Zinc compound, raw material for film formation, film, and method for producing the same

Abstract

The present application provides a zinc compound represented by the following general formula (1) or (2). (In formula (1), R 1 represents an unsubstituted alkyl group having 1 to 5 carbon atoms, etc., R 2 and R 5 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, etc., R 3 and R 4 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, etc.)(In formula (2), R 10 , R 11 , R 14 and R 15 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, etc., R 9 , R 12 , R 13 and R 16 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, etc.).

Description

Technical Field

[0001] This invention relates to zinc compounds having a specific structure, raw materials for thin film formation containing the zinc compound, thin films obtained using the raw materials for thin film formation, and methods for manufacturing the same. Background Technology

[0002] Raw materials for thin film formation containing zinc compounds exhibit unique electrical properties, and their applications are developing particularly in optoelectronic engineering fields such as semiconductor devices, solar cells, and LEDs.

[0003] Methods for manufacturing thin films include sputtering, ion plating, coating thermal decomposition, sol-gel methods (such as Metal-Organic Decomposition (MOD), Chemical Vapor Deposition (CVD), and Atomic Layer Deposition (ALD). Among these, CVD and ALD are primarily used to ensure the high quality of the resulting thin films.

[0004] CVD and ALD are thin film formation techniques that utilize chemical vapor deposition. ALD, in particular, allows for the growth of materials supplied by precursors onto substrates of various compositions, controlling the atomic layers of the thin film surface and thus enabling the formation of films with fine shapes. With the continuous miniaturization development of electronic materials and devices such as nanotechnology, capacitor electrodes, gate electrodes, and integrated circuits, the necessity of ALD is increasing. The raw materials used in ALD for thin film formation require high vapor pressure and excellent thermal stability to form high-quality films. It should be noted that high-quality films refer to films with low residual carbon content.

[0005] Zinc compounds used as raw materials for thin film formation, such as diethylzinc, are known to form films with a thickness of approximately 0.18 nm per cycle. Patent Document 1 discloses the formation of zinc oxide thin films using zinc acetylacetonate via MOCVD. Patent Document 2 discloses a bis(β-diketone)zinc compound. Furthermore, Non-Patent Document 1 describes a ketimine zinc compound exhibiting excellent vaporization properties in a temperature range of 170°C to 270°C.

[0006] [Existing Technical Documents]

[0007] [Patent Literature]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 2003-236376

[0009] [Patent Document 2] Japanese Patent Application Publication No. 2005-350423

[0010] [Non-patent literature]

[0011] [Non-Patent Literature 1] "Systematic molecular engineering of Zn-ketoiminates for application as precursors in atomic layer depositions of zinc oxide", Dalton, Trans., 2016, 45, pp. 19012-19023. Summary of the Invention

[0012] The problem that the invention aims to solve

[0013] However, diethylzinc lacks thermal stability, thus the quality of the resulting film cannot meet the requirements. The zinc compounds described in Patent Documents 1 and 2 lack the reactivity of the precursor film derived from the compound with the reactive gas, therefore the quality of the resulting film may not meet the requirements. Furthermore, the ketimine zinc compound described in Non-Patent Document 1 has the problem of a high vaporization temperature.

[0014] Therefore, the object of the present invention is to provide a zinc compound that can form vapor at low temperatures and has excellent thermal stability, enabling the manufacture of high-quality films when used as a raw material for film formation. Furthermore, the object of the present invention is to provide a raw material for film formation containing this zinc compound, a film obtained using this raw material, and a method for manufacturing the same.

[0015] Methods for solving problems

[0016] The inventors conducted repeated and in-depth research and found that zinc compounds with specific structures can solve the above-mentioned problems, thus completing this invention.

[0017] That is, the present invention is a zinc compound represented by the following general formula (1) or (2).

[0018] [Chemistry 1]

[0019]

[0020] In equation (1), R 1 R represents an alkyl group with 1 to 5 unsubstituted carbon atoms or an alkyl group with 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms. 2 and R 5 Each of the following independently represents a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms whose hydrogen atoms are partially or wholly replaced by fluorine atoms, or an alkyl group whose hydrogen atoms are partially or wholly replaced by -OR. 6Some or all of the alkyl or hydrogen atoms with 1 to 5 carbon atoms that are substituted are replaced by -NR 7 R 8 Alkyl groups with 1 to 5 carbon atoms that are substituted, R 3 and R 4 Each of the following independently represents a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms; R 6 R 7 and R 8 Each of these terms independently represents an alkyl group having 1 to 5 unsubstituted carbon atoms or an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms.

[0021] [Chemistry 2]

[0022]

[0023] In equation (2), R 10 R 11 R 14 and R 15 Each of the following independently represents a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms whose hydrogen atoms are partially or wholly replaced by fluorine atoms, or an alkyl group whose hydrogen atoms are partially or wholly replaced by -OR. 17 Some or all of the alkyl or hydrogen atoms with 1 to 5 carbon atoms that are substituted are replaced by -NR 18 R 19 Alkyl groups with 1 to 5 carbon atoms that are substituted, R 9 R 12 R 13 and R 16 Each of the following independently represents a hydrogen atom, a fluorine atom, an unsubstituted alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms; R 17 R 18 and R 19 Each of these terms independently represents an alkyl group having 1 to 5 unsubstituted carbon atoms or an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms.

[0024] The present invention relates to a raw material for thin film formation containing the above-mentioned zinc compound.

[0025] The present invention relates to a thin film obtained using the above-mentioned raw materials for thin film formation.

[0026] The present invention is a method for manufacturing a thin film, comprising: a step of introducing a raw material gas obtained by vaporizing the raw material used to form the thin film into a film-forming chamber in which a substrate is disposed; and a step of decomposing and / or chemically reacting a zinc compound in the raw material gas to form a thin film containing zinc atoms (hereinafter, sometimes referred to as a "zinc-containing thin film") on the surface of the substrate.

[0027] The effects of the invention

[0028] According to the present invention, a zinc compound capable of forming vapor at low temperatures and exhibiting excellent thermal stability can be provided, enabling the manufacture of high-quality thin films when used as a raw material for thin film formation. Furthermore, according to the present invention, high-quality zinc-containing thin films can be formed by CVD methods, particularly ALD methods. Attached Figure Description

[0029] Figure 1 This is a schematic diagram illustrating an example of an ALD apparatus used in the thin film manufacturing method of the present invention.

[0030] Figure 2 This is a schematic diagram illustrating another example of an ALD apparatus used in the thin film manufacturing method of the present invention.

[0031] Figure 3 This is a schematic diagram illustrating yet another example of the ALD apparatus used in the thin film manufacturing method of the present invention.

[0032] Figure 4 This is a schematic diagram illustrating yet another example of the ALD apparatus used in the thin film manufacturing method of the present invention. Detailed Implementation

[0033] The zinc compounds of the present invention are represented by the above general formula (1) or (2).

[0034] In the above general formula (1), R is used as 1 ~R 8 The unsubstituted alkyl group having 1 to 5 carbon atoms is represented, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, n-pentyl, sec-pentyl, tert-pentyl, isopentyl, neopentyl, etc. R is preferred. 1 ~R 8 At least one of them is a zinc compound of alkyl group having 1 to 4 carbon atoms, more preferably R 1 ~R 8 At least one of them is a zinc compound that is methyl, ethyl, isopropyl, sec-butyl or tert-butyl.

[0035] In the above general formula (1), R is used as 1 ~R 8Alkyl groups having 1 to 5 carbon atoms, where some or all of the hydrogen atoms are replaced by fluorine atoms. Examples include fluoromethyl, difluoromethyl, trifluoromethyl, fluoroethyl, difluoroethyl, trifluoroethyl, pentafluoroethyl, fluoropropyl, heptafluoropropyl, fluoropentyl, and undecylfluoropentyl. R is preferred. 1 ~R 8 At least one of them is a zinc compound of alkyl groups having 1 to 3 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms, more preferably R 1 ~R 8 At least one of them is a zinc compound of fluoromethyl, difluoromethyl, trifluoromethyl or pentafluoroethyl.

[0036] In the above general formula (1), R is used as 2 and R 5 The hydrogen atom represented by -OR is partially or entirely represented by -OR 6 The substituted alkyl group having 1 to 5 carbon atoms includes, for example, methoxymethyl, ethoxymethyl, propoxymethyl, ethoxyethyl, isopropoxyethyl, ethoxypropyl, methoxybutyl, fluoromethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, trifluoromethoxyethyl, trifluoromethoxypropyl, etc. R is preferred. 2 and R 5 At least one of them is a zinc compound of methoxymethyl, methoxyethyl, isopropoxyethyl or trifluoromethoxymethyl.

[0037] In the above general formula (1), R is used as 2 and R 5 The hydrogen atom represented by -NR is partially or completely represented by -NR. 7 R 8 Examples of substituted alkyl groups having 1 to 5 carbon atoms include dimethylaminomethyl, diethylaminomethyl, methylpropylaminomethyl, dimethylaminoethyl, ethylmethylaminomethyl, and ethylmethylaminoethyl. R is preferred. 2 and R 5 At least one of them is a zinc compound of dimethylaminomethyl, dimethylaminoethyl or ethylmethylaminomethyl.

[0038] In the above general formula (2), R is used as 9 ~R 19 The unsubstituted alkyl group having 1 to 5 carbon atoms can be represented by R in the above general formula (1). 1 ~R 8 The alkyl group exemplified is the same as the alkyl group in the example. Preferably R 9 ~R 19 At least one of them is a zinc compound containing an alkyl group having 1 to 4 carbon atoms, more preferably R 9 ~R 19 At least one of them is a zinc compound that is methyl, ethyl, isopropyl, sec-butyl or tert-butyl.

[0039] In the above general formula (2), R is used as 9 ~R 19 The alkyl group representing 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms can be exemplified by R in the above general formula (1). 1 ~R 8 The alkyl group exemplified is the same as the alkyl group in the example. Preferably R 9 ~R 19 At least one of the components is a zinc compound having an alkyl group having 1 to 3 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms, more preferably R. 9 ~R 19 At least one of them is a zinc compound of fluoromethyl, difluoromethyl, trifluoromethyl or pentafluoroethyl.

[0040] In the above general formula (2), as R 10 R 11 R 14 and R 15 The expression "-OR" indicates that the OR is used to indicate the OR. 17 The substituted alkyl group having 1 to 5 carbon atoms can be exemplified by -OR of the above general formula (1). 6 The alkyl group exemplified is the same as the alkyl group in the example. Preferably R 10 R 11 R 14 and R 15 At least one of them is a zinc compound of methoxymethyl, methoxyethyl, isopropoxyethyl or trifluoromethoxymethyl.

[0041] In the above general formula (2), R is used as 10 R 11 R 14 and R 15 The hydrogen atom represented by -NR is partially or completely represented by -NR. 18 R 19 The substituted alkyl group having 1 to 5 carbon atoms can be exemplified by -NR of the above general formula (1). 7 R 8 The alkyl group exemplified is the same as the alkyl group in the example. Preferably R 10 R 11 R 14 and R 15 At least one of them is a zinc compound of dimethylaminomethyl, dimethylaminoethyl or ethylmethylaminomethyl.

[0042] The zinc compounds of the present invention can be manufactured using known methods. For example, in the above general formula (1), R 1 R 2 and R 5 It is ethyl and R 3 and R 4The zinc compound with methyl group can be obtained by reacting diethylzinc with a dialkyl diketone imine compound in a solvent, removing the solvent, and then purifying by distillation. In the above general formula (1), R 1 Zinc compounds of the ethyl group are preferred because they have low melting points and high vapor pressures, allowing for efficient formation of zinc-containing films. Furthermore, in the above general formula (2), R... 9 R 12 R 13 and R 16 It is methyl and R 10 R 11 R 14 and R 15 The zinc compound with the ethyl group can be obtained by reacting diethylzinc with 2 equivalents of a dialkyl diketone imine compound in a solvent, followed by removal of the solvent and distillation purification. In the above general formula (2), R 9 R 12 R 13 and R 16 The zinc compounds containing two or more trifluoromethyl groups have low melting points and high vapor pressures, thus enabling efficient formation of zinc-containing films, and are therefore preferred.

[0043] Preferred examples of zinc compounds represented by the above general formulas (1) and (2) include No. 1 to No. 68 below, but the present invention is not limited to these zinc compounds. It should be noted that in the following compounds No. 1 to No. 68, "Me" represents methyl, "Et" represents ethyl, "iPr" represents isopropyl, "sBu" represents sec-butyl, "tBu" represents tert-butyl, and "CF3" represents trifluoromethyl.

[0044] [Chemistry 3]

[0045]

[0046] [Chemistry 4]

[0047]

[0048] [Chemistry 5]

[0049]

[0050] [Chemistry 6]

[0051]

[0052] [Chemistry 7]

[0053]

[0054] [Chemistry 8]

[0055]

[0056] [Chemistry 9]

[0057]

[0058] [Chemistry 10]

[0059]

[0060] [Chemistry 11]

[0061]

[0062] [Chemistry 12]

[0063]

[0064] [Chemistry 13]

[0065]

[0066] [Chemistry 14]

[0067]

[0068] [Chemistry 15]

[0069]

[0070] [Chemistry 16]

[0071]

[0072] [Chemistry 17]

[0073]

[0074] [Chemistry 18]

[0075]

[0076] [Chemistry 19]

[0077]

[0078] The zinc compound of the present invention is suitable as a precursor for thin films produced by CVD and ALD processes due to the following physical properties.

[0079] From a processability point of view, the zinc compound of the present invention is preferably a liquid at room temperature.

[0080] In the DSC chart obtained by heating the zinc compound of the present invention from room temperature to 400°C using a differential scanning calorimeter (DSC) at a heating rate of 10°C / min, if the temperature at which the exothermic reaction reaches its peak is taken as the thermal decomposition onset temperature (°C), then the higher the thermal decomposition onset temperature, the better the heat resistance of the compound of the present invention, which is therefore preferred. A preferred thermal decomposition onset temperature is 250°C or higher, more preferably 300°C or higher.

[0081] Using a thermogravimetric differential thermal analysis (TG-DTA) apparatus at 10 Torr and a heating rate of 10 °C / min, the zinc compound of the present invention was heated from room temperature to obtain a DTA chart. The temperature at which the mass of the test compound decreased by 50% by mass was taken as the temperature (°C) at which the TG-DTA decreased by 50% by mass. The lower the temperature at which the TG-DTA decreased by 50% by mass, the more readily the zinc compound could vaporize at low temperatures, which is therefore preferred. The temperature at which the TG-DTA decreased by 50% by mass is preferably below 180 °C, and more preferably below 160 °C.

[0082] Next, the raw materials for thin film formation of the present invention will be described.

[0083] Regarding the raw materials for thin film formation of the present invention, only zinc compounds represented by the above general formula (1) or (2) are required, and their composition varies depending on the type of the target thin film. For example, in the case of manufacturing a thin film containing only zinc as a metal, the raw materials for thin film formation of the present invention do not contain compounds of metals other than zinc or half-metal compounds. On the other hand, in the case of manufacturing a thin film containing multiple metals and / or half-metals, the raw materials for thin film formation of the present invention may contain compounds containing the desired metal and / or compounds containing half-metals (hereinafter referred to as "other precursors") in addition to zinc compounds represented by the above general formula (1) or (2). Furthermore, as described below, the raw materials for thin film formation of the present invention may also contain organic solvents and / or nucleophilic reagents.

[0084] The form of the raw material for thin film formation of the present invention can be appropriately selected according to the conveying and supplying method of the chemical vapor deposition method such as CVD or ALD.

[0085] As described above, there are: a gas delivery method in which the raw material for thin film formation using the atomic layer deposition method of the present invention is vaporized by heating and / or depressurizing a container (hereinafter sometimes simply referred to as a "raw material container") to form a raw material gas, and the raw material gas, together with a carrier gas such as argon, nitrogen, or helium used as needed, is introduced into a film-forming chamber (hereinafter sometimes also referred to as a "deposition reaction section") where a substrate is provided; and a liquid delivery method in which the raw material for thin film formation of the present invention is delivered to a vaporization chamber in a liquid or solution state, vaporized by heating and / or depressurizing in the vaporization chamber to form a raw material gas, and the raw material gas is introduced into the film-forming chamber. In the case of the gas delivery method, the zinc compound represented by the above general formula (1) or (2) can be used as the raw material for thin film formation. In the case of the liquid delivery method, the zinc compound represented by the above general formula (1) or (2) or a solution of the zinc compound dissolved in an organic solvent can be used as the raw material for thin film formation of the present invention. These raw materials for thin film formation may further contain other precursors, nucleophilic reagents, etc.

[0086] In addition, in multi-component chemical vapor deposition methods, there are methods where the raw materials for thin film formation are vaporized and supplied independently for each component (hereinafter referred to as the "single source method"), and methods where a mixed raw material containing multiple raw materials premixed with a desired composition is vaporized and supplied (hereinafter referred to as the "cocktail source method"). In the case of the cocktail source method, a mixture of the zinc compound represented by the above general formula (1) or (2) with other precursors, or a mixed solution formed by dissolving the mixture in an organic solvent, can be used as the raw material for thin film formation. These raw materials for thin film formation may further contain nucleophilic reagents, etc.

[0087] There are no particular limitations on the organic solvents used, and commonly known organic solvents can be used. Examples of such organic solvents include: acetate esters such as ethyl acetate, butyl acetate, and methoxyethyl acetate; ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, and dioxane; ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl pentyl ketone, cyclohexanone, and methyl cyclohexanone; and hexane, cyclohexane... Hydrocarbons such as alkanes, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, and xylene; hydrocarbons containing cyano groups such as 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and 1,4-dicyanobenzene; and pyridine and dimethylpyridine. These organic solvents can be used individually or in mixtures, depending on the solubility of the solute, the relationship between the operating temperature and boiling point / flash point.

[0088] When the above-described organic solvent is used in the raw material for thin film formation of the present invention, it is preferable that the total amount of the precursor in the solution formed by dissolving the precursor in the organic solvent, i.e., the raw material for thin film formation, is 0.01 to 2.0 mol / L, and particularly preferably 0.05 to 1.0 mol / L. The total amount of the precursor refers to the amount of the zinc compound represented by the above-described general formula (1) or (2) when the raw material for thin film formation of the present invention does not contain any other precursors besides the zinc compound represented by the above-described general formula (1) or (2), and the total amount of the zinc compound represented by the above-described general formula (1) or (2) and other precursors when the raw material for thin film formation of the present invention contains other precursors besides the zinc compound represented by the above-described general formula (1) or (2).

[0089] In addition, in the case of chemical vapor deposition in a multi-component system, there are no particular restrictions on other precursors used with the zinc compound represented by the above general formula (1) or (2), and known general precursors used in raw materials for thin film formation can be used.

[0090] Other precursors mentioned above include, for example, compounds selected from one or more compounds with silicon or metals that serve as organic ligands, such as alcohols, diols, β-diketones, cyclopentadienes, and organic amines. Additionally, metals that can be used as precursors include lithium, sodium, magnesium, aluminum, potassium, calcium, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, rubidium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, indium, tin, antimony, barium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, lead, bismuth, radium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.

[0091] Examples of alcoholic compounds that can serve as organic ligands for the other precursors mentioned above include, for example, alkyl alcohols such as methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, isobutanol, tert-butanol, pentanol, isopentanol, and tert-pentanol; 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, and 2-butoxy-1,1-dimethylethanol. Ether alcohols such as 2-(2-methoxyethoxy)-1,1-dimethylethanol, 2-propoxy-1,1-diethylethanol, 2-sec-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.

[0092] Examples of diol compounds that can be used as organic ligands for the other precursors mentioned above include: 1,2-ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2,4-butanediol, 2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol, 2-methyl-2,4-pentanediol, 2,4-hexanediol, 2,4-dimethyl-2,4-pentanediol, etc.

[0093] Examples of β-diketone compounds that serve as organic ligands for the other precursors mentioned above 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, and 2,9-dimethylnonane-4,6-dione. Alkyl-substituted β-diketones such as ketones, 2-methyl-6-ethyldecane-3,5-dione, and 2,2-dimethyl-6-ethyldecane-3,5-dione; fluorinated alkyl-substituted 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.

[0094] Examples of cyclopentadiene compounds used as organic ligands for the aforementioned other precursors include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, and tetramethylcyclopentadiene. Examples of organic amine compounds used as organic ligands for the aforementioned organic ligands include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, and isopropylmethylamine.

[0095] Organic amine compounds that serve as organic ligands for the aforementioned other precursors include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, etc.

[0096] The aforementioned precursors are well known in the art, and their manufacturing methods are also well known. For example, when using an alcohol compound as an organic ligand, the precursor can be manufactured by reacting an inorganic salt or hydrate of the aforementioned metal with an alkali metal alkoxide of the alcohol compound. Examples of inorganic salts or hydrates of the metal include, for example, metal halides and nitrates. Examples of alkali metal alkoxides include, for example, sodium alkoxides, lithium alkoxides, and potassium alkoxides.

[0097] In the case of a single-source method, as other precursors as described above, compounds whose thermal and / or oxidative decomposition behavior is similar to that of zinc compounds represented by general formula (1) or (2) are preferred. In the case of a mixed-source method, as other precursors as described above, compounds that, in addition to having thermal and / or oxidative decomposition behavior similar to that of zinc compounds represented by general formula (1) or (2) are preferred, also do not undergo modification due to chemical reactions or the like during mixing.

[0098] Furthermore, regarding the raw materials for thin film formation of the present invention, a nucleophilic reagent may be included as needed to improve the stability of the zinc compound and other precursors represented by the above general formula (1) or (2). Examples of such nucleophilic reagents include, for instance, glycol ethers such as glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether; crown ethers such as 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, and dibenzo-24-crown-8; and polyamines such as ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, and triethoxytriethyleneamine. Cyclic polyamines such as 1,4,8,11-tetraazacyclotetradecane and 1,4,7,10-tetraazacyclododecane; heterocyclic compounds such as pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, and oxothiocyclopentane; β-keto esters such as methyl acetoacetate, ethyl acetoacetate, and 2-methoxyethyl acetoacetate, or β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and dinepentylmethane. The amount of these nucleophilic reagents used is preferably in the range of 0.1 mol to 10 mol relative to the total amount of the precursor, more preferably in the range of 1 to 4 mol.

[0099] In the raw materials for thin film formation of the present invention, it is preferable that they do not contain impurity metal elements, impurity halogen elements such as impurity chlorine, and impurity organic components other than those constituting the raw materials. Regarding the impurity metal element content, for each element, it is preferably 100 ppb or less, more preferably 10 ppb or less, and for the total amount, it is preferably 1 ppm or less, more preferably 100 ppb or less. Particularly when used as a gate insulating film, gate film, or barrier layer for LSI, it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements that affect the electrical properties of the obtained thin film. The impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. The total amount of impurity organic components is preferably 500 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less. Furthermore, moisture is a cause of particle generation in CVD raw materials and during thin film formation; therefore, it is advisable to remove moisture from precursors, organic solvents, and nucleophilic reagents as much as possible before use to reduce their respective moisture content. The water content of each of the precursor, organic solvent and nucleophilic reagent is preferably less than 10 ppm, more preferably less than 1 ppm.

[0100] Furthermore, regarding the raw materials for thin film formation according to the present invention, in order to reduce or prevent particulate contamination of the formed thin film, it is preferable to avoid containing particles as much as possible. Specifically, in particle measurement using a light scattering liquid particle detector in the liquid phase, it is preferable that the number of particles larger than 0.3 μm is 100 or less in 1 ml of liquid phase, and more preferably that the number of particles larger than 0.2 μm is 100 or less in 1 ml of liquid phase.

[0101] There is no limitation on the method for manufacturing thin films using the raw materials for thin film formation of the present invention. Examples include sputtering, ion plating, coating thermal decomposition, MOD (Metal-Oxide-Delta-Deposition) methods such as sol-gel methods, and CVD methods. Among these, atomic layer deposition (sometimes also called ALD) is preferred because it has many advantages such as excellent composition control and step height difference coverage, suitability for mass production, and the ability to perform hybrid integration.

[0102] Next, the method for manufacturing the thin film of the present invention will be described.

[0103] The method for manufacturing the thin film of the present invention includes: a step of introducing a raw material gas obtained by vaporizing the raw material used to form the thin film into a film-forming chamber in which a substrate is provided; and a step of decomposing and / or chemically reacting a zinc compound in the raw material gas to form a thin film containing zinc atoms on the surface of the substrate.

[0104] Regarding the process of vaporizing the raw material for film formation of the present invention to form a raw material gas, it can be carried out in a raw material container or in a vaporization chamber. In either case, the raw material for film formation of the present invention is preferably vaporized at a temperature of 0°C to 200°C. Furthermore, when the raw material for film formation is vaporized in a raw material container or in a vaporization chamber to form a raw material gas, the pressure in the raw material container and the pressure in the vaporization chamber are preferably in the range of 1 Pa to 10000 Pa.

[0105] In addition, as a method for introducing the raw material gas obtained by vaporizing the raw material for forming the above-mentioned film into the film-forming chamber in which the substrate is provided, the above-mentioned gas delivery method, liquid delivery method, single source method, mixed source method, etc. can be listed.

[0106] As a method for decomposing and / or chemically reacting the zinc compounds in the raw material gas, a reactive gas can simply be introduced into the film-forming chamber. Examples of reactive gases include oxidizing gases such as oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, acetic acid, and acetic anhydride; reducing gases such as hydrogen; organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines, and alkylene diamines; and nitriding gases such as hydrazine and ammonia. These reactive gases can be used alone or in mixtures of two or more. Since the raw material for film formation in this invention reacts well with oxidizing gases such as oxygen, ozone, and water vapor at particularly low temperatures, gases containing oxygen, ozone, or water vapor are preferred as reactive gases. From the perspective of efficiently producing high-quality films with low residual carbon content, gases containing water vapor are preferred as reactive gases.

[0107] As one embodiment of the film manufacturing method of the present invention, a case in which a zinc-containing film is formed using the film-forming raw material of the present invention via the ALD method will be described in detail. This manufacturing method includes: a step of introducing a raw material gas obtained by vaporizing the film-forming raw material of the present invention into a film-forming chamber (processing atmosphere) (raw material gas introduction step); a step of adsorbing a zinc compound in the raw material gas onto the surface of a substrate to form a precursor film on the surface of the substrate (precursor film formation step); and a step of introducing a reactive gas into the film-forming chamber (processing atmosphere) to react the precursor film with the reactive gas to form a zinc-containing film on the surface of the substrate (zinc-containing film formation step). Furthermore, between the precursor film formation step and the zinc-containing film formation step, and after the zinc-containing film formation step, a step of venting the gas in the film-forming chamber (processing atmosphere) is included (venting step). This manufacturing method sequentially performs the raw material gas introduction step, the precursor film formation step, the venting step, the zinc-containing film formation step, and the venting step as one cycle, and by repeatedly performing this cycle, the thickness of the zinc-containing film can be adjusted. Hereinafter, each step of the film manufacturing method of the present invention will be described.

[0108] (Raw material gas introduction process)

[0109] The raw material gas introduction process is a process in which the raw material for thin film formation of the present invention is vaporized to form a raw material gas, and the raw material gas is introduced into a film forming chamber in which a substrate is provided.

[0110] Regarding the process of vaporizing the raw material for film formation of the present invention to form a raw material gas, it can be carried out in a raw material container or in a vaporization chamber. In either case, the raw material for film formation of the present invention is preferably vaporized at a temperature of 0°C to 200°C. Furthermore, when the raw material for film formation is vaporized in a raw material container or in a vaporization chamber to form a raw material gas, the pressure in the raw material container and the pressure in the vaporization chamber are preferably in the range of 1 Pa to 10000 Pa.

[0111] Methods for conveying and supplying raw materials for thin film formation include: such as Figure 1 and Figure 3 As shown, a gas delivery method is used to vaporize the raw materials for film formation of the present invention by heating and / or depressurizing them in a container (hereinafter referred to as the "raw material container"), and to introduce the raw material gas, along with a carrier gas such as argon, nitrogen, or helium, into a film-forming chamber provided with a substrate, as needed; and as shown in the figure. Figure 2 and Figure 4 As shown, a liquid transport method is used where a raw material for thin film formation is transported to a vaporization chamber in a liquid or solution state, heated and / or depressurized in the vaporization chamber to vaporize it into a raw material gas, and then introduced into a film-forming chamber. In the case of the gas transport method, the zinc compound represented by the above general formula (1) or general formula (2) can be used as the raw material for thin film formation. In the case of the liquid transport method, the zinc compound represented by the above general formula (1) or general formula (2) or a solution of the zinc compound dissolved in an organic solvent can be used as the raw material for thin film formation. These raw materials for thin film formation may further contain nucleophilic reagents, etc.

[0112] In addition to the gas delivery method and liquid delivery method described above, the single-source method and mixed-source method described above can also be used as methods for introducing raw material gas in the process. When using any of the introduction methods, the raw material for film formation of the present invention is preferably vaporized at a temperature of 0°C to 200°C. Furthermore, the process of vaporizing the raw material for film formation to form raw material gas can be performed in a raw material container or in a vaporization chamber. The pressure in the raw material container and the pressure in the vaporization chamber are preferably in the range of 1 Pa to 10000 Pa.

[0113] Here, the materials used for the substrate disposed within the film-forming chamber include, for example, silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass; and metals such as cobalt and ruthenium. The shapes of the substrate can include plate-like, spherical, fibrous, and flake-like forms. The substrate surface can be planar or a three-dimensional structure such as a trench structure.

[0114] (Precursor film formation process)

[0115] In the precursor film formation process, a zinc compound represented by the above general formula (1) or general formula (2) in the raw material gas introduced into the film-forming chamber where the substrate is provided is deposited (adsorbed) onto the surface of the substrate, thereby forming a precursor film on the surface of the substrate. At this time, heat may also be applied by heating the substrate or heating the film-forming chamber. The conditions for forming the precursor film are not particularly limited. For example, the reaction temperature (substrate temperature), reaction pressure, deposition rate, etc., can be appropriately determined according to the type and thickness of the film. The reaction temperature is preferably the temperature at which the raw material for film formation of the present invention reacts sufficiently, i.e., 100°C or higher, and more preferably 150°C to 400°C.

[0116] Furthermore, the aforementioned deposition rate can be controlled by adjusting the supply conditions of the raw materials used for film formation (vaporization temperature, vaporization pressure), reaction temperature, and reaction pressure. If the deposition rate is too high, the properties of the resulting film may deteriorate; if the deposition rate is too low, productivity issues may arise. Therefore, a rate of 0.005 nm / min to 100 nm / min is preferred, and 0.01 nm / min to 50 nm / min is more preferred.

[0117] (Exhaust process)

[0118] After the precursor film is formed, the feed gas that has not been adsorbed onto the surface of the substrate is exhausted from the film-forming chamber. Ideally, the feed gas should be completely exhausted from the film-forming chamber, but complete exhaust is not necessary. Examples of exhaust methods include purging the system within the film-forming chamber using inert gases such as helium, nitrogen, or argon; exhausting the system by reducing pressure; and combinations thereof. The pressure reduction is preferably in the range of 0.01 Pa to 300 Pa, more preferably in the range of 0.01 Pa to 100 Pa.

[0119] (Zinc-containing thin film formation process)

[0120] In the zinc-containing thin film formation process, after the venting process, a reactive gas is introduced into the film-forming chamber. Through the action of the reactive gas, or the action of the reactive gas combined with heat, a zinc-containing thin film is formed from the precursor film formed in the previous precursor film process. If the reactive gas is an oxidizing gas, a zinc oxide thin film is formed. In this process, the temperature at which heat is applied is preferably in the range of room temperature to 500°C, more preferably in the range of 100°C to 400°C. The pressure of the system (in the film-forming chamber) during this process is preferably 1 Pa to 10000 Pa, more preferably 10 Pa to 1000 Pa. Regarding the raw material for film formation of the present invention, it exhibits good reactivity with oxidizing gases such as water vapor, thus enabling the efficient production of high-quality zinc-containing thin films with low residual carbon content.

[0121] Examples of reactive gases include oxidizing gases such as oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, acetic acid, and acetic anhydride; reducing gases such as hydrogen; organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines, and alkylene diamines; and nitriding gases such as hydrazine and ammonia. These reactive gases can be used alone or in combination. In the case of the raw materials for film formation according to the present invention, oxidizing gases such as oxygen, ozone, and water vapor react well at low temperatures; therefore, gases containing oxygen, ozone, or water vapor are preferred as reactive gases. From the perspective of obtaining a thick film per cycle and being able to manufacture films with good productivity, reactive gases containing ozone or water vapor are preferred, and gases containing water vapor are more preferred.

[0122] (Exhaust process)

[0123] After the zinc-containing thin film is formed, the unreacted reactive gases and byproduct gases are exhausted from the film-forming chamber. Ideally, all reactive gases and byproduct gases should be exhausted from the film-forming chamber, but complete exhaust is not necessary. The exhaust method and the depressurization rate are the same as those after the exhaust process in the precursor thin film formation step described above.

[0124] As explained above, the following steps are performed sequentially: raw material gas introduction, precursor film formation, venting, zinc-containing film formation, and venting. This series of deposition operations constitutes one cycle, which is repeated multiple times until a film of the desired thickness is obtained. This process manufactures a zinc-containing film with the desired thickness. In the ALD method for manufacturing films, the thickness of the formed zinc-containing film can be controlled by the number of cycles described above.

[0125] Furthermore, in the method for manufacturing the thin film of the present invention, energy such as plasma, light, or voltage can be applied, and a catalyst can also be used. The timing of applying this energy and the timing of using the catalyst are not particularly limited; for example, it can be applied during the introduction of the raw material gas in the raw material gas introduction step, during heating in the precursor thin film formation step or the zinc-containing thin film formation step, during venting of the system in the venting step, during the introduction of the reactive gas in the zinc-containing thin film formation step, or between the aforementioned steps.

[0126] In the thin film manufacturing method of the present invention, if the output power is too high during plasma treatment, it will cause great damage to the substrate. Therefore, 0 to 1500W is preferred, and 50 to 600W is more preferred.

[0127] Furthermore, in the thin film manufacturing method of the present invention, after the thin film is formed, in order to obtain better electrical properties, annealing treatment can be performed under an inactive atmosphere, an oxidizing atmosphere, or a reducing atmosphere. A reflow process can also be provided when it is necessary to fill the step height difference. The temperature at this time is preferably 200°C to 1000°C, more preferably 250°C to 500°C.

[0128] The apparatus for manufacturing thin films using the raw materials for thin film formation of the present invention can be a known ALD apparatus. Examples of specific apparatus include... Figure 1 Such a device that can bubble and supply precursors, such as Figure 2 Such a device has a vaporization chamber. Additionally, examples such as... Figure 3 and Figure 4 The apparatus shown is capable of plasma treatment of reactive gases. It is not limited to... Figures 1-4 Such a single-sheet device (leaf-type device) can also be used with a batch furnace that can process multiple sheets simultaneously.

[0129] Regarding the thin films manufactured using the raw materials for thin film formation of the present invention, by appropriately selecting other precursors, reactive gases, and manufacturing conditions, desired types of thin films can be formed by coating substrates such as metals, oxide ceramics, nitride ceramics, and glass. The thin films of the present invention exhibit excellent electrical and optical properties, and therefore can be widely used, for example, in the manufacture of electrode materials for memory devices such as DRAM devices, resistive films, antimagnetic films used in the recording layers of hard disks, and catalyst materials for solid polymer fuel cells.

[0130] The present invention will now be described in further detail using examples and the like. However, the present invention is not limited to the examples and the like.

[0131] [Example 1] Synthesis of Compound No. 27

[0132] In a 100 mL three-necked flask, 6.58 mL of a 1 mol / L diethylzinc toluene solution (6.58 mmol as diethylzinc) and 25 mL of dehydrated toluene were added. Under ice-cold conditions, 1.38 g (6.58 mmol) of N,N-di-sec-butylpentane-2,4-diimide was added dropwise, and the mixture was stirred at room temperature for 17 hours. The solvent was removed by distillation under slight reduced pressure in an oil bath at 100 °C. Then, the remaining brownish-transparent liquid in the flask was purified by distillation under reduced pressure (20–30 Pa) to obtain 1.37 g (4.51 mmol, 68% yield) of an orange-colored transparent liquid as the distillate.

[0133] The resulting orange transparent liquid was obtained through 1 The analytical results of H-NMR and ICP-AES confirmed it as target compound No. 27. The analytical results of the obtained orange transparent liquid are shown below.

[0134] (1) 1 ¹H-NMR (heavy benzene)

[0135] 0.68-0.81(m,8H),1.15(d,J=6.4Hz,6H),1.48-1.65(m,7H),1.80(s,6H),3.33-3.41(m,2H),4.49(s,1H)

[0136] (2) Elemental analysis results using ICP-AES

[0137] Zn: 21.52 wt% (theoretical value: 21.52 wt%), C: 59.33 wt% (theoretical value: 59.30 wt%), H: 9.98 wt% (theoretical value: 9.95 wt%), N: 9.17 wt% (theoretical value: 9.23 wt%)

[0138] [Example 2] Synthesis of Compound No. 49

[0139] In a 100 mL three-necked flask, 6.33 mL of a 1 mol / L diethylzinc toluene solution (6.33 mmol as diethylzinc) and 25 mL of dehydrated toluene were added. Under ice-cold conditions, 1.60 g (12.7 mmol) of N,N-dimethylpentane-2,4-diimide was added, and the mixture was stirred at room temperature for 17 hours. The solvent was removed by distillation under slight reduced pressure in an oil bath at 100 °C. The remaining brownish-transparent liquid in the flask was then purified by distillation under reduced pressure (20–30 Pa) to obtain 1.80 g (5.70 mmol, 90% yield) of an orange-colored transparent liquid as the distillate.

[0140] The resulting orange transparent liquid was obtained through 1The analytical results of H-NMR and ICP-AES confirmed it as target compound No. 49. The analytical results of the obtained orange transparent liquid are shown below.

[0141] (1) 1 ¹H-NMR (heavy benzene)

[0142] 1.81(s,12H),2.97(s,12H),4.54(s,2H)

[0143] (2) Elemental analysis results using ICP-AES

[0144] Zn: 20.66 wt% (theoretical value: 20.70 wt%), C: 53.28 wt% (theoretical value: 53.25 wt%), H: 8.32 wt% (theoretical value: 8.31 wt%), N: 17.74 wt% (theoretical value: 17.74 wt%)

[0145] [Example 3] Synthesis of Compound No. 59

[0146] In a 100 mL three-necked flask, 4.17 mL of a 1 mol / L diethylzinc toluene solution (4.17 mmol, calculated as diethylzinc) and 25 mL of dehydrated toluene were added. Under ice-cold conditions, 1.74 g (8.34 mmol) of N,N-diethyl-1,1,1-trifluoropentane-2,4-diimide was added, and the mixture was stirred at room temperature for 17 hours. The solvent was removed by distillation under slight reduced pressure in an oil bath at 100 °C. Then, the remaining brownish-transparent liquid in the flask was purified by distillation under reduced pressure (20–30 Pa) to obtain 1.81 g (3.77 mmol, 90% yield) of an orange-colored transparent liquid as the distillate.

[0147] The resulting orange transparent liquid was obtained through 1 The analytical results of H-NMR and ICP-AES confirmed it as target compound No. 59. The analytical results of the obtained orange transparent liquid are shown below.

[0148] (1) 1 ¹H-NMR (heavy benzene)

[0149] 0.91(t,J=7.2Hz,6H),1.10(t,J=7.2Hz,6H),1.54(s,6H),2.93-3.08(m,4H),3.47-3.60(m,4H),5.01(s,2H)

[0150] (2) Elemental analysis results using ICP-AES

[0151] Zn: 13.60 wt% (theoretical value: 13.63 wt%), C: 45.07 wt% (theoretical value: 45.06 wt%), H: 5.93 wt% (theoretical value: 5.88 wt%), N: 11.62 wt% (theoretical value: 11.67 wt%), F: 23.78 wt% (theoretical value: 23.76 wt%)

[0152] The following evaluation was conducted using compound No. 27 obtained in Example 1, compound No. 49 obtained in Example 2, compound No. 59 obtained in Example 3, and diethylzinc as comparative compound 1.

[0153] (1) Melting point evaluation

[0154] The state of the compounds was observed visually at 25°C under normal pressure. For solid compounds, the melting point was determined using a micro melting point measuring device. The results are shown in Table 1.

[0155] (2) Thermal decomposition onset temperature (°C)

[0156] Using a differential scanning calorimeter (DSC), the temperature at which the pyrochemical reaction peaks was taken as the "thermal decomposition onset temperature (°C)" in the DSC chart measured at a heating rate of 10 °C / min and a scanning temperature range of 30–500 °C. The results are shown in Table 1.

[0157] (3) Temperature (°C) at which the mass percentage of TG-DTA50 decreases under reduced pressure

[0158] Using TG-DTA at 10 Torr, argon flow rate of 50 mL / min, heating rate of 10 °C / min, and a scanning temperature range of 30–600 °C, the temperature (°C) at which the mass of the test compound decreases by 50% by mass is evaluated as "temperature (°C) at which TG-DTA decreases by 50% by mass under reduced pressure". A lower temperature (°C) at which TG-DTA decreases by 50% by mass under reduced pressure indicates that vapor is obtained at a lower temperature. The results are shown in Table 1.

[0159] [Table 1]

[0160] compound Melting point evaluation Thermal decomposition start temperature Temperature at which TG-DTA50 mass percentage decreases under reduced pressure Compound No.27 liquid 303℃ 125℃ Compound No.49 liquid 393℃ 155℃ Compound No.59 liquid 312℃ 138℃ Compare compound 1 liquid 183℃ -

[0161] The above results confirm that compounds No. 27, No. 49, and No. 59 exhibit excellent thermal stability within the range of 300°C to 400°C, indicating the onset temperature of thermal decomposition. Furthermore, it can be confirmed that compounds No. 27, No. 49, and No. 59 all show a reduction in 50% mass of TG-DTA under reduced pressure below 160°C, yielding vapor at low temperatures. These results confirm that the zinc compounds of the present invention are useful as raw materials for thin film formation. In contrast, comparative compound 1 lacks thermal stability and therefore cannot meet the requirements as a raw material for thin film formation.

[0162] Next, the films manufactured using the zinc compound of the present invention as a raw material for film formation are evaluated.

[0163] [Example 4]

[0164] Compound No. 27 was used as a raw material for thin film formation. Figure 1 The ALD device shown herein fabricates a thin film on a silicon dioxide substrate under the following conditions. X-ray photoelectron spectroscopy analysis of the film composition confirmed that it contains zinc oxide, with residual carbon content less than the detection limit of 0.01 atomic percent. Furthermore, X-ray reflectance analysis determined the film thickness, revealing a smooth film with a thickness of 15 nm formed on the substrate, with a thickness of approximately 0.03 nm per cycle.

[0165] (condition)

[0166] Manufacturing method: ALD process

[0167] Reaction temperature (matrix temperature): 200℃

[0168] Reactive gas: water vapor

[0169] (Process)

[0170] The series of processes consisting of (1) to (4) below is considered as one cycle, and the cycle is repeated 500 times.

[0171] (1) Under the conditions of raw material container temperature of 60°C and raw material container pressure of 100Pa, the raw material gas obtained by the vaporization of raw material is introduced into the film forming chamber, and the raw material gas is adsorbed on the surface of the substrate for 10 seconds under a system pressure of 100Pa to form a precursor film.

[0172] (2) Exhaust the unadsorbed raw material gas from the system by 15 seconds of argon purging.

[0173] (3) The reactive gas is introduced into the film-forming chamber and the precursor film reacts with the reactive gas for 0.2 seconds at a system pressure of 100 Pa.

[0174] (4) Exhaust unreacted reactive gases and byproduct gases from the system by 60 seconds of argon purging.

[0175] [Example 5]

[0176] Compound No. 49 was used as a raw material for thin film formation. Figure 1 The ALD device shown herein fabricates a thin film on a silicon dioxide substrate under the following conditions. X-ray photoelectron spectroscopy analysis of the film composition confirmed that it contains zinc oxide, with residual carbon content less than the detection limit of 0.01 atomic percent. Furthermore, X-ray reflectance measurement of the film thickness revealed that the film formed on the substrate is a smooth film with a thickness of 17 nm, and the thickness obtained per cycle is approximately 0.03 nm.

[0177] (condition)

[0178] Manufacturing method: ALD process

[0179] Reaction temperature (matrix temperature): 350℃

[0180] Reactive gas: Ozone

[0181] (Process)

[0182] The series of processes consisting of (1) to (4) below is considered as one cycle, and the cycle is repeated 500 times.

[0183] (1) Under the conditions of raw material container temperature of 60°C and raw material container pressure of 100Pa, the raw material gas obtained by the vaporization of raw material is introduced into the film forming chamber, and the raw material gas is adsorbed on the surface of the substrate for 10 seconds under a system pressure of 100Pa to form a precursor film.

[0184] (2) Exhaust the unadsorbed raw material gas from the system by 15 seconds of argon purging.

[0185] (3) Introduce the reactive gas into the film-forming chamber and allow the precursor film to react with the reactive gas for 20 seconds at a system pressure of 100 Pa.

[0186] (4) Exhaust unreacted reactive gases and byproduct gases from the system by purging with argon for 30 seconds.

[0187] [Example 6]

[0188] Compound No. 59 was used as a raw material for thin film formation. Figure 1The ALD device shown fabricates a thin film on a silicon dioxide substrate under the following conditions. X-ray photoelectron spectroscopy analysis of the film composition confirmed that it contains zinc oxide, with residual carbon content less than the detection limit of 0.01 atomic percent. Furthermore, X-ray reflectance measurement of the film thickness revealed a smooth 20 nm thick film formed on the substrate, with a thickness of approximately 0.04 nm per cycle.

[0189] (condition)

[0190] Manufacturing method: ALD process

[0191] Reaction temperature (matrix temperature): 350℃

[0192] Reactive gas: Ozone

[0193] (Process)

[0194] The series of processes consisting of (1) to (4) below is considered as one cycle, and the cycle is repeated 500 times.

[0195] (1) Under the conditions of raw material container temperature of 60°C and raw material container pressure of 100Pa, the raw material gas obtained by the vaporization of raw material is introduced into the film forming chamber, and the raw material gas is adsorbed on the surface of the substrate for 10 seconds under a system pressure of 100Pa to form a precursor film.

[0196] (2) Exhaust the unadsorbed raw material gas from the system by 15 seconds of argon purging.

[0197] (3) Introduce the reactive gas into the film-forming chamber and allow the precursor film to react with the reactive gas for 20 seconds at a system pressure of 100 Pa.

[0198] (4) Unreacted reactive gases and byproduct gases are removed from the system by argon purging for 30 seconds.

[0199] [Comparative Example 1]

[0200] Comparative compound 1 (diethylzinc) was used as the raw material for thin film formation. Otherwise, a thin film was fabricated on silicon dioxide as the substrate under the same conditions as in Example 4. The composition of the thin film was analyzed using X-ray photoelectron spectroscopy, revealing that it contained zinc oxide, but residual carbon was detected. Furthermore, the state of the thin film was observed using scanning electron microscopy, revealing that the film formed on the substrate was not smooth, and the film thickness could not be determined.

[0201] As can be confirmed from the above, the zinc compound of the present invention can form vapor at low temperatures and exhibits excellent thermal stability. Furthermore, it is confirmed that by using the zinc compound-containing raw material for film formation of the present invention, high-quality zinc-containing films can be manufactured.

Claims

1. A zinc compound represented by the following general formula (1) or (2): In equation (1), R 1 It is methyl or ethyl, R 2 and R 5 Each independently represents an unsubstituted alkyl group having 1 to 5 carbon atoms, R 3 and R 4 Each independently represents an unsubstituted alkyl group having 1 to 5 carbon atoms. In equation (2), R 10 R 11 R 14 and R 15 Each independently represents an unsubstituted alkyl group having 1 to 5 carbon atoms, R 9 R 12 R 13 and R 16 Each independently represents an unsubstituted alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms whose hydrogen atoms are partially or wholly replaced by fluorine atoms. However, R 9 R 12 R 13 and R 16 Two or more of these indicate trifluoromethyl.

2. A raw material for thin film formation, comprising the zinc compound of claim 1.

3. A thin film formed using the thin film forming raw material as described in claim 2.

4. A method for manufacturing a thin film, wherein the zinc compound of claim 1 is used as a precursor to manufacture a thin film containing zinc atoms by chemical vapor deposition.

5. A method for manufacturing a thin film, comprising: The process of introducing the raw material gas obtained by vaporizing the raw material for thin film formation as described in claim 2 into a film-forming chamber provided with a substrate; and A process of decomposing and / or chemically reacting the zinc compound in the raw material gas to form a thin film containing zinc atoms on the surface of the substrate.

6. The method for manufacturing a thin film according to claim 5, comprising: The process of adsorbing the zinc compound in the raw material gas onto the surface of the substrate to form a precursor film; and A process of reacting the precursor film with a reactive gas to form a thin film containing zinc atoms on the surface of the substrate.

7. The method for manufacturing a thin film according to claim 6, wherein, The reactive gas is an oxidizing gas, and the film is a zinc oxide film.

8. The method for manufacturing a thin film according to claim 7, wherein, The oxidizing gas is a gas containing oxygen, ozone, or water vapor.

9. The method for manufacturing a thin film according to any one of claims 6 to 8, wherein, The precursor film is reacted with the reactive gas within a temperature range of 100°C to 400°C.

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