Amidinate compound, dimer compound thereof, thin-film forming raw material, and method of producing thin film

Abstract

The present invention provides an amidinate compound represented by general formula (1) or a dimer compound thereof, and a method for producing a thin film using said compound as a raw material. (In the formula, R1 and R2 each independently represent an alkyl group having 1-5 carbon atoms, R3 represents a hydrogen atom or an alkyl group having 1-5 carbon atoms, M represents a metal atom or a silicon atom, and n represents the valence of the atom represented by M. At least one hydrogen atom of R1 to R3 is substituted by a fluorine atom.)

Description

Amidinate compounds, their dimer compounds, raw materials for forming thin films, and methods for producing thin films

[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.

[0002] Thin film materials containing metal elements or silicon 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 producing the above-mentioned thin films include sputtering, ion plating, metal organic decomposition (MOD) methods such as coating pyrolysis and sol-gel methods, and chemical vapor deposition methods. Among these, chemical vapor deposition (hereinafter sometimes simply referred to as "CVD") methods including atomic layer deposition (ALD) are the most suitable production processes because they have 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 amidinate compounds and their dimer compounds used in chemical vapor deposition. For example, Patent Documents 1 and 2 disclose cobalt bis(N,N'-diisopropylacetamidinate), cobalt bis(N,N'-di-sec-butylacetamidinate), copper(N,N'-diisopropylacetamidinate) dimer, copper(N,N'-di-sec-butylacetamidinate) dimer, and the like as raw materials for producing metallic cobalt thin films. Furthermore, Patent Document 3 discloses a cobalt amidinate compound substituted with an alkylamino group.

[0005] JP-T-2006-511716A JP-A-2010-156058A International Publication No. 2018 / 088079A

[0006] In methods for forming thin films by vaporizing compounds, such as CVD, the important properties required for compounds (precursors) used as thin film-forming raw materials are a high vapor pressure, a low melting point (preferably liquid at room temperature), high thermal stability, and the ability to produce high-quality thin films with high productivity. Thin film-forming raw materials containing an amidinate compound or its dimer compound are required to have, among other things, a high vapor pressure, a low melting point, and the ability to produce high-quality thin films with high productivity when used as thin film-forming raw materials. However, conventional amidinate compounds and their dimer compounds have not fully satisfied these requirements.

[0007] Therefore, an object of the present invention is to provide a novel amidinate compound and a dimer compound thereof which have a higher vapor pressure and a lower melting point than conventional amidinate compounds and dimer compounds thereof, and which, when used as a thin film-forming raw material, can produce high-quality thin films with good productivity.

[0008] As a result of extensive investigations, the present inventors have found that an amidinate compound having a ligand with a specific structure and a dimer compound thereof can solve the above problems, and have arrived at the present invention.

[0009] That is, the present invention is an amidinate compound represented by the following general formula (1) or a dimer compound thereof.

[0010]

[0011] (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms; R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, M represents a metal atom or a silicon atom, and n represents the valence of the atom represented by M. 1 ~R 3 At least one hydrogen atom of the formula (I) is substituted with a fluorine atom.

[0012] The present invention is 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 amidinate compound represented by general formula (1) or a dimer compound thereof into a treatment atmosphere; and decomposing and / or chemically reacting the compound to form a thin film containing metal atoms or silicon atoms on the surface of the substrate.

[0014] The amidinate compound represented by the following general formula (2) or a dimer compound thereof has the same meaning as the amidinate compound represented by the above general formula (1) or a dimer compound thereof.

[0015]

[0016] (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms; R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, M represents a metal atom or a silicon atom, and n represents the valence of the atom represented by M. 1 ~R 3 At least one hydrogen atom of the formula (I) is substituted with a fluorine atom.

[0017] The amidinate compound represented by the following general formula (3) is synonymous with the amidinate compound represented by the above general formula (1) or its dimer compound in which n is 1.

[0018]

[0019] (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms; R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M represents a metal atom. 1 ~R 3 At least one hydrogen atom of the formula (I) is substituted with a fluorine atom.

[0020] The amidinate compound represented by the following general formula (4) has the same meaning as the amidinate compound represented by the above general formula (3).

[0021]

[0022] (In the formula, R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms; R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and M represents a metal atom. 1 ~R 3 At least one hydrogen atom of the formula (I) is substituted with a fluorine atom.

[0023] According to the present invention, it is possible to provide an amidinate compound and a dimer compound thereof which have a higher vapor pressure than conventional amidinate compounds and dimer compounds thereof, and which, when used as a thin film-forming material, can produce high-quality thin films with good productivity. The compound of the present invention is suitable as a thin film-forming material for a CVD method, and in particular, has an ALD window, and is therefore excellent as a thin film-forming material for use in an ALD method.

[0024] Fig. 1 is a schematic diagram showing one example of an ALD apparatus used in the thin film manufacturing method according to the present invention. Fig. 2 is a schematic diagram showing another example of an ALD apparatus used in the thin film manufacturing method according to the present invention. Fig. 3 is a schematic diagram showing yet another example of an ALD apparatus used in the thin film manufacturing method according to the present invention. Fig. 4 is a schematic diagram showing yet another example of an ALD apparatus used in the thin film manufacturing method according to the present invention.

[0025] The compound of the present invention is represented by the above general formula (1). The compound of the present invention is suitable as a precursor in a thin film manufacturing method having a vaporization step, such as an ALD method, which is a type of CVD method.

[0026] In the above general formula (1), R 1 and R 2 each independently represents an alkyl group having 1 to 5 carbon atoms; R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, M represents a metal atom or a silicon atom, and n represents the valence of the atom represented by M. 1 ~R 3 At least one hydrogen atom of the formula (I) is substituted with a fluorine atom.

[0027] Examples of the "alkyl group having 1 to 5 carbon atoms" 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.

[0028] R 1 ~R 3 At least one hydrogen atom in R must be substituted with a fluorine atom. 1 ~R 3 Of all the hydrogen atoms present in R, preferably 1 to 9, more preferably 1 to 7, even more preferably 2 to 6, and even more preferably 3 to 6 hydrogen atoms are substituted with fluorine atoms. 1 ~R 3 The amidinate compound of the present invention includes an amidinate compound in which three of all hydrogen atoms present in the above formula (I) are substituted with fluorine atoms.

[0029] Examples of alkyl groups having 1 to 5 carbon atoms in which at least one hydrogen atom has been substituted with a fluorine atom (hereinafter also referred to as "fluorinated alkyl groups") include a trifluoromethyl group (perfluoromethyl group), a difluoromethyl group, a monofluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafluoroethyl group, a perfluoropropyl group, a 2,2,3,3-tetrafluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1,1-trifluoroisopropyl group, a 1,1,1,3,3,3-hexafluoroisopropyl group, a 2,2-difluoropropyl group, a 3,3-difluoropropyl group, a 2-fluoropropyl group, a 3-fluoropropyl group, a perfluorobutyl group, a 2,2,3,4,4-pentafluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 2,2,3,4,4-pent ... fluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 4,4,4-trifluorobutyl group, 4,4-difluorobutyl group, 3,3-difluorobutyl group, 2,2-difluorobutyl group, 2-fluorobutyl group, 3-fluorobutyl group, 4-fluorobutyl group, perfluoropentyl group, 2,2,3,3,4,4,5,5,5-nonafluoropentyl group, 2,2,3,3,4,4,5,5-octafluoropentyl group, Examples of the fluoropentyl group include a 3,3,4,4,5,5,5-heptafluoropentyl group, a 4,4,5,5,5-pentafluoropentyl group, a 5,5,5-trifluoropentyl group, a 5,5-difluoropentyl group, a 2,2-difluoropentyl group, a 3,3-difluoropentyl group, a 4,4-difluoropentyl group, a 2-fluoropentyl group, a 3-fluoropentyl group, a 4-fluoropentyl group, and a 5-fluoropentyl group.

[0030] Among these fluorinated alkyl groups, a fluorinated alkyl group containing a trifluoromethyl (CF3) group is preferable, and specific examples thereof include a trifluoromethyl group, a perfluoroethyl group, a 2,2,2-trifluoroethyl group, a perfluoropropyl group, a 3,3,3-trifluoropropyl group, a 1,1,1-trifluoroisopropyl group, a 1,1,1,3,3,3-hexafluoroisopropyl group, a perfluorobutyl group, a 2,2,3,3,4,4,4-heptafluorobutyl group, a 3,3,4,4,4-pentafluorobutyl group, a 4,4,4-trifluorobutyl group, a perfluoropentyl group, a 3,3,4,4,5,5,5-heptafluoropentyl group, a 4,4,5,5,5-pentafluoropentyl group, and a 5,5,5-trifluoropentyl group.

[0031] The aziminate compound of the present invention preferably contains three fluorine atoms per compound (excluding dimers). 1 ~R 3 It is preferable that any one of the R 1 ~R 3 It is preferable that any one of the groups is a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a 1,1,1-trifluoroisopropyl group.

[0032] In general formula (1), M represents a metal atom or a silicon atom. Examples of the metal atom represented by M include a copper atom, a cobalt atom, a nickel atom, a manganese atom, a zinc atom, a tin atom, a yttrium atom, an indium atom, a titanium atom, and a gallium atom.

[0033] In the above general formula (1), R 1 ~R 3 and M are appropriately selected depending on the method of manufacturing a thin film to be applied. When used in a method of manufacturing a thin film that includes a step of vaporizing a compound, R and M are selected so that the compound has a high vapor pressure and a low melting point. 1 ~R 3 It is preferable to select M.

[0034] Due to the high vapor pressure of the compound, R 1is preferably an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen atom has been substituted with a fluorine atom (a fluorinated alkyl group), more preferably a fluorinated alkyl group having 1 to 3 carbon atoms, further preferably a trifluoromethyl group, a 2,2,2-trifluoroethyl group, or a 1,1,1-trifluoroisopropyl group, and most preferably a 2,2,2-trifluoroethyl group.

[0035] Due to the high thermal stability of the compound, R 2 As the alkyl group, an unsubstituted alkyl group having 1 to 5 carbon atoms is preferred, a branched unsubstituted alkyl group having 3 to 5 carbon atoms is more preferred, and an unsubstituted tertiary butyl group is most preferred. 3 is preferably a hydrogen atom or a linear unsubstituted alkyl group having 1 to 5 carbon atoms, more preferably a linear unsubstituted alkyl group having 1 to 3 carbon atoms, particularly preferably a methyl group or an ethyl group, and most preferably an ethyl group.

[0036] Since high-quality thin films can be produced with good productivity, M is preferably a copper atom, cobalt atom, nickel atom, manganese atom, zinc atom, tin atom, yttrium atom, indium atom, titanium atom, gallium atom, or silicon atom, and more preferably a cobalt atom or tin atom. Furthermore, since high-quality thin films can be produced with good productivity, when M is a copper atom, the compound represented by the general formula (1) is preferably a dimeric compound, and when M is a cobalt atom, nickel atom, manganese atom, zinc atom, tin atom, yttrium atom, indium atom, titanium atom, gallium atom, or silicon atom, the compound represented by the general formula (1) is preferably a monomeric compound. That is, when n in the general formula (1) is 1, the compound represented by the general formula (1) is preferably a dimeric compound, and when n is 2 or more, the compound represented by the general formula (1) is preferably a monomeric compound.

[0037] In the general formula (1), n ​​represents the valence of the atom represented by M. For example, n is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and most preferably 2.

[0038] In addition, when used in a thin film manufacturing method using the MOD method without a vaporization step, R 1 ~R 3 can be selected arbitrarily depending on the solubility in the solvent used, the thin film forming reaction, and the like.

[0039] Preferred specific examples of the compound represented by the general formula (1) include the following compounds No. 1 to No. 132. In the following compounds No. 1 to No. 132, "Me" represents a methyl group, "Et" represents an ethyl group, "nPr" represents a normal propyl group, and "iPr" represents an isopropyl group.

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051] The method for producing the compound represented by the general formula (1) is not particularly limited, and the compound can be produced by applying a known reaction. For example, an intermediate compound can be obtained by reacting iron chloride with a nitrile compound having a corresponding structure, an alkyl halide compound having a corresponding structure, and a fluorine-containing amine compound having a corresponding structure in a dichloromethane solvent, followed by purification. The resulting intermediate compound can then be reacted with a corresponding metal chloride and an alkyllithium in a tetrahydrofuran solvent, followed by filtration, distilling off the solvent from the filtrate, and then purifying the product by distillation.

[0052] The nitrile compound is R 4 -CN, and R 4 is R in the above general formula (1). 3 The alkyl halide compound has a group corresponding to R 5 -X, and R 5 is R in the above general formula (1). 2 and X represents a halogen. 6 -NH2, and R 6 is R in the above general formula (1). 1 has a group corresponding to

[0053] Next, the thin-film-forming raw material of the present invention will be described. The thin-film-forming raw material of the present invention contains a compound represented by the general formula (1) as a thin-film precursor. The form of the compound varies depending on the manufacturing process to which the thin-film-forming raw material is applied. For example, when manufacturing a thin film containing only metal atoms or silicon atoms as the metal, the thin-film-forming raw material of the present invention does not contain metal compounds or metalloid compounds other than the compound represented by the general formula (1). On the other hand, when manufacturing a thin film containing two or more metals and / or metalloids, the thin-film-forming raw material of the present invention may contain, in addition to the compound represented by the general formula (1), compounds containing the desired metals and / or compounds containing metalloids (hereinafter sometimes referred to as "other precursors"). The thin-film-forming raw material of the present invention may further contain an organic solvent and / or a nucleophilic reagent, as described below. As explained above, the physical properties of the precursor compound represented by the general formula (1) are suitable for CVD processes, and therefore the thin-film-forming raw material of the present invention is useful as a chemical vapor deposition raw material (hereinafter sometimes referred to as a "CVD raw material"). In particular, since the compound represented by the general formula (1) has an ALD window, the thin film forming material of the present invention is particularly suitable for the ALD method.

[0054] 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 used.

[0055] The transport and supply methods include a gas transport method in which the CVD source material is vaporized by heating and / or depressurizing in a container (hereinafter sometimes referred to as a "source material container") in which the source material is stored to form a source gas, and the source gas is then introduced into a deposition chamber (hereinafter sometimes referred to as a "deposition reaction section") in which a substrate is placed, along with an optional carrier gas such as argon, nitrogen, or helium; and a liquid transport method in which the CVD source material is transported in a liquid or solution state to a vaporization chamber, where it is vaporized by heating and / or depressurization in the vaporization chamber to form a source gas, and the source gas is then introduced into the deposition chamber. In the gas transport method, the compound represented by the general formula (1) itself can be used as the CVD source material. In the liquid transport method, the compound represented by the general formula (1) itself or a solution of the compound dissolved in an organic solvent can be used as the CVD source material. These CVD sources may further contain other precursors, nucleophilic reagents, etc.

[0056] Multi-component CVD methods include a method in which each component of a CVD source is vaporized and supplied independently (hereinafter sometimes referred to as a "single source method"), and a method in which a mixed source in which multiple components are mixed in advance to a desired composition is vaporized and supplied (hereinafter sometimes referred to as a "cocktail source method"). In the cocktail source method, a mixture of the compound represented by the general formula (1) above and other precursors, or a mixed solution in which such a mixture is dissolved in an organic solvent, can be used as a CVD source. This mixture or mixed solution may further contain a nucleophilic reagent, etc.

[0057] 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 temperature used and the boiling point, the flash point, and the like.

[0058] When the thin film-forming raw material of the present invention is a mixed solution with the above-mentioned organic solvent, the amount of the whole precursor 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.

[0059] Here, the total amount of precursors means the amount of the compound represented by the general formula (1) when the thin film-forming raw material of the present invention does not contain any metal compounds and semimetal compounds other than the compound represented by the general formula (1), and means the total amount of the compound represented by the general formula (1) and the other precursors when the thin film-forming raw material of the present invention contains, in addition to the compound represented by the general formula (1), compounds containing other metals and / or compounds containing semimetals (other precursors).

[0060] In the case of a multi-component CVD method, other precursors to be used together with the compound represented by the general formula (1) are not particularly limited, and well-known general precursors used as CVD raw materials can be used.

[0061] Examples of the other precursors include compounds of silicon or a metal with one or more compounds 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.

[0062] Examples of 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; 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.

[0063] 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.

[0064] Examples of the β-diketone compound used as an organic ligand for the 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 suitable fluorine-substituted alkyl β-diketones include ethyldecane-3,5-dione and 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 and 1,3-diperfluorohexylpropane-1,3-dione; and 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.

[0065] 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.

[0066] Examples of the organic amine compound used as the organic ligand of the other precursor include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, and isopropylmethylamine.

[0067] The above-mentioned other precursors are known in the art, and their production methods are also known. For example, when an alcohol compound is used as the organic ligand, the precursor can be produced by reacting the inorganic salt of the metal or a hydrate thereof described above with an alkali metal alkoxide of the alcohol compound. Examples of the inorganic salt of the metal or a hydrate thereof include metal halides and nitrates, and examples of the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, and potassium alkoxide.

[0068] 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 compound represented by the 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 compound represented by the general formula (1) and which does not undergo changes that impair the desired properties of the precursor due to chemical reactions, etc., during mixing.

[0069] Furthermore, the thin film-forming material of the present invention may contain a nucleophilic reagent, if necessary, to impart stability to the compound represented by the general formula (1) and other precursors. Examples of the nucleophilic reagent include 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; and triethylenetetramine. 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 to 10 moles, and more preferably 1 to 4 moles, per mole of the total amount of precursor.

[0070] The thin-film-forming raw material of the present invention is intended to contain as little impurity metal elements, impurity halogens such as impurity chlorine, and impurity organic components as possible, other than the components constituting the thin-film. The impurity metal element content is preferably 100 ppb or less, more preferably 10 ppb or less per element, and the total content 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, which affect the electrical properties of the resulting thin film. The impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, and most preferably 1 ppm or less. The total content of impurity organic components is preferably 500 ppm or less, more preferably 50 ppm or less, and most preferably 10 ppm or less. Furthermore, since moisture can cause particle generation in chemical vapor deposition raw materials and during thin-film formation, it is preferable to remove as much moisture as possible from precursors, organic solvents, and nucleophilic reagents before use. The water content of each of the precursor, organic solvent and nucleophilic reagent is preferably 10 ppm or less, and more preferably 1 ppm or less.

[0071] Furthermore, in order to reduce or prevent particle contamination of the thin film to be formed, it is preferable that the thin film-forming raw material of the present invention contains as few particles as possible. Specifically, in particle measurement in the liquid phase using a light scattering liquid-borne particle detector, the number of particles larger than 0.3 μm per mL of liquid phase is preferably 100 or less, the number of particles larger than 0.2 μm per mL of liquid phase is more preferably 1,000 or less, and the number of particles larger than 0.2 μm per mL of liquid phase is most preferably 100 or less.

[0072] 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 production 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 needed, are introduced into a film-forming chamber (processing 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 silicon atoms on the substrate surface. There are no particular limitations on the raw material transport and supply method, deposition method, production conditions, production equipment, etc., and well-known conditions and methods can be used.

[0073] Examples of the reactive gas used as needed include oxidizing gases such as oxygen, ozone, and water vapor; 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 compound represented by the general formula (1) has the property of reacting well with an oxidizing gas or a reducing gas, and particularly with water vapor or hydrogen. Therefore, it is preferable to use an oxidizing gas or a reducing gas as the reactive gas, and it is particularly preferable to use water vapor or hydrogen.

[0074] The above-mentioned transportation and supply method may include the gas transportation method, liquid transportation method, single source method, cocktail source method, etc.

[0075] Examples of the deposition method include thermal CVD, which deposits a thin film by reacting a source gas or a source gas with 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 separates the CVD deposition reaction into elementary steps and deposits in stages at the molecular level.

[0076] Examples of materials for 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 metallic cobalt. Examples of the shape of the substrate include plate-like, spherical, fibrous, and scale-like. The surface of the substrate may be flat, or may have a three-dimensional structure such as a trench structure.

[0077] The production conditions include the reaction temperature (substrate temperature), reaction pressure, deposition rate, etc. The reaction temperature is preferably room temperature to 500°C, and more preferably 100°C to 300°C. The reaction pressure is preferably 10 Pa to atmospheric pressure in the case of thermal CVD or photo-CVD, and is preferably 10 Pa to 2,000 Pa in the case of using plasma.

[0078] The deposition rate can be controlled by the raw material supply conditions (vaporization temperature, vaporization pressure), reaction temperature, and reaction pressure. A high deposition rate may deteriorate the properties of the resulting thin film, while a low rate may cause problems in productivity. Therefore, a deposition rate of 0.01 nm / min to 100 nm / min is preferred, and 1 nm / min to 50 nm / min is more preferred. In the case of the ALD method, the deposition rate is controlled by the number of cycles so as to obtain the desired film thickness.

[0079] Further, the above-mentioned manufacturing conditions include the temperature and pressure when the thin film forming raw material is vaporized to form a raw material gas. The step of vaporizing the thin film forming raw material to form a raw material gas may be carried out 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 a temperature of 0°C to 150°C. Furthermore, when the thin film forming raw material is vaporized in a raw material container or in a vaporization chamber to form a raw material gas, the pressure in both the raw material container and the vaporization chamber is preferably 1 Pa to 10,000 Pa.

[0080] 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 by the above-mentioned transport and supply method to form a raw material gas 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 compound in the raw material gas, an exhaust step of exhausting unreacted compound gas, and a metal-containing thin film formation step of chemically reacting the precursor thin film with a reactive gas to form a metal-containing thin film on the surface of the substrate.

[0081] Each step of the ALD method will be described in detail below, taking the formation of a metal thin film as an example. First, the aforementioned raw material introduction step is performed. The preferred temperatures and pressures when using the thin film-forming raw materials as source gases are the same as those described for the thin film manufacturing method using the CVD method. Next, the source gas introduced into the film formation chamber comes into contact with the surface of the substrate, thereby forming a precursor thin film on the substrate surface (precursor thin film formation step). At this time, heat may be applied by heating the substrate or the film formation chamber. The precursor thin film formed in this step is a thin film formed from a compound represented by the above general formula (1), or a thin film formed by partial decomposition and / or reaction of a compound represented by the above general formula (1), and has a different composition from the target metal thin film. The substrate temperature during this step is preferably room temperature to 500°C, more preferably 100°C to 300°C. The pressure of the system (in the film formation chamber) during this step is preferably 1 Pa to 10,000 Pa, more preferably 10 Pa to 1,000 Pa.

[0082] Next, unreacted compound gases and by-product gases are exhausted from the film formation chamber (exhaust process). Ideally, unreacted compound gases and by-product gases are completely exhausted from the film formation chamber, but complete exhaust is not necessarily required. Exhaust methods include purging the system with an inert gas such as nitrogen, helium, or argon, exhausting by reducing the pressure inside the system, and a combination of these. When reducing the pressure, the degree of pressure reduction is preferably 0.01 Pa to 300 Pa, and more preferably 0.01 Pa to 100 Pa.

[0083] 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). When heat is applied in this step, the temperature is preferably room temperature to 500°C, more preferably 100 to 300°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 compound represented by the general formula (1) above has good reactivity with the reducing gas, and therefore a high-quality metal thin film with a low residual carbon content can be obtained.

[0084] In the thin film manufacturing method of the present invention, when the ALD method is employed as described above, thin film deposition by a series of operations consisting of the raw material introduction step, precursor thin film formation step, evacuation step, and metal-containing thin film formation step is defined as one cycle, and this cycle may be repeated multiple times until a thin film of the required thickness is obtained. In this case, after one cycle has been performed, it is preferable to evacuate the unreacted compound gas, reactive gas, and by-product gas from the deposition reaction zone in the same manner as in the evacuation step, and then perform the next cycle.

[0085] Furthermore, in forming a metal thin film by the ALD method, energy such as plasma, light, or voltage may be applied, or a catalyst may be used. The timing of applying the energy and using the catalyst is 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 evacuating the system in the evacuation step, when introducing a reducing gas in the metal-containing thin film formation step, or between the steps.

[0086] In the thin film manufacturing method of the present invention, after the thin film deposition, an annealing treatment may be performed in an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere to obtain better electrical properties, and a reflow step may be performed if step filling is required. In this case, the temperature is 200°C to 1,000°C, and preferably 250°C to 500°C.

[0087] Well-known ALD apparatuses can be used in the thin film manufacturing method of the present invention. Specific examples of ALD apparatuses include apparatuses capable of supplying precursors by bubbling, as shown in FIGS. 1 and 3, and apparatuses having a vaporization chamber, as shown in FIGS. 2 and 4. Also included are apparatuses capable of performing plasma treatment on reactive gases, as shown in FIGS. 3 and 4. It should be noted 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 apparatuses capable of simultaneously processing multiple wafers using a batch furnace can also be used. These can also be used as CVD apparatuses.

[0088] Thin films produced using the thin-film-forming material of the present invention can be formed into desired types of thin films, such as metal, oxide ceramic, nitride ceramic, and glass, by appropriately selecting other precursors, reactive gases, and production conditions. These thin films are known to exhibit electrical and optical properties and are used in a variety of applications. Examples include metal thin films, metal oxide thin films, gold nitride thin films, alloy thin films, and metal-containing complex oxide thin films. These thin films are widely used, for example, in the production of 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.

[0089] 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.

[0090] <Production of Intermediate Compounds> The following Production Examples 1 and 2 show the production results of the following intermediate compounds 1 and 2. In the following intermediate compounds 1 and 2, "Me" represents a methyl group, "Et" represents an ethyl group, and "tBu" represents a tertiary butyl group.

[0091]

[0092] [Production Example 1] Production of Intermediate Compound 1 A 500 mL four-neck flask was charged with 40.2 g (0.25 mol) of iron chloride and 359.8 g of dichloromethane and cooled to -25°C in an IPA / dry ice bath. 10.4 g (0.25 mol) of acetonitrile was added dropwise thereto and stirred for 10 minutes. 23.1 g (0.25 mol) of 2-methyl-2-chloropropane was then added dropwise thereto. After the dropwise addition, the mixture was returned to room temperature and stirred for 1 hour. The mixture was again cooled to -35°C in an IPA / dry ice bath, and 27.1 g (0.27 mol) of 2,2,2-trifluoroethylamine was added dropwise thereto. The mixture was allowed to react for 1 hour while still cooled, then returned to room temperature and stirred for 14 hours. After stirring, the reaction was completed using an aqueous sodium hydroxide solution under ice cooling, and the organic layer was extracted and separated. Sodium sulfate was added, followed by dehydration and filtration. The solvent was removed under a slight reduced pressure in an oil bath at 65°C, and after the solvent was distilled off, distillation was carried out under a slight reduced pressure in an oil bath at 75°C to obtain 42.8 g of a colorless and transparent intermediate compound 1 in a yield of 88%. (Analytical Values) (1) 1 H NMR (solvent: deuterated benzene) (chemical shift: multiplicity: hydrogen number) (0.96: s: 3) (1.29: s: 9) (3.38-3.41: q: 2)

[0093] [Production Example 2] Production of Intermediate Compound 2 A 500 mL four-neck flask was charged with 40.3 g (0.25 mol) of iron chloride and 498.7 g of dichloromethane and cooled to -29 °C in an IPA / dry ice bath. 14.0 g (0.25 mol) of propionitrile was added dropwise thereto and stirred for 10 minutes. 23.5 g (0.25 mol) of 2-methyl-2-chloropropane was then added dropwise thereto. After the dropwise addition, the mixture was returned to room temperature and stirred for 2 hours. The mixture was again cooled to -30 °C in an IPA / dry ice bath, and 27.1 g (0.27 mol) of 2,2,2-trifluoroethylamine was added dropwise thereto. The mixture was allowed to react for 1 hour while still cooled, then returned to room temperature and stirred for 15 hours. After stirring, the reaction was completed using an aqueous sodium hydroxide solution under ice cooling, and the organic layer was extracted and separated. Sodium sulfate was added, followed by dehydration and filtration. The solvent was removed under a slight vacuum in an oil bath at 75°C, and after distilling off the solvent, distillation was carried out under a slight vacuum in an oil bath at 85°C, obtaining 41.3 g of a colorless, transparent intermediate compound 2 in an 80% yield. (Analytical Values) (1)1 NMR (Solvent: Deuterated Benzene) (Chemical Shift: Multiplicity: H Number) (0.57-0.61: t: 3) (1.31: s: 9) (1.31-1.36: q: 2) (3.45-3.50: q: 2) <Production of Amidinate Compounds and Their Dimer Compounds> The following Examples 1 to 3 show the results of producing amidinate compounds and their dimer compounds.

[0094] Example 1: Preparation of Compound No. 19 6.0 g (0.046 mol) of cobalt chloride and 32.9 g of tetrahydrofuran were charged into a 300 mL three-neck flask and stirred at room temperature. A solution prepared from 18.5 g (0.094 mol) of intermediate compound 1, 59.4 g of tetrahydrofuran, and 60 mL (0.094 mol) of nBuLi was added dropwise to the flask under ice cooling. After the dropwise addition, the mixture was returned to room temperature and stirred for 17 hours, followed by filtration. The solvent was removed from the resulting filtrate, and the residue was distilled at a bath temperature of 125°C, a pressure of 93 Pa, and an overhead temperature of 90°C to obtain Compound No. 19 as a dark blue solid. The yield was 12.6 g, a 61% yield. (Analytical values) (1) Elemental analysis (metal analysis: ICP-AES) C: 42.6% by mass, H: 6.1% by mass, Co: 13.3% by mass, F: 25.2% by mass, N: 12.8% by mass (theoretical values; C: 42.8% by mass, H: 6.3% by mass, Co: 13.1% by mass, F: 25.3% by mass, N: 12.5% ​​by mass)

[0095] Example 2: Preparation of Compound No. 20: A 500 mL three-neck flask was charged with 13.1 g (0.101 mol) of cobalt chloride and 70.3 g of tetrahydrofuran and stirred at room temperature. A solution prepared from 42.9 g (0.204 mol) of intermediate compound 2, 63.3 g of tetrahydrofuran, and 130 mL (0.204 mol) of nBuLi was added dropwise to the flask under ice cooling. After the dropwise addition, the mixture was returned to room temperature and stirred for 17 hours, followed by filtration. The solvent was removed from the resulting filtrate, and the residue was distilled at a bath temperature of 120°C, a pressure of 110 Pa, and an overhead temperature of 100°C to obtain Compound No. 20 as a dark blue liquid. The yield was 28.6 g, a 60% yield. (Analytical values) (1) Elemental analysis (metal analysis: ICP-AES) C: 45.2% by mass, H: 6.6% by mass, Co: 12.6% by mass, F: 23.8% by mass, N: 11.8% by mass (theoretical values; C: 45.3% by mass, H: 6.7% by mass, Co: 12.4% by mass, F: 23.9% by mass, N: 11.7% by mass)

[0096] Example 3: Preparation of Compound No. 68 33.8 g (0.077 mol) of bis(trimethylsilylamide)tin and 89.2 g of normal hexane were charged into a 300 mL three-neck flask and stirred at room temperature. 32.5 g (0.154 mol) of Intermediate Compound 2 was added dropwise to the flask under ice cooling. After the dropwise addition, the mixture was returned to room temperature and stirred for 17 hours, followed by filtration. The solvent was removed from the resulting filtrate, and the residue was purified at a bath temperature of 135°C and a pressure of 45 Pa to obtain Compound No. 68 as a pale yellow solid. The yield was 35.4 g, a yield of 86%. (Analytical Values) (1) 1 HNMR (solvent: heavy benzene) (chemical shift: multiplicity: H number) (0.76 to 0.79: t: 3) (1.17: s: 9) (2.06 to 2.12: q: 2) (3.76 to 3.83: q: 2) (2) Elemental analysis (metal analysis: ICP-AES) C: 40.0 mass%, H: 6.2 mass%, Sn: 22.3 mass%, F: 21.1 mass%, N: 10.4 mass% (theoretical value; C: 40.3 mass%, H: 6.0 mass%, Sn: 22.1 mass%, F: 21.2 mass%, N: 10.4 mass%)

[0097] [Evaluation Examples] The compounds of the present invention obtained in Examples 1 to 3 and the following comparative compounds 1 and 2 were evaluated as follows. In the following comparative compounds 1 and 2, "Me" represents a methyl group, "Et" represents an ethyl group, and "tBu" represents a tertiary butyl group. (1) Melting Point Evaluation The state of the compounds at 20°C was observed visually. For compounds that were solid at 20°C, the melting point was measured using a micro melting point measuring device. Compounds with low melting points have excellent transportability and can be judged to be preferable as thin film-forming raw materials. Compounds that are liquid at 20°C have particularly excellent transportability and can be judged to be particularly preferable as thin film-forming raw materials. The results are shown in Table 1. (2) Temperature (°C) at 50% mass reduction in atmospheric pressure TG-DTA Measurements were performed using a TG-DTA under atmospheric pressure with an Ar flow rate of 100 mL / min, a heating rate of 10°C / min, and a temperature scan range of 30°C to 600°C. The temperature (°C) at which the weight of the test compound had decreased by 50% by mass was evaluated as the "temperature (°C) at atmospheric pressure TG-DTA" (50% mass reduction). The results are shown in Table 1. (3) Temperature (°C) at 50% mass reduction in reduced pressure TG-DTA Measurements were performed using a TG-DTA under conditions of 10 Torr, an Ar flow rate of 50 mL / min, a heating rate of 10°C / min, and a temperature scan range of 30°C to 600°C. The temperature (°C) at which the weight of the test compound had decreased by 50% by mass was evaluated as the "temperature (°C) at 50% mass reduction in reduced pressure TG-DTA." The results are shown in Table 1.

[0098]

[0099]

[0100] As shown in Table 1 above, Compounds No. 19 and No. 20 were found to be compounds whose temperatures at normal pressure TG-DTA and reduced pressure TG-DTA were 10°C or more lower than those of Comparative Compound 1 when subjected to 50% mass reduction. Furthermore, Compound No. 68 was found to be a compound whose temperatures at normal pressure TG-DTA and reduced pressure TG-DTA were 30°C lower than those of Comparative Compound 2 when subjected to 50% mass reduction, and whose temperatures at reduced pressure TG-DTA were 20°C lower than those of Comparative Compound 2. In other words, the amidinate compound and its dimer compound of the present invention were found to have higher vapor pressures than the conventionally known amidinate compounds and their dimer compounds. Furthermore, Compounds No. 19 and No. 20 were found to have melting points 45°C or more lower than those of Comparative Compound 1. Compound No. 20 was found to be a liquid at 20°C, with a particularly low melting point. Furthermore, Compound No. 68 was found to be a compound whose temperatures at normal pressure TG-DTA and reduced pressure TG-DTA were 30°C lower than those of Comparative Compound 2 when subjected to 50% mass reduction. It was found that Compound 68 has a melting point 15°C or more lower than that of Comparative Compound 2.

[0101] <Production of Thin Films by ALD Method> Using the compounds of the present invention obtained in Examples 1 to 3 and Comparative Compounds 1 and 2 as chemical vapor deposition sources, metal cobalt thin films or tin oxide thin films were produced on silicon substrates by ALD method under the following conditions using the ALD apparatus shown in Figure 1. For the resulting thin films, film thickness was measured by X-ray reflectivity, the compounds in the thin films were identified by X-ray diffraction, and the carbon content in the thin films was measured by X-ray photoelectron spectroscopy. The results are shown in Table 2.

[0102] [Examples 4-5, Comparative Example 1] Production of Metal Cobalt Thin Film by ALD Method (Conditions) Reaction temperature (substrate temperature): 200°C, reactive gas: hydrogen (Steps) A series of steps (1) to (4) below constitute one cycle, and were repeated 600 times. (1) Vapor of chemical vapor deposition raw material vaporized under conditions of a source container heating temperature of 80°C and a source container internal pressure of 100 Pa was introduced, and deposition was carried out for 30 seconds at a system pressure of 100 Pa. (2) Unreacted raw material was removed by argon purging for 45 seconds. (3) Reactive gas was introduced, and reaction was carried out for 10 seconds at a system pressure of 100 Pa. (4) Unreacted raw material was removed by argon purging for 15 seconds.

[0103] Example 6, Comparative Example 2: Production of tin oxide thin film by ALD method (Conditions) Reaction temperature (substrate temperature): 150°C, reactive gas: water vapor (Steps) A series of steps (1) to (4) below constitute one cycle, and were repeated 700 times. (1) Vapor of chemical vapor deposition raw material vaporized under conditions of a source container heating temperature of 80°C and a source container internal pressure of 100 Pa was introduced, and deposition was carried out for 20 seconds at a system pressure of 100 Pa. (2) Unreacted raw material was removed by argon purging for 15 seconds. (3) Reactive gas was introduced, and reaction was carried out for 0.4 seconds at a system pressure of 100 Pa. (4) Unreacted raw material was removed by argon purging for 90 seconds.

[0104]

[0105] The carbon content in the metal thin films obtained by the ALD method was 5 atm% or more in Comparative Examples 1 and 2, while it was less than the detection limit of 0.1 atm% in Examples 4 to 6. This demonstrates that high-quality metal thin films can be obtained by using the amidinate compound and its dimer compound of the present invention. Furthermore, the thickness of the resulting thin films was 3.5 nm or less in Comparative Examples 1 and 2, while it was 6.5 nm or more in Examples 4 to 6. This demonstrates that metal thin films were obtained with high productivity by using the amidinate compound and its dimer compound of the present invention. In particular, Compound No. 20 is a liquid at 20°C, and when used as a chemical vapor deposition source, metal thin films could be obtained with particularly high productivity, demonstrating its superiority as a chemical vapor deposition source.

Claims

1. An amidinato compound represented by the following general formula (1) or a dimer compound thereof. (In the formula, R 1 and R 2 each independently represent an alkyl group having 1 to 5 carbon atoms, R 3 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, M represents a metal atom or a silicon atom, and n represents the valence of the atom represented by M. However, at least one hydrogen atom of R 1 to R 3 is substituted with a fluorine atom.) 2. The compound according to claim 1, wherein M in the general formula (1) is selected from the group consisting of a copper atom, a cobalt atom, a nickel atom, a manganese atom, a zinc atom, a tin atom, a yttrium atom, an indium atom, a titanium atom, a gallium atom, and a silicon atom.

3. The compound according to claim 1 or 2, wherein at least one of R 1 and R 2 is a fluoroalkyl group.

4. The compound according to any one of claims 1 to 3, wherein at least one of R 1 and R 2 in the general formula (1) is a fluoroalkyl group selected from the group consisting of a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a 1,1,1-trifluoroisopropyl group.

5. The compound according to any one of claims 1 to 4, wherein R 1 in the general formula (1) is a fluoroalkyl group.

6. A raw material for thin film formation containing the amidinato compound according to any one of claims 1 to 5 or a dimer compound thereof.

7. A method for producing a thin film containing a metal atom or a silicon atom on the surface of a substrate, the method comprising: a step of vaporizing the raw material for thin film formation according to claim 6; a step of introducing a vapor containing the vaporized amidinato compound represented by the general formula (1) or a dimer compound thereof into a treatment atmosphere; and a step of decomposing and / or chemically reacting the compound to form a thin film containing a metal atom or a silicon atom on the surface of the substrate.

8. Use of the amidinato compound or its dimer compound according to any one of claims 1 to 5 in the production of a thin film containing metal atoms or silicon atoms on the surface of a substrate.

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