WO2010131621A1 - Composition pour la production d'une couche mince d'oxyde de zinc dopée, procédé pour la production d'une couche mince d'oxyde de zinc, couche mince antistatique, couche mince bloquant les rayons ultraviolets et couche mince d'électrode transparente - Google Patents

Composition pour la production d'une couche mince d'oxyde de zinc dopée, procédé pour la production d'une couche mince d'oxyde de zinc, couche mince antistatique, couche mince bloquant les rayons ultraviolets et couche mince d'électrode transparente Download PDF

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WO2010131621A1
WO2010131621A1 PCT/JP2010/057873 JP2010057873W WO2010131621A1 WO 2010131621 A1 WO2010131621 A1 WO 2010131621A1 JP 2010057873 W JP2010057873 W JP 2010057873W WO 2010131621 A1 WO2010131621 A1 WO 2010131621A1
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thin film
zinc oxide
group
organic
compound
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PCT/JP2010/057873
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English (en)
Japanese (ja)
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裕仁 竹元
賢二 吉野
孝一郎 稲葉
浩司 豊田
健一 羽賀
功一 徳留
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国立大学法人 宮崎大学
東ソー・ファインケム株式会社
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Priority claimed from JP2009115111A external-priority patent/JP5515144B2/ja
Priority claimed from JP2010030916A external-priority patent/JP5674186B2/ja
Application filed by 国立大学法人 宮崎大学, 東ソー・ファインケム株式会社 filed Critical 国立大学法人 宮崎大学
Publication of WO2010131621A1 publication Critical patent/WO2010131621A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions

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  • the first aspect of the present invention has an average transmittance of 80% or more with respect to visible light, and an oxidation having a volume resistivity that is low enough to be used for an antistatic thin film, an ultraviolet cut thin film, a transparent electrode thin film, etc.
  • the present invention relates to a method for producing a zinc thin film, and further relates to an antistatic thin film, an ultraviolet cut thin film and a transparent electrode thin film produced by using the production method.
  • a zinc oxide thin film having a volume resistivity of less than 8 ⁇ 10 ⁇ 2 ⁇ ⁇ cm can be obtained, and spray heat When decomposition is used, a zinc oxide thin film having a volume resistivity of less than 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm can be obtained.
  • the second aspect of the present invention relates to a composition for forming a doped zinc oxide thin film and a method for producing a doped zinc oxide thin film. More specifically, the second aspect of the present invention relates to a composition for forming a zinc oxide thin film doped with a group 3B element and a method for producing a zinc oxide thin film doped with a group 3B element using the same.
  • a transparent zinc oxide thin film doped with a group 3B element having a high transparency to visible light includes a photocatalyst film, an ultraviolet cut film, an infrared reflective film, a buffer layer for CIGS solar cells, an electrode film for dye-sensitized solar cells, charging Used in prevention films, compound semiconductor light emitting devices, thin film transistors, etc., and has a wide range of uses.
  • Non-Patent Document 1 Various methods are known as methods for producing a doped transparent zinc oxide thin film (Non-Patent Document 1), but a typical method using an organic zinc compound as a raw material is a chemical vapor deposition (CVD) method (non-patent document 1).
  • Patent Document 2 and coating methods such as spray pyrolysis (Non-Patent Document 3), spin coating (Patent Document 1), and dip coating (Non-Patent Document 4).
  • the chemical vapor deposition (CVD) method requires the use of a large vacuum vessel, and the film forming speed is very slow, resulting in high manufacturing costs and the formation of the vacuum vessel depending on the size of the vacuum vessel.
  • CVD chemical vapor deposition
  • the coating method is simpler and has a higher film formation speed than the chemical vapor deposition (CVD) method, so that the productivity is high and the manufacturing cost is low. Further, there is an advantage that a large zinc oxide thin film can be formed because there is no need to use a vacuum container and there is no restriction by the vacuum container.
  • CVD chemical vapor deposition
  • solvent drying is performed simultaneously with spray coating, and then the substrate temperature is heated to 360 ° C. or higher to obtain a zinc oxide thin film coating.
  • the solvent is dried after spin coating and dip coating, and then the substrate temperature is heated to 400 ° C. or higher to obtain a zinc oxide thin film coating film.
  • the doped transparent zinc oxide thin film has come to use a plastic substrate as a substrate. Therefore, the heating applied at the time of forming the transparent zinc oxide thin film needs to be performed at a temperature lower than the heat resistance temperature of the plastic substrate.
  • the spray pyrolysis method described in Non-Patent Document 3 the spin coating method described in Patent Document 1 and the dip-coating method described in Non-Patent Document 4
  • transparent oxidation occurs when the plastic substrate is heated below the heat-resistant temperature.
  • a zinc thin film cannot be obtained.
  • the heating required for film formation is 300 ° C. or lower.
  • an aqueous solution of zinc acetate used in the spray pyrolysis method described in Non-Patent Document 3, an organic zinc compound used in the spin coating method described in Patent Document 1, and an organic A transparent zinc oxide thin film can be obtained even if a film is formed at 300 ° C. or lower using a solution comprising a solvent or a solution comprising an organic zinc compound and an organic solvent used in the dip coating method described in Non-Patent Document 4. Only an opaque zinc oxide thin film was obtained.
  • Patent Document 1 also describes a method using a hexane solution of diethylzinc, but an attempt was made to form a film at 300 ° C. or lower using this solution, but a transparent zinc oxide thin film was not obtained.
  • diethyl zinc is a compound that is ignitable in the atmosphere and must be taken with great care during storage and use. For this reason, it is practically difficult to use it in a spray pyrolysis method, spin coating method, etc., which is often performed in an atmosphere containing water without diluting diethyl zinc.
  • diethyl zinc is dissolved in an organic solvent, the risk of ignition, etc. can be reduced.
  • Patent Document 1 zinc oxide using diethyl zinc dissolved while reacting with an alcohol-based organic solvent is used. In order to form a thin film, heating was required at a high temperature of 400 ° C. or higher.
  • the object of the present invention is to prepare an organozinc compound as a raw material, but it is easy to handle because it is not ignitable, and even if heating is required, it is a low doped with a group 3B element by heating at 300 ° C. or lower.
  • the object is to provide a composition for producing a zinc oxide thin film capable of forming a transparent transparent zinc oxide thin film. Further, the object of the present invention is to take into consideration the heat resistance temperature of plastic substrates and the cost required for heating, etc., using this composition. Then, it is providing the method which can obtain the low resistance transparent zinc oxide thin film which doped the 3B group element.
  • the first aspect of the present invention is a method for producing a zinc oxide thin film, and an antistatic thin film, an ultraviolet cut thin film, and a transparent electrode thin film produced by this production method.
  • the first aspect of the present invention is as described in 1-1 to 1-17 below.
  • composition A An organozinc compound represented by the following general formula (1) A solution dissolved in a concentration of 4 to 12% by mass in an electron donating organic solvent having a boiling point of 110 ° C. or higher or a mixed organic solvent containing an electron donating organic solvent having a boiling point of 110 ° C. or higher as a main component.
  • composition B In the composition A, A composition obtained by adding an organic 3B group element compound represented by the following general formula (2) so that the molar ratio with respect to the organic zinc compound is 0.005 to 0.1.
  • 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, a linear or branched group having 1 to 7 carbon atoms.
  • composition C An organozinc compound represented by the following general formula (1); (In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms.) An organic 3B group element compound represented by the following general formula (2) or (3) having a molar ratio of 0.005 to 0.09 with respect to the organic zinc compound: (In the formula, 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, a linear or branched group having 1 to 7 carbon atoms.
  • An alkoxyl, carboxylic acid, or acetylacetonate group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)
  • M is a group 3B 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 3, and when X is sulfuric acid, c is 2.
  • D is 3, and a is an integer of 0 to 9.
  • Composition A In an inert gas atmosphere containing water vapor, Spraying onto a heated substrate surface, A method for producing a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light and having a volume resistivity of less than 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • Composition A An organozinc compound represented by the following general formula (1) A solution dissolved in a concentration of 4 to 12% by mass in an electron donating organic solvent having a boiling point of 110 ° C. or higher or a mixed organic solvent containing an electron donating organic solvent having a boiling point of 110 ° C. or higher as a main component.
  • composition B In the composition A, A composition obtained by adding an organic 3B group element compound represented by the following general formula (2) so that the molar ratio with respect to the organic zinc compound is 0.005 to 0.1.
  • 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, a linear or branched group having 1 to 7 carbon atoms.
  • composition C An organozinc compound represented by the following general formula (1); (In the formula, R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms.) An organic 3B group element compound represented by the following general formula (2) or (3) having a molar ratio of 0.005 to 0.09 with respect to the organic zinc compound: (In the formula, 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, a linear or branched group having 1 to 7 carbon atoms.
  • An alkoxyl, carboxylic acid, or acetylacetonate group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)
  • M is a group 3B 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 3, and when X is sulfuric acid, c is 2.
  • D is 3, and a is an integer of 0 to 9.
  • [1-7] Zinc oxide according to [1-5] or [1-6], wherein the water vapor is supplied such that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5 Thin film manufacturing method.
  • [1-8] The method for producing a zinc oxide thin film according to any one of [1-1] to [1-7], wherein the electron donating organic solvent has a boiling point of 230 ° C. or lower.
  • [1-9] The composition according to any one of [1-1] to [1-8], wherein the organozinc compound is diethyl zinc.
  • [1-14] The method for producing a zinc oxide thin film according to any one of [1-1] to [1-12], wherein the mixed organic solvent is a mixed solvent of 1,2-diethoxyethane and tetrahydrofuran.
  • [1-15] An antistatic thin film comprising a zinc oxide thin film produced using the production method according to any one of [1-1] to [1-14].
  • [1-16] An ultraviolet cut thin film comprising a zinc oxide thin film produced by using the production method according to any one of [1-1] to [1-14].
  • [1-17] A transparent electrode thin film comprising a zinc oxide thin film produced by using the production method according to any one of [1-1] to [1-14].
  • the second aspect of the present invention is a composition for forming a zinc oxide thin film and a method for producing a zinc oxide thin film doped with a group 3B element, as described in the following 2-1 to 2-11.
  • An organic solvent having an electron donating property contains an organic zinc compound represented by the following general formula (1) and an organic 3B group element compound represented by the following general formula (2), and the organic 3B with respect to the organic zinc compound
  • R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms
  • M is a group 3B element
  • R 20 , R 30 and R 40 are each independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms
  • [2-2] The composition according to [2-1], wherein the group 3B element is B, Al, Ga, or In. [2-3]
  • R 1 is an ethyl group
  • M is aluminum
  • R 20 , R 30, and R 40 are all ethyl groups [2-1] or [ 2-2].
  • R 1 is an ethyl group, and in the organic 3B group element compound, M is gallium, and R 20 , R 30, and R 40 are all methyl groups [2-1] or [ 2-2].
  • R 1 is an ethyl group, and in the organic 3B group element compound, M is indium, and R 20 , R 30, and R 40 are all methyl groups [2-1] or [ 2-2].
  • [2-8] Spraying the composition according to any one of [2-1] to [2-7] onto the substrate surface under atmospheric pressure or under pressure, in an atmosphere containing water, and at a substrate temperature of 300 ° C. or lower; A method for producing a zinc oxide thin film doped with a group 3B element, comprising forming a zinc oxide thin film doped with a group 3B element.
  • Spray application of the composition is performed by discharging the composition from the spray nozzle so that the droplet size is in the range of 1 to 30 ⁇ m, and the distance between the spray nozzle and the substrate is within 50 cm [2-8]
  • the manufacturing method as described in. [2-10] The production method according to [2-8] or [2-9], wherein the atmospheric temperature for spray coating is 40 ° C. or lower.
  • the zinc oxide thin film has any one of [2-8] to [2-10] having an average transmittance of 80% or more with respect to visible light and a surface resistance of 1 ⁇ 10 5 ⁇ / ⁇ or less.
  • the spin coating method and the dip coating method have an average transmittance of 80% or more with respect to visible light and a volume resistivity of 8 ⁇ 10.
  • a zinc oxide thin film having characteristics of less than ⁇ 2 ⁇ ⁇ cm can be produced.
  • the spray pyrolysis method has an average transmittance of 80% or more with respect to visible light and a volume resistivity of 1 ⁇ 10 ⁇ .
  • a zinc oxide thin film having a characteristic of less than 3 ⁇ ⁇ cm can be produced.
  • the manufactured zinc oxide thin film has excellent transparency and conductivity as described above, it can be applied to an antistatic thin film, an ultraviolet cut thin film, a transparent electrode thin film, and the like.
  • the inventors use a spin coating method to form a film composed of a group 3B element compound and an organic zinc compound described in Patent Document 1, and use a solution composed of an organic zinc compound and an organic solvent described in Non-Patent Document 2.
  • a film was formed by a spray pyrolysis method using a solution of a group 3B element compound and zinc acetate described in Non-Patent Documents 3 and 4, as described above.
  • the spin coating method the case of dip coating a volume resistivity of only obtained 1 ⁇ 10 -1 ⁇ ⁇ cm or more of the zinc oxide thin film, the volume resistivity of 1 ⁇ 10 -3 ⁇ ⁇ even spray pyrolysis method Only a zinc oxide thin film of cm or more was obtained, and a zinc oxide thin film having a lower resistance was not obtained.
  • the present inventors tried to form a film by a spin coating method using a solution of a composition obtained by partially hydrolyzing a group 3B element compound and diethyl zinc, and had an average transmittance of 80% or more for visible light.
  • a zinc oxide thin film was obtained.
  • the volume resistivity of the obtained zinc oxide thin film is 1 ⁇ 10 ⁇ 1 ⁇ ⁇ cm or more, and in order to obtain a lower resistance zinc oxide thin film, partial hydrolysis of an organic zinc compound such as diethyl zinc is performed.
  • a composition containing a partial hydrolyzate prepared by carrying out in an organic solvent having a higher boiling point can be applied to an average transmittance of 80% or more for visible light and used for an antistatic thin film, etc.
  • a zinc oxide thin film having a volume resistivity as low as possible is obtained.
  • a group 3B element-doped zinc oxide thin film having transparency with an average transmittance of 80% or more for visible light and a low resistance with a surface resistance of 1 ⁇ 10 5 ⁇ / ⁇ or less.
  • a composition for forming a doped zinc oxide thin film can be provided. Furthermore, according to the second aspect of the present invention, the composition is used, and heating is not required at the time of film formation, or even when heated, the above transparency and low resistance are obtained by heating at 300 ° C. or lower.
  • the method which can manufacture a 3B group element dope zinc oxide thin film can be provided.
  • NMR spectrum after vacuum drying of the composition obtained in Example 1-1 XRD spectrum of the zinc oxide thin film obtained in Example 1-1 XRD spectrum of the zinc oxide thin film obtained in Example 1-4 XRD spectrum of the zinc oxide thin film obtained in Reference Example 1-3
  • NMR spectrum of the composition obtained in Example 1-7 after vacuum drying It is a figure which shows a spray film forming apparatus.
  • Example 2-6 XRD spectrum of the zinc oxide thin film obtained in Example 2-1 XRD spectrum of the zinc oxide thin film obtained in Example 2-2 XRD spectrum of the zinc oxide thin film obtained in Example 2-3 XRD spectrum of the zinc oxide thin film obtained in Example 2-4 XRD spectrum of the zinc oxide thin film obtained in Example 2-5 XRD spectrum of the zinc oxide thin film obtained in Example 2-6
  • composition for producing a zinc oxide thin film used in the production method of the first aspect of the present invention includes the following three aspects.
  • Composition A Obtained by at least partially hydrolyzing the organic zinc compound by adding water to a solution in which the organic zinc compound represented by the general formula (1) is dissolved in an electron-donating organic solvent.
  • composition B After at least partially hydrolyzing the organozinc compound by adding water to a solution obtained by dissolving the organozinc compound represented by the general formula (1) in an electron-donating organic solvent, A product obtained by adding at least one 3B group element compound represented by the general formula (2) or (3) (hereinafter sometimes referred to as partial hydrolyzate 2) (Composition C) An organic zinc compound represented by the following general formula (1) and at least one group 3B element compound represented by the following general formula (2) or (3) are dissolved in an electron-donating organic solvent.
  • R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms
  • 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, a linear or branched group having 1 to 7 carbon atoms.
  • M is a group 3B 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 3, and when X is sulfuric acid, c is 2.
  • D is 3, and a is an integer of 0 to 9.
  • the electron donating organic solvent contains an electron donating organic solvent having a boiling point of 110 ° C. or higher, or an electron donating organic solvent having a boiling point of 110 ° C. or higher as a main component.
  • a mixed organic solvent is used.
  • a zinc oxide thin film having an average transmittance of 80% or more and a volume resistivity of less than 8 ⁇ 10 ⁇ 2 ⁇ ⁇ cm is formed. Found.
  • the electron-donating organic solvent is preferably an electron-donating organic solvent having a boiling point of 110 ° C. or higher in consideration of operability in the subsequent coating process, particularly drying properties. Any electron-donating organic solvent may be used as long as it has solubility in the organic zinc compound represented by the general formula (1) and water, except that the boiling point is in the above range.
  • di-n-butyl ether Boiling point 142.4 ° C
  • dihexyl ether Boiling point 226.2 ° C
  • anisole Boiling point 153.8 ° C
  • phenetole Boiling point 172 ° C
  • butylphenyl ether Boiling point 210.3 ° C
  • pentylphenyl 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
  • 1,2-dibutoxyethane Boiling point 20
  • 1,2-diethoxyethane (boiling point 121 ° C.), which is a kind of glyme, is preferable from the viewpoint of both suppression of gel during preparation of the composition and volatility of the solvent itself.
  • the upper limit of the boiling point of the electron-donating 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 mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C. or higher as a main component should be soluble in the organic zinc compound represented by the general formula (1) and water in a mixed state.
  • Examples include octane (boiling point 125.7 ° C.) and tetrahydrofuran (boiling point 66 ° C.), octane and 1,4-dioxane, nonane (boiling point 150.8 ° C.) and tetrahydrofuran, nonane and 1,4-dioxane, decane.
  • the subcomponent is preferably tetrahydrofuran.
  • the secondary component tetrahydrofuran or 1,4-dioxane, has a weight ratio of 0.05 to 0.45 with respect to the main component.
  • the concentration of the compound represented by the general formula (1) in a solution obtained by dissolving the compound represented by the general formula (1) in the electron donating organic solvent or a mixed organic solvent containing the electron donating organic solvent. Is preferably in the range of 4 to 12% by mass. Even when an electron-donating organic solvent having a boiling point of 110 ° C. or higher is used, when the concentration of the compound represented by the general formula (1) is less than 4% by mass or more than 12% by mass, desired transparency and This is because the formation of a conductive zinc oxide thin film tends to be difficult.
  • the concentration of the compound represented by the general formula (1) in the solution dissolved in the organic solvent is preferably in the range of 6 to 10% by mass.
  • the amount of water added is such that the molar ratio to the organic zinc compound is in the range of 0.4 to 0.8.
  • the organic zinc compound and 3B The molar ratio with respect to the total amount of the group element compound is in the range of 0.4 to 0.8.
  • the amount of water added is within this range, in the case of spin coating or dip coating, the reaction product containing the partial hydrolyzate obtained has a volume resistivity of less than 8 ⁇ 10 ⁇ 2 ⁇ ⁇ cm.
  • a zinc oxide thin film having a volume resistivity of less than 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm can be formed.
  • an organic zinc composition containing a product obtained by partially hydrolyzing an organic zinc compound with a high yield of 90% or more based on zinc contained in the raw material is obtained. Can do.
  • an appropriate amount of the Group 3B element compound is also partially hydrolyzed.
  • the molar ratio of water is preferably in the range of 0.6 to 0.8, more preferably in the range of 0.6 to 0.75.
  • the group 3B element compound is added after adding water to the organic zinc compound, depending on the amount of water added, the added water was consumed for hydrolysis of the organic zinc compound.
  • the product usually does not contain a hydrolyzate of the group 3B element compound.
  • the group 3B element compound is not hydrolyzed and is contained as a raw material, or the organic group of the partial hydrolyzate of the organozinc compound and the organic group (ligand) of the group 3B element compound are exchanged ( Ligand exchange) may also occur.
  • water is added to the mixed solution of the organozinc compound and the group 3B element compound, so that the product usually contains a hydrolyzate of the group 3B element compound.
  • the hydrolyzate of 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.
  • reaction of water and the compound represented by general formula (1) and the compound represented by general formula (2) or (3), or water and the compound represented by general formula (1) after addition of water 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.
  • 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.
  • Specific examples of the metal represented by M in the group 3B element compound represented by the general formula (2) include B, Al, Ga, and In.
  • Specific examples of the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid.
  • the group 3B element compound represented by the general formula (2) includes, in particular, 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, and indium nitrate pentahydrate.
  • R 2 , R 3 and R 4 are preferably hydrogen.
  • R 2 , R 3 , and R 4 are preferably alkyl groups.
  • Specific examples of 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.
  • R 2 , R 3 and R 4 is hydrogen and the rest is an alkyl group.
  • Examples of the ligand represented by L include trimethylamine, triethylamine, triphenylamine, pyridine, monofoline, N, N-dimethylaniline, N, N-diethylaniline, triphenylphosphine, dimethylsulfur, diethyl ether, and tetrahydrofuran. be able to.
  • the group 3B element compound represented by the general formula (3) includes, in particular, diborane, borane-tetrahydrofuran complex, borane-trimethylamine complex, borane-triethylamine complex, triethylborane, tributylborane, alane-trimethylamine complex, alane-triethylamine complex, Mention may be made of trimethylaluminum, dimethylamylnium hydride, triisobutylaluminum, diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, trimethylindium and triethylindium. Triethylaluminum, triisobutylaluminum, trimethylgallium, and trimethylindium are particularly preferable because they are inexpensive and easily available.
  • the general formula (2) for the organic zinc compound and the organic zinc compound represented by the general formula (1) ) Or the molar ratio of the Group 3B element compound represented by (3) is added in a ratio of 0.005 to 0.09 to obtain a zinc oxide thin film in which the effect of adding the Group 3B element is appropriately exhibited.
  • the partial hydrolyzate 2 water is added to the solution containing the organozinc compound to obtain a partial hydrolyzate, and then the 3B group element compound is added at the molar ratio described above.
  • water is added to the solution containing an organic zinc compound and a 3B group element compound by the said molar ratio, and a partial hydrolyzate is obtained.
  • the organic solvent, the organic zinc compound of the general formula (1) as a raw material, and water or a mixed solvent with water can be introduced into the reaction vessel according to any conventional method.
  • 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) and the group 3B element compound of the general formula (2) or (3), or the organozinc compound of the general formula (1) are partially separated by water. Hydrolysis yields a product containing a partial hydrolyzate.
  • 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 hydrolysates 1 and 2 are presumed to be compounds represented by the following general formula (4) or a mixture of plural kinds of compounds having different m. (Wherein R 1 is the same as R 1 in the general formula (1), and p 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 (5) and (6) and the following general formula (7) for the partial hydrolyzate 3.
  • the compound is a combination of structural units or a mixture of a plurality of types of compounds having different m.
  • R 1 is the same as R 1 in the general formula (1), and m is an integer of 2 to 20
  • M is the same as M in the general formula (2) or (3), and Q is the same as any one of X, R 2 , R 3 and R 4 in the general formula (2) or (3).
  • M is an integer from 2 to 20.
  • the 3B group compound of the general formula (2) or (3) is added after completion of the reaction.
  • the addition amount of the group 3B element compound is suitably 0.005 to 0.09 with respect to the charged amount of the organozinc compound.
  • a part or all of the product After completion of the hydrolysis reaction, a part or all of the product can be recovered and purified by a general method such as filtration, concentration, extraction, column chromatography and the like. Moreover, when adding a 3B group element compound after completion
  • the organozinc compound of the general formula (1) which is a raw material, remains in the reaction product, it can be recovered by the above method and is preferably recovered.
  • the reaction product after recovering the remaining raw materials by these methods is preferably one that does not contain the organozinc compound represented by the general formula (1) in any of the partial hydrolysates 1 to 3.
  • the content of the organic zinc compound represented by the general formula (1) is preferably 0.5 wt% or less.
  • the compositions A, B and C used in the first aspect of the present invention do not contain the unreacted organic zinc compound represented by the general formula (1). From the viewpoint of forming a uniform film.
  • the solution prepared by the above method can be used as it is as a coating solution for forming a zinc 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 a zinc oxide thin film. preferable.
  • a 1st aspect of this invention is related with the manufacturing method of a zinc oxide thin film.
  • This manufacturing method is a method in which the composition for forming a zinc oxide thin film is applied to the substrate surface, and then the obtained coating film is heated to obtain a zinc oxide thin film.
  • coating is performed by, for example, spin coating or dip coating, a zinc oxide thin film having an average transmittance of 80% or more and a volume resistivity of less than 8 ⁇ 10 ⁇ 2 ⁇ ⁇ cm is obtained.
  • a zinc oxide thin film having an average transmittance of 80% or more for visible light and a volume resistivity of less than 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. can be formed.
  • the coating on the substrate surface can be carried out by conventional means such as dip coating, spin coating, spray pyrolysis, ink jet, and screen printing.
  • 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.
  • 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 conditions, in addition to drying, the reaction of the partial hydrolyzate of the organozinc compound with zinc oxide may proceed at least partially. Therefore, the zinc 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 of the present invention.
  • 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.
  • a substrate is placed on the substrate holder 2 and heated to a predetermined temperature using a heater if necessary.
  • an inert gas compressed from a spray nozzle 3 disposed above the substrate A zinc oxide thin film can be formed on a substrate by simultaneously supplying the coating liquid and atomizing and spraying the coating liquid.
  • the zinc oxide thin film is formed by spray coating without additional heating.
  • 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. It is preferable from the viewpoint that a zinc oxide thin film having characteristics can be manufactured.
  • the size of the droplets discharged from the spray nozzle is preferably 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 zinc oxide thin film can be satisfactorily formed.
  • the amount of water vapor introduced is preferably 0.1 to 5 in terms of a molar ratio to zinc in the supplied composition, and from the viewpoint of obtaining a zinc oxide thin film having a lower volume resistivity, it is 0.3. More preferably, it is ⁇ 2.
  • the amount of water vapor introduced is in the range of 0.3 to 2 in terms of the molar ratio, a zinc oxide thin film having better film characteristics with a volume resistivity of less than 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm can be formed. .
  • the method for introducing water vapor can be introduced into the zinc oxide thin film production vessel 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 coating the coating liquid on the substrate surface, the substrate is brought to a predetermined temperature if necessary, the solvent is dried, and then heated at the predetermined temperature to form a zinc oxide thin film.
  • 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 zinc 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 zinc oxide formation at the same time by making the solvent drying temperature the same as the heating temperature for the subsequent zinc oxide formation.
  • the film thickness of the zinc oxide thin film is not particularly limited, but is practically preferably in the range of 0.05 to 2 ⁇ m. According to the manufacturing method of the first aspect of the present invention, in the case other than the spray pyrolysis method, a thin film having a film thickness in the above range can be appropriately manufactured by repeating the application (drying) heating at least once. .
  • the zinc oxide thin film formed by the manufacturing method of the first aspect of the present invention varies depending on the coating method and subsequent drying and heating conditions, but preferably has a volume resistivity of less than 8 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. More preferably, it has a volume resistivity of less than 1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm.
  • 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 spray is designed so that the volume resistivity of the thin film is 8 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. It is preferable to set the heating conditions (temperature and time) during or after application.
  • the zinc oxide thin film formed by the production method of the first aspect of the present invention preferably has an average transmittance of 80% or more with respect to visible light, and more preferably 85% or more with respect to visible light.
  • Average transmittance “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.
  • the substrate used in the first embodiment of the present invention can be, for example, alkali glass, non-alkali glass, or a transparent substrate film, and the transparent substrate film can be a plastic film.
  • the transparent substrate film can be a plastic film.
  • substrate in the 2nd aspect of this invention mentioned later can also be utilized.
  • the zinc oxide thin film produced by the above method can be used as an antistatic film, an ultraviolet cut film, a transparent conductive film and the like.
  • the antistatic film can be used in the field of building materials such as solid electric field condensers, chemically amplified resists, and 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. Available in However, it is not intended to be limited to these fields.
  • the zinc oxide thin film produced by the method of the first aspect of the present invention has high transparency to visible light, is transparent, and has a volume resistivity of 8 ⁇ 10 ⁇ 2 ⁇ ⁇
  • Zinc oxide thin films having characteristics of less than cm are FPD (flat panel display) electrodes, resistive touch panels and capacitive touch panel electrodes, thin film silicon solar cells and compounds (CdTe, CIS (copper indium diselenide)). It is used for the top electrode of organic thin film solar cells, dye-sensitized solar cells, organic thin film solar cells, UV cut films, antistatic films, infrared reflective films, etc., and has a wide range of applications.
  • composition for forming a doped zinc oxide thin film is represented by an organic zinc compound represented by the following general formula (1) and the following general formula (20) in an organic solvent having an electron donating property.
  • the organic 3B group element compound is contained, and the molar ratio of the organic 3B group element compound to the organic zinc compound is in the range of 0.001 to 0.3.
  • R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms
  • M is a group 3B element
  • R 2 , R 3 and R 4 are independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms
  • alkyl group represented by R 1 in the organic zinc compound represented by the general formula (1) examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, Mention may be made of tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl, 2-hexyl and heptyl.
  • 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 particularly preferably diethyl zinc in which R 1 is an ethyl group.
  • Examples of the 3B group element represented as M in the organic 3B group element compound represented by the general formula (20) include B, Al, Ga, In, and Tl.
  • Specific examples of the alkyl group represented by R 20 , R 30 , and R 40 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • M is B, Al, Ga, or In
  • R 20 , R 30 , and R 40 are independently hydrogen, or have 1, 2, 3, 4, A compound of 5 or 6 is preferred.
  • the compound represented by the general formula (20) is particularly preferably borane, alane triethylamine, triethylaluminum, trimethylgallium, triethylgallium, trimethylindium, and triethylindium.
  • M is aluminum, R 20 , R 30 and R 40 are all ethyl ethyl groups, M is gallium, and R 20 , R 30 and R 40 are all.
  • the molar ratio of the organic 3B group element compound represented by the general formula (20) to the organozinc compound represented by the general formula (1) is preferably 0.001 to 0.3, preferably 0.01 to 0.00. 1 is more preferable.
  • Examples of the solvent having an electron donating property include amine solvents such as trimethylamine, triethylamine, triphenylamine, diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, glyme, diglyme, triglyme, etc.
  • amine solvents such as trimethylamine, triethylamine, triphenylamine, diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, glyme, diglyme, triglyme, etc.
  • Examples include ether solvents.
  • diisopropyl ether is particularly preferable.
  • the total concentration of the organic zinc compound and the organic 3B group compound is preferably 15% by mass or less from the viewpoint of producing a transparent zinc oxide thin film.
  • the total concentration of the organic zinc compound and the organic 3B group compound is preferably 1 to 10% by mass, more preferably 3 to 10% by mass.
  • the total concentration of the organic zinc compound and the organic 3B group compound has an effect on the risk of the zinc oxide thin film production such as ignition. It can be manufactured safely without paying.
  • the concentration of the organic 3B group element compound in the composition is appropriately determined in consideration of the molar ratio of the organic 3B group element compound to the organic zinc compound.
  • composition of the second aspect of the present invention can be produced by dissolving the organic zinc compound of the general formula (1) and the organic 3B compound of the general formula (2) in an organic solvent having an electron donating property.
  • the compound of the general formula (1) and the compound of the general formula (2) can be dissolved according to any conventional method, and can also be produced by dissolving a mixture with a solvent.
  • the compound of the general formula (1) and the compound of the general formula (2) may be dissolved in any order.
  • the method for producing a zinc oxide thin film doped with a Group 3B element according to the present invention comprises the composition according to the second aspect of the present invention described above at atmospheric pressure or under pressure, in an atmosphere containing water and at a substrate temperature of 300 ° C. or lower.
  • the object is spray-coated on the substrate surface to form a zinc oxide thin film doped with a group 3B element.
  • the spray coating method is used in the manufacturing method of the second aspect of the present invention.
  • the spray coating on the surface of the substrate is performed under an atmosphere containing water as an oxygen source of the zinc oxide thin film at atmospheric pressure or under pressure.
  • Under pressure for example, the pressure is in the range of 101.3-202.6 kPa.
  • the spray coating in the method of the second aspect of the present invention can be carried out under reduced pressure, but there is no merit to carry out under reduced pressure.
  • the “atmosphere in which water exists” in spray application to the substrate surface can be, for example, an air atmosphere containing water corresponding to a relative humidity of 20 to 90%. Instead of performing in an air atmosphere, it may be performed in an atmosphere of a mixed gas in which nitrogen and water are mixed.
  • the relative humidity is more preferably in the range of 30 to 70% from the viewpoint of smooth formation of the zinc oxide thin film.
  • Spray coating on the substrate surface can be performed at a substrate temperature of 300 ° C. or lower. More specifically, it is preferable that the atmospheric temperature for spray coating is 40 ° C. or lower and the substrate temperature is 300 ° C. or lower. From the viewpoint of smooth production of the zinc oxide thin film, the atmospheric temperature for spray coating is preferably in the range of 10 to 30 ° C., and the substrate temperature is preferably 10 to 200 ° C., more preferably 20 to 100 ° C. It is the range of ° C.
  • FIG. 7 shows a spray film forming apparatus that can be used in the second embodiment of the present invention.
  • 1 is a spray bottle filled with a coating composition
  • 2 is a substrate holder
  • 3 is a spray nozzle
  • 4 is a compressor
  • 5 is a substrate.
  • the substrate is placed on the substrate holder 2 and heated to a predetermined temperature of 300 ° C. or lower using a heater if necessary, and then placed in the atmosphere (at atmospheric pressure and in air) above the substrate.
  • a zinc oxide thin film can be formed on the substrate by simultaneously supplying the compressed inert gas and the coating composition from the spray nozzle 3 and atomizing and spraying the coating composition.
  • the zinc oxide thin film doped with the group 3B element is formed by spray coating without additional heating.
  • Spray coating of the coating composition is performed by discharging the coating composition from the spray nozzle so that the droplet size is in the range of 1 to 30 ⁇ m, and the distance between the spray nozzle and the substrate is within 50 cm. From the viewpoint that a good transparent zinc oxide thin film can be produced. Furthermore, it is preferable that the atmospheric temperature for spray coating is 40 ° C. or less and the temperature of the substrate is 300 ° C. or less from the viewpoint of the influence of heat on the substrate and energy cost.
  • 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 zinc oxide thin film can be satisfactorily formed.
  • a highly transparent zinc oxide thin film doped with a Group 3B element may be formed on the substrate. it can.
  • the zinc oxide thin film doped with the group 3B element formed by the manufacturing method according to the second aspect of the present invention is one in which the group 3B element is contained in the zinc oxide as an oxide.
  • the oxide of the group 3B element is dissolved in zinc oxide, the group 3B element oxide is mixed with zinc oxide, or both of them coexist.
  • the film thickness of the zinc oxide thin film doped with the group 3B element formed by the manufacturing method of the second aspect of the present invention is not particularly limited. For example, it can be appropriately adjusted in the range of 100 to 2000 nm.
  • the film thickness of the zinc oxide thin film can be appropriately adjusted by adjusting the concentration of the coating composition used for spray coating and the spray coating time.
  • the spray application operation can be performed in two or more times if necessary.
  • the zinc oxide thin film doped with the group 3B element formed by the production method of the second aspect of the present invention preferably has an average transmittance of 80% or more with respect to visible light, more preferably visible. It has an average transmittance of 85% or more for light rays.
  • the “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 zinc oxide thin film doped with the group 3B element formed by the production method of the second aspect of the present invention preferably has a surface resistance of 1 ⁇ 10 5 ⁇ / ⁇ or less. More preferably, the surface resistance is 5 ⁇ 10 4 ⁇ / ⁇ or less, and still more preferably, the surface resistance is 1 ⁇ 10 4 ⁇ / ⁇ or less.
  • a transparent substrate film can be used as the substrate, and the transparent substrate film can be a plastic film.
  • Polymers forming the plastic film include polyesters (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)), poly (meth) acrylic (for example, polymethylmethacrylate (PMMA)), Examples thereof include polycarbonate (PC), polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, cyclic polyolefin (COP), ethylene-vinyl acetate copolymer, polyurethane, triacetate, and cellophane.
  • PET, PC, and PMMA are preferable.
  • the transparent substrate film may be an unstretched film or a stretched film depending on the type of polymer.
  • a polyester film such as a PET film is usually a biaxially stretched film, and a PC film, a triacetate film, a cellophane film, etc. are usually unstretched films.
  • the surface resistance was measured using a Lorester GP manufactured by Mitsubishi Chemical by a four-probe method according to JIS K 7194.
  • Example 1-1 3.49 g (equivalent to 8.7% by mass) of diethylzinc was added to 39.9 g of 1,2-diethoxyethane (boiling point 121 ° C.). After sufficiently stirring, it was cooled to -12 ° C. A 1,4-dioxane (boiling point: 101.1 ° C.) solution containing 5.0% water was added dropwise so that the molar ratio of water to diethylzinc was 0.6 (total amount added: 6.02 g). Then, it heated up to room temperature (24 degreeC), made it react at room temperature for 18 hours, and obtained 48.1g of partial hydrolyzate solutions (concentration 6.5 mass%) by filtering with a membrane filter. The spectrum of FIG. 2 was obtained by NMR (THF-d8, ppm) measurement after removing the solvent and the like by vacuum drying.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 5 times.
  • the formed thin film had a surface resistance of 1300 ⁇ / ⁇ , a film thickness of 0.35 ⁇ m, and a volume resistivity of 4.6 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Furthermore, it was confirmed that it was zinc oxide by XRD (see FIG. 3). Further, the visible light transmittance at 550 nm was 90%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-2 A partial hydrolyzate containing indium by adding trimethylindium to the diethylzinc partial hydrolyzate solution prepared in Example 1-1 in a molar ratio of 0.03 to the charged diethylzinc. 488.1 g of solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 5 times.
  • the formed thin film had a surface resistance of 587 ⁇ / ⁇ , a film thickness of 0.37 ⁇ m, and a volume resistivity of 2.2 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 91%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-3 The product-containing coating solution containing the partial hydrolyzate obtained as in Example 1-2 was coated on the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 30 times.
  • the formed thin film had a surface resistance of 55 ⁇ / ⁇ , a film thickness of 1.71 ⁇ m, and a volume resistivity of 9.4 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 85%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-4 To 200.3 g of 1,2-diethoxyethane (boiling point 121 ° C.) was added 17.45 g (equivalent to 8.7% by mass) of diethylzinc. After sufficiently stirring, it was cooled to -12 ° C. A tetrahydrofuran (boiling point 66 ° C.) solution containing 5.0% water was added dropwise so that the molar ratio of water to diethylzinc was 0.6 (total amount added: 30.1 g). Then, it heated up to room temperature (24 degreeC), made it react at room temperature for 18 hours, and obtained 245.2g of partial hydrolyzate solutions (concentration 6.4 mass%) by filtering with a membrane filter. 245.3 g of a partial hydrolyzate solution containing indium was obtained by adding to this partial hydrolyzate solution a molar ratio of 0.01 with respect to diethylzinc charged with trimethylindium.
  • the coating solution obtained as described above was filled in a spray bottle in the spray film forming apparatus of FIG.
  • An 18 mm square Corning 1737 glass substrate was placed on the substrate holder.
  • water was introduced by introducing nitrogen gas bubbling 24 ° C. water at 16 L / min.
  • the coating solution was sprayed at 4 ml / min for 16 minutes from the spray nozzle.
  • the size of droplets discharged from the spray nozzle was in the range of 3 to 20 ⁇ m, and the distance between the spray nozzle and the substrate was 30 cm.
  • the formed thin film had a surface resistance of 15 ⁇ / ⁇ , a film thickness of 0.49 ⁇ m, and a volume resistivity of 7.4 ⁇ 10 ⁇ 4 ⁇ ⁇ cm. Furthermore, it was confirmed that it was zinc oxide by XRD (see FIG. 4). The visible light transmittance at 550 nm was 83%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-5 It was confirmed that the zinc oxide thin films obtained in Examples 1-1 to 1-4 have an antistatic function and can be used as an antistatic thin film. Further, it was confirmed that the zinc oxide thin films obtained in Examples 1-1 to 1-4 have an ultraviolet cut function and can be used as an ultraviolet cut thin film.
  • Example 1-6 It was confirmed that the zinc oxide thin film obtained in Example 1-4 was a transparent electrode, and it was confirmed that it could be used as a transparent conductive thin film.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Then, the solvent was dried by heating the substrate at 500 ° C. for 4 minutes. The above operation was further repeated 5 times.
  • the formed thin film has a surface resistance of> 10 7 ⁇ / ⁇ (out of measurement range), visible light transmittance of 550 nm is 16%, and only an opaque and high resistance thin film with a transmittance of 80% or less can be obtained. There wasn't.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Then, the solvent was dried by heating the substrate at 500 ° C. for 4 minutes. The above operation was further repeated 5 times.
  • the formed thin film had a surface resistance of> 10 7 ⁇ / ⁇ (out of the measurement range), the visible light transmittance at 550 nm was 88%, and only a high resistance thin film was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated twice.
  • the formed thin film had a surface resistance of 2.2 ⁇ 10 5 ⁇ / ⁇ , a visible light transmittance of 4% at 550 nm, and only an opaque thin film was obtained. As shown in FIG. 5, it was confirmed by XRD that zinc was formed in addition to zinc oxide.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Then, the solvent was dried by heating the substrate at 500 ° C. for 4 minutes. The above operation was further repeated twice.
  • the formed thin film had a surface resistance of 1.9 ⁇ 10 5 ⁇ / ⁇ , a film thickness of 0.37 ⁇ m, and a volume resistivity of 4.8 ⁇ 10 ⁇ 1 ⁇ ⁇ cm.
  • the visible light transmittance at 550 nm was 95%, and only a high-resistance thin film was obtained.
  • Reference Example 1-6 The product-containing coating solution containing the partial hydrolyzate obtained as in Reference Example 5 was coated on the surface of a Corning 1737 glass substrate of 18 mm square by spin coating. Then, the solvent was dried by heating the substrate at 500 ° C. for 4 minutes. The above operation was further repeated 5 times. However, the formed thin film had a surface resistance of 9.3 ⁇ 10 4 ⁇ / ⁇ , a film thickness of 0.35 ⁇ m, and a volume resistivity of 3.2 ⁇ 10 ⁇ 1 ⁇ ⁇ cm. The visible light transmittance at 550 nm was 67%, and only a high-resistance and opaque thin film was obtained.
  • Example 1-7 3.49 g (equivalent to 8.7% by mass) of diethylzinc was added to 39.9 g of 1,2-diethoxyethane (boiling point 121 ° C.). After sufficiently stirring, it was cooled to -12 ° C. A tetrahydrofuran (boiling point: 66.0 ° C.) solution containing 5.0% water was added dropwise so that the molar ratio of water to diethylzinc was 0.6 (total amount added: 6.11 g). Then, it heated up to room temperature (24 degreeC), made it react at room temperature for 18 hours, and obtained 48.6g of partial hydrolyzate solutions (concentration 6.5 mass%) by filtering with a membrane filter. The spectrum of FIG. 6 was obtained by NMR (THF-d8, ppm) measurement after removing the solvent and the like by vacuum drying.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 5 times.
  • the formed thin film had a surface resistance of 1050 ⁇ / ⁇ , a film thickness of 0.35 ⁇ m, and a volume resistivity of 3.7 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 89%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-8 A partial hydrolyzate containing indium by adding trimethylgallium to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 in a molar ratio of 0.03 to the charged diethylzinc. 48.7 g of solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 5 times.
  • the formed thin film had a surface resistance of 420 ⁇ / ⁇ , a film thickness of 0.37 ⁇ m, and a volume resistivity of 1.6 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-9 Partial hydrolysis containing aluminum by adding trioctylaluminum to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 in a molar ratio of 0.01 to the charged diethylzinc. 48.7g of product solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 44 ⁇ / ⁇ , a film thickness of 1.91 ⁇ m, and a volume resistivity of 8.4 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 84%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-10 To the partially hydrolyzed solution of diethylzinc prepared in Example 1-7, a 0.5 M aluminum hydride / triethylamine complex toluene solution is added so as to have a molar ratio of 0.01 with respect to the charged diethylzinc. As a result, 48.4 g of a partial hydrolyzate solution containing aluminum was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 57 ⁇ / ⁇ , a film thickness of 1.86 ⁇ m, and a volume resistivity of 1.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 84%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-11 The partial hydrolyzate containing gallium by adding trimethylgallium to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 in a molar ratio of 0.03 to the charged diethylzinc. 48.5 g of solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 62 ⁇ / ⁇ , a film thickness of 1.74 ⁇ m, and a volume resistivity of 1.1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 91%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-12 Partial hydrolyzate containing gallium by adding triethylgallium to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 in a molar ratio of 0.03 to the charged diethylzinc. 48.2g of solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 40 ⁇ / ⁇ , a film thickness of 1.66 ⁇ m, and a volume resistivity of 6.6 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-13 Partially hydrolyzate containing gallium by adding gallium chloride to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 at a molar ratio of 0.03 to the charged diethylzinc. 48.6g of solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 38 ⁇ / ⁇ , a film thickness of 1.66 ⁇ m, and a volume resistivity of 6.6 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide. Further, the visible light transmittance at 550 nm was 90%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-14 The partial hydrolyzate containing gallium by adding indium chloride to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 in a molar ratio of 0.03 to the charged diethylzinc. 48.3 g of solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 35 ⁇ / ⁇ , a film thickness of 1.76 ⁇ m, and a volume resistivity of 6.6 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-15 By adding acetylacetonatogallium to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 at a molar ratio of 0.03 to the charged diethylzinc, partial hydrolysis containing gallium is performed. 48.4g of decomposition product solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film has a surface resistance of 41 ⁇ / ⁇ , the thickness is 1.63, and the volume resistivity was 6.7 ⁇ 10 -3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 91%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-16 By adding acetylacetonatoindium to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 at a molar ratio of 0.03 to the charged diethylzinc, partial hydrolysis containing gallium is performed. 48.2g of decomposition product solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 42 ⁇ / ⁇ , a film thickness of 1.61 ⁇ m, and a volume resistivity of 6.8 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 94%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 1-17 A partial hydrolyzate containing gallium by adding indium acetate to the diethylzinc partial hydrolyzate solution prepared in Example 1-7 in a molar ratio of 0.03 to the charged diethylzinc. 48.5 g of solution was obtained.
  • the product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 500 ° C. for 4 minutes to dry the solvent and simultaneously form zinc oxide. The above operation was further repeated 29 times.
  • the formed thin film had a surface resistance of 38 ⁇ / ⁇ , a film thickness of 1.60 ⁇ m, and a volume resistivity of 6.1 ⁇ 10 ⁇ 3 ⁇ ⁇ cm. Furthermore, it was confirmed by XRD that it was zinc oxide.
  • the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 2-1 The coating composition was prepared in a nitrogen gas atmosphere, and all solvents were dehydrated and degassed before use. To 200.1 g of diisopropyl ether, 10.54 g of diethyl zinc and 1.0 mol% (0.11 g) of triethylaluminum with respect to diethyl zinc were added. The composition for application
  • the coating composition obtained as described above was filled in a spray bottle in the spray film forming apparatus of FIG.
  • a slide glass substrate was placed on the substrate holder.
  • the coating composition was sprayed at 3 ml / min for 10 minutes from a spray nozzle in air at 25 ° C., 60% relative humidity and water at atmospheric pressure.
  • the size of droplets discharged from the spray nozzle was in the range of 3 to 20 ⁇ m, and the distance between the spray nozzle and the substrate was 40 cm.
  • the film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 240 nm. As shown in FIG. 8, the thin film formed on the substrate was confirmed to be zinc oxide by XRD.
  • the average transmittance of visible light is 84%
  • the surface resistance is 4.2 ⁇ 10 4 ⁇ / ⁇
  • the transparency is 80% or more
  • the surface resistance is 1 ⁇ 10 5 ⁇ / ⁇ or less.
  • a low-resistance zinc oxide thin film was obtained.
  • Example 2-2 All operations were performed in the same manner as in Example 1 except that triethylaluminum was changed to trimethylgallium.
  • the film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 210 nm. As shown in FIG. 9, the thin film formed on the substrate was confirmed to be zinc oxide by XRD. The average visible light transmittance was 86%, the surface resistance was 4.3 ⁇ 10 4 ⁇ / ⁇ , and a transparent and low-resistance zinc oxide thin film with a transmittance of 80% or more was obtained.
  • Example 2-3 All operations were performed in the same manner as in Example 1 except that triethylaluminum was changed to trimethylindium.
  • the film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 150 nm.
  • the thin film formed on the substrate was confirmed to be zinc oxide by XRD.
  • the average visible light transmittance was 83%
  • the surface resistance was 6.7 ⁇ 10 3 ⁇ / ⁇
  • Example 2-4 The same procedure as in Example 1 was performed except that the glass substrate was heated to 200 ° C.
  • the film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 300 nm.
  • the thin film formed on the substrate was confirmed to be zinc oxide by XRD.
  • a transparent and low-resistance zinc oxide thin film having an average visible light transmittance of 82%, a surface resistance of 1.7 ⁇ 10 4 ⁇ / ⁇ , and a transmittance of 80% or more was obtained.
  • Example 2-5 The same procedure as in Example 2 was performed except that the glass substrate was heated to 200 ° C.
  • the film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 250 nm.
  • the thin film formed on the substrate was confirmed to be zinc oxide by XRD. Further, an average transmittance of visible light was 86%, a surface resistance was 8.0 ⁇ 10 3 ⁇ / ⁇ , and a transparent and low resistance zinc oxide thin film having a transmittance of 80% or more was obtained.
  • Example 2-6 The same procedure as in Example 3 was performed except that the glass substrate was heated to 200 ° C.
  • the film thickness of the thin film formed on the substrate was determined by SEM measurement and was about 280 nm.
  • the thin film formed on the substrate was confirmed to be zinc oxide by XRD. Further, an average transmittance of visible light was 89%, a surface resistance was 3.6 ⁇ 10 3 ⁇ / ⁇ , and a transparent and low resistance zinc oxide thin film having a transmittance of 80% or more was obtained.
  • the coating composition obtained as described above was filled in a spray bottle in the spray film forming apparatus of FIG.
  • a slide glass substrate was placed on the substrate holder.
  • the coating composition was sprayed from the nozzle at 3 ml / min for 10 minutes.
  • a peak derived from zinc oxide was not confirmed from XRD (not shown).
  • the average transmittance of visible light was 10%, the surface resistance was> 1.0 ⁇ 10 7 ⁇ / ⁇ (out of measurement range), and only an opaque and high resistance thin film was obtained.
  • Comparative Example 2-2 All were carried out in the same manner as in Comparative Example 1 except that aluminum chloride hexahydrate was changed to gallium chloride. A peak derived from zinc oxide was not confirmed from XRD (not shown). Further, the average transmittance of visible light was 9%, the surface resistance was> 1.0 ⁇ 10 7 ⁇ / ⁇ (out of the measurement range), and only an opaque and high resistance thin film was obtained.
  • Comparative Example 2-3 All were carried out in the same manner as in Comparative Example 1 except that aluminum chloride hexahydrate was changed to indium chloride tetrahydrate. A peak derived from zinc oxide was not confirmed from XRD (not shown). Further, the average transmittance of visible light was 12%, the surface resistance was> 1.0 ⁇ 10 7 ⁇ / ⁇ (out of the measurement range), and only an opaque and high resistance thin film was obtained.
  • the present invention is useful in the field of manufacturing doped zinc oxide thin films.

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Abstract

L'invention porte sur une composition pour la production d'une couche mince d'oxyde zinc, qui contient un composé organique du zinc comme matière première, qui est non inflammable, qui est facile à manipuler, qui permet la formation d'une couche mince d'oxyde de zinc transparente dopée avec un élément du groupe 3B par chauffage à une température inférieure ou égale à 300°C ; et un procédé pour la production d'une couche mince d'oxyde de zinc transparente dopée avec un élément du groupe 3B utilisant la composition. La composition pour la production d'une couche mince d'oxyde de zinc contient un produit obtenu par ajout d'eau à une solution d'un composé organique du zinc et d'un composé d'un élément du groupe 3B pour hydrolyser partiellement le composé organique du zinc. Une couche mince d'oxyde de zinc dopée avec un élément du groupe 3B peut être formée par application de la composition sur la surface d'un substrat et chauffage du substrat. L'invention porte également sur une couche mince antistatique, une couche mince bloquant les rayons ultraviolets et une couche mince d'électrode transparente, chacune desquelles comprend la couche mince d'oxyde de zinc.
PCT/JP2010/057873 2009-05-12 2010-05-10 Composition pour la production d'une couche mince d'oxyde de zinc dopée, procédé pour la production d'une couche mince d'oxyde de zinc, couche mince antistatique, couche mince bloquant les rayons ultraviolets et couche mince d'électrode transparente WO2010131621A1 (fr)

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JP2009-115111 2009-05-12
JP2010030916A JP5674186B2 (ja) 2010-02-16 2010-02-16 酸化亜鉛薄膜製造方法、およびこの方法で製造した帯電防止薄膜、紫外線カット薄膜、透明電極薄膜
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WO2013161735A1 (fr) * 2012-04-25 2013-10-31 東ソー・ファインケム株式会社 Composition pour produire une couche mince d'oxyde composé, procédé de production d'une couche mince à l'aide de la composition et couche mince d'oxyde composé
TWI474872B (zh) * 2011-09-13 2015-03-01 Toshiba Mitsubishi Elec Inc 氧化膜成膜方法及氧化膜成膜裝置
WO2016063699A1 (fr) * 2014-10-24 2016-04-28 東ソー・ファインケム株式会社 Composition pour la production d'un film mince d'oxyde de zinc contenant un élément du groupe 2 et procédé de production associé
WO2019167669A1 (fr) * 2018-02-28 2019-09-06 東ソー・ファインケム株式会社 Composition pour former un film mince d'oxyde de zinc, et procédé de production d'un film mince d'oxyde de zinc

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TWI474872B (zh) * 2011-09-13 2015-03-01 Toshiba Mitsubishi Elec Inc 氧化膜成膜方法及氧化膜成膜裝置
US10016785B2 (en) 2011-09-13 2018-07-10 Toshiba Mitsubishi-Electric Industrial Systems Corporation Oxide film deposition method and oxide film deposition device
JPWO2013161735A1 (ja) * 2012-04-25 2015-12-24 東ソー・ファインケム株式会社 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
WO2013161735A1 (fr) * 2012-04-25 2013-10-31 東ソー・ファインケム株式会社 Composition pour produire une couche mince d'oxyde composé, procédé de production d'une couche mince à l'aide de la composition et couche mince d'oxyde composé
KR20140140654A (ko) * 2012-04-25 2014-12-09 토소 화인켐 가부시키가이샤 복합 산화물 박막 제조용 조성물 및 이 조성물을 이용한 박막의 제조 방법, 및 복합 산화물 박막
KR101980413B1 (ko) * 2012-04-25 2019-05-20 토소 화인켐 가부시키가이샤 복합 산화물 박막 제조용 조성물 및 이 조성물을 이용한 박막의 제조 방법, 및 복합 산화물 박막
WO2016063699A1 (fr) * 2014-10-24 2016-04-28 東ソー・ファインケム株式会社 Composition pour la production d'un film mince d'oxyde de zinc contenant un élément du groupe 2 et procédé de production associé
JP2016084253A (ja) * 2014-10-24 2016-05-19 東ソー・ファインケム株式会社 第２族元素を含有する酸化亜鉛薄膜製造用組成物およびその製造方法
WO2019167669A1 (fr) * 2018-02-28 2019-09-06 東ソー・ファインケム株式会社 Composition pour former un film mince d'oxyde de zinc, et procédé de production d'un film mince d'oxyde de zinc
JP2019152702A (ja) * 2018-02-28 2019-09-12 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
CN111758053A (zh) * 2018-02-28 2020-10-09 东曹精细化工株式会社 氧化锌薄膜形成用组合物和氧化锌薄膜的制造方法
EP3761083A4 (fr) * 2018-02-28 2021-11-24 Tosoh Finechem Corporation Composition pour former un film mince d'oxyde de zinc, et procédé de production d'un film mince d'oxyde de zinc
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

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