WO2017030150A1 - Procédé de fabrication d'un film d'oxyde d'aluminium, matériau pour la fabrication de film d'oxyde d'aluminium et composé d'aluminium - Google Patents

Procédé de fabrication d'un film d'oxyde d'aluminium, matériau pour la fabrication de film d'oxyde d'aluminium et composé d'aluminium Download PDF

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WO2017030150A1
WO2017030150A1 PCT/JP2016/074032 JP2016074032W WO2017030150A1 WO 2017030150 A1 WO2017030150 A1 WO 2017030150A1 JP 2016074032 W JP2016074032 W JP 2016074032W WO 2017030150 A1 WO2017030150 A1 WO 2017030150A1
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aluminum oxide
oxide film
aluminum
compound
amidinato
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PCT/JP2016/074032
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English (en)
Japanese (ja)
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白井　昌志
央 二瓶
貴匡 宮崎
純一 向
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宇部興産株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/06—Aluminium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides

Definitions

  • the present disclosure relates to a method for manufacturing an aluminum oxide film, a raw material for manufacturing an aluminum oxide film, and an aluminum compound.
  • the aluminum oxide film is useful as a gate insulating film and has been widely applied in the semiconductor field. Therefore, an aluminum compound (a raw material for producing an aluminum oxide film) for producing an aluminum oxide film has been studied (see, for example, Patent Documents 1 to 4).
  • Non-Patent Document 1 discloses (ditertiary butyl (methyl) amidinato) dimethylaluminum as a polymerization catalyst. However, no physical property values and characteristics are described.
  • Non-Patent Document 2 discloses a synthesis example of (ditertiary butyl (ethyl) amidinato) diethylaluminum. However, no properties are described.
  • JP 2006-526705 A Japanese Patent No. 4716193 JP 2007-138296 A Korean Registered Patent No. 10-121861
  • a method for manufacturing an aluminum oxide film that can stably manufacture an aluminum oxide film with reduced thickness variation is provided. Moreover, in another side, the manufacturing raw material used suitably for the said manufacturing method and an aluminum compound are provided.
  • the present invention supplies an aluminum compound represented by the following formula (1) onto a heated film formation target, and oxidizes the aluminum compound to form an aluminum oxide film on the film formation target.
  • a method for manufacturing an aluminum oxide film which includes a forming step.
  • R represents a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R may be the same or different from each other.
  • t-Bu represents a tertiary butyl group.
  • an aluminum oxide film with reduced thickness variation can be stably manufactured.
  • the reason for this is presumably because the aluminum compound represented by the above formula (1) can be easily decomposed under heating and can stably deposit aluminum oxide into a film under heating.
  • the film formation target is preferably heated to 300 to 500 ° C. Thereby, the variation in the thickness of the aluminum oxide film can be further reduced.
  • a high-quality aluminum oxide film can be manufactured by sufficiently reducing impurities contained in the aluminum oxide film.
  • the aluminum compound may contain a compound represented by the following formula (1-1).
  • R 1 and R 2 represent different alkyl groups.
  • R 1 and R 2 each independently represent a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R 1 may be the same or different from each other.
  • t-Bu represents a tertiary butyl group.
  • the aluminum compound represented by the above formula (1-1) contains a methyl group, the vapor pressure becomes high and energy required for vaporization can be reduced.
  • an atomic layer deposition method (Atomic Layer Deposition; hereinafter referred to as “ALD method”) or a chemical vapor deposition method (Chemical Vapor Deposition method; hereinafter referred to as “CVD method”). )
  • ALD method atomic layer deposition method
  • CVD method chemical vapor deposition method
  • the present invention provides a raw material for producing an aluminum oxide film containing an aluminum compound represented by the following formula (1).
  • R represents a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R may be the same or different from each other.
  • t-Bu represents a tertiary butyl group.
  • the aluminum compound represented by the above formula (1) is used as a raw material for producing an aluminum oxide film, an aluminum oxide film with reduced thickness variation can be stably produced. This is presumably because the aluminum compound can be easily decomposed by heating in the presence of an oxygen source, and can stably deposit aluminum oxide into a film.
  • the aluminum compound may contain a compound represented by the following formula (1-1).
  • R 1 and R 2 are different alkyl groups.
  • R 1 and R 2 each independently represent a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R 1 may be the same or different from each other.
  • t-Bu represents a tertiary butyl group.
  • the aluminum compound represented by the above formula (1-1) contains a methyl group, the vapor pressure becomes high and energy required for vaporization can be reduced.
  • the present invention provides an aluminum compound represented by the following formula (1-1).
  • R 1 and R 2 represent different alkyl groups.
  • R 1 and R 2 each independently represent a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R 1 may be the same or different from each other.
  • t-Bu represents a tertiary butyl group.
  • the aluminum compound can be easily decomposed under heating, and can stably deposit aluminum oxide into a film even under heating. Therefore, an aluminum oxide film having a predetermined thickness can be stably manufactured.
  • the manufacturing raw material used suitably for the said manufacturing method and an aluminum compound can be provided.
  • the method for manufacturing an aluminum oxide film according to the present embodiment includes a step of supplying an aluminum compound onto a heated film formation target and oxidizing the aluminum compound to form the aluminum oxide film on the film formation target. Have.
  • the aluminum compound used in the method for producing an aluminum oxide film is a (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound represented by the following formula (1).
  • R represents a linear alkyl group having 1 to 2 carbon atoms, and a plurality of R may be the same or different.
  • t-Bu represents a tertiary butyl group.
  • R (alkyl group) in formula (1) include a methyl group and an ethyl group.
  • the (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound represented by the above formula (1) preferably contains a compound represented by the following formula (1-1).
  • R 1 and R 2 are different alkyl groups.
  • R 1 and R 2 each independently represents a linear alkyl group having 1 to 2 carbon atoms.
  • the two R 1 s may be the same or different from each other.
  • it is preferable that two R ⁇ 1 > is the same from a viewpoint of reduction of manufacturing cost and the ease of raw material acquisition.
  • t-Bu represents a tertiary butyl group.
  • suitable aluminum compounds used in the method for producing an aluminum oxide film include compounds represented by the following formulas (2) to (5).
  • t-Bu represents a tertiary butyl group
  • Me and Et represent a methyl group and an ethyl group, respectively. That is, the compound represented by the formula (2) is (ditertiary butyl (methyl) amidinato) dimethylaluminum, and the compound represented by the formula (3) is (ditertiary butyl (ethyl) amidinato) diethylaluminum.
  • the compound represented by the formula (4) is (ditertiary butyl (ethyl) amidinato) dimethylaluminum, and the compound represented by the formula (5) is (ditertiary butyl (methyl) amidinato) diethylaluminum.
  • Each aluminum compound represented by the above formulas (1), (1-1), (2) to (5) can be suitably used for forming an aluminum oxide film on a film formation target. That is, it is suitable for the use of forming an aluminum oxide film on a film formation target. It can also be said that the aluminum compound represented by the above formula (1), (1-1) or (2) to (5) is used for forming the aluminum oxide film.
  • dialkylaluminum compound can be produced, for example, by the following (Method 1) or (Method 2).
  • Method 1 is a method in which ditertiary butyl carbodiimide is reacted with an alkyl alkali metal compound or ditertiary butyl carbodiimide is reacted with an alkyl alkaline earth metal compound to obtain a metal salt of ditertiary butyl (alkyl) amidine.
  • One step and a second step of reacting the obtained metal salt with a dialkylaluminum halide is a method in which ditertiary butyl carbodiimide is reacted with an alkyl alkali metal compound or ditertiary butyl carbodiimide is reacted with an alkyl alkaline earth metal compound to obtain a metal salt of ditertiary butyl (alkyl) amidine.
  • Method 2 has a step of reacting ditertiary butyl carbodiimide and trialkylaluminum.
  • Examples of the metal compound used in Method 1 include methyl lithium, ethyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, diethyl magnesium, ethyl butyl magnesium, and dibutyl magnesium. You may use 1 type of these individually or in combination of 2 or more types. Of the above metal compounds, methyllithium is preferred from the viewpoints of reducing production costs, availability of raw materials, and improving reaction yield.
  • the amount of the alkali metal compound used is preferably 0.4 to 1.4 mol, more preferably 0.6 to 1.2 mol, with respect to 1 mol of ditertiary butylcarbodiimide.
  • the amount of the alkaline earth metal compound used is preferably 0.2 to 0.7 mol, more preferably 0.3 to 0.6 mol, with respect to 1 mol of ditertiary butylcarbodiimide.
  • dialkylaluminum halide examples include dimethylaluminum chloride, dimethylaluminum bromide, diethylaluminum chloride, and diethylaluminum bromide. You may use 1 type of these individually or in combination of 2 or more types. Of the dialkylaluminum halides, diethylaluminum chloride is preferred from the viewpoints of reducing production cost, availability of raw materials, and improving reaction yield.
  • dialkylaluminum halide used is preferably 0.1 to 1.6 mol, more preferably 0.5 mol, per 1 mol of ditertiary butyl (alkyl) amidine in the metal salt of ditertiary butyl (alkyl) amidine. ⁇ 1.2 mol.
  • trialkylaluminum used in Method 2 examples include trimethylaluminum and triethylaluminum.
  • the amount of trialkylaluminum used is preferably 0.1 to 1.6 mol, more preferably 0.5 to 1.2 mol, per 1 mol of ditertiary butylcarbodiimide.
  • Method 1 and Method 2 are each preferably performed in an organic solvent.
  • the organic solvent is not particularly limited as long as it does not inhibit the reaction. Examples include ethers such as diethyl ether, tetrahydrofuran, dimethoxyethane, and dioxane; aliphatic hydrocarbons such as hexane, heptane, cyclohexane, methylcyclohexane, and ethylcyclohexane; aromatic hydrocarbons such as toluene and xylene. Of these, ethers, aliphatic hydrocarbons, and mixed solvents of ethers and aliphatic hydrocarbons are preferable. In addition, these organic solvents may be used independently and may be used in combination of 2 or more types.
  • the amount of the organic solvent used in Method 1 and Method 2 is preferably 1 to 100 g, more preferably 5 to 50 g based on 1 g of dialkylaluminum halide or 1 g of trialkylaluminum.
  • the reaction of Method 1 can be performed, for example, by the following procedure.
  • first step ditertiary butyl carbodiimide, an alkyl alkali metal compound and an organic solvent are mixed and reacted with stirring to give an alkali metal salt of ditertiary butyl (alkyl) amidine (ditertiary butyl (alkyl) amidinato. Compound).
  • second step a dialkylaluminum halide is added and further reacted with stirring.
  • the reaction temperature in the first step and the second step is preferably ⁇ 100 to 100 ° C., more preferably ⁇ 80 to 40 ° C.
  • the reaction pressure at this time is not particularly limited.
  • the ditertiary butyl (alkyl) amidinato compound obtained in the first step may be once isolated or used as it is before the reaction with the dialkylaluminum halide in the second step.
  • the reaction of the method 2 includes, for example, a step of mixing and reacting ditertiary butylcarbodiimide, trialkylaluminum, and an organic solvent.
  • the reaction temperature at that time is preferably ⁇ 100 to 100 ° C., more preferably ⁇ 80 to 40 ° C.
  • the reaction pressure at this time is not particularly limited.
  • a dialkylaluminum compound can be obtained by the reaction of Method 1 or Method 2 (ditertiary butyl (alkyl) amidinato). After completion of the reaction, the (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound may be isolated or purified by a known method. Known methods include extraction, filtration, concentration, distillation, sublimation, recrystallization, column chromatography, and the like. One of these may be used alone or in combination of two or more.
  • dialkylaluminum compounds are often unstable to moisture and oxygen in the atmosphere. For this reason, it is preferable to perform each process of Method 1 or Method 2, and post-treatment of the reaction solution as necessary under anhydrous conditions or inert gas conditions.
  • (Ditertiary butyl (alkyl) amidinato) dialkylaluminum compound is suitably used as a production raw material (production raw material) for producing an aluminum oxide film.
  • the production raw material (production raw material) for producing the aluminum oxide film is preferably composed only of (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound.
  • the above production raw material (production raw material) is a small amount of impurities (aluminum compound, etc.) other than (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound as long as the quality of the formed aluminum oxide film is not greatly affected. ) May be included.
  • Examples of a method for forming an aluminum oxide film on a film formation target include a chemical vapor deposition method (CVD method) and an atomic layer deposition method (ALD method).
  • the ALD method is more preferably used in terms of easy control of the film thickness and easy formation of a thin film.
  • the step of forming the aluminum oxide film on the film formation target is performed, for example, according to the following procedure.
  • a gas containing (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound and a reactive gas are supplied onto the heated film formation target.
  • the reactive gas has oxygen as a constituent element. Examples thereof include oxidizing gases such as oxygen and ozone; water; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, and n-butanol.
  • the (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound is oxidized by the reactive gas. Thereby, aluminum oxide is vapor-deposited on the film formation target, and an aluminum oxide film is formed.
  • the gas containing (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound may be a gas (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound diluted with an inert gas or the like. Further, the (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound contained in the gas may be in the form of a mist (droplet).
  • the step of forming an aluminum oxide film on the film formation target may be performed by a plasma CVD method instead of the ALD method.
  • an aluminum oxide film can be formed on the film formation target by supplying the same raw material onto the film formation target.
  • a method of vaporizing a (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound by filling or transporting it into a vaporizing chamber can be mentioned.
  • the (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound is diluted in a suitable solvent to prepare a solution.
  • a method (solution method) in which this solution is introduced into a vaporizing chamber with a liquid transfer pump and vaporized is exemplified.
  • solvent used here examples include aliphatic hydrocarbons such as hexane, cyclohexane, methylcyclohexane, ethylcyclohexane, heptane, and octane; aromatic hydrocarbons such as toluene, ethylbenzene, and xylene; glyme, diglyme, triglyme, dioxane, Examples include ethers such as tetrahydrofuran. One of these may be used alone or in combination of two or more.
  • the pressure in the reaction system when forming an aluminum oxide film by vapor-depositing aluminum oxide using a (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound is preferably 1 Pa to 200 kPa, more preferably 10 Pa to 110 kPa. .
  • the temperature of the film formation target when forming an aluminum oxide film using (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound is preferably 200 to 600 ° C., more preferably 300 to 500 ° C. Thereby, the variation in the thickness of the aluminum oxide film can be further reduced. In addition, a high-quality aluminum oxide film can be manufactured by sufficiently reducing impurities contained in the aluminum oxide film. Further, when the temperature is 300 to 500 ° C., it is possible to suppress the change in the film thickness even if there is some variation in the temperature on the film formation target. Therefore, an aluminum oxide film having excellent film thickness uniformity can be easily manufactured.
  • the temperature at which the (ditertiary butyl (alkyl) amidinato) dialkylaluminum compound is vaporized is preferably 30 to 250 ° C., more preferably 60 to 200 ° C.
  • an oxygen source for example, oxidizing gas, water vapor or alcohol vapor, or these
  • the content ratio of the reactive gas to be a mixed gas is preferably 3 to 99% by volume, more preferably 5 to 98% by volume.
  • the aluminum oxide film of this embodiment is formed on a film formation target by supplying an aluminum compound onto the heated film formation target and oxidizing the aluminum compound.
  • the aluminum oxide film has a thickness of, for example, 1 to 100 nm, preferably 5 to 50 mm.
  • the aluminum oxide film can have a satisfactory quality by sufficiently reducing the impurity concentration.
  • the content of aluminum oxide in the aluminum oxide film is, for example, 95% by mass or more, preferably 98% by mass or more, and more preferably 99% by mass or more.
  • Such a high-quality aluminum oxide film having a high purity and a small thickness is useful in the semiconductor field.
  • the aluminum oxide film may be composed only of aluminum oxide, or may be composed only of aluminum oxide and aluminum carbide. In the present specification, an aluminum oxide content of 90% by mass or more is referred to as an “aluminum oxide film”.
  • the variation in thickness of the aluminum oxide film is, for example, less than 10 nm.
  • the variation in the thickness of the aluminum oxide film is a difference in film thickness (maximum value ⁇ minimum value) measured at an arbitrarily selected location.
  • the film formation target includes a substrate containing an inorganic oxide. By forming an aluminum oxide film on such a substrate, a stacked body having the aluminum oxide film on the substrate and the substrate can be obtained.
  • (Ditertiary butyl (methyl) amidinato) dimethylaluminum is a compound in which R in the above formula (1) is a methyl group (a compound in the above formula (2)).
  • the physical properties of the obtained (ditertiary butyl (methyl) amidinato) dimethylaluminum were as follows.
  • reaction solution was concentrated, and the concentrate was distilled under reduced pressure (oil bath temperature: 80 ° C., pressure in the flask: 133.3 Pa) to give a colorless transparent liquid (ditertiary butyl (ethyl) amidinato) diethyl. 4.43 g of aluminum was obtained (isolation yield: 94%).
  • (Ditertiary butyl (ethyl) amidinato) diethylaluminum is a compound in which R in the above formula (1) is an ethyl group (compound of the above formula (3)).
  • the physical properties of the obtained (ditertiary butyl (ethyl) amidinato) diethylaluminum were as follows.
  • (Ditertiary butyl (ethyl) amidinato) dimethylaluminum is a compound of the above formula (4).
  • the physical properties of the obtained (ditertiary butyl (ethyl) amidinato) dimethylaluminum were as follows.
  • Example 5 [Production of aluminum oxide film] An aluminum oxide film was formed on the substrate by the ALD method using (ditertiary butyl (ethyl) amidinato) diethylaluminum synthesized in Example 2 as the aluminum compound, that is, the compound represented by the above formula (3). . The aluminum oxide film was formed using the apparatus shown in FIG.
  • the apparatus shown in FIG. 1 includes a vaporizer 1 (SUS ampule) that vaporizes an aluminum compound 2, a vaporizer 6 (SUS ampule) that vaporizes water 7 and supplies water vapor as a reactive gas, and a substrate 15. And a reactor 11 having a heater 14 for heating the substrate 15 and reacting the aluminum compound 2 with water vapor to form an aluminum oxide film on the substrate 15.
  • a vacuum pump is connected to the reactor 11 via a flow path.
  • a pressure gauge 13, a pressure control valve 12 and a trap 16 are provided in the flow path. Thereby, the pressure in the reactor 11 is adjusted to a predetermined range. The gas led out from the reactor 11 is exhausted to the atmosphere through the trap 16 and the vacuum pump.
  • the aluminum compound 2 and the water 7 synthesized in Example 2 were accommodated in the vaporizer 1 and the vaporizer 6 respectively including the heater 3 and the constant temperature bath 8.
  • the vaporizer 1 was supplied with argon gas whose flow rate was adjusted by the mass flow controller 4 and preheated by the preheater 5. As a result, argon gas containing the aluminum compound 2 was introduced into the reactor 11 from the vaporizer 1.
  • water vapor that was vaporized by being adjusted to a constant temperature by the thermostatic chamber 8 was introduced into the reactor 11 from the vaporizer 6.
  • the argon gas containing the aluminum compound 2 from the vaporizer 1 and the water vapor from the vaporizer 6 were alternately introduced into the reactor 11.
  • the introduction amounts of argon gas and water vapor containing the aluminum compound 2 were adjusted by a valve 17 and a valve 18, respectively.
  • the argon gas and water vapor containing the aluminum compound 2 were each adjusted in flow rate by the mass flow controller 9 and introduced into the reactor 11 along with the dilution argon gas preheated by the preheater 10.
  • Aluminum compound 2 and water 7 were alternately supplied to the reactor 11 to form an aluminum oxide film 20 on the substrate 15 heated to a predetermined temperature by the heater 14.
  • the operating conditions of the apparatus of FIG. 1 were as follows.
  • the vaporization temperature of the aluminum compound 2 (vaporizer 1): 90 ° C Ar gas (carrier gas) flow rate: 5 mL / min (adjusted with mass flow controller 4)
  • Aluminum compound 2 supply time 1 second
  • Aluminum compound 2 purge time 5 seconds
  • Water 7 vaporization temperature 10 ° C.
  • Water 7 supply time 1 second
  • Ar gas flow rate for dilution 50 mL / min.
  • Material of substrate 15: SiO 2 / Si Size of substrate 15: vertical x horizontal 20 mm x 20 mm
  • the temperature of the substrate 15 300 ° C. Pressure in the reactor 11: 1333 Pa Number of cycles: 500 times (introduction of argon gas containing aluminum compound 2 and introduction of water vapor from the vaporizer 6 were repeated 500 times)
  • the aluminum oxide film 20 was formed on the substrate 15 under the above conditions.
  • the thickness of the formed aluminum oxide film 20 was measured using a reflection spectral film thickness meter.
  • the composition of the aluminum oxide film 20 was analyzed using an XPS (X-ray photoelectron spectroscopy) measuring apparatus. The results of thickness and composition analysis were as shown in Table 1.
  • the thickness of the aluminum oxide film 20 was performed at five arbitrarily selected locations, and the maximum value and the minimum value were obtained.
  • the maximum value ⁇ the minimum value ⁇ 10 nm the arithmetic average value is shown in the table.
  • the maximum value ⁇ minimum value ⁇ 10 nm the maximum value and the minimum value were shown.
  • Example 6 to 10 [Production of aluminum oxide film] An aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that the temperature of the substrate 15 was changed as shown in Table 1. The analysis results of the thickness and composition of the formed aluminum oxide film 20 were as shown in Table 1.
  • the aluminum oxide films of Examples 5 to 10 had no thickness variation and excellent thickness uniformity. Further, it was confirmed that when the temperature of the substrate 15 is in the range of 300 to 500 ° C., the thickness of the aluminum oxide film does not change much. From this, it was confirmed that the aluminum oxide film can be formed stably by using (ditertiary butyl (ethyl) amidinato) diethylaluminum synthesized in Example 2.
  • the aluminum oxide content in the aluminum oxide film of Example 10 was 95% by mass or more, and the aluminum carbide content was 5% by mass or less.
  • Example 11 [Production of aluminum oxide film]
  • the aluminum compound (ditertiary butyl (methyl) amidinato) diethylaluminum synthesized in Example 3, that is, the compound represented by the above formula (5) was used.
  • An aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that this aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was set to 80 ° C.
  • the analysis results of the thickness and composition of the formed aluminum oxide film 20 were as shown in Table 2.
  • Example 12 to 16 [Production of aluminum oxide film] An aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 11 except that the temperature of the substrate 15 was changed as shown in Table 2. The analysis results of the thickness and composition of the formed aluminum oxide film 20 were as shown in Table 2.
  • the aluminum oxide films of Examples 11 to 16 had no thickness variation and were excellent in thickness uniformity. Further, it was confirmed that when the temperature of the substrate 15 is in the range of 300 to 500 ° C., the thickness of the aluminum oxide film does not change much. From this, it was confirmed that by using (ditertiary butyl (methyl) amidinato) diethylaluminum synthesized in Example 3, an aluminum oxide film can be formed stably.
  • Example 17 [Production of aluminum oxide film]
  • the aluminum compound (ditertiary butyl (ethyl) amidinato) dimethylaluminum synthesized in Example 4, that is, the compound represented by the formula (4) was used.
  • An aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that this aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was set to 70 ° C.
  • the analysis results of the thickness and composition of the formed aluminum oxide film 20 are as shown in Table 3.
  • Example 18 to 20 [Production of aluminum oxide film] An aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 17 except that the temperature of the substrate 15 was changed as shown in Table 3. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are as shown in Table 3.
  • the aluminum oxide films of Examples 17 to 20 had no thickness variation and excellent thickness uniformity. Further, it was confirmed that the thickness of the aluminum oxide film did not change when the temperature of the substrate 15 was in the range of 300 to 500 ° C. From this, it was confirmed that the aluminum oxide film can be stably formed by using (ditertiary butyl (ethyl) amidinato) dimethylaluminum synthesized in Example 4.
  • Example 21 [Production of aluminum oxide film]
  • the aluminum compound (ditertiary butyl (methyl) amidinato) dimethylaluminum synthesized in Example 1, that is, the compound represented by the formula (2) was used.
  • An aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 5 except that this aluminum compound was used and the vaporization temperature of the aluminum compound in the vaporizer 1 was set to 70 ° C.
  • the analysis results of the thickness and composition of the formed aluminum oxide film 20 are as shown in Table 4.
  • Example 22 to 24 [Production of aluminum oxide film] An aluminum oxide film 20 was formed on the substrate 15 in the same manner as in Example 21 except that the temperature of the substrate 15 was changed as shown in Table 4. The analysis results of the thickness and composition of the formed aluminum oxide film 20 are as shown in Table 4.
  • the aluminum oxide films of Examples 21 to 24 had no thickness variation and were excellent in thickness uniformity. Further, it was confirmed that the thickness of the aluminum oxide film did not change when the temperature of the substrate 15 was in the range of 300 to 500 ° C. From this, it was confirmed that the aluminum oxide film can be stably formed by using the ditertiary butyl (methyl) amidinato) dimethylaluminum synthesized in Example 1.
  • reaction solution was concentrated, and the concentrate was distilled under reduced pressure (oil bath temperature 70 ° C., pressure in the flask: 133.3 Pa) to obtain 4.94 g of a transparent liquid (diisopropyl (methyl) amidinato) dimethylaluminum. Obtained (isolation yield: 90% by mass).
  • (Diisopropyl (methyl) amidinato) dimethylaluminum is represented by the following chemical formula.
  • the physical properties of the obtained (diisopropyl (methyl) amidinato) dimethylaluminum were as follows.
  • the obtained concentrate was distilled under reduced pressure (oil bath temperature 90 ° C., pressure in the flask: 133.3 Pa) to obtain 3.02 g of (dimethylamido) diethylaluminum as a transparent liquid (isolated yield: 82% by mass). ).
  • the thickness variation of the aluminum oxide film of Comparative Example 5 was small.
  • the aluminum compounds represented by the above formulas (2) to (5) used in the above examples were sufficiently excellent in safety. Further, since the aluminum thin film was formed under the above conditions, the aluminum compounds represented by the formulas (2) to (5) had good reactivity with the reactive gas. It has also been found that the vapor containing the aluminum compound represented by the above formulas (2) to (5) has excellent adsorptivity to the substrate surface. Furthermore, by setting the temperature of the substrate to 300 to 500 ° C., an aluminum oxide film with high aluminum oxide purity can be formed while reducing the change in thickness. That is, a high quality aluminum oxide film can be manufactured.
  • a method for producing an aluminum oxide film capable of stably producing an aluminum oxide film with reduced thickness variation. Production raw materials and aluminum compounds that are suitably used in the production method are provided.

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention concerne un procédé de fabrication de film d'oxyde d'aluminium, comprenant l'étape consistant à former un film d'oxyde d'aluminium sur la cible de formation de film par la fourniture d'un composé d'aluminium représenté par la formule (1) sur une cible de formation de film chauffée et par l'oxydation du composé d'aluminium. Dans la formule (1), R représente un groupe alkyle linéaire ayant de 1 à 2 atomes de carbone, et de multiples instances de R peuvent être identiques ou différentes. t-Bu représente un groupe butyle tertiaire.
PCT/JP2016/074032 2015-08-20 2016-08-17 Procédé de fabrication d'un film d'oxyde d'aluminium, matériau pour la fabrication de film d'oxyde d'aluminium et composé d'aluminium WO2017030150A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022080169A1 (fr) * 2020-10-12 2022-04-21 東京エレクトロン株式会社 Procédé d'incorporation et dispositif de formation de film

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007015436A1 (fr) * 2005-08-04 2007-02-08 Tosoh Corporation Compose contenant du metal, procede de fabrication associe, fine pellicule contenant du metal, procede de realisation associe

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007015436A1 (fr) * 2005-08-04 2007-02-08 Tosoh Corporation Compose contenant du metal, procede de fabrication associe, fine pellicule contenant du metal, procede de realisation associe

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHANG, CHUNG-CHENG ET AL.: "Carbodiimide Insertion into Organoaluminum Compounds and Thermal Rearrangement of the Products", ORGANOMETALLICS, vol. 17, no. 8, April 1998 (1998-04-01), pages 1595 - 1601, XP055365794 *
MEIER, ROBERT J. ET AL.: "A Role for Dinuclear Aluminum Amidinate Complexes in Ethlene Polymerization?", J. PHYS. CHEM. A, vol. 105, no. 15, April 2001 (2001-04-01), pages 3867 - 3874, XP055365791 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022080169A1 (fr) * 2020-10-12 2022-04-21 東京エレクトロン株式会社 Procédé d'incorporation et dispositif de formation de film

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