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WO2022220153A1 - Charge d'alimentation de formation de couche mince destinée à être utilisée en dépôt de couche atomique, couche mince, procédé de production de couche mince et composé de ruthénium - Google Patents

Charge d'alimentation de formation de couche mince destinée à être utilisée en dépôt de couche atomique, couche mince, procédé de production de couche mince et composé de ruthénium Download PDF

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WO2022220153A1
WO2022220153A1 PCT/JP2022/016488 JP2022016488W WO2022220153A1 WO 2022220153 A1 WO2022220153 A1 WO 2022220153A1 JP 2022016488 W JP2022016488 W JP 2022016488W WO 2022220153 A1 WO2022220153 A1 WO 2022220153A1
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thin film
ruthenium
raw material
atomic layer
layer deposition
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Japanese (ja)
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雅子 畑▲瀬▼
正揮 遠津
若菜 布施
亮太 福島
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Adeka Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/08—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with only one hydroxy group and one amino group bound to the carbon skeleton
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • 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
    • C23C16/16—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 metal carbonyl 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
    • C23C16/06—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
    • C23C16/44—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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a raw material for forming a thin film for atomic layer deposition containing a ruthenium compound having a specific structure, a thin film formed by using the raw material for forming a thin film for atomic layer deposition, a method for producing the thin film, and a ruthenium compound.
  • Ruthenium is a low-resistance, thermally and chemically stable metal.
  • Thin films containing ruthenium exhibit specific electrical properties, and are used for example as electrode materials for memory devices represented by DRAM devices, resistive films, diamagnetic films used in the recording layer of hard disks, polymer electrolyte fuel cells, and the like. It is used for various purposes such as a catalyst material for electronic devices and a metal gate material for MOS-FETs.
  • Methods for producing thin films containing ruthenium include the sputtering method, the ion plating method, the metal organic decomposition (MOD) method such as the coating pyrolysis method and the sol-gel method, and the chemical vapor deposition (CVD) method. , a vapor-phase thin film forming method such as an atomic layer deposition (ALD) method, and the like.
  • the ALD method is the most suitable manufacturing process because it has many advantages such as excellent composition controllability and step coverage, suitability for mass production, and possibility of hybrid integration.
  • Patent Document 1 discloses a ruthenium compound composed of two six-membered rings containing two carbonyl groups, a ruthenium atom and a ketimine group in the ring structure.
  • Patent Document 2 discloses the production of a thin film containing ruthenium by a thermal CVD method using a ruthenium complex mixture and a reducing gas.
  • Non-Patent Document 1 discloses a ruthenium complex in which two carbonyl groups and two ketoimine groups having a five-membered ring structure are bonded to ruthenium.
  • Non-Patent Document 1 does not discuss whether or not the ruthenium complex has an ALD window, and does not describe or suggest using the ruthenium complex in the ALD method.
  • the present invention provides a thin film for atomic layer deposition that can produce a high-quality thin film containing ruthenium atoms with little residual carbon (hereinafter sometimes referred to as a "ruthenium-containing thin film”) using the ALD method. It is an object of the present invention to provide a forming raw material, a thin film using the atomic layer deposition thin film forming raw material, and a method for producing the thin film.
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or and a plurality of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different.
  • a method for producing a thin film containing ruthenium atoms on the surface of a substrate by an atomic layer deposition method comprising: step 1 of forming a precursor thin film by adsorbing it on the surface of a substrate; step 2 of exhausting unreacted raw material gas; reacting the precursor thin film with a reactive gas to form ruthenium atoms on the surface of the substrate; and a step 3 of forming a thin film containing.
  • R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine atom-containing alkyl group having 1 to 4 carbon atoms, and a plurality of R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are , may be different or the same.
  • a raw material for forming a thin film for atomic layer deposition that can produce a high-quality ruthenium-containing thin film with little residual carbon using the ALD method, and a raw material for forming a thin film for atomic layer deposition is used. It is possible to provide a thin film and a method for manufacturing the thin film.
  • FIG. 1 is a schematic diagram showing an example of an ALD apparatus used in the thin film manufacturing method of the present invention.
  • FIG. 2 is a schematic diagram showing another example of an ALD apparatus used in the thin film manufacturing method of the present invention.
  • FIG. 3 is a schematic diagram showing another example of an ALD apparatus used in the thin film manufacturing method of the present invention.
  • FIG. 4 is a schematic diagram showing another example of an ALD apparatus used in the thin film manufacturing method of the present invention.
  • the raw material for forming a thin film for atomic layer deposition of the present invention is characterized by containing the ruthenium compound represented by the general formula (1).
  • R 1 , R 2 , R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 4 carbon atoms. and a plurality of R 1 , R 2 , R 3 , R 4 , R 5 and R 6 may be the same or different.
  • alkyl groups having 1 to 4 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 include methyl group, ethyl group, n-propyl group, isopropyl group, n -butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
  • the fluorine atom-containing alkyl group having 1 to 4 carbon atoms represented by R 1 , R 2 , R 3 , R 4 , R 5 and R 6 includes monofluoromethyl group, difluoromethyl group, trifluoromethyl group, trifluoroethyl group, pentafluoroethyl group, trifluoropropyl group, heptafluoropropyl group, nonafluorotert-butyl group and the like.
  • At least one of R 1 and R 2 is preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom-containing alkyl group having 1 to 3 carbon atoms from the viewpoint that the vapor of the ruthenium compound is easily obtained at low temperatures.
  • An alkyl group having 1 to 2 carbon atoms or a fluorine atom-containing alkyl group having 1 to 2 carbon atoms is preferable, and a methyl group or a trifluoromethyl group is most preferable.
  • R 1 and R 2 may be the same or different, but both R 1 and R 2 are C 1-4 alkyl groups or C 1-4 In the case of a fluorine atom-containing alkyl group, R 1 and R 2 are preferably the same from the viewpoint of improving the vapor pressure of the ruthenium compound.
  • R 3 and R 4 are preferably hydrogen atoms from the viewpoint of facilitating the formation of high-quality ruthenium-containing thin films with low residual carbon with good productivity.
  • At least one of R 5 and R 6 is preferably a hydrogen atom, more preferably one of R 5 and R 6 is a hydrogen atom, from the viewpoint of easily obtaining a ruthenium compound with a low melting point. Furthermore, from the viewpoint that a ruthenium compound having a low melting point and high thermal stability can be easily obtained, one of R 5 and R 6 is an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 3 carbon atoms.
  • the ruthenium compound represented by the general formula (1) used in the raw material for forming a thin film for atomic layer deposition of the present invention include the following No. 1 to No. 60, but the invention is not limited to these ruthenium compounds.
  • the following No. 1 to No. In the ruthenium compounds of No. 60, "Me” represents a methyl group, “Et” represents an ethyl group, “nPr” represents an n-propyl group, “iPr” represents an isopropyl group, and “CF 3 " represents a tri represents a fluoromethyl group, and "C 2 F 5 " represents a pentafluoroethyl group.
  • the ruthenium compound No. 48 is preferred because it easily forms a high-quality ruthenium-containing thin film with little residual carbon. 2, No. 9 and no. 10 ruthenium compounds are more preferred because of their good vapor pressure; Ruthenium compounds of No. 10 are more preferred due to their excellent thermal stability.
  • a ruthenium compound represented by the general formula (1) can be produced using a well-known reaction.
  • the ruthenium compound represented by the general formula (1) can be prepared, for example, by mixing triruthenium dodecacarbonyl (Ru 3 (CO) 12 ) and an arbitrary amino alcohol in the presence or absence of a solvent, and heating and stirring to react. can be obtained by letting
  • the raw material for forming a thin film for atomic layer deposition according to the present invention may contain a ruthenium compound represented by the general formula (1) as a precursor of a thin film, and its composition may vary depending on the type of the desired thin film. different. For example, when producing a thin film containing only ruthenium atoms as metal, the raw material for thin film formation for atomic layer deposition of the present invention does not contain metal compounds and metalloid compounds other than ruthenium.
  • the raw material for thin film formation for atomic layer deposition of the present invention is ruthenium represented by the general formula (1)
  • a desired metal-containing compound and/or metalloid-containing compound hereinafter sometimes referred to as "another precursor"
  • the raw material for forming a thin film for atomic layer deposition of the present invention may further contain an organic solvent and/or a nucleophilic reagent, as described later.
  • ruthenium compound represented by the general formula (1) are not particularly limited, and include: Well-known and common precursors used for raw materials can be used.
  • precursors for example, one or two types selected from the group consisting of compounds used as organic ligands such as alcohol compounds, glycol compounds, ⁇ -diketone compounds, cyclopentadiene compounds, organic amine compounds, etc.
  • Organic ligands such as alcohol compounds, glycol compounds, ⁇ -diketone compounds, cyclopentadiene compounds, organic amine compounds, etc.
  • Metal species of precursors include lithium, sodium, potassium, magnesium, calcium, strontium, barium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, osmium, ruthenium, and cobalt.
  • alcohol compounds used as organic ligands of the other precursors mentioned above include methanol, ethanol, propanol, isopropyl alcohol, butanol, sec-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, pentyl alcohol, and isopentyl alcohol.
  • tert-pentyl alcohol and other alkyl alcohols 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 and other ether alcohols; dimethylaminoethanol, ethylmethylaminoethanol, diethylaminoethanol, dimethylamino-2-pentanol, ethylmethylamino-2-pentanol, dimethylamino-2-methyl-2-pentanol, ethyl
  • Glycol compounds used as organic ligands for other precursors mentioned above include, for example, 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-hexane diol, 2,4-dimethyl-2,4-pentanediol and the like.
  • Examples of the ⁇ -diketone compound used as the organic ligand of the above other precursors include acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione, heptane-2,4-dione.
  • cyclopentadiene compounds used as organic ligands of the other precursors mentioned above include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, sec-butylcyclopentadiene, isobutylcyclopentadiene, tert-butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, pentamethylcyclopentadiene and the like.
  • organic amine compounds used as organic ligands of other precursors mentioned above include methylamine, ethylamine, propylamine, isopropylamine, butylamine, sec-butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, and dipropyl.
  • the other precursors mentioned above are known in the art, and their production methods are also known.
  • the production method for example, when an alcohol compound is used as the organic ligand, the inorganic salt of the metal described above or a hydrate thereof is reacted with an alkali metal alkoxide of the alcohol compound. can produce the precursor.
  • metal inorganic salts or hydrates thereof include metal halides and nitrates.
  • alkali metal alkoxides include sodium alkoxide, lithium alkoxide, potassium alkoxide and the like.
  • the multi-component ALD method there is a method of vaporizing and supplying each component independently of a raw material for forming a thin film for atomic layer deposition (hereinafter sometimes referred to as a “single source method”), and a method of supplying multiple components.
  • a single source method a method of vaporizing and supplying a mixed raw material obtained by mixing component raw materials in advance with a desired composition
  • the other precursor is preferably a compound whose thermal and/or oxidative decomposition behavior is similar to that of the ruthenium compound represented by general formula (1).
  • the other precursors mentioned above are similar to the ruthenium compound represented by the general formula (1) in terms of thermal and/or oxidative decomposition behavior, and in addition, are modified by chemical reactions during mixing. Compounds that do not cause
  • a mixture of the ruthenium compound represented by the general formula (1) and other precursors, or a mixed solution obtained by dissolving the mixture in an organic solvent is subjected to an atomic layer deposition method. It can be used as a raw material for thin film formation.
  • organic solvent examples include acetic esters such as ethyl acetate, butyl acetate and methoxyethyl acetate; ethers such as tetrahydrofuran (THF), 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 methylcyclohexanone; , toluene, and xylene; , 1,4-dicyanocyclohexane, 1,4-dicyanobenzene and other hydrocarbons having a
  • the total amount of the precursor in the raw material for forming a thin film for atomic layer deposition is 0.01 mol/liter to 2.0 mol/liter. It may be adjusted to 0 mol/liter, particularly 0.05 mol/liter to 1.0 mol/liter. This is because it facilitates formation of a high-quality ruthenium-containing thin film with little residual carbon.
  • the total amount of the precursor is represented by the general formula (1) when the raw material for forming a thin film for atomic layer deposition does not contain any precursor other than the ruthenium compound represented by the general formula (1).
  • the raw material for forming a thin film for atomic layer deposition contains other precursors in addition to the ruthenium compound represented by the general formula (1), it is represented by the general formula (1) It represents the total amount of the ruthenium compound and other precursors.
  • the raw material for forming a thin film for atomic layer deposition of the present invention optionally contains a nucleophilic reagent in order to improve the stability of the ruthenium compound represented by the general formula (1) and other precursors.
  • a nucleophilic reagent include ethylene glycol ethers such as glyme, diglyme, triglyme and tetraglyme, 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8 and dicyclohexyl-24-crown.
  • crown ethers such as dibenzo-24-crown-8, ethylenediamine, N,N'-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7, Polyamines such as 7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine and triethoxytriethyleneamine; cyclic polyamines such as cyclam and cyclene; pyridine, pyrrolidine, piperidine, morpholine , N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, heterocyclic compounds such as oxathiolane, methyl acetoacetate, ethyl acetoacetate, acetoacetate- ⁇ -
  • the amount of these nucleophilic reagents used is preferably in the range of 0.1 mol to 10 mol, preferably 1 mol to 4 mol, relative to 1 mol of the total amount of the precursor, from the viewpoint of easy adjustment of stability. is more preferred.
  • the material for forming a thin film for atomic layer deposition according to the present invention should contain as little as possible impurity metal elements, impurity halogens such as impurity chlorine, and impurity organics other than the constituent components.
  • the impurity metal element content is preferably 100 ppb or less for each element, more preferably 10 ppb or less, and the total amount is preferably 1 ppm or less, more preferably 100 ppb or less.
  • LSI gate insulating film, gate film, or barrier layer it is necessary to reduce the content of alkali metal elements and alkaline earth metal elements that affect the electrical characteristics of the resulting thin film.
  • the impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less.
  • the total amount of organic impurities is preferably 500 ppm or less, more preferably 50 ppm or less, and even more preferably 10 ppm or less.
  • Moisture causes particle generation in raw materials for thin film formation for atomic layer deposition and particle generation during thin film formation. For this reason, it is better to remove as much moisture 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.
  • a high-quality ruthenium-containing thin film with little residual carbon is formed by reducing the impurity metal element content, impurity halogen content, impurity organic content, and water content in the raw material for forming a thin film for atomic layer deposition according to the present invention to the above values or less. easier to do.
  • the raw material for thin film formation for atomic layer deposition of the present invention preferably contains particles as little as possible.
  • the number of particles larger than 0.3 ⁇ m in the particle measurement with a light scattering type in-liquid particle detector in the liquid phase is the thin film for atomic layer deposition.
  • the number of particles larger than 0.2 ⁇ m is preferably 100 or less in 1 mL of the raw material for formation, and more preferably 100 or less in 1 mL of the raw material for thin film formation for atomic layer deposition.
  • the ruthenium compound of the present invention is represented by the above general formula (2).
  • the ruthenium compound of the present invention can be preferably used as a raw material for forming thin films for vapor phase epitaxy, and since it has an ALD window, it can be suitably used as a raw material for forming thin films for atomic layer deposition.
  • R 7 and R 8 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 9 , R 10 , R 11 and R 12 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or a fluorine atom-containing alkyl group having 1 to 4 carbon atoms
  • a plurality of R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are , may be different or the same.
  • alkyl groups having 1 to 4 carbon atoms represented by R 7 , R 8 , R 9 , R 10 , R 11 and R 12 include methyl group, ethyl group, n-propyl group and isopropyl group. , n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like.
  • fluorine atom-containing alkyl groups having 1 to 4 carbon atoms represented by R 9 , R 10 , R 11 and R 12 include monofluoromethyl group, difluoromethyl group, trifluoromethyl group and trifluoroethyl group. , pentafluoroethyl group, trifluoropropyl group, heptafluoropropyl group, nonafluorotert-butyl group and the like.
  • At least one of R 7 and R 8 is preferably an alkyl group having 1 to 3 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms. is more preferred, and a methyl group is most preferred.
  • R 7 and R 8 may be the same or different, but from the viewpoint of improving the vapor pressure of the ruthenium compound, R 7 and R 8 are preferably the same. preferable.
  • R 9 and R 10 are preferably hydrogen atoms from the viewpoint of facilitating the formation of high-quality ruthenium-containing thin films with low residual carbon with good productivity.
  • At least one of R 11 and R 12 is preferably a hydrogen atom, more preferably one of R 11 and R 12 is a hydrogen atom, from the viewpoint of easily obtaining a ruthenium compound with a low melting point. Furthermore, from the viewpoint of easily obtaining a ruthenium compound having a low melting point and high thermal stability, one of R 11 and R 12 is an alkyl group having 1 to 3 carbon atoms or a It is preferably a fluorine atom-containing alkyl group, more preferably an alkyl group having 1 to 2 carbon atoms or a fluorine atom-containing alkyl group having 1 to 2 carbon atoms, and being a methyl group or a trifluoromethyl group. is most preferred.
  • Preferred specific examples of the ruthenium compound represented by general formula (2) include, for example, the above No. 1 to No. 8, No. 13 to No. 20, No. 25 to No. 32, No. 37 to No. 44, No. 49 to No.
  • a ruthenium compound represented by 56 and the like can be mentioned, but the present invention is not limited to these ruthenium compounds.
  • these ruthenium compounds No. 2, No. 3, No. 38 and no.
  • the ruthenium compound No. 39 is preferred because it easily forms a high-quality ruthenium-containing thin film with little residual carbon.
  • the ruthenium compound of No. 2 is more preferred due to its low melting point and good vapor pressure.
  • a ruthenium compound represented by the general formula (2) can be produced using a well-known reaction.
  • the ruthenium compound represented by the general formula (2) can be prepared, for example, by mixing triruthenium dodecacarbonyl (Ru 3 (CO) 12 ) and an arbitrary amino alcohol in the presence or absence of a solvent, and heating and stirring the reaction. can be obtained by letting
  • a ruthenium-containing thin film is formed on the surface of a substrate by ALD using the above-described raw material for thin film formation for atomic layer deposition.
  • a material for forming a thin film for atomic layer deposition in a material container as shown in FIG. 1 is vaporized by heating and/or reduced pressure.
  • a device capable of supplying a raw material gas to a film forming chamber together with a carrier gas as needed, or a device for forming a thin film for atomic layer deposition in a raw material container as shown in FIG. Examples include an apparatus capable of transporting a raw material in a liquid or solution state to a vaporization chamber, vaporizing the raw material by heating and/or decompressing it in the vaporizing chamber to form a raw material gas, and supplying the raw material gas to the film forming chamber. It should be noted that not only the single-wafer type apparatus having the film formation chamber shown in FIGS. 1 and 2, but also an apparatus capable of simultaneously processing a large number of wafers using a batch furnace can be used.
  • a raw material gas obtained by vaporizing the raw material for thin film formation for atomic layer deposition described above is introduced into a film formation chamber in which a substrate is installed, and the raw material gas is adsorbed on the surface of the substrate.
  • step 1 precursor thin film forming step
  • step 2 exhausting step
  • unreacted raw material gas with a reactive gas to form a ruthenium-containing thin film on the surface of the substrate (ruthenium-containing thin film forming step).
  • the method for producing a thin film of the present invention includes step 4 (exhaust step) of evacuating the gas in the deposition chamber after step 3. It is preferable to have
  • step 1 precursor thin film formation step
  • step 2 exhaust step
  • step 3 ruthenium-containing thin film formation step
  • step 4 exhaust step
  • Step 1 a raw material gas obtained by vaporizing the raw material for forming a thin film for atomic layer deposition is introduced into a film formation chamber in which a substrate is installed, and the raw material gas is adsorbed on the surface of the substrate to form a precursor thin film. It is a step of forming As a method of introducing the raw material gas obtained by vaporizing the raw material for thin film formation for the atomic layer deposition method into the film formation chamber in which the substrate is installed, as shown in FIGS.
  • a raw material for forming a thin film for a layer deposition method is vaporized by heating and/or under reduced pressure to form a raw material gas, and the raw material gas is introduced into a film formation chamber together with a carrier gas such as argon, nitrogen, helium, etc. as necessary.
  • a carrier gas such as argon, nitrogen, helium, etc.
  • FIG. There is a liquid transportation method in which a source gas for forming a thin film for atomic layer deposition is vaporized by reducing the pressure, and the source gas is introduced into a film forming chamber.
  • the ruthenium compound represented by the general formula (1) itself can be used as a raw material for forming a thin film for atomic layer deposition.
  • the ruthenium compound represented by the general formula (1) or a solution obtained by dissolving the ruthenium compound in an organic solvent can be used as a raw material for forming a thin film for the atomic layer deposition method.
  • These raw materials for forming thin films for atomic layer deposition may further contain nucleophilic reagents and the like.
  • methods for introducing the raw material gas into the film formation chamber include the single source method and the cocktail source method, which are described as multi-component ALD methods including a plurality of precursors.
  • the raw material for forming a thin film for atomic layer deposition used in the method for producing a thin film of the present invention is vaporized in the range of 50° C. or higher and 200° C. or lower from the viewpoint of handling.
  • the pressure inside the raw material container and the pressure inside the vaporizing chamber are From the viewpoint of facilitating vaporization, the pressure is preferably 1 Pa or more and 10,000 Pa or less.
  • the material of the substrate placed in the deposition chamber includes, for example, silicon; ceramics such as silicon nitride, titanium nitride, tantalum nitride, titanium oxide, ruthenium oxide, zirconium oxide, hafnium oxide, and lanthanum oxide; glass; Metals such as cobalt and ruthenium are included.
  • the shape of the substrate include plate-like, spherical, fibrous, and scale-like.
  • the substrate surface may be flat or may have a three-dimensional structure such as a trench structure.
  • the precursor thin film can be formed on the substrate surface by allowing the raw material gas to be adsorbed on the substrate surface.
  • the substrate may be heated, or the inside of the film forming chamber may be heated.
  • the conditions for forming the precursor thin film are not particularly limited, and for example, the adsorption temperature (substrate temperature), system pressure, etc. can be appropriately determined according to the kind of the raw material for forming the thin film for atomic layer deposition.
  • Step 1 is preferably performed with the substrate heated to 100° C. or higher, and more preferably performed with the substrate heated to 150° C. or higher and lower than 350° C. from the viewpoint that a uniform precursor thin film can be easily obtained.
  • the system pressure is not particularly limited, but is preferably 1 Pa or more and 10,000 Pa or less, and more preferably 10 Pa or more and 1,000 Pa or less from the viewpoint that a uniform precursor thin film can be easily obtained.
  • Step 2 is a step of evacuating the raw material gas that has not been adsorbed on the surface of the substrate from the deposition chamber after the precursor thin film is formed in step 1 .
  • step 2 it is ideal that the raw material gas that has not been adsorbed is completely exhausted from the deposition chamber, but it is not necessary to exhaust it completely.
  • Exhaust methods include, for example, a method of purging the inside of the deposition chamber system with an inert gas such as helium, nitrogen, and argon, a method of evacuating the inside of the system by reducing the pressure, and a combination of these methods. .
  • the degree of pressure reduction when reducing the pressure in the system is preferably in the range of 0.01 Pa or more and 300 Pa or less, and more preferably in the range of 0.01 Pa or more and 100 Pa or less from the viewpoint of promoting the evacuation of the raw material gas that has not been adsorbed.
  • Step 3 In step 3, after step 2, a reactive gas is introduced into the film-forming chamber, and the precursor thin film formed on the surface of the substrate is reacted with the reactive gas by the action of the reactive gas and the action of heat. This is the step of forming a ruthenium-containing thin film.
  • the reactive gas examples include oxidizing gases such as oxygen and ozone, and reducing gases such as ammonia, hydrogen, monosilane and hydrazine.
  • the reactive gas may be used singly or in combination of two or more.
  • the reactive gas contains at least one selected from the group consisting of hydrogen, ammonia, oxygen and ozone from the viewpoint that it is easy to form a high-quality ruthenium-containing thin film with little residual carbon. It is preferably a gas that
  • the temperature (substrate temperature) at which the precursor thin film is reacted with the reactive gas is preferably 100° C. or higher and 450° C. or lower. °C or higher and lower than 400 °C, and more preferably 150 °C or higher and lower than 350 °C.
  • the pressure in the film forming chamber when step 3 is performed is preferably 1 Pa or more and 10,000 Pa or less, and from the viewpoint that the reaction between the precursor thin film and the reactive gas is favorable, 10 Pa or more and 1 ,000 Pa or less.
  • Step 4 is a step of exhausting unreacted reactive gas and by-product gas from the deposition chamber after step 3.
  • the unreacted reactive gas represents the reactive gas that did not react with the precursor thin film in step 3.
  • the by-product gas represents the gas generated after reacting the precursor thin film with the reactive gas in step 3.
  • the deposition chamber should ideally be completely evacuated of reactive gases and by-product gases, but not necessarily. The evacuation method and the degree of pressure reduction when reducing the pressure are the same as in step 2 described above.
  • the series of operations of the above steps 1, 2, 3 and optional step 4 is regarded as one cycle, and the thickness of the ruthenium-containing thin film obtained is adjusted by the number of cycles. can do.
  • energy such as plasma, light, or voltage may be applied in the deposition chamber, or a catalyst may be used.
  • the timing of applying the energy and the timing of using the catalyst are not particularly limited. In 3, when the reactive gas is introduced into the film formation chamber, or when the reactive gas is reacted with the precursor thin film, or when the system is exhausted in step 2 or step 4, during each of the above steps It's okay.
  • annealing may be performed in an inert atmosphere, an oxidizing atmosphere, or a reducing atmosphere in order to obtain better electrical characteristics.
  • a reflow process may be provided when step embedding is required.
  • the temperature in this case is preferably 200° C. or higher and 1,000° C. or lower, and more preferably 250° C. or higher and 500° C. or lower from the viewpoint that thermal damage to the thin film or substrate can be suppressed.
  • Thin films manufactured by the thin film manufacturing method of the present invention include thin films of ruthenium metal, ruthenium oxide and ruthenium nitride.
  • the thin film manufacturing method of the present invention can efficiently manufacture a ruthenium metal thin film.
  • the thin film of the present invention can be made into a desired type of thin film by appropriately selecting other precursors, reactive gases, and manufacturing conditions in the above thin film manufacturing method. Since the thin film of the present invention has excellent electrical and optical properties, it can be used, for example, as an electrode material for memory elements represented by DRAM elements, a wiring material for semiconductor elements, a diamagnetic film used for the recording layer of a hard disk, and a polymer electrolyte fuel. It can be widely used in the production of catalyst materials for batteries and the like.
  • the solvent was distilled off under reflux and reduced pressure, and hexane was added to the resulting residue, followed by filtration.
  • the solvent of the filtrate was distilled off under reduced pressure, and the residue obtained from the filtrate was purified by sublimation under conditions of 110°C and 20 Pa to obtain 0.25 g of white crystals (yield 12.5%).
  • the obtained white crystals were analyzed by 1 H-NMR and ICP-AES, and the objective compound No. 2 ruthenium compound.
  • the 1 H-NMR and ICP-AES analysis results of the obtained white crystals are shown below.
  • Example 2 No. Synthesis of ruthenium compound of 9 0.97 g of triruthenium dodecacarbonyl, 1.36 g of 1-trifluoromethyl-2-(methylamino)ethyl alcohol and 1.40 mL of heptane are added to a reaction flask, heated to 110 ° C., and 7 The reaction was allowed to reflux for an hour. After refluxing, the solvent was distilled off under reduced pressure, and the resulting residue was purified by sublimation under conditions of 175°C and 45 Pa to obtain 0.34 g of brown solid (yield 17.0%). The obtained brown solid was analyzed by 1 H-NMR and ICP-AES, and the objective compound No. 9 ruthenium compound. The 1 H-NMR and ICP-AES analysis results of the resulting brown solid are shown below.
  • Comparative compound 1 bis (2,4-dimethylpentadienyl) ruthenium
  • Comparative compound 2 bis (5-(ethylimino)-2,6-dimethylhept-3-ene-3-oleate) ruthenium dicarbonyl
  • a thin film was manufactured using the compound evaluated above as a raw material for forming a thin film for atomic layer deposition.
  • Example 4 No. Using the ruthenium compound No. 10 as a raw material for thin film formation for atomic layer deposition, using the ALD apparatus shown in FIG. When the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a ruthenium metal thin film and that the amount of residual carbon in the thin film was less than the detection limit of 0.01 atm %. Further, when the film thickness of the thin film was measured using an X-ray reflectance method, the thin film formed on the substrate was a smooth film with a film thickness of 9.3 nm, and the film thickness obtained per cycle was It was about 0.047 nm.
  • Step 1 A vapor (raw material gas) of a raw material for thin film formation for atomic layer deposition vaporized under conditions of a raw material container temperature of 130° C. and a raw material container internal pressure of 26.67 Pa is introduced into the film forming chamber, and the system pressure is set to 26.0 Pa. At 67 Pa for 20 seconds, the raw material gas is adsorbed on the substrate surface to form a precursor thin film.
  • Step 2 By purging with argon for 10 seconds, the raw material gas that has not been adsorbed is exhausted from the system.
  • Step 3 A reactive gas is introduced into the deposition chamber, and the precursor thin film and the reactive gas are allowed to react at a system pressure of 100 Pa for 1 second.
  • Step 4 Exhaust unreacted reactive gas and by-product gas from the system by purging with argon for 10 seconds.
  • Example 5 No. 10 ruthenium compounds, no. A thin film was produced in the same manner as in Example 4, except that the ruthenium compound of No. 2 was used.
  • the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a ruthenium metal thin film and that the amount of residual carbon in the thin film was less than the detection limit of 0.01 atm %.
  • the film thickness of the thin film was measured using an X-ray reflectance method, the thin film formed on the substrate was a smooth film with a film thickness of 12.3 nm, and the film thickness obtained per cycle was It was about 0.062 nm.
  • Example 6 No. 10 ruthenium compounds, no. A thin film was produced in the same manner as in Example 4, except that the ruthenium compound No. 9 was used.
  • the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, it was confirmed that the thin film was a ruthenium metal thin film and that the amount of residual carbon in the thin film was less than the detection limit of 0.01 atm %.
  • the film thickness of the thin film was measured using an X-ray reflectance method, the thin film formed on the substrate was a smooth film with a film thickness of 9.2 nm, and the film thickness obtained per cycle was It was about 0.046 nm.
  • Example 1 A thin film was produced in the same manner as in Example 4, except that the ruthenium compound No. 10 was changed to the comparative compound No. 1.
  • the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, the thin film was a ruthenium metal thin film, and the amount of residual carbon in the thin film was 8.0 atm %.
  • the film thickness of the thin film was measured using an X-ray reflectance method, it was found to be a smooth film with a film thickness of 2.3 nm, and the film thickness obtained per cycle was approximately 0.012 nm.
  • Example 2 No. A thin film was produced in the same manner as in Example 4, except that the ruthenium compound No. 10 was changed to the comparative compound No. 2.
  • the composition of the thin film was analyzed using X-ray photoelectron spectroscopy, the thin film was a ruthenium metal thin film, and the amount of residual carbon in the thin film was 8.2 atm %.
  • the film thickness of the thin film was measured using the X-ray reflectance method, it was found to be a smooth film with a film thickness of 8.7 nm, and the film thickness obtained per cycle was approximately 0.044 nm.
  • a high-quality ruthenium-containing thin film with little residual carbon can be formed by an atomic layer deposition method using a thin film forming raw material for atomic layer deposition containing a ruthenium compound having a specific structure of the present invention.
  • the ruthenium-containing thin film produced by the method for producing a thin film of the present invention has a significantly thick film thickness per cycle, it is suggested that the method for producing a thin film of the present invention can achieve high productivity.

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Abstract

L'invention concerne une charge d'alimentation de formation de couche mince, destinée à être utilisée en dépôt de couche atomique, qui contient un composé de ruthénium représenté par la formule générale (1) ci-dessous. (Dans la formule (1), R1, R2, R3, R4, R5 et R6 représentent chacun indépendamment un atome d'hydrogène, un groupe alkyle ayant de 1 à 4 atomes de carbone, ou un groupe alkyle contenant un atome de fluor ayant de 1 à 4 atomes de carbone, dans laquelle chaque élément de la pluralité constituée de R1, R2, R3, R4, R5 et R6 peut être identique ou différent.)
PCT/JP2022/016488 2021-04-16 2022-03-31 Charge d'alimentation de formation de couche mince destinée à être utilisée en dépôt de couche atomique, couche mince, procédé de production de couche mince et composé de ruthénium Ceased WO2022220153A1 (fr)

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Citations (5)

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WO2006049059A1 (fr) * 2004-11-02 2006-05-11 Adeka Corporation Composé métallique, matériau permettant de former une couche mince, et méthode de fabrication de couche mince
JP2009001896A (ja) * 2007-04-16 2009-01-08 Air Products & Chemicals Inc 化学蒸着用金属前駆体溶液
WO2010071364A2 (fr) * 2008-12-19 2010-06-24 주식회사 유피케미칼 Composé précurseur organométallique pour dépôt en phase vapeur de couches minces métalliques ou en oxyde de métal, et procédé de dépôt en phase vapeur de couches minces utilisant ce composé
JP6509128B2 (ja) * 2013-12-20 2019-05-08 株式会社Adeka ルテニウム化合物、薄膜形成用原料及び薄膜の製造方法
WO2019097768A1 (fr) * 2017-11-16 2019-05-23 株式会社Adeka Composé ruthénium, matière de départ pour formation de film mince, et procédé de fabrication de film mince

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WO2006049059A1 (fr) * 2004-11-02 2006-05-11 Adeka Corporation Composé métallique, matériau permettant de former une couche mince, et méthode de fabrication de couche mince
JP2009001896A (ja) * 2007-04-16 2009-01-08 Air Products & Chemicals Inc 化学蒸着用金属前駆体溶液
WO2010071364A2 (fr) * 2008-12-19 2010-06-24 주식회사 유피케미칼 Composé précurseur organométallique pour dépôt en phase vapeur de couches minces métalliques ou en oxyde de métal, et procédé de dépôt en phase vapeur de couches minces utilisant ce composé
JP6509128B2 (ja) * 2013-12-20 2019-05-08 株式会社Adeka ルテニウム化合物、薄膜形成用原料及び薄膜の製造方法
WO2019097768A1 (fr) * 2017-11-16 2019-05-23 株式会社Adeka Composé ruthénium, matière de départ pour formation de film mince, et procédé de fabrication de film mince

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