WO2020170853A1 - Matériau de départ pour former un film mince contenant du nitrure de gallium pour un procédé de dépôt de couche atomique, et procédé de production de film mince contenant du nitrure de gallium - Google Patents

Matériau de départ pour former un film mince contenant du nitrure de gallium pour un procédé de dépôt de couche atomique, et procédé de production de film mince contenant du nitrure de gallium Download PDF

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WO2020170853A1
WO2020170853A1 PCT/JP2020/004786 JP2020004786W WO2020170853A1 WO 2020170853 A1 WO2020170853 A1 WO 2020170853A1 JP 2020004786 W JP2020004786 W JP 2020004786W WO 2020170853 A1 WO2020170853 A1 WO 2020170853A1
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thin film
gallium nitride
gallium
raw material
containing thin
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Japanese (ja)
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桜井　淳
雅子 畑▲瀬▼
奈奈 岡田
敦史 山下
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株式会社Adeka
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02373—Group 14 semiconducting materials
    • H01L21/02381—Silicon, silicon germanium, germanium
    • 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
    • C23C16/06—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 metallic material
    • C23C16/18—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 metallic material from metallo-organic 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
    • C23C16/34—Nitrides
    • 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
    • C23C16/44—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 method of coating
    • C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

Definitions

  • the present invention relates to a raw material for forming a gallium nitride-containing thin film for an atomic layer deposition method containing a gallium compound having a specific structure and a method for producing a gallium nitride-containing thin film.
  • the gallium nitride-containing thin film exhibits unique electrical characteristics. Therefore, the gallium nitride-containing thin film is applied to various applications such as semiconductor materials and light emitting diode materials.
  • the thin film manufacturing method includes, for example, a sputtering method, an ion plating method, a MOD method such as a coating thermal decomposition method and a sol-gel method, and a CVD method.
  • a sputtering method an ion plating method
  • a MOD method such as a coating thermal decomposition method and a sol-gel method
  • a CVD method a CVD method.
  • the thin film forming raw material applicable to the ALD method needs to have a sufficiently wide temperature region called an ALD window. Therefore, it is a common general knowledge in the technical field that a thin film forming raw material that can be used in the CVD method is often not suitable for the ALD method.
  • Patent Documents 1 to 4 disclose trialkylgallium such as trimethylgallium and triethylgallium, and tris(dialkylamino)gallium such as tris(dimethylamino)gallium and tris(diethylamino)gallium.
  • Non-Patent Document 1 discloses that gallium sulfide is produced by an ALD method using tris(dialkylamino)gallium as a raw material.
  • Non-Patent Document 2 discloses that gallium oxide is produced by an ALD method using tris(dialkylamino)gallium as a raw material.
  • Non-Patent Document 3 discloses that gallium nitride is produced by an ALD method using trimethylgallium as a raw material.
  • Non-Patent Document 3 the ALD method using trimethylgallium as a raw material requires plasma irradiation during the process. Since the substrate and peripheral members are damaged by plasma irradiation, a method of forming a gallium nitride thin film without plasma irradiation has been desired.
  • the present invention provides a raw material for forming a thin film for an atomic layer deposition method capable of forming a high-quality gallium nitride-containing thin film without irradiating plasma, and a method for producing a thin film using the raw material. To aim.
  • the present inventors have found that the above problems can be solved by using a gallium compound having a specific structure as a raw material for forming a thin film for an atomic layer deposition method, and to complete the present invention.
  • the present invention is a raw material for forming a gallium nitride-containing thin film for an atomic layer deposition method, which contains a gallium compound represented by the following general formula (1).
  • R 1 to R 4 each independently represents a methyl group or an ethyl group.
  • the present invention is a method for producing a gallium nitride-containing thin film on the surface of a substrate by an atomic layer deposition method, wherein the gallium nitride-containing thin film forming raw material for the atomic layer deposition method is vaporized to contain a gallium compound. And a step of introducing the vapor into a treatment atmosphere, and a step of decomposing and/or chemically reacting the gallium compound to deposit the gallium compound on the surface of the base body. Is the way.
  • the present invention it is possible to provide a raw material for forming a thin film, which can produce a high-quality gallium nitride-containing thin film by an atomic layer deposition method with good productivity without irradiating plasma. Further, according to the present invention, it is possible to provide a thin film manufacturing method capable of manufacturing a high-quality gallium nitride-containing thin film with high productivity.
  • a raw material for forming a gallium nitride-containing thin film for an atomic layer deposition method of the present invention contains a gallium compound represented by the above general formula (1).
  • gallium nitride-containing thin film in the present specification is not particularly limited as long as it is a thin film containing gallium nitride, and for example, gallium nitride thin film, gallium nitride and aluminum, manganese, metal such as indium and the like. Examples thereof include alloys of Al., and gallium nitride thin films doped with rare earth atoms such as lanthanum.
  • R 1 to R 4 each independently represent a methyl group or an ethyl group.
  • R 1 and R 3 are methyl groups, and R 2 and R 4 are methyl groups, since a high quality gallium nitride-containing thin film can be obtained.
  • a gallium compound having an ethyl group is preferred, and a gallium compound having R 1 to R 4 a methyl group is particularly preferred.
  • gallium compound represented by the general formula (1) examples include the following compound No. 1 to No. 6 is mentioned.
  • compound No. 1 to No. In 6 “Me” represents a methyl group and “Et” represents an ethyl group.
  • the gallium compound represented by the general formula (1) is not particularly limited by the production method, and can be produced by a well-known synthetic method.
  • the gallium compound represented by the general formula (1) can be obtained by, for example, reacting gallium chloride with a dialkylamine halide by a Grignard reaction.
  • the raw material for forming a thin film of the present invention may be any as long as it contains the gallium compound represented by the general formula (1), and its composition varies depending on the type of the desired thin film. For example, when a thin film containing only gallium as a metal is produced, the thin film forming raw material of the present invention does not contain a metal compound and a semimetal compound other than the gallium compound represented by the general formula (1). On the other hand, when a thin film containing gallium and a metal and/or a semimetal other than gallium is produced, the thin film forming raw material of the present invention contains a gallium compound other than gallium in addition to the gallium compound represented by the general formula (1).
  • the compound containing a metal and/or the compound containing a semimetal (hereinafter, also referred to as other precursor).
  • the raw material for forming a thin film of the present invention may further contain an organic solvent and/or a nucleophilic reagent as described later.
  • the form of the raw material for forming a thin film of the present invention is appropriately selected depending on the method such as the transport supply method of the atomic layer deposition method used.
  • the thin film forming raw material of the present invention is vaporized by heating and/or depressurizing it in a container (hereinafter, also simply referred to as “raw material container”) in a container.
  • a gas that introduces the vapor into a film forming chamber in which a substrate is installed hereinafter, also referred to as a "deposition reaction section" together with a carrier gas such as argon, nitrogen, or helium that is used as necessary.
  • Transport method transporting the thin film forming raw material of the present invention in a liquid or solution state to a vaporization chamber, and vaporizing by vaporizing by heating and/or depressurizing in the vaporization chamber, and introducing the vapor into the film forming chamber
  • a liquid transportation method In the case of the gas transport method, the gallium compound itself represented by the general formula (1) can be used as the raw material for forming a gallium nitride-containing thin film for the atomic layer deposition method.
  • the gallium compound itself represented by the general formula (1) or a solution obtained by dissolving the gallium compound in an organic solvent can be used as a raw material for forming a gallium nitride-containing thin film for the atomic layer deposition method.
  • These gallium nitride-containing thin film forming raw materials for atomic layer deposition may further contain other precursors, nucleophilic reagents and the like.
  • the multi-component ALD method a method of vaporizing and supplying a raw material for forming a gallium nitride-containing thin film for an atomic layer deposition method independently of each component (hereinafter, also referred to as “single source method”), There is 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, also referred to as “cocktail sauce method”).
  • a mixture of the gallium compound represented by the general formula (1) and another precursor or a mixed solution obtained by dissolving the mixture in an organic solvent is used as a raw material for forming a gallium nitride-containing thin film for the atomic layer deposition method. can do.
  • This mixture or mixed solution may further contain a nucleophilic reagent or the like.
  • organic solvent is not particularly limited, and well-known general organic solvents can be used.
  • organic solvent include acetic acid esters such as ethyl acetate, butyl acetate and methoxyethyl acetate; ethers such as tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether and dioxane; methyl.
  • Ketones such as butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, methylcyclohexanone; hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, Hydrocarbons such as xylene; 1-cyanopropane, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1, Hydrocarbons having a cyano group such as 4-dicyanocyclohexane and 1,4-d
  • 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, the flash point, and the like.
  • the total amount of the precursor in the raw material which is a solution prepared by dissolving the precursor in the organic solvent, is 0.01 mol/liter to 2.0 mol/liter, particularly 0.05 mol/liter to 1 It is preferably adjusted to be 0.0 mol/liter.
  • the raw material for forming a thin film of the present invention does not contain a metal compound and a metalloid compound other than the gallium compound represented by the general formula (1), the amount of the whole precursor is the amount of the gallium compound.
  • the raw material for forming a thin film of the present invention contains a compound containing another metal and/or a compound containing a metalloid (another precursor) in addition to the gallium compound, the total amount of the gallium compound and the other precursor. Is.
  • the other precursor used together with the gallium compound represented by the general formula (1) is not particularly limited and is used as a raw material for forming a thin film for the atomic layer deposition method.
  • Known general precursors can be used.
  • Other precursors include one or more selected from the group consisting of compounds used as organic ligands such as alcohol compounds, glycol compounds, ⁇ -diketone compounds, cyclopentadiene compounds and organic amine compounds, and silicon or metal. Compounds.
  • precursor metal species include lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, ruthenium, cobalt, rhodium.
  • Iridium Iridium, nickel, palladium, platinum, copper, silver, gold, zinc, aluminum, indium, germanium, tin, lead, antimony, bismuth, scandium, ruthenium, yttrium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium , Gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium.
  • Alcohol compounds include alkyl alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, secondary butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, pentyl alcohol, isopentyl alcohol and tertiary pentyl alcohol; 2-methoxyethanol , 2-ethoxyethanol, 2-butoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1,1-dimethylethanol, 2-ethoxy-1,1-dimethyl Ethanol, 2-isopropoxy-1,1-dimethylethanol, 2-butoxy-1,1-dimethylethanol, 2-(2-methoxyethoxy)-1,1-dimethylethanol, 2-propoxy-1,1-diethyl Ether alcohols such as ethanol, 2-s-butoxy-1,1-diethylethanol, 3-methoxy-1,1-dimethylpropanol; dimethylaminoethanol, e
  • glycol compound 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. Is mentioned.
  • ⁇ -diketone compounds include acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione, heptane-2,4-dione, 2-methylheptane-3,5-dione, 5-methyl Heptane-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,
  • cyclopentadiene compound examples include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, tert-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetra Methylcyclopentadiene and the like can be mentioned.
  • organic amine compound examples include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, sec-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, propylmethylamine, Isopropylmethylamine and the like can be mentioned.
  • the above-mentioned other precursors are known in the art, and their manufacturing methods are also known.
  • the production method for example, when an alcohol compound is used as an organic ligand, the above-mentioned inorganic salt of a metal or a hydrate thereof is reacted with an alkali metal alkoxide of the alcohol compound. By doing so, the precursor can be manufactured.
  • the inorganic salt of metal or its hydrate include metal halides and nitrates.
  • the alkali metal alkoxide include sodium alkoxide, lithium alkoxide, potassium alkoxide and the like.
  • a compound having a thermal and/or oxidative decomposition behavior similar to that of the gallium compound represented by the general formula (1) is preferable.
  • other precursors are similar to the gallium compound represented by the above general formula (1) in behavior of heat and/or oxidative decomposition, and in addition, alteration due to chemical reaction during mixing is performed. Compounds that do not occur are preferred.
  • the raw material for forming a thin film of the present invention may contain a nucleophilic reagent, if necessary, in order to improve the stability of the gallium compound represented by the general formula (1) and other precursors. ..
  • the nucleophilic reagent include ethylene glycol ethers such as glyme, diglyme, triglyme, and tetraglyme, 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8.
  • Crown ethers such as dibenzo-24-crown-8, ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7- Polyamines such as pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine and triethoxytriethyleneamine, cyclic polyamines such as cyclam and cyclen, pyridine, pyrrolidine, piperidine, morpholine, N Heterocyclic compounds such as -methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, oxathiolane, methyl acetoacetate, ethyl acetoacetate, acetoacetic acid-2- Examples
  • the raw material for forming a thin film of the present invention should contain as much as possible impurities metal element components other than the constituent components thereof, impurity halogen components such as impurity chlorine, and impurity organic components.
  • the impurity metal element content is preferably 100 ppb or less for each element, more preferably 10 ppb or less, and total amount is preferably 1 ppm or less, more preferably 100 ppb or less.
  • it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements that affect the electrical characteristics of the obtained thin film.
  • the impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, most preferably 1 ppm or less.
  • the total amount of organic impurities is preferably 500 ppm or less, more preferably 50 ppm or less, most preferably 10 ppm or less.
  • the precursor, the organic solvent and the nucleophilic reagent are used to reduce the respective water contents. In addition, it is better to remove water as much as possible before use.
  • the water content of each of the precursor, organic solvent and nucleophilic reagent is preferably 10 ppm or less, more preferably 1 ppm or less.
  • the thin film forming raw material of the present invention does not contain particles as much as possible in order to reduce or prevent particle contamination of the formed thin film.
  • the number of particles larger than 0.3 ⁇ m is preferably 100 or less in 1 mL of the liquid phase, and larger than 0.2 ⁇ m. More preferably, the number of particles is 1000 or less in 1 mL of the liquid phase, and most preferably the number of particles larger than 0.2 ⁇ m is 100 or less in 1 mL of the liquid phase.
  • the method for producing a gallium nitride-containing thin film of the present invention is characterized by forming a thin film by the ALD method using the above-mentioned thin film forming raw material.
  • the method of producing a gallium nitride-containing thin film on the surface of a substrate by the ALD method according to the present invention includes the steps of introducing into a film forming chamber in which a substrate is installed, and then decomposing and/or chemically reacting a gallium compound on the substrate to grow and deposit a thin film containing gallium nitride on the surface of the substrate.
  • Examples of the material of the base include silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, titanium nitride, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass; metals such as metallic cobalt.
  • Examples of the shape of the substrate include a plate shape, a spherical shape, a fibrous shape, and a scaly shape.
  • the surface of the substrate may be flat or may have a three-dimensional structure such as a trench structure.
  • Examples of the above-mentioned reactive gas include reducing gas such as hydrogen, organic amine compounds such as monoalkylamine, dialkylamine, trialkylamine and alkylenediamine, and nitriding gas such as hydrazine and ammonia. These reactive gases may be used alone or in combination of two or more.
  • the gallium compound represented by the general formula (1) has a property of reacting well with ammonia, hydrazine and hydrogen, and has a property of reacting particularly well with ammonia. Therefore, it is preferable to use ammonia as the reactive gas.
  • the above manufacturing conditions include the temperature and pressure at which the thin film forming raw material of the present invention is vaporized into steam.
  • the step of vaporizing the raw material for forming a thin film of the present invention into vapor may be performed in the raw material container or in the vaporization chamber.
  • the thin film forming raw material of the present invention is preferably evaporated at 0°C to 200°C.
  • both the pressure in the raw material container and the pressure in the vaporization chamber are preferably 1 Pa to 10000 Pa.
  • reaction temperature substrate temperature
  • reaction pressure reaction pressure
  • deposition rate deposition rate
  • the reaction temperature is set within an ALD window matched to the reactive gas, but is preferably 100° C. or higher at which the gallium compound represented by the general formula (1) sufficiently reacts, and 100° C. to 250° C. More preferable.
  • ammonia is used as the reactive gas, it is preferable that the temperature is in the range of 120° C. to 200° C. because a gallium nitride-containing thin film with less residual carbon and good quality can be produced with good productivity.
  • each step of the ALD method will be described in detail by taking an example of forming a gallium nitride thin film using ammonia gas as a reactive gas.
  • the vapor of the thin film forming raw material of the present invention is introduced into the film forming chamber (raw material introducing step).
  • the preferable temperature and pressure when the raw material for forming a thin film of the present invention is vaporized are in the range of 0° C. to 200° C. and 1 Pa to 10000 Pa.
  • the vapor introduced into the film forming chamber is deposited on the surface of the substrate to form a precursor thin film on the surface of the substrate (precursor thin film forming step).
  • the substrate may be heated, or the processing atmosphere in the film forming chamber may be heated.
  • the temperature of the substrate or the temperature of the treatment atmosphere when this step is performed is preferably room temperature to 250°C, more preferably 100°C to 250°C.
  • the ALD window is generally in the range of 120°C to 200°C.
  • the pressure of the system (in the film forming chamber) when this step is performed is preferably 1 Pa to 10000 Pa, more preferably 10 Pa to 1000 Pa.
  • the unreacted thin film forming material vapor and by-produced gas are exhausted from the film forming chamber (exhaust process).
  • the unreacted thin film forming raw material vapor and the by-product gas are ideally completely exhausted from the film forming chamber, but they are not necessarily completely exhausted.
  • Examples of the exhaust method include a method of purging the system with an inert gas such as nitrogen, helium, and argon, a method of exhausting by depressurizing the system, and a method of combining these.
  • the degree of pressure reduction is preferably 0.01 Pa to 300 Pa, more preferably 0.01 Pa to 100 Pa.
  • ammonia gas is introduced as a reactive gas into the film forming chamber, and the gallium nitride-containing thin film is formed from the precursor thin film formed in the precursor thin film forming step by the action of ammonia gas or the action of ammonia gas and heat.
  • Forming (gallium nitride-containing thin film forming step).
  • the temperature when heat is applied in this step is preferably room temperature to 250°C, more preferably 100°C to 250°C.
  • the ALD window is generally in the range of 120° C. to 200° C. Therefore, it is preferable to react the precursor thin film with ammonia gas within this temperature range. ..
  • the pressure of the system (in the film forming chamber) when this step is performed is preferably 1 Pa to 10000 Pa, more preferably 10 Pa to 1000 Pa.
  • thin film deposition by a series of operations including the above raw material introducing step, precursor thin film forming step, evacuation step and gallium nitride containing thin film forming step is defined as one cycle, and this cycle is It may be repeated several times until a thin film having a required film thickness is obtained. In this case, after carrying out one cycle, it is preferable to carry out the next one cycle after exhausting the unreacted reactive gas and the by-produced gas from the film forming chamber in the same manner as the exhaust step.
  • the method for producing a gallium nitride-containing thin film of the present invention energy such as 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, at the time of introducing the vapor of the raw material for forming a thin film for the atomic layer deposition method in the raw material introducing step, the precursor thin film forming step or the gallium nitride-containing thin film.
  • the heating may be performed in the forming step, the system may be exhausted in the exhausting step, the reactive gas may be introduced in the gallium nitride-containing thin film forming step, or the above steps may be performed.
  • an annealing treatment is performed under an inert atmosphere, an oxidizing atmosphere or a reducing atmosphere in order to obtain better electric characteristics.
  • a reflow process may be provided when step filling is required.
  • the temperature is 200°C to 1000°C, preferably 250°C to 500°C.
  • a well-known device for atomic layer deposition can be used as a device for producing a gallium nitride-containing thin film using the thin film forming raw material of the present invention.
  • 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. Not only the single-wafer type apparatus as shown in FIGS. 1 and 2, but also an apparatus capable of simultaneously processing a large number of sheets using a batch furnace can be used.
  • This gallium chloride solution was slowly added dropwise to the above-mentioned suspension of lithium dimethylamide, and the mixture was reacted overnight at room temperature. Then, the mixture was heated and stirred at 80° C. for 8 hours. After allowing to cool, the reaction solution was filtered with a 0.2 ⁇ m membrane filter to collect the filtrate. The solvent is removed from the filtrate under an argon atmosphere at an oil bath temperature of 80°C to 100°C at atmospheric pressure to a slight reduced pressure, and then heated at an oil bath temperature of 100°C to 120°C under reduced pressure until a white solid precipitates. Dried.
  • a white solid was purified by sublimation at a pressure of 40 Pa and an oil bath temperature of 125°C to obtain a target substance (trisdimethylamide gallium (III)) as a white solid (melting point 102°C).
  • the yield was 2.6 g, and the yield was 65%.
  • This gallium chloride solution was slowly added dropwise to the above-mentioned suspension of lithium ethylmethylamide under ice-cooling conditions, and the mixture was reacted at room temperature overnight. Then, the mixture was heated and stirred at 50° C. for 8 hours. After allowing to cool, the reaction solution was filtered with a 0.2 ⁇ m membrane filter and the filtrate was collected. The solvent is removed from the filtrate under an argon atmosphere at an oil bath temperature of 80°C to 100°C at atmospheric pressure to a slight reduced pressure, and then heated and dried at an oil bath temperature of 100°C to 120°C under reduced pressure to obtain a viscous liquid.
  • the viscous liquid obtained was purified by distillation at a pressure of 10 Pa to 15 Pa and an oil bath temperature of 140° C. to obtain the target product (trisethylmethylamide gallium (III)) as a pale yellow liquid.
  • the yield was 1.0 g, and the yield was 50%.
  • Example 1 Production of gallium nitride thin film Compound No. Using No. 1 as a raw material for forming a thin film, a gallium nitride thin film was produced on a silicon wafer by the ALD method under the following conditions using the apparatus shown in FIG.
  • the composition of the obtained thin film was confirmed by X-ray photoelectron spectroscopy, the obtained thin film was gallium nitride, and the residual carbon content was less than 0.1 atom %. Further, when the film thickness was measured by the X-ray reflectance method and the average value was calculated, the film thickness was 10 nm on average, and the film thickness obtained per cycle was 0.20 nm on average.
  • Substrate Silicon wafer Reaction temperature (silicon wafer temperature): 150°C Reactive gas: Ammonia
  • the material for forming a thin film which is vaporized under the conditions of the temperature of the raw material container: 100° C. and the pressure in the raw material container: 100 Pa, is introduced into the film forming chamber and deposited at a system pressure of 100 Pa for 30 seconds.
  • Argon purge for 15 seconds removes the thin film forming raw material that has not deposited.
  • a reactive gas is introduced into the film forming chamber, and the reaction is performed for 60 seconds at a system pressure of 100 Pa. (4) Unreacted reactive gas and by-product gas are removed by argon purge for 15 seconds.
  • Example 2 Production of gallium nitride thin film Compound No. 3 was used as a raw material for forming a thin film.
  • a gallium nitride thin film was manufactured under the same conditions as in Example 1 except that No. 6 was used.
  • the composition of the thin film was confirmed by X-ray photoelectron spectroscopy, the obtained thin film was gallium nitride and the residual carbon content was 1.0 atom %.
  • the film thickness was measured by the X-ray reflectance method, and the average value was calculated. The film thickness was 6.5 nm on average, and the film thickness obtained per cycle was 0.13 nm on average.
  • Example 1 Production of gallium nitride thin film A gallium nitride thin film was produced under the same conditions as in Example 1 except that the following comparative compound 1 was used as a raw material for forming a thin film.
  • the composition of the obtained thin film was confirmed by X-ray photoelectron spectroscopy, the obtained thin film was a mixture in which gallium nitride and gallium carbide were formed nonuniformly, and the residual carbon content was 20.0 atom%. Met.
  • the film thickness was measured by the X-ray reflectance method and the average value was calculated, the film thickness was 1.5 nm on average, and the film thickness obtained per cycle was 0.030 nm on average.
  • Example 2 Production of gallium nitride thin film A gallium nitride thin film was produced under the same conditions as in Example 1 except that the following comparative compound 2 ("iPr" represents an isopropyl group) was used as a raw material for forming a thin film.
  • the composition of the obtained thin film was confirmed by X-ray photoelectron spectroscopy, the obtained thin film was a mixture in which gallium nitride and gallium carbide were formed nonuniformly, and the residual carbon content was 25.0 atom%. Met. Further, when the film thickness was measured by the X-ray reflectance method and the average value was calculated, the film thickness was 5.0 nm on average, and the film thickness obtained per cycle was 0.10 nm on average.
  • Example 1 From the results of Examples 1 and 2, it was possible to manufacture a high-quality gallium nitride thin film having a low residual carbon content without requiring a step of plasma irradiation. Among them, it was found that the gallium nitride thin film obtained in Example 1 had a very low residual carbon content and was a particularly good quality gallium nitride thin film. On the other hand, in Comparative Examples 1 and 2, the residual carbon content of the obtained thin film was 20 atom% or more, so that the quality was poor, and the gallium nitride and the gallium carbide were nonuniformly formed. A good gallium nitride thin film could not be obtained.

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Abstract

L'invention concerne un matériau de départ pour former un film mince contenant du nitrure de gallium pour un procédé de dépôt de couche atomique, qui contient un composé de gallium qui est représenté par la formule générale (1). (Dans la formule, chacun de R1-R4 représente indépendamment un groupe méthyle ou un groupe éthyle.)
PCT/JP2020/004786 2019-02-20 2020-02-07 Matériau de départ pour former un film mince contenant du nitrure de gallium pour un procédé de dépôt de couche atomique, et procédé de production de film mince contenant du nitrure de gallium WO2020170853A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2022176999A1 (fr) 2021-02-22 2022-08-25 日産化学株式会社 Substrat à couche mince, et substrat à semi-conducteur

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013149979A (ja) * 2012-01-18 2013-08-01 Crystalwise Technology Inc 複合基材及びその製造方法並びに発光素子
JP2018500767A (ja) * 2014-12-18 2018-01-11 ザ リージェンツ オブ ザ ユニバーシティ オブ コロラド，ア ボディー コーポレイトＴＨＥ ＲＥＧＥＮＴＳ ＯＦ ＴＨＥ ＵＮＩＶＥＲＳＩＴＹ ＯＦ ＣＯＬＯＲＡＤＯ，ａ ｂｏｄｙ ｃｏｒｐｏｒａｔｅ 逐次的な自己制御熱反応を使用する原子層エッチング（ａｌｅ）の新規の方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013149979A (ja) * 2012-01-18 2013-08-01 Crystalwise Technology Inc 複合基材及びその製造方法並びに発光素子
JP2018500767A (ja) * 2014-12-18 2018-01-11 ザ リージェンツ オブ ザ ユニバーシティ オブ コロラド，ア ボディー コーポレイトＴＨＥ ＲＥＧＥＮＴＳ ＯＦ ＴＨＥ ＵＮＩＶＥＲＳＩＴＹ ＯＦ ＣＯＬＯＲＡＤＯ，ａ ｂｏｄｙ ｃｏｒｐｏｒａｔｅ 逐次的な自己制御熱反応を使用する原子層エッチング（ａｌｅ）の新規の方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022176999A1 (fr) 2021-02-22 2022-08-25 日産化学株式会社 Substrat à couche mince, et substrat à semi-conducteur

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