35 g (2.94 mmol, 68% yield) of compound No. 40 was obtained as a distillate in the form of white crystals.

[0083] (Analysis value) (1) Elemental analysis (metal analysis: ICP-AES) C: 31.6% by mass, H: 4.6% by mass, F: 24.9% by mass, N: 5.9% by mass, Sn: 26.1% by mass, O: 6.9% by mass (Theoretical values; C: 31.4% by mass, H: 4.8% by mass, F: 24.8% by mass, N: 6.1% by mass, Sn: 25.9% by mass, O: 7.0% by mass) (2) 1H-NMR (heavy benzene) 4.27ppm(s, 2H), 2.38-1.95ppm(m, 8H), 1.53ppm(s, 6H), 0.81ppm(t, J=6.8Hz, 6H)

[0084] [Example 3] Preparation of Compound No. 110 In a 100 ml four-neck flask, 0.60 g (6.3 mmol) of copper (II) methoxide complex and 20 ml of dehydrated toluene were added at room temperature, and 3-(ethylmethylamino)-1,1,1-trifluoropropan-2-ol (2.2 g, 13 mmol) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 20 hours. The by-product methanol and toluene solvent were distilled off at a slight reduced pressure in an oil bath of 70 to 90 °C. The purple solid remaining in the flask was then purified by sublimation under reduced pressure (40 Pa), and 2.0 g (5.0 mmol, 79% yield) of purple solid compound No. 110 was obtained as a volatile matter.

[0085] (Analysis value) (1) Elemental analysis (metal analysis: ICP-AES) C: 35.6% by mass, H: 5.4% by mass, F: 28.2% by mass, N: 7.1% by mass, Cu: 15.9% by mass, O: 7.8% by mass (Theoretical values; C: 35.7% by mass, H: 5.5% by mass, F: 28.2% by mass, N: 7.0% by mass, Cu: 15.7% by mass, O: 7.9% by mass) (2) Structural analysis (single crystal X-ray analysis) Crystal lattice size: 0.15mm x 0.14mm x 0.11mm Crystal system: Monoclinic (2 molecules in asymmetric unit, R1=0.0931, wR2=0.2671) Lattice parameters: a=5.866(7)Å b=8.094(9)Å c=17.59(2)Å β=91.923(13)° V=835(2)Å 3

[0086] [Example 4] Preparation of Compound No. 76 In a 100 ml four-neck flask, add cobalt bismuth ( Trimethylsilyl ) The amide complex (1.90 g, 5.01 mmol) was dissolved in dehydrated toluene (30 ml) at room temperature. 3-(Ethylmethylamino)-1,1,1-trifluoropropan-2-ol (1.71 g, 10.0 mmol) was added to this solution, and the mixture was stirred at room temperature for 22 hours. The solvent was distilled off in an oil bath at 100°C under slightly reduced pressure. The purple viscous liquid remaining in the flask was then purified by sublimation under reduced pressure (20-30 Pa), and 0.33 g (0.827 mmol, 16% yield) of compound No. 76 was obtained as a distillate in the form of a deep purple solid. (Analysis value) (1) Elemental analysis (metal analysis: ICP-AES) C: 36.2% by mass, H: 5.4% by mass, F: 28.6% by mass, N: 7.1% by mass, Co: 14.9% by mass, O: 7.8% by mass (Theoretical values; C: 36.1% by mass, H: 5.6% by mass, F: 28.5% by mass, N: 7.0% by mass, Co: 14.8% by mass, O: 8.0% by mass) (2) Structural analysis (ATR method: FT-IR) ν=425.80(m),480.99(m),522.23(m),587.55(w),618.01(m),640.43(m),692.77( m),793.96(m),851.63(m),862.70(m),916.91(m),1019.39(m),1052.74(m),1080. 08(s),1100.28(s),1136.77(m),1178.03(m),1266.04(m),1279.58(m),1309.33( w),1381.41(w),1455.30(w),2826.25(w),2872.25(w),2922.69(w),2986.57(w)cm -1

[0087] [Example 5] Preparation of Compound No. 109 In a 100 ml four-neck flask, 0.60 g (6.3 mmol) of copper (II) methoxide complex and 20 ml of dehydrated toluene were added at room temperature, and 3-(dimethylamino)-1,1,1-trifluoropropan-2-ol (2.0 g, 13 mmol) was added dropwise under ice cooling, and the mixture was stirred at room temperature for 20 hours. The by-product methanol and toluene solvent were distilled off at a slight reduced pressure in an oil bath of 70 to 90 °C. The purple solid remaining in the flask was then purified by sublimation under reduced pressure (40 Pa), and 1.4 g (3.7 mmol, 59% yield) of compound No. 109 was obtained as a purple solid as a volatile matter.

[0088] (Analysis value) (1) Elemental analysis (metal analysis: ICP-AES) C: 32.2% by mass, H: 4.5% by mass, F: 30.1% by mass, N: 7.4% by mass, Cu: 17.2% by mass, O: 8.6% by mass (Theoretical values; C: 32.0 mass%, H: 4.8 mass%, F: 30.3 mass%, N: 7.5 mass%, Cu: 16.9 mass%, O: 8.5 mass%) (2) Structural analysis (single crystal X-ray analysis) Crystal lattice size: 0.31mm x 0.18mm x 0.16mm Crystal system: Monoclinic (2 molecules in asymmetric unit, R1=0.0834, wR2=0.2527) Lattice parameters: a=5.771(10)Å b=10.64(2)Å c=12.07(2)Å β=93.28(3)° γ=63.91° V=740(3)Å 3

[0089] [Evaluation Examples 1-4, Comparative Evaluation Examples 1-4] Thermal Stability Evaluation The following thermal stability evaluation was carried out for the compounds of the present invention obtained in Examples 1 to 4 and the following Comparative Compounds 1 to 4. In the following Comparative Compounds 1 to 4, "Me" represents a methyl group, "Et" represents an ethyl group, and "tBu" represents a tertiary butyl group. (Thermal stability evaluation) The thermal decomposition onset temperature was measured using a DSC measuring device. Materials with a high thermal decomposition onset temperature have high thermal stability and can be judged to be preferable as thin film forming materials. The results are shown in Table 1.

[0090] [ka]

[0091] [Table 1]

[0092] As shown in Table 1 above, compound No. 4 was found to have a higher thermal decomposition onset temperature than comparative compound 1. Compound No. 40 was found to have a higher thermal decomposition onset temperature than comparative compound 2. Compound No. 110 was found to have a higher thermal decomposition onset temperature than comparative compound 3. Compound No. 76 was found to have a higher thermal decomposition onset temperature than comparative compound 4. In other words, the alkoxide compounds of the present invention were found to have a higher thermal decomposition onset temperature than conventionally known alkoxide compounds.

[0093] [Evaluation Examples 5-7, Comparative Evaluation Examples 5-7] Vapor pressure evaluation The compounds of the present invention obtained in Examples 1 to 3 and Comparative Compounds 1 to 3 were subjected to the following vapor pressure evaluation. (Vapor pressure rating) Using TG-DTA, measurements were taken at normal pressure, Ar flow rate: 100 mL / min, heating rate: 10 ° C / min, and scanning temperature range: 30 ° C to 600 ° C, and the temperature ( ° C) at which the weight of the test compound was reduced by 50% by mass was evaluated as "normal pressure TG-DTA 50% mass reduction temperature ( ° C)". Note that, for the copper compound, since comparative compound 3 was thermally decomposed, measurements were taken separately at a reduced pressure of 10 Torr, Ar flow rate: 50 mL / min, heating rate: 10 ° C / min, and scanning temperature range: 30 ° C to 600 ° C, and the temperature ( ° C) at which the weight of the test compound was reduced by 50% by mass was evaluated as "reduced pressure TG-DTA 50% mass reduction temperature ( ° C)". Those with low "normal pressure TG-DTA 50% mass reduction temperature ( ° C)" or "reduced pressure TG-DTA 50% mass reduction temperature ( ° C)" have a high vapor pressure and can be judged to be preferable as a thin film formation raw material. The results are shown in Table 2.

[0094] [Table 2]

[0095] As shown in Table 2 above, it was found that compound No. 4 is a compound with a lower temperature when reduced by 50% by mass in normal pressure TG-DTA compared to comparative compound 1. It was also found that compound No. 40 is a compound with a lower temperature when reduced by 50% by mass in normal pressure TG-DTA compared to comparative compound 2. Since comparative compound 3 was thermally decomposed during normal pressure TG-DTA measurement, compound No. 110 and comparative compound 3 were separately evaluated by reduced pressure TG-DTA. As a result, it was found that compound No. 110 is a compound with a lower temperature when reduced by 50% by mass in reduced pressure TG-DTA compared to comparative compound 3. In other words, it was found that the alkoxide compound of the present invention is a compound with a higher vapor pressure than conventionally known alkoxide compounds.

[0096] [Examples 6 to 10 and Comparative Examples 1 to 4] Production of metal thin films and metal oxide thin films by ALD method The compounds of the present invention obtained in Examples 1 to 5 and Comparative Compounds 1 to 4 were used as chemical vapor deposition raw materials, and a metal thin film and a metal oxide thin film were produced on a silicon substrate by the ALD method under the following conditions using the ALD apparatus shown in Figure 1. The film thickness of the obtained thin film was measured by X-ray reflectivity and spectroscopic ellipsometry, the compounds in the thin film were confirmed by X-ray diffraction, and the carbon content in the thin film was measured by X-ray photoelectron spectroscopy. The results are shown in Table 3.

[0097] (conditions) Reaction temperature (substrate temperature): 150 to 300°C, reactive gas: hydrogen, water vapor, or ozone (Process) A series of steps consisting of the following steps (1) to (4) was defined as one cycle, and 1000 cycles were repeated. (1) The vapor of the chemical vapor deposition source material vaporized under the conditions of a source container heating temperature of 50 to 150° C. and a source container internal pressure of 100 Pa is introduced and deposited at a system pressure of 100 Pa for 30 seconds. (2) Unreacted materials are removed by purging with argon for 10 seconds. (3) A reactive gas is introduced and reacted at a system pressure of 100 Pa for 1 to 30 seconds. (4) Unreacted raw materials are removed by purging with argon for 10 to 30 seconds.

[0098] [Table 3]

[0099] The carbon content in the metal thin film obtained by the ALD method was 5 atm% or more in Comparative Examples 1 to 4, whereas it was less than the detection limit of 0.1 atm% in Examples 6 to 10. In other words, it was demonstrated that high-quality metal thin films and metal oxide thin films can be obtained by using the alkoxide compound of the present invention. In addition, the thickness of the obtained thin films was 20 nm or less in Comparative Examples 1 to 4, whereas it was 30 nm or more in Examples 6 to 10. This shows that metal thin films and metal oxide thin films can be produced with high productivity by using the alkoxide compound of the present invention. ThinnessThe above results demonstrate that the alkoxide compound of the present invention is an excellent raw material for chemical vapor deposition.

Claims

1. An alkoxide compound represented by the following general formula (1): 【Chemistry 1】 (In the formula, R １ and R ２ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms; R ３ and R ４ each independently represents an alkyl group having 1 to 5 carbon atoms or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms; R ５ represents a hydrogen atom, a group containing a fluorine atom, or an alkyl group having 1 to 5 carbon atoms; R ６ represents a group containing a fluorine atom, M represents a nickel atom, a tin atom, a copper atom or a cobalt atom, and n represents the valence of the atom represented by M. However, when M is a copper atom, R ３ and R ４ each independently represents an alkyl group having 1 to 2 carbon atoms; R ５ represents a hydrogen atom.)

2. R ５ The alkoxide compound according to claim 1, wherein represents a hydrogen atom, a fluoro group, a fluorine atom-containing alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms.

3. R ６ The alkoxide compound according to claim 1 or 2, wherein represents a fluoro group or a fluorine atom-containing alkyl group having 1 to 5 carbon atoms.

4. R ６ The alkoxide compound according to any one of claims 1 to 3, wherein the fluorine atom-containing group is a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a 3,3,3-trifluoropropyl group.

5. A thin film-forming material comprising the alkoxide compound according to any one of claims 1 to 4.

6. A method for producing a thin film containing metal atoms or semi-metal atoms on a surface of a substrate, comprising the steps of:

6. A method for producing a thin film, comprising the steps of: vaporizing the thin film-forming raw material according to claim 5; introducing vapor containing the vaporized alkoxide compound into a treatment atmosphere; and decomposing and / or chemically reacting the compound to form a thin film containing metal atoms or semi-metal atoms on the surface of the substrate.

7. Use of the alkoxide compound according to any one of claims 1 to 4 for producing a thin film containing metal atoms or semi-metal atoms on the surface of a substrate.

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