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

Abstract

Provided is a zinc compound represented by general formula (1) or (2). (In formula (1), R1 represents an unsubstituted C1-5 alkyl group or the like, R2 and R5 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted C1-5 alkyl group, or the like, and R3 and R4 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted C1-5 alkyl group, or the like.) (In formula (2), R10, R11, R14, and R15 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted C1-5 alkyl group, or the like, and R9, R12, R13, and R16 each independently represent a hydrogen atom, a fluorine atom, an unsubstituted C1-5 alkyl group, or the like.)

Description

Technical Field

[0001] The present invention relates to a zinc compound having a specific structure, a raw material for forming a thin film containing the zinc compound, a thin film obtained by using the raw material for forming a thin film, and a method for producing the same.

Background Art

[0002] A raw material for forming a thin film containing a zinc compound exhibits specific electrical properties, and in particular, its application to optoelectronic engineering uses such as semiconductor elements, solar cells, and LEDs is being promoted.

[0003] As methods for manufacturing thin films, there are sputtering methods, ion plating methods, metal organic compound decomposition (MOD) methods such as coating pyrolysis methods and sol-gel methods, chemical vapor deposition (CVD) methods, atomic layer deposition (ALD) methods, and the like. Among these, CVD methods and ALD methods are mainly used because the quality of the obtained thin films is good.

[0004] CVD methods and ALD methods are thin film formation technologies by chemical vapor deposition. In particular, the ALD method can grow the material supplied by the precursor on the surface of a substrate with various compositions to control the atomic layer on the thin film surface, so that it is possible to form a thin film with a fine shape. Since electronic material devices such as nanotechnology, capacitor electrodes, gate electrodes, and integrated circuits are constantly being developed for miniaturization, the need for the ALD method is increasing. The raw material for forming a thin film used in the ALD method is required to have a high vapor pressure and excellent thermal stability, and to be able to form a high-quality thin film. Note that a high-quality thin film means that the amount of residual carbon in the film is small.

[0005] As a zinc compound used as a raw material for film formation, for example, diethylzinc is known to have a thick film thickness that can be formed per cycle (~0.18 nm / cycle). Patent Document 1 discloses forming a zinc oxide thin film using zinc acetylacetonate by the MOCVD method. Patent Document 2 discloses a bis(β-diketonato)zinc compound. Non-Patent Document 1 describes that a zinc ketimine compound exhibits excellent vapor properties in the temperature range of 170°C to 270°C.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Non-Patent Documents

[0007]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0008] However, since diethylzinc has poor thermal stability, the quality of the obtained thin film was not satisfactory. The zinc compounds described in Patent Document 1 and Patent Document 2 have poor reactivity between the precursor thin film derived from the compound and the reactive gas, so the quality of the obtained thin film was not necessarily satisfactory. In addition, the zinc ketimine compound described in Non-Patent Document 1 has a problem that the temperature at which it becomes vapor is high.

[0009] Accordingly, an object of the present invention is to provide a zinc compound that can be vaporized at a low temperature, has excellent thermal stability, and can produce a high-quality thin film when used as a raw material for thin film formation. Another object of the present invention is to provide a raw material for thin film formation containing the zinc compound, a thin film obtained by using the raw material for thin film formation, and a method for producing the same.

Means for Solving the Problems

[0010] As a result of intensive studies, the present inventors have found that a zinc compound having a specific structure can solve the above problems, and have completed the present invention. That is, the present invention is a zinc compound represented by the following general formula (1) or (2).

[0011]

Chemical formula

[0012] In formula (1), R 1 represents 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 substituted with fluorine atoms, and R 2 and R 5 each independently represent 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 in which some or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with -OR 6 or an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with -NR 7 R 8 and R 3 and R 4 each independently represent 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 substituted with fluorine atoms, and R 6 , R 7 and R 8Each independently represents an unsubstituted alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms.

[0013]

Chemical formula

[0014] In formula (2), R 10 , R 11 , R 14 and R 15 each 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 in which part or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with -OR 17 , or an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with -NR 18 R 19 . R 9 , R 12 , R 13 and R 16 each 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 part or all of the hydrogen atoms are substituted with fluorine atoms, and R 17 , R 18 and R 19 each independently represents an unsubstituted alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms.

[0015] The present invention is a raw material for forming a thin film containing the above zinc compound.

[0016] The present invention is a thin film obtained by using the above raw material for forming a thin film.

[0017] The present invention includes a step of introducing a source gas obtained by vaporizing the above-described raw material for thin film formation into a film formation chamber in which a substrate is installed, and a step of decomposing and / or chemically reacting a zinc compound in the source 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.

Advantages of the Invention

[0018] According to the present invention, it is possible to provide a zinc compound that can be vaporized at a low temperature, has excellent thermal stability, and can produce a high-quality thin film when used as a raw material for thin film formation. Further, according to the present invention, a high-quality zinc-containing thin film can be formed by the CVD method, particularly the ALD method.

Brief Description of the Drawings

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Figure 1

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Embodiments for Carrying Out the Invention

[0020] The zinc compound of the present invention is represented by the above general formula (1) or (2).

[0021] In the above general formula (1), R 1 ~R 8Examples of the unsubstituted 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. R 1 ~R 8 A zinc compound in which at least one of is an alkyl group having 1 to 4 carbon atoms is preferable, and R 1 ~R 8 A zinc compound in which at least one of is a methyl group, an ethyl group, an isopropyl group, a sec-butyl group or a tert-butyl group is more preferable.

[0022] In the above general formula (1), R 1 ~R 8 Examples of the alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms represented by 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. R 1 ~R 8 A zinc compound in which at least one of is an alkyl group having 1 to 3 carbon atoms in which some or all of the hydrogen atoms are substituted with fluorine atoms is preferable, and R 1 ~R 8 A zinc compound in which at least one of is a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group or a pentafluoroethyl group is more preferable.

[0023] In the above general formula (1), R 2 and R 5 Some or all of the hydrogen atoms represented by are -OR 6Examples of the alkyl group having 1 to 5 carbon atoms replaced by [alkyl group] include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, an ethoxyethyl group, an isopropoxyethyl group, an ethoxypropyl group, a methoxybutyl group, a fluoromethoxymethyl group, a difluoromethoxymethyl group, a trifluoromethoxymethyl group, a trifluoromethoxyethyl group, a trifluoromethoxypropyl group, etc. R 2 and R 5 A zinc compound in which at least one of them is a methoxymethyl group, a methoxyethyl group, an isopropoxyethyl group or a trifluoromethoxymethyl group is preferable.

[0024] In the above general formula (1), a part or all of the hydrogen atoms represented by R 2 and R 5 are replaced by -NR 7 R 8 Examples of the alkyl group having 1 to 5 carbon atoms include a dimethylaminomethyl group, a diethylaminomethyl group, a methylpropylaminomethyl group, a dimethylaminoethyl group, an ethylmethylaminomethyl group, an ethylmethylaminoethyl group, etc. R 2 and R 5 A zinc compound in which at least one of them is a dimethylaminomethyl group, a dimethylaminoethyl group or an ethylmethylaminomethyl group is preferable.

[0025] In the above general formula (2), examples of the unsubstituted alkyl group having 1 to 5 carbon atoms represented by R 9 ~R 19 are the same as those exemplified for R 1 ~R 8 in the above general formula (1). R 9 ~R 19 A zinc compound in which at least one of them is an alkyl group having 1 to 4 carbon atoms is preferable, and a zinc compound in which at least one of R 9 ~R 19 is a methyl group, an ethyl group, an isopropyl group, a sec-butyl group or a tert-butyl group is more preferable.

[0026] In the above general formula (2), R 9 ~R19 Examples of the alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms, represented by R in the general formula (1) 1 ~R 8 are the same as those exemplified above. Zinc compounds in which at least one of R 9 ~R 19 is an alkyl group having 1 to 3 carbon atoms in which some or all of the hydrogen atoms are replaced by fluorine atoms are preferred, and zinc compounds in which at least one of R 9 ~R 19 is a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group or a pentafluoroethyl group are more preferred.

[0027] In the general formula (2), examples of the alkyl group having 1 to 5 carbon atoms substituted with -OR 10 represented by R 11 , R 14 and R 15 are the same as those exemplified by -OR 17 in the general formula (1). Zinc compounds in which at least one of R 6 is a methoxymethyl group, a methoxyethyl group, an isopropoxyethyl group or a trifluoromethoxymethyl group are preferred. 10 , R 11 , R 14 and R 15 In the general formula (2), examples of the alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by -NR

[0028] represented by R 10 , R 11 and R 14 are the same as those exemplified by -NR 15 in the general formula (1). Zinc compounds in which at least one of R 18 R 19 is a dimethylaminomethyl group, a dimethylaminoethyl group or an ethylmethylaminomethyl group are preferred. 7 R 8 Examples of the alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by -NR 10 represented by R 11 and R 14 are the same as those exemplified above. Zinc compounds in which at least one of R 15 is a dimethylaminomethyl group, a dimethylaminoethyl group or an ethylmethylaminomethyl group are preferred.

[0029] The zinc compound of the present invention can be produced by using a well-known method. For example, in the above general formula (1), R 1 , R 2 and R 5 are ethyl groups and R 3 and R 4 are methyl groups. The zinc compound can be obtained by reacting diethylzinc with a dialkyldiketimine compound in a solvent, then removing the solvent and purifying by distillation. In the above general formula (1), the zinc compound in which R 1 is an ethyl group is preferable because it has a low melting point and a high vapor pressure, and thus a zinc-containing thin film can be formed with good productivity. Further, in the above general formula (2), R 9 , R 12 , R 13 and R 16 are methyl groups and R 10 , R 11 , R 14 and R 15 are ethyl groups. The zinc compound can be obtained by reacting diethylzinc with two equivalents of a dialkyldiketimine compound in a solvent, then removing the solvent and purifying by distillation. In the above general formula (2), the zinc compound in which two or more of R 9 , R 12 , R 13 and R 16 have a trifluoromethyl group is preferable because it has a low melting point and a high vapor pressure, and thus a zinc-containing thin film can be formed with good productivity.

[0030] Preferable specific examples of the zinc compounds represented by the above general formulas (1) and (2) include the following No.1 to No.68, but the present invention is not limited to these zinc compounds. In the following Compounds No.1 to No.68, "Me" represents a methyl group, "Et" represents an ethyl group, "iPr" represents an isopropyl group, "sBu" represents a sec-butyl group, "tBu" represents a tert-butyl group, and "CF3" represents a trifluoromethyl group.

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[0047] [Chemistry]

[0048] The zinc compound of the present invention can be suitably used as a precursor for thin films by CVD method or ALD method because it has the following physical properties.

[0049] From the viewpoint of handleability, the zinc compound of the present invention is preferably liquid at room temperature.

[0050] When the zinc compound of the present invention is heated from room temperature to 400 °C at a heating rate of 10 °C / min using a differential scanning calorimeter (DSC), and the temperature at which the exothermic reaction reaches the peak top is defined as the thermal decomposition start temperature (°C), the higher the thermal decomposition start temperature, the better the heat resistance of the compound of the present invention, which is preferable. The preferable thermal decomposition start temperature is 250 °C or higher, and more preferably 300 °C or higher.

[0051] The zinc compound of the present invention was heated from room temperature under the conditions of 10 Torr and a heating rate of 10 °C / min using a thermogravimetric differential thermal analyzer (TG-DTA). In the obtained DTA chart, the temperature at which the mass of the test compound decreased by 50% by mass is defined as the temperature (°C) at the time of 50% by mass decrease in TG-DTA. The lower the temperature at the time of 50% by mass decrease in TG-DTA, the more preferable it is because the zinc compound can be made into vapor at a lower temperature. The temperature at the time of 50% by mass decrease in TG-DTA is preferably 180 °C or lower, and more preferably 160 °C or lower.

[0052] Next, the raw material for thin film formation of the present invention will be described. The raw material for thin film formation of the present invention may contain a zinc compound represented by the above general formula (1) or (2), and its composition varies depending on the type of the target thin film. For example, when producing a thin film containing only zinc as a metal, the raw material for thin film formation of the present invention does not contain compounds of metals other than zinc and metalloid compounds. On the other hand, when producing a thin film containing a plurality of metals and / or metalloids, the raw material for thin film formation of the present invention may contain, in addition to the zinc compound represented by the above general formula (1) or (2), 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 of the present invention may further contain an organic solvent and / or a nucleophilic reagent.

[0053] The form of the raw material for thin film formation of the present invention is appropriately selected by a method such as a transport supply method of a chemical vapor deposition method such as the CVD method or ALD method used.

[0054] As the above-described transportation and supply method, the raw material for thin film formation by the atomic layer deposition method of the present invention is vaporized by heating and / or reducing the pressure in a container in which the raw material is stored (hereinafter, may be simply referred to as "raw material container"), and used as a raw material gas together with a carrier gas such as argon, nitrogen, helium, etc. as required, and 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"). There is a gas transportation method, a liquid transportation method in which the raw material for thin film formation of the present invention is transported to a vaporization chamber in a liquid or solution state, vaporized by heating and / or reducing the pressure in the vaporization chamber, and used as a raw material gas, and the raw material gas is introduced into the film formation chamber. In the case of the gas transportation method, the zinc compound itself 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 transportation method, the zinc compound itself represented by the above general formula (1) or (2) or a solution in which the zinc compound is 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.

[0055] Also, in the case of a multi-component chemical vapor deposition method, there are a method of vaporizing and supplying the raw material for thin film formation independently for each component (hereinafter, referred to as "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, referred to as "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) and another precursor or a mixed solution in which the mixture is dissolved in an organic solvent can be used as the raw material for thin film formation. These raw materials for thin film formation may further contain a nucleophilic reagent or the like.

[0056] As the above-mentioned organic solvent, there is no particular limitation, and well-known general organic solvents can be used. Examples of the organic solvent 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 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 and the boiling point and flash point.

[0057] In the raw material for thin film formation of the present invention, when the above-mentioned organic solvent is used, it is preferable that the total amount of the precursor in the raw material for thin film formation, 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 zinc compound represented by the above general formula (1) or (2) when the raw material for thin film formation of the present invention does not contain other precursors in addition to the zinc compound represented by the above general formula (1) or (2), and when the raw material for thin film formation of the present invention contains other precursors in addition to the zinc compound represented by the above general formula (1) or (2), it is the total amount of the zinc compound represented by the above general formula (1) or (2) and other precursors.

[0058] In the case of a multi-component chemical vapor deposition method, there are no particular restrictions on the other precursor used together with the zinc compound represented by the general formula (1) or (2), and well-known general precursors used as raw materials for thin film formation can be used.

[0059] Examples of the other precursor 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. Further, examples of the metal species of the precursor 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.

[0060] Examples of the alcohol compounds used as the organic ligand of the other precursor 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.

[0061] Examples of the glycol compounds used as the organic ligand of the other precursor 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.

[0062] Examples of the β-diketone compounds used as the organic ligand of the above 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, and the like.

[0063] Examples of the cyclopentadiene compound used as the organic ligand of the other precursor described above include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, etc. Examples of the organic amine compound used as the organic ligand described above include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, etc.

[0064] Examples of the organic amine compound used as the organic ligand of the other precursor described above include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, etc.

[0065] The other precursors described above are known in the art, and their production methods are also known. For example, when an alcohol compound is used as the organic ligand, the precursor can be produced by reacting the metal inorganic salt or its hydrate described above with the alkali metal alkoxide of the alcohol compound. Here, examples of the metal inorganic salt or its hydrate include metal halides, nitrates, etc. Examples of the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, potassium alkoxide, etc.

[0066] In the case of the single-source method, as the other precursors described above, compounds whose thermal and / or oxidative decomposition behavior is similar to that of the zinc compound represented by the above general formula (1) or (2) are preferable. In the case of the cocktail-source method, as the other precursors described above, in addition to the thermal and / or oxidative decomposition behavior being similar to that of the zinc compound represented by the above general formula (1) or (2), compounds that do not cause alteration due to chemical reactions or the like during mixing are preferable.

[0067] Further, the raw material for thin film formation of the present invention may contain a nucleophilic reagent, if necessary, in order to improve the stability of the zinc compound represented by the above general formula (1) or (2) 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 to 4 mol, per 1 mol of the total amount of the precursors.

[0068] For the raw material for thin film formation of the present invention, it is desirable to minimize the content of impurity metal element components other than the components constituting the raw material, impurity halogen components such as impurity chlorine, and impurity organic components. For the impurity metal element components, it is preferably 100 ppb or less, more preferably 10 ppb or less for each element, and preferably 1 ppm or less, more preferably 100 ppb or less in total. 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. 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 impurity organic content is preferably 500 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less in total. Also, since moisture causes particle generation during CVD raw materials and during thin film formation, for precursors, organic solvents, and nucleophilic reagents, it is better to remove as much moisture as possible in advance during use to reduce the moisture content of each. 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.

[0069] In addition, for the raw material for thin film formation of the present invention, in order to reduce or prevent particle contamination of the formed thin film, it is preferable to minimize the inclusion of particles. 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, and the number of particles larger than 0.2 μm is more preferably 100 or less in 1 ml of the liquid phase.

[0070] The method for manufacturing a thin film using the raw material for thin film formation of the present invention is not limited, and examples include sputtering methods, ion plating methods, MOD methods such as coating pyrolysis methods and sol-gel methods, CVD methods, etc. Among these, the atomic layer deposition method (sometimes referred to as the ALD method) is preferred because it has many advantages such as excellent composition controllability and step coverage, suitability for mass production, and the ability to perform hybrid integration.

[0071] Next, a method for manufacturing the thin film of the present invention will be described. The method for manufacturing the thin film of the present invention includes a step of introducing a source gas obtained by vaporizing the above-described raw material for thin film formation into a film formation chamber in which a substrate is installed, and a step of decomposing and / or chemically reacting a zinc compound in the source gas to form a thin film containing zinc atoms on the surface of the substrate.

[0072] The step of vaporizing the raw material for thin film formation of the present invention to obtain a source gas may be performed in a raw material container or in a vaporization chamber. In either case, the raw material for thin film formation of the present invention is preferably vaporized at 0°C to 200°C. Further, when the raw material for thin film formation is vaporized in the raw material container or in the vaporization chamber to obtain a source 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.

[0073] Examples of the method of introducing the source gas obtained by vaporizing the above-described raw material for thin film formation into a film formation chamber in which a substrate is installed include the gas transport method, liquid transport method, single source method, cocktail source method, etc. described above.

[0074] As a method for decomposing and / or chemically reacting the zinc compound in the source gas, a reactive gas may be introduced into the film formation chamber. 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. Among these, since the raw material for thin film formation of the present invention reacts well specifically with oxidizing gases such as 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. In terms of being able to produce a high-quality thin film with a small amount of residual carbon with high productivity, it is preferable to use a gas containing water vapor as the reactive gas.

[0075] As an embodiment of the method for manufacturing a thin film of the present invention, taking the case of forming a zinc-containing thin film by ALD method using the raw material for thin film formation of the present invention as an example, it will be described in detail. This manufacturing method includes a step of introducing a raw material gas obtained by vaporizing the raw material for thin film formation of the present invention into a film formation chamber (processing atmosphere) (raw material gas introduction step), a step of adsorbing a zinc compound in the raw material gas on 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 zinc-containing thin film on the surface of the substrate (zinc-containing thin film formation step). Further, between the precursor thin film formation step and the zinc-containing thin film formation step, and after the zinc-containing thin film formation step, there is a step of exhausting the gas in the film formation chamber (processing atmosphere) (exhausting step). This manufacturing method performs the raw material gas introduction step, the precursor thin film formation step, the exhausting step, the zinc-containing thin film formation step, and the exhausting step in order as one cycle, and by repeating this cycle, the thickness of the zinc-containing thin film can be adjusted. Hereinafter, each step of the method for manufacturing a thin film of the present invention will be described.

[0076] (Raw material gas introduction step) The raw material gas introduction step is a step of vaporizing the raw material for thin film formation of the present invention to obtain a raw material gas and introducing the raw material gas into a film formation chamber where a substrate is installed. The step of vaporizing the raw material for thin film formation of the present invention to obtain a raw material gas may be performed in a raw material container or in a vaporization chamber. In any case, the raw material for thin film formation of the present invention is preferably vaporized at 0°C to 200°C. Further, when the raw material for thin film formation is vaporized in the raw material container or in 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.

[0077] As a method for transporting and supplying the raw material for thin film formation, as shown in FIGS. 1 and 3, the raw material for thin film formation 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 where a substrate is installed. This is a gas transport method. As shown in FIGS. 2 and 4, there is also a liquid transport method in which the raw material for thin film formation 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 zinc compound itself 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 itself represented by the above general formula (1) or general formula (2) or a solution in which the zinc compound is 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 a nucleophilic reagent or the like.

[0078] 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-described single source method and cocktail source method can be used. However, in any case of the introduction method used, the raw material for thin film formation of the present invention is preferably vaporized at 0°C to 200°C. Further, the step of vaporizing the raw material for thin film formation to obtain a raw material gas may be performed in the raw material container or in the 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 10,000 Pa.

[0079] 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 a flat surface or may have a three-dimensional structure such as a trench structure.

[0080] (Precursor thin film formation step) In the precursor thin film formation step, a zinc compound represented by the general formula (1) or general formula (2) 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, and for example, the reaction temperature (substrate temperature), reaction pressure, deposition rate, etc. can be appropriately determined according to the type and thickness of the thin film. The reaction temperature is preferably 100°C or higher, more preferably 150°C to 400°C, which is the temperature at which the raw material for thin film formation of the present invention reacts sufficiently.

[0081] In addition, the above deposition rate can be controlled by the supply conditions (vaporization temperature, vaporization pressure) of the raw material for thin film formation, reaction temperature, and reaction pressure. If the deposition rate is large, the characteristics of the obtained thin film may deteriorate, and if the deposition rate is small, 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.

[0082] (Exhaust step) 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, more preferably in the range of 0.01 Pa to 100 Pa.

[0083] (Zinc-containing thin film formation step) In the zinc-containing thin film forming process, after the evacuation process, a reactive gas is introduced into the film forming chamber, and a zinc-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 zinc oxide thin film is formed. In this process, when heat is used for the action, the temperature range of room temperature to 500 °C is preferable, and the range of 100 °C to 400 °C is more preferable. The pressure of the system (inside the film forming chamber) when this process is performed is preferably 1 Pa to 10,000 Pa, and more preferably 10 Pa to 1,000 Pa. Since the raw material for thin film formation of the present invention has good reactivity with an oxidizing gas such as water vapor, a high-quality zinc-containing thin film with a small amount of residual carbon can be produced with good productivity.

[0084] 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. Among these, since the raw material for thin film formation of the present invention reacts well with oxidizing gases such as 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. In terms of the film thickness obtained per cycle being thick and the ability to produce a thin film with good productivity, the reactive gas is preferably a gas containing ozone or water vapor, and more preferably a gas containing water vapor.

[0085] (Evacuation process) After the formation of the zinc-containing thin film, the unreacted reactive gas and by-product gas are evacuated from the film forming chamber. At this time, it is ideal for the reactive gas and by-product gas to be completely evacuated from the film forming chamber, but it is not necessarily required to be completely evacuated. The evacuation method and the degree of pressure reduction when reducing the pressure are the same as those in the evacuation process after the above-mentioned precursor thin film forming process.

[0086] As described above, the raw material gas introduction step, the precursor thin film formation step, the exhaust step, the zinc-containing thin film formation step, and the exhaust step are performed 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 a required film thickness is obtained, a zinc-containing thin film with a desired film thickness is manufactured. In the method for manufacturing a thin film using the ALD method, the film thickness of the formed zinc-containing thin film can be controlled by the number of the above cycles.

[0087] In addition, 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 the raw material gas in the raw material gas introduction step, when heating in the precursor thin film formation step or the zinc-containing thin film formation step, when exhausting the system in the exhaust step, when introducing the reactive gas in the zinc-containing thin film formation step, or between any of the above steps.

[0088] When performing plasma treatment in the method for manufacturing a thin film of the present invention, if the output is too large, the damage to the substrate is significant. Therefore, 0 to 1,500 W is preferable, and 50 to 600 W is more preferable.

[0089] In addition, in the method for manufacturing a thin film of the present invention, after the thin film is formed, 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.

[0090] For the apparatus for manufacturing a thin film using the raw material for thin film formation 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. In addition, an apparatus capable of performing plasma treatment on the 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.

[0091] The thin film produced using the raw material for thin film formation of the present invention can coat substrates such as metals, oxide ceramics, nitride ceramics, and glass by appropriately selecting other precursors, reactive gases, and manufacturing conditions to form a thin film of a desired type. Since the thin film of the present invention is excellent in electrical and optical properties, 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.

[0092] Hereinafter, the present invention will be described in more detail using examples and the like. However, the present invention is not limited by the following examples and the like.

[0093] [Example 1] Synthesis of Compound No. 27 To 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, and 1.38 g (6.58 mmol) of N,N-di-sec-butylpentane-2,4-diamine was added dropwise under ice cooling, followed by stirring at room temperature for 17 hours. Under slightly reduced pressure, the solvent was distilled off at an oil bath temperature of 100 °C, and then the brown transparent liquid remaining in the flask was purified by distillation under reduced pressure (20 - 30 Pa) to obtain 1.37 g (4.51 mmol, yield 68%) of an orange transparent liquid as the distillate. The obtained orange transparent liquid 1 As a result of analysis by 1H-NMR and ICP-AES, it was confirmed that it was Compound No. 27 of the target compound. The analysis results of the obtained orange transparent liquid are shown below.

[0094] (1) 1 1H-NMR (deuterated benzene) 0.68 - 0.81 (m, 8H), 1.15 (d, J = 6.4 Hz, 6H), 1.48 - 1.65 (m, 7H), 1.80 (s, 6H), 3.33 - 3.41 (m, 2H), 4.49 (s, 1H)

[0095] (2) Elemental analysis results by ICP-AES Zn: 21.52 mass% (theoretical value: 21.52 mass%), C: 59.33 mass% (theoretical value: 59.30 mass%), H: 9.98 mass% (theoretical value: 9.95 mass%), N: 9.17 mass% (theoretical value: 9.23 mass%)

[0096] 〔Example 2〕Synthesis of Compound No. 49 To 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. 1.60 g (12.7 mmol) of N,N-dimethylpentane-2,4-diimine was added under ice-cooling, and the mixture was stirred at room temperature for 17 hours. Under slightly reduced pressure, the solvent was distilled off at an oil bath temperature of 100 °C. Then, the brown transparent liquid remaining in the flask was purified by distillation under reduced pressure (20 - 30 Pa), and 1.80 g (5.70 mmol, yield 90%) of an orange transparent liquid was obtained as the distillate. The obtained orange transparent liquid 1 As a result of analysis by \(^1H-NMR\) and ICP-AES, it was confirmed that it was Compound No. 49 of the target compound. The analysis results of the obtained orange transparent liquid are shown below.

[0097] (1) 1 \(^1H-NMR\) (benzene-d6) 1.81 (s, 12H), 2.97 (s, 12H), 4.54 (s, 2H)

[0098] (2) Results of elemental analysis by ICP-AES Zn: 20.66 mass% (theoretical value: 20.70 mass%), C: 53.28 mass% (theoretical value: 53.25 mass%), H: 8.32 mass% (theoretical value: 8.31 mass%), N: 17.74 mass% (theoretical value: 17.74 mass%)

[0099] 〔Example 3〕Synthesis of Compound No. 59 Add 4.17 ml of a 1 mol / L diethylzinc toluene solution (4.17 mmol as diethylzinc) and 25 ml of dehydrated toluene to a 100 ml three-necked flask. Add 1.74 g (8.34 mmol) of N,N-diethyl-1,1,1-trifluoropentane-2,4-diimine under ice cooling, and stir at room temperature for 17 hours. Under slightly reduced pressure, distill off the solvent at 100 °C in an oil bath. Then, purify the brown transparent liquid remaining in the flask by distillation under reduced pressure (20 - 30 Pa) to obtain 1.81 g (3.77 mmol, yield 90%) of an orange transparent liquid as the distillate. The obtained orange transparent liquid 1 As a result of analysis by 1H-NMR and ICP-AES, it was confirmed that it is Compound No. 59 of the target compound. The analysis results of the obtained orange transparent liquid are shown below.

[0100] (1) 1 1H-NMR (benzene-d6) 0.91 (t, J = 7.2 Hz, 6H), 1.10 (t, J = 7.2 Hz, 6H), 1.54 (s, 6H), 2.93 - 3.08 (m, 4H), 3.47 - 3.60 (m, 4H), 5.01 (s, 2H)

[0101] (2) Elemental analysis results by ICP-AES Zn: 13.60 mass% (theoretical value: 13.63 mass%), C: 45.07 mass% (theoretical value: 45.06 mass%), H: 5.93 mass% (theoretical value: 5.88 mass%), N: 11.62 mass% (theoretical value: 11.67 mass%), F: 23.78 mass% (theoretical value: 23.76 mass%)

[0102] Using the compound No. 27 obtained in Example 1, the compound No. 49 obtained in Example 2, the compound No. 59 obtained in Example 3, and diethylzinc as Comparative Compound 1, the following evaluations were carried out.

[0103] (1) Melting point evaluation Visually observe the state of the compound at 25 °C under normal pressure, and for solid compounds, measure the melting point using a micro melting point measuring device. The results are shown in Table 1.

[0104] (2) Thermal decomposition start temperature (°C) Using a differential scanning calorimeter (DSC), in the DSC chart measured with a heating rate of 10 °C / min and a scanning temperature range of 30 to 500 °C, the temperature at which the exothermic reaction reaches the peak top was defined as the "thermal decomposition start temperature (°C)". The results are shown in Table 1.

[0105] (3) Temperature (°C) at 50% mass reduction in vacuum TG-DTA Using TG-DTA, measured at 10 Torr, argon flow rate: 50 mL / min, heating rate of 10 °C / min, and scanning temperature range of 30 to 600 °C, the temperature (°C) when the mass of the test compound decreased by 50% was evaluated as the "temperature (°C) at 50% mass reduction in vacuum TG-DTA". The lower the temperature (°C) at 50% mass reduction in vacuum TG-DTA, the more steam can be obtained at a lower temperature. The results are shown in Table 1.

[0106]

Table 1

[0107] From the above results, it was confirmed that Compound No. 27, Compound No. 49, and Compound No. 59 have a thermal decomposition start temperature in the range of 300 °C to 400 °C and are excellent in thermal stability. Also, for Compound No. 27, Compound No. 49, and Compound No. 59, the temperature at 50% mass reduction in vacuum TG-DTA was less than 160 °C for all of them, and it was confirmed that steam can be obtained at a low temperature. From these results, it was confirmed that the zinc compound of the present invention is useful as a raw material for thin film formation. In contrast, Comparative Compound 1 was not satisfactory as a raw material for thin film formation because of its poor thermal stability.

[0108] Next, the thin film produced using the zinc compound of the present invention as a raw material for thin film formation was evaluated.

[0109] 〔Example 4〕 Using Compound No. 27 as a raw material for thin film formation, a thin film was fabricated on silicon dioxide as the substrate using the ALD apparatus shown in Fig. 1 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 zinc oxide and that the residual carbon content was less than the detection limit of 0.01 atom%. Also, when the film thickness of the thin film was measured using X-ray reflectometry, the thin film formed on the substrate was a smooth film with a thickness of 15 nm, and the film thickness obtained per cycle was approximately 0.03 nm.

[0110] (Conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 200 °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 raw material gas obtained by vaporizing the raw material for thin film formation under the conditions of a raw material container temperature of 60 °C and a raw material container internal pressure of 100 Pa was introduced into the film formation chamber, and the raw material 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 raw material 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.

[0112] [Example 5] Using Compound No. 49 as a raw material for thin film formation and the ALD apparatus shown in Fig. 1, a thin film was fabricated on silicon dioxide, which is 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 contains zinc oxide and the residual carbon content is less than the detection limit of 0.01 atom%. Also, when the film thickness of the thin film was measured using X-ray reflectivity method, the thin film formed on the substrate was a smooth film with a film thickness of 17 nm, and the film thickness obtained per cycle was approximately 0.03 nm.

[0113] (Conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 350 °C Reactive gas: Ozone

[0114] (Steps) A series of steps consisting of the following (1) to (4) was defined as one cycle and repeated 500 times. (1) The raw material gas obtained by vaporizing the raw material for thin film formation under the conditions of a raw material container temperature of 60 °C and a raw material container internal pressure of 100 Pa 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 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 and the reactive gas were reacted for 20 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 30 seconds.

[0115] 〔Example 6〕 Using Compound No. 59 as a raw material for thin film formation and the ALD apparatus shown in Fig. 1, a thin film was produced on silicon dioxide, which is 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 contained zinc oxide and the residual carbon content was less than the detection limit of 0.01 atom%. Also, when the film thickness of the thin film was measured using X-ray reflectivity method, the thin film formed on the substrate was a smooth film with a film thickness of 20 nm, and the film thickness obtained per cycle was about 0.04 nm.

[0116] (Conditions) Manufacturing method: ALD method Reaction temperature (substrate temperature): 350 °C Reactive gas: Ozone

[0117] (Steps) A series of steps consisting of the following (1) to (4) was repeated 500 cycles as one cycle. (1) Under the conditions of a raw material container temperature of 60 °C and a pressure inside the raw material container of 100 Pa, the raw material gas obtained by vaporizing the raw material for thin film formation 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 was reacted with the reactive gas for 20 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 30 seconds.

[0118] [Comparative Example 1] A thin film was produced on silicon dioxide, which is a substrate, under the same conditions as in Example 4 except that Comparative Compound 1 (diethylzinc) was used as the raw material for thin film formation. When the composition of the thin film was analyzed using X-ray electron spectroscopy, the thin film contained zinc oxide, but residual carbon was detected. Also, when the state of the thin film was observed using scanning electron microscopy, the thin film formed on the substrate was not smooth and the film thickness could not be measured.

[0119] From the above, it was confirmed that the zinc compound of the present invention can be vaporized at a low temperature and has excellent thermal stability. Further, it was confirmed that a high-quality zinc-containing thin film can be produced by using the raw material for thin film formation containing the zinc compound of the present invention.

Claims

1. A zinc compound represented by the following general formula (1), (2), or Compound No.

51. 【Chemical 1】 (In formula (1), R １ represents an unsubstituted alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms, and R ２ and R ５ each independently represent 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 in which part or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with -OR ６ , or an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with -NR ７ R ８ . R ３ and R ４ each independently represent 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 part or all of the hydrogen atoms are substituted with fluorine atoms. R ６ , R ７ and R ８ each independently represent an unsubstituted alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms.) [Chemical 2] (In formula (2), R １０ , R １１ , R １４ and R １５ each 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 in which some or all of the hydrogen atoms are substituted with fluorine atoms, an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with -OR １７ , or an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are substituted with -NR １８ R １９ . R ９ , R １２ , R １３ and R １６ each 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 substituted with fluorine atoms, provided that two or more of R9, R12, R13 and R16 represent a trifluoromethyl group, and R １７ , R １８ and R １９ each independently represents 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 substituted with fluorine atoms.). 【Chemical Formula 3】

2. A raw material for thin film formation containing the zinc compound according to Claim 1.

3. A thin film formed using the raw material for thin film formation according to Claim 2.

4. A method for producing a thin film containing zinc atoms by chemical vapor deposition using the zinc compound according to Claim 1 as a precursor.

5. A step of introducing a source gas obtained by vaporizing the raw material for thin film formation according to Claim 2 into a film-forming chamber where a substrate is installed; A step of decomposing and / or chemically reacting the zinc compound in the source gas to form a thin film containing zinc atoms on the surface of the substrate A method for producing a thin film including the above steps.

6. A step of adsorbing the zinc compound in the source gas 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 zinc atoms on the surface of the substrate A method for producing a thin film according to Claim 5 including the above steps.

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

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

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

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