Raw material for forming thin film for atomic layer deposition method and method for manufacturing thin film

Abstract

Provided is a material that is for formation of a thin film for use in atomic layer deposition and that contains a compound represented by formula (1).　(In formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1-5 carbon atoms, L represents a group represented by formula (L-1) or (L-2), and M represents an indium atom or a gallium atom.) (In formula (L-1), R11-R12 each independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1-5 carbon atoms, or an alkoxy group having 1-5 carbon atoms, and * represents the location where binding with M in formula (1) occur.) (In formula (L-2), R21-R23 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1-5 carbon atoms, and * represents the location where binding with M in formula (1) occur. However, R21 and R22 are groups different from each other.)

Description

Technical Field

[0001] The present invention relates to a raw material for forming a thin film for atomic layer deposition containing a gallium compound or an indium compound having a specific structure, and a method for producing a thin film containing gallium atoms or indium atoms using this raw material for forming a thin film.

Background Art

[0002] Raw materials for forming thin films containing gallium elements or indium elements exhibit specific electrical properties, and in particular, their applications in optoelectronic engineering fields such as semiconductor devices, solar cells, and LEDs have become prominent.

[0003] Examples of methods for manufacturing thin films include sputtering methods, ion plating methods, metal organic compound decomposition (MOD) methods such as coating pyrolysis methods and sol-gel methods, and chemical vapor deposition (CVD) methods. Among these, an atomic layer deposition (ALD) method, which is a type of chemical vapor deposition method, is the most suitable manufacturing process because it has many advantages such as excellent composition controllability, step coverage, suitability for mass production, and the ability to perform hybrid integration.

[0004] Although various materials that can be used in thin film forming methods such as CVD methods and ALD methods have been reported, it is necessary that the temperature range called the ALD window is sufficiently wide for raw materials for forming thin films applicable to the ALD method. Therefore, it is common general knowledge in the art that even raw materials for forming thin films that can be used in CVD methods are often not suitable for the ALD method.

[0005] Patent Document 1 discloses that an oxide film can be formed using trimethylgallium, triethylgallium, trimethylindium, etc. as raw materials for forming a thin film for atomic layer deposition. Patent Document 2 proposes a manufacturing method for forming a metal thin film using dialkylamidinatoindium, dialkylguanidinatoindium, etc. Patent Document 3 discloses that an indium-containing thin film can be formed by the MOCVD method using a β-diketonatoindium complex. Patent Document 4 proposes a method for forming a gallium-doped silicon nitride film using metal precursors such as gallium chloride, trimethylgallium, triethylgallium, tris(dimethylamino)gallium, tris(diethylamino)gallium, tris(ethylmethylamino)gallium, etc.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0007] As raw materials for forming a thin film by atomic layer deposition, those having excellent thermal stability and capable of producing a high-quality thin film are required. Compounds such as trialkylgallium, trialkylindium, dialkylamidinatoindium, dialkylguanidinatoindium, and trihalide gallium disclosed in Patent Documents 1 and 2 have insufficient thermal stability, so it has been difficult to form a high-quality thin film using the ALD method. Further, Patent Document 3 does not mention at all whether a β-diketonatoindium complex can be applied to the ALD method. Patent Document 4 describes depositing a gallium nitride layer by the ALD method using trimethylgallium, but since trimethylgallium has insufficient thermal stability, it has been difficult to form a high-quality thin film.

[0008] Therefore, an object of the present invention is to provide a raw material for forming a thin film by atomic layer deposition containing a compound having excellent thermal stability and capable of producing a high-quality thin film, and a method for producing a thin film using the raw material for forming a thin film.

Means for Solving the Problems

[0009] As a result of intensive studies, the present inventors have found that a raw material for forming a thin film by atomic layer deposition containing a gallium compound or an indium compound having a specific structure can solve the above problems, and have reached the present invention. That is, the present invention is a raw material for forming a thin film by atomic layer deposition containing a compound represented by the following general formula (1).

[0010]

Chemical formula

[0011] In formula (1), R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, L represents a group represented by the following general formula (L-1) or (L-2), and M represents an indium atom or a gallium atom. In the alkyl group, part or all of the hydrogen atoms may be substituted with fluorine atoms.

[0012]

Chem.

[0013] In formula (L-1), R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and * represents the bonding position with M in general formula (1). In the alkyl group, part or all of the hydrogen atoms may be substituted with fluorine atoms.

[0014]

Chem.

[0015] In formula (L-2), R 21 ~R 23 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, and * represents the bonding position with M in general formula (1). However, R 21 and R 22 are different groups. In the alkyl group, part or all of the hydrogen atoms may be substituted with fluorine atoms.

[0016] Moreover, the present invention is a method for manufacturing a thin film containing indium atoms or gallium atoms on the surface of a substrate, which includes a step of adsorbing the above compound in the source gas obtained by vaporizing the raw material for thin film formation for the above atomic layer deposition method on the surface of the substrate to form a precursor thin film, and a step of reacting the precursor thin film with a reactive gas to form a thin film containing indium atoms or gallium atoms on the surface of the substrate.

Advantages of the Invention

[0017] According to the present invention, it is possible to provide a raw material for thin film formation for atomic layer deposition, which contains a compound having excellent thermal stability and can produce a high-quality thin film. Further, the raw material for thin film formation for atomic layer deposition of the present invention can form a high-quality thin film by the ALD method.

Brief Description of Drawings

[0018]

Figure 1

Figure 2

Figure 3

Figure 4

Embodiments for Carrying Out the Invention

[0019] The raw material for thin film formation for atomic layer deposition of the present invention contains a compound represented by the above general formula (1).

[0020] In the above general formula (1), R 1 and R 2 Examples of the alkyl group having 1 to 5 carbon atoms represented by include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, an n-pentyl group, a sec-pentyl group, a tert-pentyl group, an isopentyl group, a neopentyl group, and the like. Examples of the alkyl group in which some or all of the hydrogen atoms are substituted with fluorine atoms include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a pentafluoroethyl group, a fluoropropyl group, a heptafluoropropyl group, a fluoropentyl group, an undecylfluoropentyl group, and the like.

[0021] In the group represented by the general formula (L-1) or (L-2), R 11 , R 12 and R 21 ~R 23 The alkyl group having 1 to 5 carbon atoms represented by is the same as those represented by R 1 and R 2 in the general formula (1).

[0022] In the group represented by the general formula (L-1), the alkoxy group having 1 to 5 carbon atoms represented by R 11 and R 12 includes, for example, methoxy group, ethoxy group, isopropoxy group, butoxy group, sec-butoxy group, tert-butoxy group, isobutoxy group, n-pentyloxy group, sec-pentyloxy group, tert-pentyloxy group, isopentyloxy group, neopentyloxy group and the like.

[0023] In the general formula (1), compounds in which R 1 and R 2 are methyl groups are preferable because they have a low melting point and a high vapor pressure, and can form a thin film with good productivity.

[0024] Preferable specific examples of the compound represented by the general formula (1) include the following Compound No.1 to Compound No.80, but the present invention is not limited to these compounds. In the following Compound No.1 to Compound No.80, "Me" represents a methyl group, "Et" represents an ethyl group, "iPr" represents an isopropyl group, "tBu" represents a tert-butyl group, and "CF3" represents a trifluoromethyl group.

[0025]

Chemical formula

[0026]

Chemical formula

[0027]

Chem.

[0028]

Chem.

[0029]

Chem.

[0030]

Chem.

[0031]

Chem.

[0032]

Chem.

[0033]

Chem.

[0034]

Chem.

[0035]

Chem.

[0036]

Chem.

[0037]

Chem.

[0038] [Chemical formula]

[0039] [Chemical formula]

[0040] [Chemical formula]

[0041] The compound represented by the above general formula (1) can be produced using a well-known method. For example, when M is indium, R 1 and R 2 are methyl groups and L is a group represented by (L-1), the compound can be obtained by reacting trimethylindium with a β-diketone compound in a solvent, removing the solvent, and then subjecting it to distillation purification. Further, when M is indium, R 1 and R 2 are methyl groups and L is a group represented by (L-2), the compound can be obtained by reacting trimethylindium with a dialkylamidine compound in a solvent, removing the solvent, and then subjecting it to distillation purification.

[0042] In order to ensure the transportability in the piping in the ALD apparatus used when manufacturing a thin film using the raw material for thin film formation for atomic layer deposition method of the present invention, the melting point of the compound represented by the above general formula (1) is preferably less than 100°C, and more preferably a liquid at room temperature.

[0043] The raw material for thin film formation used in the atomic layer deposition method of the present invention may contain a compound represented by the above general formula (1), and its composition varies depending on the type of the target thin film. For example, when manufacturing a thin film containing only gallium or indium as a metal, the raw material for thin film formation used in the atomic layer deposition method of the present invention does not contain a compound of a metal other than the metal and a metalloid compound. On the other hand, when manufacturing a thin film containing a metal and / or a metalloid other than gallium and indium, the raw material for thin film formation used in the atomic layer deposition method of the present invention may contain, in addition to the compound represented by the above general formula (1), a compound containing a desired metal and / or a compound containing a metalloid (hereinafter referred to as "other precursor"). Further, as will be described later, the raw material for thin film formation used in the atomic layer deposition method of the present invention may further contain an organic solvent and / or a nucleophilic reagent.

[0044] The form of the raw material for thin film formation used in the atomic layer deposition method of the present invention is appropriately selected according to techniques such as the transport and supply method of the atomic layer deposition method used.

[0045] As the above transport and supply method, the raw material for thin film formation used in the atomic layer deposition method of the present invention is vaporized by heating and / or depressurizing in a container in which the raw material for thin film formation is stored (hereinafter, may be simply referred to as "raw material container") to form a raw material gas, and together with a carrier gas such as argon, nitrogen, or helium used as necessary, the raw material gas is introduced into a film formation chamber in which a substrate is installed (hereinafter, may be referred to as "deposition reaction part"), a gas transport method, the raw material for thin film formation used in the atomic layer deposition method of the present invention is transported 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 there is a liquid transport method of introducing the raw material gas into the film formation chamber. In the case of the gas transport method, the compound itself represented by the above general formula (1) can be used as the raw material for thin film formation used in the atomic layer deposition method. In the case of the liquid transport method, the compound itself represented by the above general formula (1) or a solution in which the compound is dissolved in an organic solvent can be used as the raw material for thin film formation used in the atomic layer deposition method of the present invention. These raw materials for thin film formation used in the atomic layer deposition method may further contain other precursors, nucleophilic reagents, and the like.

[0046] In addition, in the ALD method for multi-component systems, there are a method of vaporizing and supplying the raw materials for thin film formation for atomic layer deposition independently for each component (hereinafter, sometimes referred to as the "single-source method"), and a method of vaporizing and supplying a mixed raw material in which multi-component raw materials are mixed in a desired composition in advance (hereinafter, sometimes referred to as the "cocktail-source method"). In the case of the cocktail-source method, a mixture of the compound represented by the general formula (1) and another precursor or a mixed solution obtained by dissolving the mixture in an organic solvent can be used as the raw material for thin film formation for the atomic layer deposition method of the present invention. These raw materials for thin film formation for atomic layer deposition may further contain a nucleophilic reagent or the like.

[0047] The above organic solvents are not particularly limited, and well-known general organic solvents can be used. Examples of the organic solvents include acetic acid esters such as ethyl acetate, butyl acetate, and methoxyethyl acetate; ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether, and dioxane; ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and methyl cyclohexanone; hydrocarbons such as hexane, cyclohexane, methyl cyclohexane, dimethyl cyclohexane, ethyl cyclohexane, heptane, octane, toluene, and xylene; hydrocarbons having a cyano group such as 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, and 1,4-dicyanobenzene; pyridine, lutidine, and the like. These organic solvents may be used alone or in combination of two or more depending on the solubility of the solute, the relationship between the use temperature, boiling point, and flash point.

[0048] In the raw material for thin film formation used in the atomic layer deposition method of the present invention, when the above organic solvent is used, it is preferable that the total amount of the precursor in the raw material for thin film formation used in the atomic layer deposition method, which is a solution obtained by dissolving the precursor in the organic solvent, is 0.01 to 2.0 mol / liter, particularly 0.05 to 1.0 mol / liter. The total amount of the precursor means the amount of the compound represented by the above general formula (1) when the raw material for thin film formation used in the atomic layer deposition method of the present invention does not contain other precursors in addition to the compound represented by the above general formula (1), and when the raw material for thin film formation used in the atomic layer deposition method of the present invention contains other precursors in addition to the compound represented by the above general formula (1), it is the total amount of the compound represented by the above general formula (1) and other precursors.

[0049] In the case of the multi-component ALD method, the other precursors used together with the compound represented by the above general formula (1) are not particularly limited, and well-known general precursors used in the raw material for thin film formation used in the atomic layer deposition method can be used.

[0050] Examples of the above other precursors include one or more selected from the group consisting of compounds used as organic ligands such as alcohol compounds, glycol compounds, β-diketone compounds, cyclopentadiene compounds, and organic amine compounds, and compounds of silicon or metal. Examples of the metal species of the precursor include lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, osmium, ruthenium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, gallium, indium, germanium, lead, antimony, bismuth, radium, scandium, ruthenium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, or lutetium.

[0051] Examples of the alcohol compounds used as the organic ligand of the other precursor described above include alkyl alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentyl alcohol, isopentyl alcohol, tert-pentyl alcohol, etc.; ether alcohols such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1,1-dimethylethanol, 2-ethoxy-1,1-dimethylethanol, 2-isopropoxy-1,1-dimethylethanol, 2-butoxy-1,1-dimethylethanol, 2-(2-methoxyethoxy)-1,1-dimethylethanol, 2-propoxy-1,1-diethylethanol, 2-sec-butoxy-1,1-diethylethanol, 3-methoxy-1,1-dimethylpropanol, etc.; dialkylamino alcohols such as dimethylaminoethanol, ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol, ethylmethylamino-2-pentanol, dimethylamino-2-methyl-2-pentanol, ethylmethylamino-2-methyl-2-pentanol, diethylamino-2-methyl-2-pentanol, etc.

[0052] Examples of the glycol compounds used as the organic ligand of the other precursor described above 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, 2,4-dimethyl-2,4-pentanediol, etc.

[0053] Examples of β-diketone compounds used as organic ligands of the above-mentioned other precursors include alkyl-substituted β-diketones such as 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-ethyldecane-3,5-dione, 2,2-dimethyl-6-ethyldecane-3,5-dione; fluorine-substituted alkyl β-diketones such as 1,1,1-trifluoropentane-2,4-dione, 1,1,1-trifluoro-5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 1,3-diperfluorohexylpropane-1,3-dione; 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, 2,2,6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-dione, etc.

[0054] Examples of cyclopentadiene compounds used as organic ligands of the above-mentioned other precursors include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, etc.

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

[0056] The above 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, a precursor can be produced by reacting the above-mentioned metal inorganic salt or its hydrate with the alkali metal alkoxide of the alcohol compound. Here, examples of the metal inorganic salt or its hydrate include metal halides, nitrates, and the like. Examples of the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, potassium alkoxide, and the like.

[0057] In the case of the single-source method, as the above other precursor, a compound whose thermal and / or oxidative decomposition behavior is similar to that of the compound represented by the above general formula (1) is preferable. In the case of the cocktail-source method, as the above other precursor, in addition to the thermal and / or oxidative decomposition behavior being similar to that of the compound represented by the above general formula (1), a compound that does not cause alteration due to chemical reaction or the like during mixing is preferable.

[0058] In addition, the raw material for thin film formation used in the atomic layer deposition method of the present invention may contain a nucleophilic reagent, if necessary, to improve the stability of 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; 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 triethoxytriethylenamine; 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; or 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 in the range of 0.1 mol to 10 mol, more preferably in the range of 1 mol to 4 mol, per 1 mol of the total amount of the precursors.

[0059] In the raw material for thin film formation used in the atomic layer deposition method of the present invention, impurity metal element components other than the components constituting the raw material, impurity halogen components such as impurity chlorine, and impurity organic components are minimized. For the impurity metal element components, it is preferably 100 ppb or less, more preferably 10 ppb or less, for each element, and in total, it 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 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. For the impurity halogen components, it is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less. For the impurity organic components, the total amount is preferably 500 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less. Also, since moisture causes particle generation in the raw material for thin film formation used in the atomic layer deposition method and particle generation during thin film formation, for the precursor, organic solvent, and nucleophilic reagent, in order to reduce the moisture content of each, it is better to remove as much moisture as possible in advance when in use. The moisture content of each of the precursor, organic solvent, and nucleophilic reagent is preferably 10 ppm or less, more preferably 1 ppm or less.

[0060] In addition, the raw material for thin film formation used in the atomic layer deposition method of the present invention is preferably made to contain as few particles as possible in order to reduce or prevent particle contamination of the formed thin film. Specifically, in particle measurement by a light scattering type in-liquid particle detector in the liquid phase, the number of particles larger than 0.3 μm is preferably 100 or less in 1 mL of the liquid phase, more preferably the number of particles larger than 0.2 μm is 1000 or less in 1 mL of the liquid phase, and even more preferably the number of particles larger than 0.2 μm is 100 or less in 1 mL of the liquid phase.

[0061] The method for manufacturing the thin film of the present invention is by the ALD method using the raw material for forming the thin film for the atomic layer deposition method, and includes a step of introducing a raw material gas obtained by vaporizing the raw material for forming the thin film for the atomic layer deposition method into a film formation chamber (processing atmosphere) (raw material gas introduction step), a step of adsorbing a gallium compound or an indium compound in the raw material gas onto the surface of a substrate to form a precursor thin film (precursor thin film formation step), a step of introducing a reactive gas into the film formation chamber (processing atmosphere) and reacting the precursor thin film with the reactive gas to form a thin film containing gallium atoms or indium atoms on the surface of the substrate (metal-containing thin film formation step). Further, between the precursor thin film formation step and the metal-containing thin film formation step and after the metal-containing thin film formation step, there is a step of exhausting the gas in the film formation chamber (processing atmosphere) (exhausting step).

[0062] Examples of the material of the substrate include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, lanthanum oxide; glass; metals such as metal cobalt. Examples of the shape of the substrate include plate shape, spherical shape, fibrous shape, and flaky shape. The surface of the substrate may be a flat surface or may have a three-dimensional structure such as a trench structure.

[0063] Examples of the method for introducing the raw material gas obtained by vaporizing the raw material for forming the thin film for the atomic layer deposition method into the film formation chamber in which the substrate is installed include the gas transport method, liquid transport method, single source method, cocktail source method, etc. described above.

[0064] Examples of the reactive gas include oxidizing gases such as oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, acetic acid, acetic anhydride, etc., reducing gases such as hydrogen, organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine, alkylenediamine, etc., and nitriding gases such as hydrazine and ammonia. These reactive gases may be used alone or in combination of two or more. Among these, since the raw material for thin film formation by the atomic layer deposition method of the present invention reacts well specifically with oxygen, ozone and water vapor at a low temperature, it is preferable to use a gas containing oxygen, ozone or water vapor as the reactive gas. From the viewpoint that a high-quality thin film with a small amount of residual carbon can be produced with high productivity, it is more preferable to use a gas containing water vapor as the reactive gas.

[0065] As an embodiment of the method for manufacturing a thin film of the present invention, the case of forming a gallium oxide thin film will be described in detail as an example. This manufacturing method includes a raw material gas introduction step, a precursor thin film formation step, an exhaust step, a metal-containing thin film formation step, and an exhaust step in this order as one cycle, and by repeating this cycle, the thickness of the thin film can be adjusted. Hereinafter, each step of the method for manufacturing a thin film of the present invention will be described.

[0066] (Raw material gas introduction step) The raw material gas introduction step is a step of vaporizing the raw material for thin film formation by the atomic layer deposition method of the present invention to obtain a raw material gas, and introducing the raw material gas into a film formation chamber in which a substrate is installed. The preferable temperature and pressure for vaporizing the raw material for thin film formation by the atomic layer deposition method are in the range of 0°C to 200°C and 1 Pa to 10,000 Pa.

[0067] As a method for transporting and supplying a raw material for forming a thin film by atomic layer deposition, as shown in FIGS. 1 and 3, the raw material for forming a thin film by atomic layer deposition of the present invention is vaporized by heating and / or depressurizing in a container (hereinafter referred to as "raw material container") in which the raw material is stored to obtain a raw material gas. As needed, together with a carrier gas such as argon, nitrogen, or helium, the raw material gas is introduced into a film formation chamber in which a substrate is installed. As shown in FIGS. 2 and 4, there is also a liquid transport method in which the raw material for forming a thin film by atomic layer deposition is transported to a vaporization chamber in a liquid or solution state, vaporized by heating and / or depressurizing in the vaporization chamber to obtain a raw material gas, and the raw material gas is introduced into the film formation chamber. In the case of the gas transport method, the compound itself represented by the above general formula (1) can be used as the raw material for forming a thin film by atomic layer deposition. In the case of the liquid transport method, the compound itself represented by the above general formula (1) or a solution in which the compound is dissolved in an organic solvent can be used as the raw material for forming a thin film by atomic layer deposition. These raw materials for forming a thin film by atomic layer deposition may further contain a nucleophilic reagent or the like.

[0068] In addition to the above gas transport method and liquid transport method, as a method used in the raw material gas introduction step, the above single source method and cocktail source method can be used. However, in any case of using these introduction methods, the raw material for forming a thin film by atomic layer deposition of the present invention is preferably vaporized at 0°C to 200°C. Further, when the raw material for forming a thin film by atomic layer deposition is vaporized in the raw material container or the vaporization chamber to obtain 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 10,000 Pa.

[0069] Here, examples of the material of the substrate installed in the film formation chamber include 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 metal cobalt and metal ruthenium. Examples of the shape of the substrate include plate-like, spherical, fibrous, and flaky. The surface of the substrate may be flat or may have a three-dimensional structure such as a trench structure.

[0070] (Precursor thin film formation process) In the precursor thin film formation process, the compound represented by the general formula (1) in the source gas introduced into the film formation chamber where the substrate is installed is deposited (adsorbed) on the surface of the substrate to form a precursor thin film on the surface of the substrate. At this time, the substrate may be heated or heat may be applied by heating the inside of the film formation chamber. The conditions for forming the precursor thin 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 of raw material for thin film formation. The reaction temperature is preferably in the range of 0°C to 400°C, and more preferably in the range of 150°C to 400°C, which is the temperature at which the raw material for thin film formation for the atomic layer deposition method of the present invention reacts sufficiently. Note that the ALD window when the raw material for thin film formation for the atomic layer deposition method of the present invention is used in combination with a reactive gas is generally in the range of 150°C to 400°C. The reaction pressure is preferably 1 Pa to 10,000 Pa, and more preferably 10 Pa to 1,000 Pa.

[0071] Also, the above deposition rate can be controlled by the supply conditions (vaporization temperature, vaporization pressure) of the raw material for thin film formation for the atomic layer deposition method, reaction temperature, and reaction pressure. If the deposition rate is too high, the characteristics of the obtained thin film may deteriorate, and if it is too low, there may be a problem with productivity. Therefore, 0.005 nm / min to 100 nm / min is preferable, and 0.01 nm / min to 50 nm / min is more preferable.

[0072] (Exhaust process) After forming the precursor thin film, the source gas that did not adsorb on the surface of the substrate is exhausted from the film formation chamber. At this time, it is ideal for the source gas to be completely exhausted from the film formation chamber, but it is not necessarily required to be completely exhausted. Examples of the exhaust method include a method of purging the inside of the film formation chamber with an inert gas such as helium, nitrogen, or argon, a method of exhausting by reducing the pressure inside the system, and a method combining these. The degree of pressure reduction in the case of reducing the pressure is preferably in the range of 0.01 Pa to 300 Pa, and more preferably in the range of 0.01 Pa to 100 Pa.

[0073] (Metal-containing thin film formation process) In the metal-containing thin film formation process, after the evacuation process, a reactive gas is introduced into the film formation chamber, and a metal-containing thin film is formed from the precursor thin film formed in the previous precursor thin film process by the action of the reactive gas or the action of the reactive gas and the action of heat. When the reactive gas is an oxidizing gas, a gallium oxide thin film or an indium oxide thin film is formed. In this process, the temperature when heat is applied is preferably from room temperature to 500 °C, more preferably from 100 °C to 400 °C. The pressure of the system (inside the film formation chamber) when this process is carried out is preferably from 1 Pa to 10,000 Pa, more preferably from 10 Pa to 1,000 Pa. Since the raw material for thin film formation for the atomic layer deposition method of the present invention has good reactivity with oxidizing gases such as water vapor, a high-quality metal-containing thin film with a low residual carbon content can be produced with high productivity.

[0074] Examples of the reactive gas include oxidizing gases such as oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, acetic acid, acetic anhydride, reducing gases such as hydrogen, organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine, alkylenediamine, and nitriding gases such as hydrazine and ammonia. These reactive gases may be used alone or in combination of two or more.

[0075] (Evacuation process) After the formation of the metal-containing thin film, unreacted reactive gas and by-product gas are evacuated from the film formation chamber. At this time, it is ideal for the reactive gas and by-product gas to be completely evacuated from the film formation chamber, but it is not necessarily required to be completely evacuated. The evacuation method and the degree of vacuum when reducing the pressure are the same as those in the evacuation process after the above-mentioned precursor thin film formation process.

[0076] As described above, the raw material gas introduction process, the precursor thin film formation process, the evacuation process, the metal-containing thin film formation process, and the evacuation process are carried out in order, and the deposition by a series of operations is defined as one cycle. By repeating this cycle a plurality of times until a thin film with the required film thickness is obtained, a metal-containing thin film with the desired film thickness is manufactured. In the method for manufacturing a thin film using the ALD method, the film thickness of the formed metal-containing thin film can be controlled by the number of the above cycles.

[0077] In the method for manufacturing a thin film of the present invention, energy such as plasma, light, and voltage may be applied, or a catalyst may be used. The timing of applying the energy and the timing of using the catalyst are not particularly limited. For example, it may be when introducing a source gas in the source gas introduction step, when heating in the precursor thin film formation step or the metal-containing thin film formation step, when evacuating the inside of the system in the evacuation step, when introducing an oxidizing gas in the metal-containing thin film formation step, or between any of the above steps.

[0078] In the method for manufacturing a thin film of the present invention, after forming the thin film, annealing treatment may be performed in an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere in order to obtain better electrical characteristics. When step filling is required, a reflow process may be provided. The temperature in this case is preferably 200°C to 1,000°C, and more preferably 250°C to 500°C.

[0079] As the apparatus for manufacturing a thin film using the raw material for thin film formation for atomic layer deposition method of the present invention, a well-known ALD apparatus can be used. Specific examples of the apparatus include an apparatus capable of bubbling and supplying a precursor as shown in FIG. 1, and an apparatus having a vaporization chamber as shown in FIG. 2. Further, an apparatus capable of performing plasma treatment on a reactive gas as shown in FIGS. 3 and 4 can be mentioned. The apparatus is not limited to a single-wafer type apparatus as shown in FIGS. 1 to 4, and an apparatus capable of simultaneously processing multiple wafers using a batch furnace can also be used.

[0080] The thin film manufactured using the raw material for thin film formation for atomic layer deposition method of the present invention can coat a substrate such as metal, oxide ceramics, nitride ceramics, glass, etc. by appropriately selecting other precursors, reactive gases, and manufacturing conditions to obtain a thin film of a desired type. Since the thin film obtained by the present invention is excellent in electrical characteristics and optical characteristics, it can be widely used, for example, in the manufacture of electrode materials for memory elements typified by DRAM elements, resistance films, antiferromagnetic films used for the recording layer of hard disks, and catalyst materials for solid polymer fuel cells.

Example

[0081] The present invention will be described in more detail below with reference to Examples and the like. However, the present invention is not limited by the following Examples and the like.

[0082] Example 1: Synthesis of Compound No. 9 To a 100 ml three-necked flask, 1.07 g (6.7 mmol) of trimethylindium and 15 ml of dehydrated tetrahydrofuran (THF) were added at room temperature. 1.05 g (6.7 mmol) of N-ethyl-N'-tert-butyl-propionamidine was added dropwise under ice-cooling, and the mixture was stirred at room temperature for 19 hours. THF was distilled off at 70 °C in an oil bath under slightly reduced pressure. Thereafter, the pale yellow transparent liquid remaining in the flask was distilled under reduced pressure (40 Pa), and 0.92 g (3.1 mmol, yield 46%) of a colorless transparent liquid was obtained as the distillate. The obtained colorless transparent liquid 1 As a result of analysis by 1H-NMR and ICP-AES, it was confirmed that the obtained compound was Compound No. 9, which is the target compound. The analysis results of the obtained colorless transparent liquid are shown below.

[0083] (1) 1 1H-NMR (benzene-d6) 0.114 ppm (6H, singlet), 0.888 - 0.956 ppm (6H, multiplet), 1.108 ppm (9H, singlet), 2.009 - 2.065 (2H, quartet), 2.958 - 3.012 (2H, quartet)

[0084] (2) Elemental analysis results by ICP-AES In: 38.31 mass% (theoretical value: 38.25 mass%), C: 44.00 mass% (theoretical value: 44.02 mass%), H: 8.41 mass% (theoretical value: 8.40 mass%), N: 9.28 mass% (theoretical value: 9.33 mass%)

[0085] Example 2: Synthesis of Compound No. 46 To a 100 ml three-necked flask, 0.98 g (6.1 mmol) of trimethylindium and 15 ml of dehydrated THF were added at room temperature. 1.12 g (6.1 mmol) of dipivaloylmethane was added dropwise under ice-cooling, and the mixture was stirred at room temperature for 20 hours. THF was distilled off at 70 °C in an oil bath under slightly reduced pressure. Thereafter, the pale yellow transparent liquid remaining in the flask was distilled under reduced pressure (50 Pa), and 1.32 g (4.0 mmol, yield 66%) of a colorless transparent liquid was obtained as the distillate. The obtained colorless transparent liquid 1 As a result of analysis by H-NMR and ICP-AES, it was confirmed that it was Compound No. 46, the target compound. The analysis results of the obtained colorless transparent liquid are shown below.

[0086] (1) 1 H-NMR (benzene-d6) 0.015 ppm (6H, singlet), 1.145 ppm (18H, singlet), 5.743 ppm (1H, singlet)

[0087] (2) Results of elemental analysis by ICP-AES In: 35.02 mass% (theoretical value: 34.99 mass%), C: 47.55 mass% (theoretical value: 47.58 mass%), H: 7.72 mass% (theoretical value: 7.68 mass%), O: 9.71 mass% (theoretical value: 9.75 mass%)

[0088] Example 3 Synthesis of Compound No. 66 To a 100 ml three-necked flask, 0.81 g (7.1 mmol) of trimethylgallium and 15 ml of dehydrated THF were added at room temperature. 1.31 g (7.1 mmol) of dipivaloylmethane was added dropwise under ice-cooling, and the mixture was stirred at room temperature for 20 hours. THF was distilled off at 70 °C in an oil bath under slightly reduced pressure. Thereafter, the pale yellow transparent liquid remaining in the flask was distilled under reduced pressure (50 Pa), and 1.25 g (4.4 mmol, yield 62%) of a colorless transparent liquid was obtained as the distillate. The obtained colorless transparent liquid 1 As a result of analysis by H-NMR and ICP-AES, it was confirmed that it was Compound No. 66, the target compound. The analysis results of the obtained colorless transparent liquid are shown below.

[0089] (1) 1 H-NMR (heavy benzene) 0.052 ppm (6H, singlet), 1.061 ppm (18H, singlet), 5.735 ppm (1H, singlet)

[0090] (2) Elemental analysis results by ICP-AES Ga: 24.64 mass% (theoretical value: 24.63 mass%), C: 55.11 mass% (theoretical value: 55.16 mass%), H: 8.91 mass% (theoretical value: 8.90 mass%), O: 11.34 mass% (theoretical value: 11.31 mass%)

[0091] Using Compound No. 9 obtained in Example 1, Compound No. 46 obtained in Example 2, Comparative Compounds 1 and 2 shown in Table 1, and Comparative Compound 3 shown in Table 2, the following evaluations were conducted.

[0092] (1) Melting point evaluation Visually observe the state of the compound at 25°C under normal pressure. For solid compounds, measure the melting point using a micro melting point measuring device. The results are shown in Table 1 and Table 2.

[0093] (2) Thermal decomposition start temperature (°C) Enclose the test compound in a sealed container, measure the differential scanning calorimetry (DSC) up to 500°C under the condition of a heating rate of 10°C / min, and evaluate the temperature at which the thermal decomposition of the test compound starts. The lower the thermal decomposition start temperature, the poorer the thermal stability of the test compound. The results are shown in Table 1 and Table 2.

[0094]

Table 1

[0095]

Table 2

[0096] Using Compound No. 66 obtained in Example 3 and Comparative Compound 4 shown in Table 3, the following evaluations were conducted.

[0097] (1) Melting point evaluation The melting points were measured under the same conditions as those for the melting point evaluations of Compound No. 9 and Compound No. 46. The results are shown in Table 3.

[0098] (2) Temperature (°C) at 50% mass loss in vacuum TG-DTA Using TG-DTA, measurements were carried out at 10 Torr, an argon flow rate of 50 mL / min, a heating rate of 10 °C / min, and a scanning temperature range of 30 °C to 600 °C. The temperature (°C) at which the weight of the test compound decreased by 50% was evaluated as the "temperature (°C) at 50% mass loss in vacuum TG-DTA". The lower the temperature (°C) at 50% mass loss in vacuum TG-DTA, the more steam can be obtained at a lower temperature. The results are shown in Table 3.

[0099] (3) Temperature (°C) at 50% mass loss in atmospheric pressure TG-DTA Using TG-DTA, measurements were carried out at 760 Torr, an argon flow rate of 100 mL / min, a heating rate of 10 °C / min, and a scanning temperature range of 30 °C to 400 °C. The temperature (°C) at which the weight of the test compound decreased by 50% was evaluated as the "temperature (°C) at 50% mass loss in atmospheric pressure TG-DTA". The lower the temperature (°C) at 50% mass loss in atmospheric pressure TG-DTA, the more steam can be obtained at a lower temperature. The results are shown in Table 3.

[0100] (4) Thermal decomposition start temperature (°C) The thermal decomposition start temperatures were measured under the same conditions as those for the thermal decomposition start temperature measurements of Compound No. 9 and Compound No. 46. The results are shown in Table 3.

[0101]

Table 3

[0102] From the above results, it was confirmed that Compound No. 9, Compound No. 46, and Compound No. 66 had a thermal decomposition start temperature of 290°C or higher and excellent thermal stability. Also, since the temperature at which Compound No. 66 showed a 50% mass reduction in TG-DTA under reduced pressure was 60°C and that under normal pressure was 130°C, it was confirmed that Compound No. 66 had a high vapor pressure and vaporized at a lower temperature.

[0103] [Example 4] Compound No. 66 was used as a raw material for thin film formation by atomic layer deposition method, and using the ALD apparatus shown in Fig. 1, a thin film was produced on the surface of a silicon wafer as a substrate under the following conditions. When the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a thin film containing gallium oxide and the residual carbon amount was less than 0.1 atom%, which was the detection limit. Also, when the film thickness of the thin film was measured using scanning electron microscopy, the thin film formed on the silicon wafer surface was a smooth film with a thickness of 10 nm, and the film thickness obtained per cycle was about 0.02 nm.

[0104] (Conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 300°C Reactive gas: Water vapor

[0105] (Steps) A series of steps consisting of the following (1) to (4) was defined as one cycle, and this cycle was repeated 500 times. (1) Under the conditions of a raw material container temperature of 40°C and a raw material container internal pressure of 100 Pa, the raw material gas obtained by vaporizing the raw material for thin film formation by atomic layer deposition method was introduced into the film formation chamber, and the raw material gas was adsorbed on the surface of the substrate for 10 seconds at a system pressure of 100 Pa to form a precursor thin film. (2) The unadsorbed raw material gas was exhausted from the system by purging with argon for 15 seconds. (3) The reactive gas was introduced into the film formation chamber, and the precursor thin film and the reactive gas were reacted for 0.2 seconds at a system pressure of 100 Pa. (4) The unreacted reactive gas and by-product gas were exhausted from the system by purging with argon for 60 seconds.

[0106] [Example 5] Compound No. 9 was used as a raw material for thin film formation by atomic layer deposition method. Using the ALD apparatus shown in Fig. 1, a thin film was produced on the surface of a silicon wafer as a substrate under the following conditions. When the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a thin film containing indium oxide and the residual carbon amount was less than 0.1 atom%, which is the detection limit. Also, when the film thickness of the thin film was measured using scanning electron microscopy, the thin film formed on the silicon wafer surface was a smooth film with a thickness of 20 nm, and the film thickness obtained per cycle was about 0.04 nm.

[0107] (Conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 250 °C Reactive gas: water vapor

[0108] (Process) A series of steps consisting of the following (1) to (4) was defined as one cycle, and this cycle was repeated 500 times. (1) A source gas obtained by vaporizing a raw material for thin film formation by atomic layer deposition method under the conditions of a source container temperature of 50 °C and a source container internal pressure of 100 Pa was introduced into the film formation chamber, and the source gas was adsorbed on the surface of the substrate for 10 seconds at a system pressure of 100 Pa to form a precursor thin film. (2) The unadsorbed source gas was evacuated from the system by argon purging for 15 seconds. (3) The reactive gas was introduced into the film formation chamber, and the precursor thin film was reacted with the reactive gas for 0.2 seconds at a system pressure of 100 Pa. (4) The unreacted reactive gas and by-product gas were evacuated from the system by argon purging for 60 seconds.

[0109] [Example 6] Compound No. 46 was used as a raw material for thin film formation by atomic layer deposition. Using the ALD apparatus shown in Fig. 1, a thin film was fabricated on the surface of a silicon wafer, which was the substrate, under the following conditions. When the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, it was confirmed that the thin film contained indium oxide and the residual carbon content was less than the detection limit of 0.1 atom%. Also, when the film thickness of the thin film was measured using scanning electron microscopy, the thin film formed on the silicon wafer surface was a smooth film with a thickness of 16 nm, and the film thickness obtained per cycle was approximately 0.03 nm.

[0110] (Conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 300 °C Reactive gas: Water vapor

[0111] (Process) A series of steps consisting of the following (1) to (4) was defined as one cycle, and this cycle was repeated 500 times. (1) The source gas obtained by vaporizing the raw material for thin film formation by atomic layer deposition under the conditions of a source container temperature of 50 °C and a source container internal pressure of 100 Pa was introduced into the film formation chamber, and the source gas was adsorbed onto the surface of the substrate for 10 seconds at a system pressure of 100 Pa to form a precursor thin film. (2) The unadsorbed source gas was evacuated from the system by an argon purge for 15 seconds. (3) The reactive gas was introduced into the film formation chamber, and the precursor thin film was reacted with the reactive gas for 0.2 seconds at a system pressure of 100 Pa. (4) The unreacted reactive gas and by-product gas were evacuated from the system by an argon purge for 60 seconds.

[0112] [Comparative Example 1] Comparative Compound 4 (tri(dimethylamino)gallium) was used as a raw material for forming a thin film by atomic layer deposition, and a thin film was produced on the surface of a silicon wafer as a substrate under the same conditions as in Example 4 except that the temperature of the raw material container was changed to 80°C. When the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, the thin film was a thin film containing gallium oxide, but residual carbon was detected. Further, when the state of the thin film was observed using scanning electron microscopy, the thin film formed on the surface of the silicon wafer was not smooth and the film thickness could not be measured.

[0113] From the above, it was confirmed that the raw material for forming a thin film for atomic layer deposition of the present invention exhibits excellent thermal stability and high vapor pressure. It was confirmed that a high-quality metal-containing thin film can be produced by using the raw material for forming a thin film for atomic layer deposition of the present invention.

Claims

Claim 1 A raw material for forming a thin film for atomic layer deposition, containing a compound represented by the following general formula (1). 【Chemical 1】 (In the formula, R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, L represents a group represented by the following general formula (L-1) or (L-2), and M represents an indium atom or a gallium atom. In the alkyl group, part or all of the hydrogen atoms may be substituted with fluorine atoms.) 【Chemical 2】 (wherein, R 11 and R 12 each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and * represents the bonding position with M in the general formula (1). In the alkyl group, part or all of the hydrogen atoms may be substituted with fluorine atoms.) 【Chemical 3】 (In the formula, R 21 to R 23 each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms, and * represents the bonding position with M in the general formula (1). However, R 21 and R 22 are different groups. In the alkyl group, part or all of the hydrogen atoms may be substituted with fluorine atoms.) Claim 2 R 1 and R 2 The raw material for thin film formation for atomic layer deposition according to claim 1, wherein Claim 3 A method for manufacturing a thin film containing indium atoms or gallium atoms on the surface of a substrate, comprising: a step of adsorbing the compound in the source gas obtained by vaporizing the raw material for forming a thin film for atomic layer deposition according to Claim 1 or 2 on the surface of the substrate to form a precursor thin film; a step of reacting the precursor thin film with a reactive gas to form a thin film containing indium atoms or gallium atoms on the surface of the substrate A method for manufacturing a thin film including these steps. Claim 4 The method for manufacturing a thin film according to Claim 3, wherein the reactive gas is an oxidizing gas, and the thin film is an indium oxide thin film or a gallium oxide thin film. Claim 5 The method for manufacturing a thin film according to Claim 4, wherein the oxidizing gas is a gas containing oxygen, ozone, or water vapor. Claim 6 The method for manufacturing a thin film according to Claim 4 or 5, wherein the precursor thin film is reacted with the reactive gas in the range of 100°C to 400°C.

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