WO2013161735A1 - 複合酸化物薄膜製造用組成物及びこの組成物を用いた薄膜の製造方法、並びに複合酸化物薄膜 - Google Patents

複合酸化物薄膜製造用組成物及びこの組成物を用いた薄膜の製造方法、並びに複合酸化物薄膜 Download PDF

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WO2013161735A1
WO2013161735A1 PCT/JP2013/061729 JP2013061729W WO2013161735A1 WO 2013161735 A1 WO2013161735 A1 WO 2013161735A1 JP 2013061729 W JP2013061729 W JP 2013061729W WO 2013161735 A1 WO2013161735 A1 WO 2013161735A1
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group
compound
composition
thin film
water
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PCT/JP2013/061729
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English (en)
French (fr)
Japanese (ja)
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裕仁 竹元
健一 羽賀
孝一郎 稲葉
豊田　浩司
功一 徳留
賢二 吉野
稔 小嶋
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東ソー・ファインケム株式会社
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Priority to JP2014512541A priority Critical patent/JP6322573B2/ja
Priority to KR1020147032942A priority patent/KR101980413B1/ko
Priority to CN201380021829.3A priority patent/CN104254495B/zh
Publication of WO2013161735A1 publication Critical patent/WO2013161735A1/ja

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    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
    • 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
    • H01L21/02551—Group 12/16 materials
    • H01L21/02554—Oxides
    • 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
    • H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
    • 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
    • H01L21/02623—Liquid deposition
    • H01L21/02628—Liquid deposition using solutions

Definitions

  • the present invention has an average transmittance of 80% or more with respect to visible light, and is an oxide semiconductor film such as ZTO or ATO used for a switching element (thin film transistor) such as a liquid crystal display device or a thin film electroluminescence display device. It is related with the composition for complex oxide thin-film manufacture which can prepare the complex oxide thin film applicable to these. Furthermore, the present invention relates to a method for producing a complex oxide thin film applicable to the oxide semiconductor film and the like, and a complex oxide thin film produced using the production method.
  • the composition for producing a complex oxide thin film of the present invention is prepared using a compound containing at least two elements from an organic zinc compound, a group 4A element compound, a group 3B element compound, and a group 4B element compound as a raw material, and has an ignitability. It is easy to handle and provides a composite oxide thin film having an average transmittance of 80% or more for visible light when used as a raw material for spin coating, dip coating, or spray pyrolysis coating. it can.
  • a compound containing at least two or more elements is prepared from an organic zinc compound, a group 4A element compound, a group 3B element compound, and a group 4B element compound as a raw material, Further, when used as a spin coat coating material, a dip coat coating material, or a spray pyrolysis coating material, a composite oxide thin film having an average transmittance of 80% or more for visible light can be provided.
  • an oxide semiconductor film made of a metal composite oxide that is one of complex oxides for example, an oxide semiconductor film made of an oxide of In, Ga, and Zn (IGZO) is known, which is more than an amorphous Si film.
  • IGZO oxide semiconductor film made of an oxide of In, Ga, and Zn
  • IGZO oxide semiconductor film made of an oxide of In, Ga, and Zn
  • an oxide of Zn and Sn (ZTO), an oxide of Al and Sn (ATO), and a composite oxide containing 3B group elements such as Ga, In, and Al and 4A group elements such as Zr and Hf in ZTO ATO is interested in the thin film properties of complex oxides containing 3B group elements such as Zn, Ga and In and 4A group elements such as Zr and Hf in ATO. It is being advanced.
  • a method for forming this amorphous oxide film As a method for forming this amorphous oxide film, a method of forming a thin film by treating a sintered body of IGZO in vacuum, such as PVD method and sputtering method, is generally known. It is known that an IGZO sputtering target is used to form an amorphous oxide film (Patent Document 1, Non-Patent Documents 1 and 2).
  • Examples of a general coating method for forming an oxide thin film include a spin coating method (Patent Document 2), a dip coating method (Non Patent Literature 3), and a spray pyrolysis method (Non Patent Literatures 4 and 5).
  • a material for forming a zinc oxide thin film intended for a transparent conductive film or the like is known. Specifically, zinc acetate, an alcohol-based organic solvent is used. Diethyl zinc dissolved while reacting with bismuth, a composition obtained by partially hydrolyzing diethyl zinc, and the like are used.
  • ZTO Zn and Sn oxides
  • ATO Al and Sn oxides
  • Zn and Sn chlorides, acetates, acetylacetonate compounds, alkoxides, etc. have been studied.
  • the inventors adjusted the composition of the above-described ZTO, ATO, or the like using the material described in Non-Patent Document 6, and attempted film formation by spin coating, dip coating, or spray pyrolysis. However, it was difficult to obtain a transparent oxide thin film at 200 ° C. or lower.
  • the present invention relates to a group 3B element compound or a group 3B element compound such as a partial hydrolyzate of an organozinc compound such as diethylzinc or diethylzinc, an alkylaluminum such as triethylaluminum or a partial hydrolyzate of an organoaluminum such as alkylaluminum.
  • An object of the present invention is to provide a new means capable of forming an oxide thin film such as ZTO or ATO with a composition based on a partial hydrolyzate by water.
  • an organozinc compound such as diethylzinc or diethylzinc
  • an alkylaluminum such as triethylaluminum
  • an organoaluminum such as alkylaluminum.
  • a novel composition containing a group 4B element compound such as Sn or a group 4B element such as Zr or Hf based on a partial hydrolyzate of a group 3B element compound or a group 3B element compound with water is used. It was found that by forming a film, an oxide thin film such as ZTO or ATO can be easily obtained with an average transmittance of 80% or more for visible light, and the present invention was completed.
  • a composition for producing a complex oxide comprising at least one element selected from the group consisting of zinc element and group 3B element, and at least one element selected from the group consisting of group 4A element and group 4B element, At least one compound selected from the group consisting of a compound containing zinc element and a compound containing group 3B element, a partial hydrolyzate of the compound with water or the compound and the partial hydrolyzate, and a compound containing a group 4A element And at least one compound selected from the group consisting of compounds containing a group 4B element, a partial hydrolyzate of the compound with water, or the composition and the composition containing the partial hydrolyzate.
  • composition according to 1-1 wherein the compound containing zinc element is an organic zinc compound represented by the following general formula (1).
  • R 1 —Zn—R 1 (1) (In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms.)
  • the partial hydrolyzate of the organozinc compound with water is prepared by mixing the organozinc compound represented by the general formula (1) and water so that the molar ratio is in the range of 0.05 to 0.8.
  • the composition according to 1-2 which is a product obtained by partially hydrolyzing a zinc compound.
  • the partial hydrolyzate of the group 3B element compound with water is prepared by mixing the group 3B element compound represented by the general formula (2) and water so that the molar ratio is in the range of 0.05 to 0.8.
  • the composition according to 1-4 which is a product obtained by partially hydrolyzing the Group 3B element compound.
  • M is a 4A group element or a 4B group element
  • R 5 , R 6 , R 7 and R 8 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, 1 carbon atom, A linear or branched alkoxyl group, an acyloxy group, an acetylacetonate group or an amide group of 7 to 7, L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9 .
  • M is a 4A group element or 4B group element
  • X is a halogen atom, nitric acid or sulfuric acid
  • X is a halogen atom or nitric acid
  • c is 1, d is 3, and X is sulfuric acid.
  • the partial hydrolyzate of the Group 4A element compound and the Group 4B element compound with water has a molar ratio of the compound represented by the general formula (3) or (4) to water in the range of 0.05 to 0.8.
  • the composition according to 1-6 which is a product obtained by partially hydrolyzing at least the Group 4A element compound and the Group 4B element compound by mixing in such a manner.
  • the partial hydrolyzate of at least one selected compound with water is: And at least one compound selected from the group consisting of the compound containing the group 4A element and the compound containing the group 4B element, and at least one compound selected from the group consisting of the compound containing the zinc element and the compound containing the group 3B element.
  • 1-1 to 7 are products obtained by partially hydrolyzing the compound by adding water so that the molar ratio to the total of the compound is in the range of 0.05 to 0.8.
  • the composition according to any one of the above. (1-9) 9.
  • the composition according to 1-9 or 10 wherein the organic solvent has a boiling point of 230 ° C. or lower.
  • the electron donating solvent includes 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, dioxane, and at least one selected from the group consisting of hexane, heptane, octane, toluene, xylene, and cyclohexane as a hydrocarbon solvent.
  • the composition according to -10 (1-13) 13. The composition according to any one of 1-2 to 12, wherein the organozinc compound is diethyl zinc.
  • the group 3B element compound of the general formula (2) is at least one selected from the group consisting of trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trimethylborane, and triethylborane.
  • the composition according to any one of 1-1 to 14, wherein the group 3B element is Al, Ga, and In.
  • (1-16) The composition according to any one of 1-1 to 15, wherein the Group 4A element is Ti, Zr, and Hf.
  • group 4B element is Si, Ge, and Sn.
  • At least one compound selected from the group consisting of compounds containing group 4B elements, a partial hydrolyzate of the compound with water, or a group consisting of zinc elements and group 3B elements containing the compound and the partial hydrolysate A composite oxide manufacturing composition containing at least one element selected from the group consisting of a group 4A element and a group 4B element on the substrate surface in an inert gas atmosphere.
  • the production method according to 2-1 wherein the compound containing zinc element is an organic zinc compound represented by the following general formula (1).
  • R 1 —Zn—R 1 (1) (In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms.)
  • the partial hydrolyzate of the organozinc compound with water is prepared by mixing the organozinc compound represented by the general formula (1) and water so that the molar ratio is in the range of 0.05 to 0.8.
  • the production method according to 2-2 which is a product obtained by partially hydrolyzing a zinc compound.
  • (2-4) 4. The production method according to any one of 2-1 to 3, wherein the compound containing a group 3B element is a group 3B element compound represented by the following general formula (2).
  • M is a Group 3B element
  • R 2 , R 3 and R 4 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, and L is nitrogen, oxygen or phosphorus And n is an integer of 0 to 9.
  • the partial hydrolyzate of the group 3B element compound with water is prepared by mixing the group 3B element compound represented by the general formula (2) and water so that the molar ratio is in the range of 0.05 to 0.8.
  • the production method according to 2-4 which is a product obtained by partially hydrolyzing the group 3B element compound.
  • (2-6) Any one of 2-1 to 5 wherein the compound containing the group 4A element and the compound containing the group 4B element are a group 4A element compound and a group 4B element compound represented by the following general formula (3) or (4): The production method according to item.
  • M is a 4A group element or a 4B group element
  • R 5 , R 6 , R 7 and R 8 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, 1 carbon atom, A linear or branched alkoxyl group, an acyloxy group, an acetylacetonate group or an amide group of 7 to 7, L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9 .
  • M is a 4A group element or 4B group element
  • X is a halogen atom, nitric acid or sulfuric acid
  • X is a halogen atom or nitric acid
  • c is 1, d is 3, and X is sulfuric acid.
  • the partial hydrolyzate of the Group 4A element compound and the Group 4B element compound with water has a molar ratio of the compound represented by the general formula (3) or (4) to water in the range of 0.05 to 0.8.
  • the production method according to 2-6 which is a product obtained by partially hydrolyzing at least the Group 4A element compound and the Group 4B element compound.
  • the partial hydrolyzate of at least one selected compound with water is: And at least one compound selected from the group consisting of the compound containing the group 4A element and the compound containing the group 4B element, and at least one compound selected from the group consisting of the compound containing the zinc element and the compound containing the group 3B element.
  • 2-1-7 which are products obtained by adding water such that the molar ratio to the total of the compounds is in the range of 0.05 to 0.8 and partially hydrolyzing the compounds.
  • the manufacturing method of any one of Claims. (2-9) 9. The production method according to any one of 2-1 to 8, wherein the composition further contains an organic solvent.
  • the production method according to 2-9 or 10 wherein the boiling point of the organic solvent is 230 ° C. or lower.
  • the electron donating solvent includes 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, dioxane, and at least one selected from the group consisting of hexane, heptane, octane, toluene, xylene, and cyclohexane as a hydrocarbon solvent.
  • the production method according to -10 The production method according to -10.
  • the group 3B element compound of the general formula (2) is at least one selected from the group consisting of trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trimethylborane, and triethylborane.
  • a useful composite oxide thin film such as an oxide semiconductor film such as ZTO or ATO can be applied by spin coating, dip coating, spray pyrolysis or the like.
  • a composite oxide thin film which can be easily formed by a film and has an average transmittance of 80% or more with respect to visible light can be produced.
  • the composite oxide thin film manufacturing composition of the present invention has at least one element selected from the group consisting of zinc element and 3B group element, and at least one element selected from the group consisting of group 4A element and group 4B element A composition for producing a composite oxide.
  • This composition includes at least one compound selected from the group consisting of a compound containing a zinc element and a compound containing a group 3B element, a partial hydrolyzate of the compound with water or the compound and the partial hydrolyzate, and 4A.
  • Compound containing zinc element examples include organic zinc compounds represented by the following general formula (1).
  • R 1 —Zn—R 1 (1) (In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms.)
  • alkyl group represented by R 1 in the organozinc compound represented by the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group.
  • R 1 is preferably a compound having 1, 2, 3, 4, 5, or 6 carbon atoms.
  • the compound represented by the general formula (1) is preferably diethyl zinc, in which R 1 has 2 carbon atoms.
  • R 2 , R 3 , and R 4 are preferably hydrogen or an alkyl group.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group.
  • Ligands represented as L include trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, N, N-diethylaniline, triphenylphosphine, dimethylsulfur, diethyl ether, and tetrahydrofuran. Can be mentioned.
  • R 2 , R 3 , and R 4 are preferably compounds having 1, 2, 3, 4, 5, or 6 carbon atoms.
  • Examples thereof include isobutylaluminum, diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, trimethylindium, triethylindium, trimethylborane, triethylborane, and coordination compounds thereof using a ligand thereof.
  • Compound containing group 4A element and compound containing group 4B element examples include, for example, the group 4A represented by the following general formula (3) or (4) An element compound and a 4B group element compound can be mentioned.
  • M is a 4A group element or a 4B group element
  • R 5 , R 6 , R 7 and R 8 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, 1 carbon atom, A linear or branched alkoxyl group, an acyloxy group, an acetylacetonate group or an amide group of 7 to 7, L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9 .
  • M is a 4A group element or 4B group element
  • X is a halogen atom, nitric acid or sulfuric acid
  • X is a halogen atom or nitric acid
  • c is 1, d is 3, and X is sulfuric acid.
  • C is 2, d is 3, and a is an integer from 0 to 9.
  • Specific examples of the metal represented by M in the group 4A element compound represented by the general formula (3) include Ti, Zr, and Hf. These alkyl compounds are generally unstable, and R 5 , R 6 , R 7 and R 8 in the formula are oxygen and nitrogen elements such as alkoxyl groups, acyloxy groups, acetoxy groups, acetylacetonato groups, amide groups, etc. It is preferable that it is a ligand containing.
  • specific examples of these ligands include generally known alkoxyl groups, acetoxy groups, acyloxy groups, acetylacetonato groups, amide groups, and the like.
  • alkoxyl group examples include methoxy group, ethoxy group, isopropoxide group, tert-butoxy group and the like. Further examples include an acyloxy group such as an acetoxy group, an acetylacetonato group, an amide group such as trimethylamide, triethylamide, isopropylamide, and tert-butylamide.
  • Specific examples of the element represented by M in the group 4B element compound represented by the general formula (3) include Si, Ge, and Sn. Specific examples of these compounds include generally known alkyl groups, alkoxyl groups, acyloxy groups, acetylacetonato groups and amide groups. Specific examples of the alkyl group represented by R 5 , R 6 , R 7 , and R 8 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and pentyl.
  • alkoxyl group examples include methoxy group, ethoxy group, isopropoxide group, tert-butoxy group and the like.
  • acyloxy group such as an acetoxy group, an acetylacetonato group, an amide group such as trimethylamide, triethylamide, isopropylamide, and tert-butylamide.
  • the group 4B element compound represented by the general formula (3) includes, in particular, ethyl tin, butyl tin, methoxy silicon, ethoxy silicon, isopropoxy silicon, tert-butoxy silicon, methoxy germanium, ethoxy germanium, isopropoxy germanium, and tert-butoxy.
  • the ligand represented by L in the group 4A and 4B element compounds represented by the general formula (3) is trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, N, N— Examples thereof include diethylaniline, triphenylphosphine, dimethyl sulfur, diethyl ether, and tetrahydrofuran.
  • the group 4A element compound represented by the general formula (3) is, for example, methoxy titanium, ethoxy titanium, isopropoxy titanium, butoxy titanium, methoxy zirconium, ethoxy zirconium, isopropoxy zirconium, butoxy zirconium, methoxy hafnium, isopropoxy.
  • the metal represented by M in the group 4A element compound represented by the general formula (4) include Ti, Zr, and Hf.
  • Specific examples of the partner that forms the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid.
  • the group 4A element compound represented by the general formula (4) includes, for example, titanium fluoride, zirconium fluoride, hafnium fluoride, titanium chloride, zirconium chloride, hafnium chloride, titanium nitrate, zirconium nitrate, hafnium nitrate, sulfuric acid. Examples thereof include titanium, zirconium sulfate, hafnium sulfate and hydrates thereof.
  • the metal represented by M in the group 4B element compound represented by the general formula (4) include Si, Ge, and Sn.
  • Specific examples of the partner that forms the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid.
  • the group 4B element compound represented by the general formula (4) includes, for example, silicon fluoride, germanium fluoride, tin fluoride, silicon chloride, germanium chloride, tin chloride, tin bromide, germanium nitrate, tin nitrate, Examples thereof include tin sulfate and hydrates thereof.
  • the above-described composition for producing a complex oxide thin film of the present invention includes the following aspects.
  • compositions 1 to 9 as a compound containing a group 4A element and a compound containing a group 4B element, a group 4A element compound and / or a group 4B element compound represented by the general formula (3) or (4), A product obtained by partially hydrolyzing the group 4A element compound and / or the group 4B element compound represented by the general formula (3) or (4), or the general formula (3) or (4) The composition which added the product obtained by partially hydrolyzing the 4A group element compound and / or 4B group element compound which were represented, and this compound.
  • composition 1 A composition comprising an organozinc compound represented by the general formula (1) and a group 3B element compound represented by the general formula (2) (hereinafter sometimes referred to as the composition 1)
  • composition 2 A composition containing a partial hydrolyzate of the organic zinc compound represented by the general formula (1) and the group 3B element compound represented by the general formula (2) with water
  • composition 3 Water-containing portion of the organozinc compound represented by the general formula (1), the 3B group element compound represented by the general formula (2), and the 3B group element compound represented by the general formula (2) Composition containing hydrolyzate (hereinafter sometimes referred to as composition 3)
  • composition 4 A composition containing a partial hydrolyzate of the organic zinc compound represented by the general formula (1) with water and a group 3B element compound
  • composition 5 A composition containing a partial hydrolyzate of the organic zinc compound represented by the general formula (1) in water and a partial hydrolyzate of the group 3B element compound in water (hereinafter referred to as composition 5). is there)
  • composition containing a partial hydrolyzate of a group element compound with water hereinafter, sometimes referred to as composition 6
  • composition containing the organic zinc compound represented by the general formula (1), a partial hydrolyzate of the organic zinc compound with water, and a group 3B element compound represented by the general formula (2) Sometimes referred to as composition 7)
  • a zinc compound represented by the following general formula (5) or (6) can be added as a compound other than the general formula (1).
  • R 9 -MR 10 ⁇ (L) n (5) (Wherein, M is a zinc element, R 9 and R 10 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms (R 9 and R 10 both exclude alkyl groups) 1 to 7 linear or branched alkoxyl group, acyloxy group, acetylacetonate group or amide group, L is a coordination organic compound containing nitrogen, oxygen or phosphorus, and n is 0 to 9 (It is an integer.) M c X d ⁇ aH 2 O (6) (Wherein M is a zinc element, X is a halogen atom, nitric acid or sulfuric acid, when X is a halogen atom or nitric acid, c is 1, d is 2, and when
  • the zinc compound represented by the general formula (5) that can be added as a compound other than the general formula (1) include, for example, a generally known alkyl group (in the general formula (5) , R 9 and R 10 both exclude an alkyl group), an alkoxyl group, an acyloxy group, an acetylacetonato group and an amide group.
  • a generally known alkyl group in the general formula (5) , R 9 and R 10 both exclude an alkyl group
  • an alkoxyl group include methoxy group, ethoxy group, isopropoxide group, tert-butoxy group and the like.
  • acyloxy group such as an acetoxy group, an acetylacetonato group, an amide group such as trimethylamide, triethylamide, isopropylamide, and tert-butylamide.
  • the ligand represented by L in the general formula (5) is trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, N, N-diethylaniline, triphenylphosphine, dimethyl Sulfur, diethyl ether and tetrahydrofuran can be mentioned.
  • zinc compounds represented by the general formula (5) include dimethoxy zinc, diethoxy zinc, diisopropoxy zinc, tert-butoxy zinc, zinc acetate, acetylacetonato zinc, bisdimethylamide zinc, bisdiisopropylamide zinc and the like. And coordination compounds thereof.
  • Examples of the partner forming the salt represented by X in the zinc compound represented by the general formula (6) include fluorine, chlorine, bromine, iodine, nitric acid and sulfuric acid.
  • examples of the zinc compound represented by the general formula (6) include zinc fluoride, zinc chloride, zinc nitrate, zinc carbonate, zinc sulfate, and hydrates thereof.
  • a group 3B element compound for example, a group 3B element compound represented by the following formula (7) or (8) can be added as a compound other than the formula (2).
  • M is a group 3B element
  • R 11 , R 12 , and R 13 are each independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms
  • R 11 , R 12 , R 13 are all A linear or branched alkoxyl group having 1 to 7 carbon atoms, an acyloxy group, an acetylacetonate group or an amide group
  • L is a coordinating organic compound containing nitrogen, oxygen or phosphorus.
  • M is a group 3B element, X is a halogen atom, nitric acid or sulfuric acid, c is 1, when d is a halogen atom or nitric acid, d is 3, and when X is sulfuric acid, c is 2 D is 3, and a is an integer of 0 to 9.
  • R 11 , R 12 , and R 13 can include hydrogen and an alkyl group (R 11 , R 12 , and R 13 all exclude an alkyl group).
  • R 11 , R 12 , and R 13 all exclude an alkyl group.
  • Specific examples of the alkyl group include a methyl group, an ethyl group, and the like.
  • alkoxyl group examples include methoxy group, ethoxy group, isopropoxide group, tert-butoxy group and the like. Further examples include an acyloxy group such as an acetoxy group, an acetylacetonate group, an amide group such as trimethylamide, triethylamide, and isopropylamide.
  • the ligand represented by L in the general formula (7) is trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, N, N-diethylaniline, triphenylphosphine, dimethyl Sulfur, diethyl ether and tetrahydrofuran can be mentioned.
  • the group 3B element compound represented by the general formula (7) includes, in particular, diborane, borane-tetrahydrofuran complex, borane-trimethylamine complex, borane-triethylamine complex, triethylborane, tributylborane, alane-trimethylamine complex, alane-triethylamine complex, Trimethylaluminum, dimethylaluminum hydride, triisobutylaluminum, diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, trimethylindium, triethylindium, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triiso Examples include propoxyaluminum, tritert-butoxyindium, and tritert-butoxygallium.
  • Rukoto can. Triethylaluminum, triisobutylaluminum, trimethylgallium, trimethylindium, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, tritert. -Butoxyindium and tritert-butoxygallium are particularly preferred.
  • Specific examples of the group 3B element in the group 3B element compound and the metal represented by M in the group 3B element compound represented by the general formula (8) include B, Al, Ga, and In. .
  • Specific examples of the partner that forms the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid.
  • Examples of the group 3B element compound represented by the general formula (8) include boron fluoride, boron chloride, aluminum chloride, aluminum chloride hexahydrate, aluminum nitrate nonahydrate, gallium chloride, gallium nitrate hydrate, Examples thereof include indium chloride, indium chloride tetrahydrate, indium nitrate pentahydrate and the like.
  • the compound represented by the general formulas (1) and (2) is a linear or branched alkyl group having 1 to 7 carbon atoms in which R 5 , R 6 , R 7 and R 7 in the general formula (3).
  • the composition of the present invention also includes a composition containing a compound generated by such a substituent exchange reaction.
  • the present invention includes the above composition further containing an organic solvent.
  • composition of this invention can be mentioned as a more specific example of the composition of this invention. However, these are not intended to be limited.
  • A In a solution obtained by dissolving the organic zinc compound represented by the general formula (1) in an organic solvent, the group 4A element compound represented by the general formula (3) and / or the general formula (4) and / or A composition comprising a product containing a group 4B element compound (hereinafter sometimes referred to as a mixture 1).
  • B In a solution obtained by dissolving the group 3B element compound represented by the general formula (2) in an organic solvent, the group 4A element compound represented by the general formula (3) and / or the general formula (4) and / or Or the composition containing the product (henceforth the mixture 2) containing a 4B group element compound.
  • a composition comprising a product obtained by at least partial hydrolysis (hereinafter sometimes referred to as partial hydrolyzate 4).
  • an organic solvent can be used to dissolve the compound containing the above-mentioned metal.
  • This organic solvent dissolves the aforementioned zinc, 3B group element, 4A group element, 4B group element compound, or a partial hydrolyzate of these compounds, and is not particularly limited as long as there is no problem in use.
  • an electron-donating organic solvent such as ether or a hydrocarbon compound such as hexane or toluene which is generally used industrially.
  • These organic solvents may be used alone or as a mixture with other solvents.
  • Examples of the electron-donating organic solvent include ether compounds, amine compounds and the like, and those having solubility in raw material compounds such as an organic zinc compound represented by the general formula (1) and water. That's fine.
  • Examples of preferable electron donating organic solvents include those having a boiling point of 230 ° C.
  • di-n-butyl ether (boiling point 142.4 ° C.), dihexyl ether (boiling point 226.2 ° C.), Anisole (boiling point 153.8 ° C.), phenetol (boiling point 172 ° C.), butyl phenyl ether (boiling point 210.3 ° C.), pentyl phenyl ether (boiling point 214 ° C.), methoxytoluene (boiling point 171.8 ° C.), benzyl ethyl ether ( Boiling point 189 ° C), diphenyl ether (boiling point 258.3 ° C), veratrol (boiling point 206.7 ° C), trioxane (boiling point 114.5 ° C) and 1,2-diethoxyethane (boiling point 121 ° C), 1,2- Glyme such as dibutoxyethane (boiling
  • 1,2-diethoxyethane (boiling point 121 ° C.), which is a kind of glyme, is preferable from the viewpoints of both gel suppression and volatility of the solvent itself.
  • the upper limit of the boiling point of the electron-donating organic solvent is not particularly limited, but is 230 ° C. or less from the viewpoint that the drying time is relatively short when the solvent is removed after application of the obtained composition to form a coating film. It is preferable that
  • a hydrocarbon compound can be used as a solvent.
  • the hydrocarbon compound is a straight chain, branched hydrocarbon compound or cyclic hydrocarbon compound having 5 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. And aromatic hydrocarbon compounds and mixtures thereof.
  • hydrocarbon compounds include pentane, n-hexane, heptane, isohexane, methylpentane, octane, 2,2,4-trimethylpentane (isooctane), n-nonane, n-decane, n-hexadecane, Aliphatic hydrocarbons such as octadecane, eicosane, methylheptane, 2,2-dimethylhexane, 2-methyloctane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexanemethylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, cumene, Aromatic hydrocarbons such as trimethylbenzene, hydrocarbon solvents such as mineral spirits, solvent naphtha, kerosene, petroleum ether, etc. can be raised.
  • the upper limit of the boiling point of the organic solvent and hydrocarbon compound different from the above electron-donating organic solvent is not particularly limited, but the drying time when the solvent is removed after application of the obtained composition to form a coating film From the viewpoint that is relatively short, the temperature is preferably 230 ° C. or lower as in the case of the electron donating compound. Further, from the viewpoint of improving the stability of the compound containing a metal, it is desirable that the electron donating compound is contained in the composition of the present invention.
  • the concentration of the raw material compound is preferably in the range of 4 to 12% by mass.
  • the concentration of the raw material compounds represented by the general formulas (1) to (4) in the solution dissolved in the organic solvent is preferably in the range of 6 to 10% by mass.
  • a composition in which the compound or the partial hydrolyzate is dissolved in an organic solvent is obtained by dissolving or reacting as described above to become a composition as it is, or after obtaining a product by, for example, a partial hydrolysis reaction,
  • an organic solvent such as a donating organic solvent or a hydrocarbon compound
  • the composition of the present invention can be obtained.
  • the amount of water added in the preparation of the partial hydrolyzate is, for example, that in the partial hydrolyzate 1, the molar ratio with respect to the organozinc compound of the general formula (1) is in the range of 0.05 to 0.8.
  • the molar ratio with respect to the total amount of the group 3B element compound is preferably in the range of 0.05 to 0.8.
  • the molar ratio with respect to the total amount of the organic zinc compound and the group 3B element compound is preferably in the range of 0.05 to 0.8.
  • the molar ratio with respect to the total amount of the organozinc compound and the 3B group element compound is preferably in the range of 0.05 to 0.8, but the 4A group element compound and the 4B group element compound are also subject to hydrolysis. If so, water in the range of 0.01 to 0.8 can be added to the molar ratio relative to the total amount within a range in which the reaction of the organozinc compound and the group 3B element compound does not affect.
  • a reaction product containing a partial hydrolyzate obtained by adding water in this range forms a transparent and conductive zinc oxide thin film in spin coating, dip coating and spray pyrolysis. Can do. Also when the group 3B element compound is partially hydrolyzed alone, the molar ratio of water to the group 3B element compound is preferably in the range of 0.05 to 0.8.
  • the organic zinc compound when the organic zinc compound is partially hydrolyzed by setting the molar ratio of water to 0.4 or more, the organic zinc compound is partially hydrolyzed with a high yield of 90% or more based on the zinc contained in the raw material. A partially hydrolyzed product can be obtained.
  • an appropriate amount of the Group 3B element compound is also partially hydrolyzed.
  • the molar ratio 0.4 or more in the case of the partial hydrolyzate 1, the remaining amount of the organic zinc compound that is an unreacted raw material is used.
  • the organic zinc compound and the group 3B The residual amount of elemental compounds can be suppressed.
  • the upper limit of the molar ratio of water is preferably 0.8, more preferably 0.75.
  • the physical properties such as viscosity and boiling point of the composition can be controlled by controlling the amount of water added.
  • the oxide film can be easily formed by increasing the amount of water added.
  • the composition of the present invention obtained by using a compound that does not hydrolyze in the spray method or the like, or by using a partially hydrolyzed product with less addition of water, facilitates film formation at a low temperature. It can be carried out.
  • the product since water is added to the organic zinc compound and then the group 3B element compound is added, depending on the amount of water added, the added water is consumed for hydrolysis of the organic zinc compound.
  • the product usually does not include a hydrolyzate such as the group 3B element compound.
  • the group 3B element compound or the like is not hydrolyzed and is contained as it is as a raw material, or the organic group (ligand) such as the group 3B element compound and the organic group that the partial hydrolyzate of the organic zinc compound has There is also a possibility of exchange (ligand exchange).
  • water is added to a mixed solution of an organozinc compound and a group 3B element compound, so that the product usually contains a hydrolyzate such as the group 3B element compound.
  • the hydrolyzate such as the group 3B element compound may be a partial hydrolyzate depending on the amount of water added.
  • the addition of water can be performed with water alone without mixing water with another solvent, or can be performed with a mixed solvent obtained by mixing water with another solvent. From the viewpoint of suppressing the progress of local hydrolysis, it is preferable to use a mixed solvent, and the content of water in the mixed solvent can be, for example, in the range of 1 to 50% by mass, preferably 2 to 20% by mass.
  • the solvent that can be used for the mixed solvent with water can be, for example, the above-described electron-donating organic solvent.
  • the electron-donating organic solvent may be an organic solvent having a boiling point of 110 ° C. or higher or an organic solvent having a boiling point of less than 110 ° C. However, an organic solvent having a boiling point of less than 110 ° C. is preferable from the viewpoint of being inert to diethyl zinc and requiring high water solubility.
  • water can be added over 60 seconds to 10 hours, for example. From the viewpoint that the yield of the product is good, it is preferable to add water or a mixed solvent with water dropwise to the organic zinc compound of the general formula (1) as a raw material.
  • the addition of water can be carried out without stirring (while standing) or stirring the solution of the compound represented by the general formula (1) and the electron donating organic solvent.
  • any temperature between ⁇ 90 to 150 ° C. can be selected.
  • a temperature of ⁇ 15 to 30 ° C. is preferable from the viewpoint of the reactivity between water and the organozinc compound.
  • the hydrolysis of the group 3B element compound of the general formula (2) is slightly more intense than the reaction of the organozinc compound of the general formula (1), but should be performed in the same manner as the reaction of the organozinc compound of the general formula (1).
  • the reaction can be similarly controlled by appropriately selecting the reaction conditions described above.
  • 4A group element compound or 4B group element compound of general formula (3) and general formula (4), zinc compound of general formula (5) and general formula (6), 3B of general formula (7) and general formula (8) The same applies to hydrolysis of group element compounds.
  • the reaction between water and the compound represented by the general formula (1) and the compound represented by the general formulas (2) to (4), or water and the compound represented by the general formula (1) For example, leave for 1 minute to 48 hours without stirring (still standing) or stir.
  • the reaction temperature the reaction can be carried out at any temperature between -90 to 150 ° C.
  • the reaction temperature is preferably in the range of 5 to 80 ° C. from the viewpoint of obtaining a partial hydrolyzate in high yield.
  • the reaction pressure is not limited. Usually, it can be carried out at normal pressure (atmospheric pressure).
  • the progress of the reaction between water and the compound represented by the general formula (1) is monitored by sampling the reaction mixture, analyzing the sample by NMR or IR, or sampling the generated gas, if necessary. Can do.
  • the compound, the zinc compound of the general formula (5) and the general formula (6), the group 3B element compound of the general formula (7) and the general formula (8), and water or a mixed solvent with water are used in a reaction vessel according to any conventional method. Can be introduced. These reaction steps may be a batch operation method, a semi-batch operation method, or a continuous operation method, and are not particularly limited, but a batch operation method is desirable.
  • the organozinc compound of the general formula (1), the group 3B element compound of the general formula (2), and the mixture thereof are partially hydrolyzed with water to include a partially hydrolyzed product. Is obtained.
  • the organozinc compound of the general formula (1) is diethyl zinc
  • the analysis of the product obtained by reaction with water has been conducted for a long time, but the results differ depending on the report, and the composition of the product is clearly It is not specified. Further, the composition of the product can be changed depending on the molar ratio of water, the reaction time, and the like.
  • the partial hydrolyzate 1 is presumed to be a compound represented by the following general formula (9) or a mixture of plural kinds of compounds having different p.
  • R 1 —Zn— [O—Zn] p —R 1 (9) (Wherein R 1 is the same as R 1 in the general formula (1), and p is an integer of 2 to 20)
  • R 1 is the same as R 1 in the general formula (1), and p is an integer of 2 to 20)
  • R 1 is the same as R 1 in the general formula (1), and p is an integer of 2 to 20
  • p is an integer of 2 to 20
  • M is the same as M in the general formula (2)
  • Q is the same as any of R 2 , R 3 and R 4 in the general formula (2)
  • m is an integer of 2 to 20.
  • the main component of the product is represented by the structural unit represented by the following general formulas (11) and (12) and the above-described general formula (10) for the partial hydrolyzate 3, for example. It is inferred that the compound is a combination of structural units or a mixture of a plurality of types of compounds having different m. (R 1 -Zn)-(11) -[O-Zn] m- (12) (Wherein R 1 is the same as R 1 in the general formula (1), and m is an integer of 2 to 20)
  • composition ratio of each element of Zn to 4B in the composition is a general formula (1) to (1) used in the present invention so that the composition of the oxide containing a composite oxide of a desired combination of each element of the present invention is obtained. It is possible to arbitrarily adjust the molar ratio of each compound of (8).
  • This molar ratio can be adjusted so that the general composition of the reported composite oxides and their oxygen-deficient compounds can be obtained.
  • the other composition ratios are not limited to integer ratios, and the amount of each element added. It is possible to prepare an arbitrary composition by adjusting.
  • the composition for the purpose of forming a film of ZTO or ATO includes Sn as a 4B group element in zinc or aluminum in the composition.
  • the molar ratio of Zn and Sn and Al and Sn can be arbitrarily adjusted so that the composition ratio is a desired oxide composition containing ZTO or ATO. This molar ratio can be adjusted to obtain the reported general composition of ZTO and ATO and their oxygen-deficient compounds, etc.
  • the other composition ratios are not limited to integer ratios, and the addition amount of each element It is possible to prepare an arbitrary composition by adjusting.
  • the composite oxide containing zinc element (Zn), group 3B element (3B), group 4A element (4A), group 4B element (4B) obtained by using the composition of the present invention includes the following oxides and those The oxide containing can be illustrated.
  • Example of Zn-4A Zn x Ti y O t, Zn x Zr y O t, Zn x Hf y O t, Zn x Ti y Zr y O t, Zn x Zr y Hf y O t, Zn x Hf y Ti y O t like
  • Example of Zn-4A-4B Zn x Sn y Zr y O t , Zn x Ge y Zr y O t, Zn x Si y Zr y O t like, Zn x Sn y Zr y Hf y O t, Zn x Sn y Zr y Si y O t, Zn x Sn y Hf y O t , Zn x Sn y Ti y O t, Zn x Sn y Ge y Zr y Hf y O t like,
  • Example for 3B-4A Al x Ti y O t, Al x Zr y O t, Al x Hf y O t, Al x Ti y Zr y O t, Al x Zr y Hf y O t, Al x Hf y Ti y O t, In x Ti y O t, In x Zr y O t, In x Hf y O t, In x Ti y Zr y O t, In x Zr y Hf y O t, In x Hf y Ti y O t, Ga x Ti y O t, Ga x Zr y O t, Ga x Hf y O t, Ga x Ti y Zr y O t, Ga x Ti y Zr y O t, Ga x Zr y Hf y O t, Ga x Hf y Ti t, In x Al x Ti y O t
  • Example for 3B-4B Al x Sn y O t , Al x Ge y O t , Al x Si y O t , Al x Sn y Si y O t , Al x Ge y Sn y O t , Al x Si y Ge y O t , Ga x Sn y O t , Ga x Ge y O t , Ga x Si y O t , Ga x Sn y Si y O t , Ga x Ge y Sn y O t , Ga x Si y Ge y O t , In x Sn y O t , In x Ge y O t , In x Si y O t , In x Si y O t , In x Sn y Si y O t , In x Ge y Sn y O t , In x Si y Ge t , In x Si y
  • Example of 3B-4A-4B Al x Sn y Zr y O t , Al x Ge y Zr y O t, Al x Si y Zr y O t, Al x Sn y Zr y Hf y O t, Al x Sn y Zr y Si y O t, Al x Sn y Hf y O t, Al x Sn y Ti y O t, Al x Sn y Ge y Zr y Hf y O t, Ga x Sn y Zr y O t, Ga x Ge y Zr y O t, Ga x Si y Zr y O t, Ga x Sn y Zr y Hf y O t, Ga x Sn y Zr y Si t, Ga x Sn y Zr y Si t, Ga x Sn y Zr y Si t, Ga x Sn y
  • Example of Zn-3B-4A Zn x Al x Ti y O t , Zn x Al x Zr y O t, Zn x Al x Hf y O t, Zn x Al x Ti y Zr y O t, Zn x Al x Zr y Hf y O t, Zn x Al x Hf y Ti y O t, Zn x Ga x Ti y O t, Zn x Ga x Zr y O t, Zn x Ga x Hf y O t, Zn x Ga x Ti y Zr y O t, Zn x Ga x Zr y Hf y O t , Zn x Ga x Hf y Ti y O t, Zn x Ga x Ti y O t, Zn x Ga x Zr y Hf y O t , Zn x Ga x Hf y Ti
  • Example of Zn-3B-4B Zn x Al x Sn y O t , Zn x Al x Si y O t, Zn x Al x Ge y O t, Zn x Al x Sn y Ge y O t, Zn x Al x Sn y Si y O t, Zn x Al x Si y Ge y O t , Zn x Ga x Sn y O t , Zn x Ga x Ge y O t , Zn x Ga x Si y O t , Zn x Ga x Sn y Ge y O t , Zn x Ga x Si y Ge y O t , Zn x Ga x Si y Ge y O t , Zn x Ga x Si y Ge y O t , Zn x Ga x Si y Ge y O t , Zn x Ga x Sn y
  • Example of Zn-3B-4A-4B Zn x Al x Zr y Sn y O t, Zn x In x Zr y Sn y O t, Zn x Ga x Zr y Sn y O t, Zn x Ga x Al x Ti y Zr y Sn y O t, Zn x Ga x In x Al x Zr y Hf y Sn y O t, Zn x In x Ga x Hf y Ti y Sn y O t, Zn x In x Ga x Hf y Ti y Ge y O t like.
  • x, y, z, s, and t which are ratios of each element, are not particularly limited as long as an oxide is obtained, and may be any number depending on a desired composite oxide.
  • the composition can be obtained by adjusting the molar ratio of each compound of the above general formulas (1) to (8) so that they are obtained.
  • This composite oxide can be prepared so as to obtain those oxygen-deficient compounds, etc.
  • Other composition ratios are not limited to integer ratios, and those of any composition can be prepared by adjusting the addition amount of each element. Preparation is possible.
  • oxide thin films such as Zn and Sn oxides (ZTO) and Al and Sn oxides (ATO).
  • elements other than Zn3B, 4A and 4B of the present invention alkali metals which are Group 1A elements, alkaline earth metals which are Group 2A elements, rare earths such as lanthanoids and actinoids, Group 3A, 5A, 6A and 7A elements,
  • a metal compound capable of forming other oxides such as Group 8 elements such as noble metals, transition metals, and Group 5B elements
  • composite oxides containing Zn to 4B elements and other elements can be formed.
  • Such a composition may be used.
  • the composition of the present invention is a partially hydrolyzed organic zinc compound represented by the following general formula (1) and an organic zinc compound such as diethyl zinc and water as a compound containing zinc prepared as described above. Can be used.
  • This addition is carried out by hydrolyzing the composition, so that the alkyl group R 1 (wherein R 1 is the number of carbon atoms) bonded to the organic zinc compound and the product obtained by partial hydrolysis of the organic zinc compound and water. It is confirmed by identification and quantification of hydrocarbon R 1 H mainly produced from 1 to 7 linear or branched alkyl groups.
  • the main component of the gas produced by hydrolysis is ethane.
  • the organic zinc compound and an alkyl group R 1 bonded to the product obtained by partial hydrolysis of the organic zinc compound and water (where R 1 is a linear or branched alkyl having 1 to 7 carbon atoms).
  • R 1 is a linear or branched alkyl having 1 to 7 carbon atoms.
  • Group is R 2 , R 3 , R 4 (R 2 , R 3 , R 4 in the general formula (2) of the coexisting group 3B element compound, independently hydrogen, straight chain of 1 to 7 carbon atoms Alternatively, it may be produced by an exchange reaction with a branched alkyl group.
  • the solution prepared by the above method can be used as it is as a coating solution for forming a complex oxide thin film. Alternatively, it can be appropriately diluted or concentrated, but from the viewpoint that the production process can be simplified, the solution prepared by the above method should be a concentration that can be used as it is as a coating solution for forming an oxide complex oxide. Is preferred.
  • the method for producing a complex oxide thin film of the present invention is a method for producing a complex oxide thin film using the composition for forming a complex oxide thin film of the present invention.
  • the composite oxide thin film-forming composition of the present invention is applied to the substrate surface, and then the obtained coating film is heated to obtain a composite oxide thin film.
  • Application to the substrate surface can be performed by conventional means such as dip coating, spin coating, spray pyrolysis, ink jet, and screen printing.
  • coating is performed by, for example, spin coating, dip coating, or spray pyrolysis, a composite oxide thin film having an average transmittance of 80% or more with respect to visible light can be formed.
  • the coating method is performed by, for example, a spin coating method, a dip coating method, or a spray pyrolysis method. It is preferable.
  • the composition is applied to the substrate surface under an inert gas atmosphere such as nitrogen, an air atmosphere, an air atmosphere containing a large amount of water vapor, a high relative humidity, an oxidizing gas atmosphere such as oxygen, or a reducing gas atmosphere such as hydrogen. Or under any atmosphere such as a mixed gas atmosphere thereof and at atmospheric pressure or under pressure.
  • an inert gas atmosphere such as nitrogen, an air atmosphere, an air atmosphere containing a large amount of water vapor, a high relative humidity, an oxidizing gas atmosphere such as oxygen, or a reducing gas atmosphere such as hydrogen.
  • composition to the substrate surface is preferably carried out in an inert gas atmosphere such as nitrogen.
  • the pressure of the coating film forming atmosphere can be performed under atmospheric pressure or increased pressure, and can also be performed under reduced pressure.
  • a small amount of oxygen or moisture may be used as an oxygen source necessary for the formation of oxides, and oxygen or moisture within a range that does not affect the quality of the inert gas thin film.
  • a gas component containing oxygen, such as, may be contained.
  • the spin coating method and the dip coating method may be performed in an inert gas atmosphere, or may be performed in an atmosphere having a relative humidity of 2 to 15% by mixing an inert gas and water vapor. .
  • the spray pyrolysis method is a method that can be performed while heating the substrate. Therefore, the solvent can be dried in parallel with the application, and heating for solvent drying may not be necessary depending on conditions. Furthermore, depending on the conditions, in addition to drying, the reaction of the composition of the present invention into the composite oxide may proceed at least partially. Therefore, there is a case where a complex oxide thin film can be formed more easily by heating at a predetermined temperature, which is a subsequent process.
  • the heating temperature of the substrate can be in the range of 50 to 550 ° C., for example.
  • Fig. 1 shows a spray film-forming apparatus that can be used in the spray pyrolysis method.
  • 1 is a spray bottle filled with a coating solution
  • 2 is a substrate holder
  • 4 is a compressor
  • 5 is a substrate
  • 6 is a water vapor introducing tube.
  • spray coating a substrate is placed on the substrate holder 2 and heated to a predetermined temperature using a heater if necessary. Then, in a predetermined atmosphere, an inert gas compressed from a spray nozzle 3 disposed above the substrate
  • a composite oxide thin film can be formed on a substrate by simultaneously supplying the coating liquid and atomizing and spraying the coating liquid.
  • the composite oxide thin film is formed by spray coating without additional heating or the like.
  • a good film can be formed by spraying the coating solution by discharging the coating solution from the spray nozzle so that the droplet size is in the range of 1 to 15 ⁇ m and keeping the distance between the spray nozzle and the substrate within 50 cm. This is preferable from the viewpoint that a complex oxide thin film having characteristics can be produced.
  • the size of the droplets discharged from the spray nozzle is in the range of 1 to 30 ⁇ m.
  • the droplet size is more preferably in the range of 3 to 20 ⁇ m.
  • the distance between the spray nozzle and the substrate is preferably within 50 cm.
  • the distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint that the composite oxide thin film can be satisfactorily formed.
  • the amount of water vapor introduced is preferably 0.05 to 5 in terms of a molar ratio with respect to the total amount of zinc, 3B group element, 4A group element, and 4B group element in the supplied composition, and has high transparency. From the viewpoint of obtaining a complex oxide thin film, it is more preferably 0.1 to 3.
  • the method for introducing water vapor can be introduced into the complex oxide thin film production apparatus according to any conventional method. It is preferable that the water vapor and the composition react near the heated substrate. For example, an inert gas containing water vapor produced by bubbling water with an inert gas is introduced into the vicinity of the heated substrate through a tube. Can be mentioned.
  • the substrate After applying the coating solution to the substrate surface, the substrate is brought to a predetermined temperature if necessary, and after drying the solvent, a complex oxide thin film is formed by heating at the predetermined temperature.
  • the temperature at which the solvent is dried can be, for example, in the range of 20 to 200 ° C., and can be set as appropriate according to the type of the coexisting organic solvent.
  • the heating temperature for forming the composite oxide after drying the solvent is, for example, in the range of 50 to 550 ° C., and preferably in the range of 50 to 500 ° C. It is also possible to perform the solvent drying and the complex oxide formation at the same time by setting the solvent drying temperature and the heating temperature for the subsequent complex oxide formation to be the same.
  • the film thickness of the composite oxide thin film is not particularly limited, but is practically preferably in the range of 0.05 to 2 ⁇ m.
  • coating (dry) heating can be suitably manufactured by repeating the said application
  • the composite oxide thin film formed by the above manufacturing method varies depending on the coating method and the subsequent drying and heating conditions.
  • the volume resistivity is a resistance per unit volume, and is obtained by multiplying the surface resistance and the film thickness.
  • the surface resistance is measured by, for example, a four-probe method, and the film thickness is measured by, for example, SEM measurement, a stylus type step thickness meter or the like.
  • the volume resistivity changes (increases) depending on the degree of formation of the composite oxide by spray application or by heating after application, so that the volume resistivity of the thin film becomes a desired resistance value. It is preferable to set the heating conditions (temperature and time) after application.
  • the composite oxide thin film formed by the above production method preferably has an average transmittance of 80% or more with respect to visible light, and more preferably has an average transmittance of 85% or more with respect to visible light.
  • Average transmittance for visible light is defined and measured as follows.
  • the average transmittance for visible light means the average of the transmittance of light in the range of 380 to 780 nm, and is measured by an ultraviolet-visible spectrophotometer.
  • the average transmittance for visible light can also be expressed by presenting the visible light transmittance of 550 nm.
  • Visible light transmittance changes (increases) depending on the degree of zinc oxide formation during spray coating or heating after coating, so that the transmittance of the thin film with respect to visible light is considered to be 80% or more during spray coating. Or it is preferable to set the heating conditions (temperature and time) after application.
  • alkali glass, non-alkali glass, or a transparent base film can be used as the substrate, and the transparent base film can be a plastic film.
  • the transparent base film can be a plastic film.
  • the composite oxide thin film produced by the above method has excellent transparency and mobility, it can be used as an antistatic film, an ultraviolet cut film, a transparent conductive film and the like.
  • the antistatic film can be used, for example, in fields such as solid electric field condensers, chemically amplified resists, and building materials such as window glass.
  • the ultraviolet cut film can be used in fields such as a front filter of an image display device, an imaging device such as a drive recorder, a lighting device such as a high-pressure discharge lamp, a building material such as a watch cover glass and a window glass.
  • the transparent conductive film is, for example, FPD, resistive touch panel and capacitive touch panel, thin film silicon solar cell and compound (CdTe, CIS) thin film solar cell, dye-sensitized solar cell, organic thin film solar cell, etc. Can be used in the field of
  • complex oxides such as ZTO and ATO are characterized by having higher mobility than an amorphous Si film together with an oxide semiconductor film made of oxides of In, Ga and Zn (IGZO) as an oxide semiconductor film made of them.
  • IGZO oxide semiconductor film made of oxides of In, Ga and Zn
  • It can be used in the field of switching elements (thin film transistors) such as liquid crystal display devices and thin film electroluminescence display devices.
  • Field effect transistors such as thin film transistors (TFTs) are widely used as unit electronic elements, high frequency signal amplifying elements, liquid crystal driving elements, etc. for semiconductor memory integrated circuits, and are currently the most widely used electronic devices. is there. However, it is not intended to be limited to these fields.
  • Example 1 6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxytin was dissolved and 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of diethylzinc was dissolved were mixed at room temperature, and combined oxidation
  • the composition was prepared so that ZTO was obtained as a product.
  • This composition is intended for film formation of ZnSnO x (x is an arbitrary number depending on the film formation conditions) as ZTO from the approximate abundance ratio.
  • Example 3 A mixture of 7.2 g of 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxytin is dissolved and 2.0 g of 1,2-diethoxyethane solution in which 0.2 g of triethylaluminum is dissolved are mixed at room temperature.
  • the composition was prepared so that ATO was obtained as a product.
  • This composition is intended for film formation of AlSnO x (x is an arbitrary number depending on the film formation conditions) as ATO from the approximate abundance ratio.
  • Example 4 6.6 g of 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxytin was dissolved, 0.092 g of 1,2-diethoxyethane solution in which 0.0092 g of triethylaluminum was dissolved and 0.2 g of diethylzinc were dissolved
  • the 1,2-diethoxyethane solution (2.0 g) was mixed at room temperature to prepare a composition so that ZTAO was obtained as a composite oxide.
  • This composition is intended for film formation of Zn 10 Sn 10 AlO x (x is an arbitrary number depending on the film formation conditions) as ZTAO based on the approximate abundance ratio.
  • Example 5 6.6 g of 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxytin was dissolved, 0.25 g of 1,2-diethoxyethane solution in which 0.025 g of triethylgallium was dissolved, and 0.2 g of diethylzinc were dissolved
  • the 1,2-diethoxyethane solution (2.0 g) was mixed at room temperature to prepare a composition so that ZTGO was obtained as a composite oxide.
  • This composition is intended to form a film of Zn 10 Sn 10 GaO x (x is an arbitrary number depending on the film forming conditions) as ZTGO from an approximate integer ratio.
  • Example 6 6.6 g of 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxytin was dissolved, 0.26 g of 1,2-diethoxyethane solution in which 0.026 g of trimethylindium was dissolved and 0.2 g of diethylzinc were dissolved
  • the resulting 1,2-diethoxyethane solution (2.0 g) was mixed at room temperature to prepare a composition so that ZTIO was obtained as a composite oxide.
  • This composition is intended for film formation of Zn 10 Sn 10 InO x (x is an arbitrary number depending on the film formation conditions) as ZTIO from the approximate abundance ratio.
  • Example 7 6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxytin was dissolved, 0.62 g of a 1,2-diethoxyethane solution in which 0.062 g of tetra-tert-butoxyzirconium was dissolved, and 0.63 g of diethylzinc.
  • This composition is intended to form a film of Zn 10 Sn 10 ZrO x (x is an arbitrary number depending on the film forming conditions) as ZTZrO from the approximate abundance ratio.
  • Example 10 5.3 g of 1,2-diethoxyethane solution in which 0.53 g of tetra-tert-butoxytin was dissolved, 0.62 g of 1,2-diethoxyethane solution in which 0.062 g of trimethylindium was dissolved, and diethylzinc and water were mixed with O.
  • This composition is intended for film formation of Zn 10 Sn 10 InO x (x is an arbitrary number depending on the film formation conditions) as ZTIO from the approximate abundance ratio.
  • This composition is intended to form a film of Zn 10 Sn 10 ZrO x (x is an arbitrary number depending on the film forming conditions) as ZTZrO from the approximate abundance ratio.
  • Example 12 7.2 g of 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxytin was dissolved, 0.27 g of 1,2-diethoxyethane solution in which 0.022 g of diethylzinc was dissolved and 1 g of 0.2 g of triethylaluminum were dissolved , 2-diethoxyethane solution was mixed at room temperature to prepare a composition so that ATZO was obtained as a composite oxide.
  • This composition is intended for film formation of Al 10 Sn 10 ZnO x (x is an arbitrary number depending on the film formation conditions) as ATZO from the approximate abundance ratio.
  • Example 13 7.2 g of 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxytin was dissolved, 0.27 g of 1,2-diethoxyethane solution in which 0.027 g of triethylgallium was dissolved, and 0.2 g of triethylaluminum were dissolved , 2-diethoxyethane solution was mixed at room temperature to prepare a composition so that ATGO was obtained as a composite oxide.
  • This composition is intended for film formation of Al 10 Sn 10 GaO x (x is an arbitrary number depending on the film formation conditions) as ATGO from the approximate abundance ratio.
  • Example 14 7.2 g of 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxytin was dissolved, 0.28 g of 1,2-diethoxyethane solution in which 0.028 g of trimethylindium was dissolved, and 1 g of 0.2 g of triethylaluminum were dissolved , 2-diethoxyethane solution was mixed at room temperature to prepare a composition so that ATIO was obtained as a composite oxide.
  • This composition is intended for film formation of Al 10 Sn 10 InO x (x is an arbitrary number depending on the film formation conditions) as ATIO from the approximate abundance ratio.
  • Example 15 7.2 g of 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxytin was dissolved, 0.67 g of 1,2-diethoxyethane solution in which 0.067 g of tetra-tert-butoxyzirconium was dissolved, and 0.
  • a composition was prepared so that 2.0 g of a 1,2-diethoxyethane solution in which 2 g was dissolved was mixed at room temperature to obtain ATZrO as a composite oxide.
  • This composition is intended for film formation of Al 10 Sn 10 ZrO x (x is an arbitrary number depending on film formation conditions) as ATZrO from the approximate abundance ratio.
  • Example 16 A transparent and clear solution portion (filtered with a 0.2 ⁇ m PTFE filter) of the composition intended for film formation of ZnSnO x (x is an arbitrary number depending on the film formation conditions) obtained in Example 1 was used as a coating solution. Used for membrane. This product-containing coating solution was coated on a 18 mm square EAGLE XG (R) (made by Corning) glass substrate surface at room temperature in a nitrogen atmosphere by spin coating. Then, the solvent was dried by heating the substrate at 150 ° C. for 5 minutes, and further heated at 200 ° C. for 5 minutes. The formed thin film was taken out in the air. The obtained thin film was transparent, and the transmittance was 93% at 550 nm.
  • this thin film was analyzed by FT-IR, and disappearance of peaks attributed to each vibration of CH such as tert-butoxy group and ethyl group derived from the raw material was confirmed. Furthermore, this thin film was analyzed by XRD, and it was confirmed that there was no crystalline peak.
  • Example 17 The same operation as in Example 16 was repeated 3 times. The formed thin film was taken out in the air. The obtained thin film was transparent, and the transmittance was 89% at 550 nm. Further, this thin film was analyzed by FT-IR, and disappearance of peaks attributed to each vibration of CH such as tert-butoxy group and ethyl group derived from the raw material was confirmed.
  • Example 18 The same operation as in Example 16 was repeated 5 times. The formed thin film was taken out in the air. The obtained thin film was transparent, and the transmittance was 85% at 550 nm.
  • Example 19 to 32 Using the compositions obtained in Examples 2 to 15 as coating solutions, coating film formation was performed once in the same manner as in Example 16 to form a complex oxide thin film. Each composition was used by using a clear and clear solution portion or by filtering with a 0.2 ⁇ m PTFE filter in the same manner as in Example 1. The formed thin film was taken out in the air. Table 1 shows the appearance and transmittance of the obtained thin film.
  • Examples 33 to 46 Using the compositions obtained in Examples 2 to 15 as coating solutions, coating film formation was performed three times in the same manner as in Example 17 to form a complex oxide thin film. The formed thin film was taken out in the air. Table 2 shows the appearance and transmittance of the obtained thin film.
  • Examples 47 to 60 Using the compositions obtained in Examples 2 to 15 as coating solutions, coating film formation was performed 5 times in the same manner as in Example 18 to form a complex oxide thin film. The formed thin film was taken out in the air. Table 3 shows the appearance and transmittance of the obtained thin film.
  • Example 61 to 72 A film was formed using the composition obtained in the above example as a coating solution, and the composite oxide thin film obtained in Examples 47 to 60 was formed at 300 ° C. for 5 minutes, 400 ° C. for 5 minutes, 500 ° C. in a nitrogen atmosphere. Heat treatment was sequentially performed under the conditions of 5 minutes at 5 ° C. The heated thin film was taken out in the air. The transmittance of the obtained thin film is shown in Tables 4, 5 and 6.
  • Example 95 The transparent and clear solution portion of each product-containing coating solution obtained in Example 2 was used for coating film formation.
  • This product-containing coating solution was applied onto a quartz glass substrate surface of 18 mm square at room temperature by a spin coating method in a nitrogen atmosphere. Then, the solvent was dried by heating the substrate at 150 ° C. for 5 minutes. In this film formation, baking was simultaneously performed within the drying temperature and time of the solvent. This operation was repeated to apply a total of 3 times to form a thin film. The formed thin film was taken out in the air.
  • the thin film obtained was transparent and the transmittance was 94% at 550 nm. Further, this thin film was analyzed by FT-IR, and disappearance of peaks attributed to each vibration of CH such as tert-butoxy group and ethyl group derived from the raw material was confirmed.
  • Example 96 to 99 Using the coating solutions obtained in Examples 8, 9, 10 and 11, film formation and physical property evaluation similar to those in Example 95 were performed. The obtained thin film properties and physical properties are shown in Table 7.
  • RTA Rapid Thermal Annealing
  • RTA Rapid Thermal Annealing
  • Example 1 In Example 1, application of the same composition was carried out using bisacetylacetonatotin instead of tetra-tert-butoxytin, zinc acetate instead of diethylzinc, 2-methoxyethanol as the solvent, and ethanolamine as the auxiliary. A liquid was prepared.
  • the obtained coating solution was deposited at 200 ° C. in the same manner as in Example 18 to obtain a thin film.
  • the visible light transmittance at 550 nm was 60%, and only a thin film with low transmittance was obtained.
  • Example 3 a coating solution having the same composition was prepared using tin chloride and aluminum acetate instead of tetra-tert-butoxytin, using 2-methoxyethanol as a solvent and ethanolamine as an auxiliary agent. did.
  • the obtained coating solution was deposited at 200 ° C. in the same manner as in Example 18 to obtain a thin film.
  • the visible light transmittance at 550 nm was 65%, and only a thin film with low transmittance was obtained.
  • the present invention is useful in the field of manufacturing complex oxide thin films containing oxides of zinc, group 3B elements, group 4A elements and / or group 4B elements.

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WO2019167669A1 (ja) * 2018-02-28 2019-09-06 東ソー・ファインケム株式会社 酸化亜鉛薄膜形成用組成物及び酸化亜鉛薄膜の製造方法
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JP7060406B2 (ja) 2018-02-28 2022-04-26 東ソー・ファインケム株式会社 酸化亜鉛薄膜形成用組成物及び酸化亜鉛薄膜の製造方法
JP2021061360A (ja) * 2019-10-09 2021-04-15 国立大学法人京都工芸繊維大学 強誘電体薄膜の製造方法、強誘電体薄膜製造装置および強誘電体薄膜
JP7480951B2 (ja) 2019-10-09 2024-05-10 国立大学法人京都工芸繊維大学 強誘電体薄膜の製造方法および強誘電体薄膜製造装置
EP4106019A4 (en) * 2020-10-09 2023-10-18 Kabushiki Kaisha Toshiba SOLAR CELL, MULTIPLE SOLAR CELL, SOLAR CELL MODULE AND SOLAR POWER GENERATION SYSTEM

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