TW201402470A - Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film - Google Patents

Abstract

Provided are a composition with which a compound oxide thin film that can be used for an oxide semiconductor film, and the like can be formed by spray pyrolysis, and the like, and a method for forming a compound oxide thin film using the composition. The present invention relates to a composition for producing a compound oxide comprising at least one compound selected from the group consisting of compounds containing elemental zinc and compounds containing group 3B elements, the product of partial hydrolysis by water of the above-mentioned compound, or the above-mentioned compound and the above-mentioned partial hydrolysis product, as well as at least one compound selected from the group consisting of compounds containing group 4A elements and compounds containing group 4B elements, the product of partial hydrolysis by water of the above-mentioned compound, or the above-mentioned compound and the above-mentioned partial hydrolysis product. The present invention relates to a method for producing a compound oxide thin film having an average permeability of 80% or more by visible light rays, which comprises performing at least once a step for coating a substrate surface with the composition under an inert gas atmosphere and then heating the resulting coating film.

Description

Composition for producing composite oxide film, method for producing film using the same, and composite oxide film [Cross-reference to related applications]

The present application claims the priority of Japanese Patent Application No. 2012-100168, filed on Apr. 25, 2012, and the Japanese Patent Application No. 2012-100174, filed on Apr. 25, 2012. The description is specifically incorporated herein by reference.

The present invention relates to a composition for producing a composite oxide film which can produce an average transmittance of 80% or more for visible light, and can be applied to a switching element of a liquid crystal display device, a thin film electroluminescence display device or the like (thin film transistor) A composite oxide film such as an oxide semiconductor film such as ZTO or ATO used. Further, the present invention relates to a method for producing a composite oxide film which can be applied to the above oxide semiconductor film or the like, and a composite oxide film produced by using the method.

The composition for producing a composite oxide film of the present invention is prepared by using a compound containing at least two or more elements derived from an organozinc compound, a group 4A element compound, a group 3B element compound, and a group 4B element compound as a raw material, and It is easy to handle by flammability, and when used as a spin coating coating material, a dip coating coating material, or a spray pyrolysis coating material, it can provide a composite having an average transmittance of 80% or more for visible light. Oxide film. Furthermore, the method for producing a composite oxide film according to the present invention is prepared by using a compound containing at least two or more elements derived from an organozinc compound, a group 4A element compound, a group 3B element compound, and a group 4B element compound as a raw material. A composition for producing a composite oxide film, which is further used as a spin coating material, and a dip coating coating In the case where the raw material or the spray thermally decomposes the coated raw material, a composite oxide film having an average transmittance of 80% or more with respect to visible light can be provided.

As an oxide semiconductor film containing a metal composite oxide which is one of composite oxides, an oxide semiconductor film containing an oxide such as In, Ga, and Zn (IGZO) having an electron mobility greater than that of amorphous is known. The Si film is characteristic and has attracted attention in recent years. In addition, since such an oxide semiconductor film has a larger electron mobility and a higher visible light transmittance than an amorphous Si film, it is expected to be a switching element (thin film transistor) such as a liquid crystal display device or a thin film electroluminescence display device. The application in etc. is therefore attracting attention.

On the other hand, the industry's oxides of Zn and Sn (ZTO), oxides of Al and Sn (ATO), and ZTO contain complex oxidation of Group 3B elements such as Ga, In, and Al, and Group 4A elements such as Zr and Hf. The material or the ATO contains a film material property of a composite oxide of a Group 3B element such as Zn, Ga or In, or a Group 4A element such as Zr or Hf, and has been continuously applied to an electronic device and the like in the same manner as IGZO.

As a method of forming the amorphous oxide film, a method of forming a thin film by processing a sintered body of IGZO in a vacuum, such as a PVD (Physical Vapor Deposition) method or a sputtering method, is generally known. It is known that a sputtering target of IGZO is used in the formation of an amorphous oxide film (Patent Document 1, Non-Patent Documents 1 and 2).

On the other hand, when an oxide film is formed, film formation by a coating method is known. The coating method has the following advantages: the device is simple and the film formation speed is fast, so the productivity is high and the manufacturing cost is low, and the vacuum container is not required, and the vacuum container is not restricted, so that it can be made into a large scale. Oxide film.

The coating method for forming an oxide thin film is generally a spin coating method (Patent Document 2), a dip coating method (Non-Patent Document 3), and a spray pyrolysis method (Non-Patent Documents 4 and 5). Wait.

As an example of the material for forming the oxide film for coating method, a transparent guide is known. A material for forming a zinc oxide thin film for the purpose of use for an electric film or the like, specifically, zinc acetate, diethyl zinc dissolved in an alcohol-based organic solvent while partially reacting, and a composition obtained by partially hydrolyzing diethyl zinc Wait.

On the other hand, regarding the formation of oxides of Zn and Sn (ZTO), Al and Sn oxides (ATO), the industry is working on chloride, acetate or acetonide compounds of Zn or Sn. Alkoxides and the like have been studied (Non-Patent Document 6).

Prior technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-73312

Patent Document 2: Japanese Patent Laid-Open No. 7-182939

Non-patent literature

Non-Patent Document 1: Edited by the Japan Society for the Promotion of Science, Transparent Oxide Photoelectron Materials, 166th Committee, Technology of Transparent Conductive Film, Revised 2nd Edition (2006), p165~173

Non-Patent Document 2: H. Q. Chiang, et al. Appl. Phys. Lett., 86 (13503), 2005

Non-Patent Document 3: Y. Ohya, et al. J. Mater. Sci., 4099 (29), 1994

Non-Patent Document 4: F. Paraguay D, et al. Thin Solid Films., 16 (366), 2000

Non-Patent Document 5: L. Castaneda, et al. Thin Solid Films., 212 (503), 2006

Non-Patent Document 6: C. Seok-Jun, et al., J. Phys. D: Appl. Phys., 42 (035106), 2009

The inventors have adjusted the composition described in Non-Patent Document 6 to the above-described composition such as ZTO or ATO, and tried to form by spin coating method, dip coating method, or spray pyrolysis method. membrane. However, it is difficult to obtain a transparent oxide film below 200 °C.

An object of the present invention is to provide a novel method for forming an oxide film such as ZTO or ATO by using a composition which is a partial hydrolyzate of an organozinc compound such as diethyl zinc or diethyl zinc, or A 3B group element compound such as a partial aluminum hydrolyzate such as an aluminum alkyl such as triethylaluminum or an aluminum alkyl or a partial hydrolyzate of a 3B group element compound which is produced by using water.

In order to achieve the above object, the inventors of the present invention have conducted an effort to find a partial hydrolyzate of an organozinc compound such as diethylzinc or diethylzinc or an alkylaluminum or alkyl group such as triethylaluminum. a novel composition of a Group 3B element compound such as a partially hydrolyzate such as aluminum or a Group 3B element compound based on a partial hydrolyzate produced by water and containing a Group 4B element such as Sn or a Group 4A element such as Zr or Hf. The film is formed by coating, and an oxide film such as ZTO or ATO having an average transmittance of 80% or more with respect to visible light can be easily obtained, and the present invention has been completed.

The present invention for solving the above problems is as follows.

(1-1)

A composition for producing a composite oxide, comprising at least one element selected from the group consisting of a zinc element and a group 3B element, and at least one element selected from the group consisting of a group 4A element and a group 4B element And containing 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 produced by using the above compound or the above-mentioned compound and the above-mentioned partial hydrolyzate, and selected from At least one compound selected from the group consisting of a compound of a Group 4A element and a compound containing a Group 4B element, a partial hydrolyzate produced by using the above compound, or the above compound and the above partial hydrolyzate.

(1-2)

A composition according to 1-1, wherein the compound containing a zinc element is an organozinc compound represented by the following formula (1), R ¹ -Zn-R ¹ (1)

(wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms).

(1-3)

The composition of 1-2, wherein the partial hydrolyzate produced by using the water of the organozinc compound is mixed with the organic zinc compound represented by the formula (1) and water in a range of 0.05 to 0.8. A product obtained by partially hydrolyzing the above-mentioned organozinc compound.

(1-4)

The composition according to any one of items 1 to 3, wherein the compound containing a Group 3B element is a compound of a Group 3B compound represented by the following formula (2),

(wherein M is a Group 3B element, R ² , R ³ , and R ^{4 are} independently hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, and L is a coordinating organic group containing nitrogen, oxygen, or phosphorus. Compound, n is an integer from 0 to 9).

(1-5)

The composition of 1-4, wherein the partial hydrolyzate produced by using the water of the group 3B element compound is a method in which the compound of the group 3B represented by the formula (2) and water have a molar ratio of 0.05 to 0.8. Mixing, at least a product obtained by partially hydrolyzing the above-mentioned Group 3B element compound.

(1-6)

The composition of any one of 1-1 to 1-5, wherein the compound containing a Group 4A element and the compound containing a Group 4B element are a compound of a Group 4A compound represented by the following formula (3) or (4) And 4B elemental compounds,

(wherein M is a Group 4A element or a Group 4B element, and R ⁵ , R ⁶ , R ⁷ , and R ^{8 are} independently hydrogen, a straight or branched alkyl group having a carbon number of 1 to 7, and a carbon number of 1 to 7; Chain or branched alkoxy group, decyloxy group, acetamyl acetonyl group, decylamino group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer from 0 to 9)

M _c X _d . a H ₂ O (4)

(wherein M is a Group 4A element or a Group 4B element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, and d is 3, and when X is sulfuric acid, c is 2, d is 3, and a is an integer from 0 to 9.)

(1-7)

A composition according to any one of the preceding claims, wherein the part of the hydrolyzate produced by using the water of the compound of the above formula (3) or (4) is 0.05 with a molar ratio of the compound represented by the formula (3) or (4). A product obtained by partially hydrolyzing at least the above-mentioned Group 4A element compound and Group 4B element compound in a range of ~0.8.

(1-8)

The composition of any one of 1-1 to 1-7, wherein the partial hydrolysis by water is at least one selected from the group consisting of a compound containing a Group 4A element and a compound containing a Group 4B element. The partial hydrolyzate produced by using water and at least one compound selected from the group consisting of a compound containing a zinc element and a compound containing a group 3B element is selected from the group consisting of a compound containing a group 4A element and a group 4B. At least one compound selected from the group consisting of a compound of the element and at least one compound selected from the group consisting of a compound containing a zinc element and a compound containing a group 3B element, The product obtained by partially hydrolyzing the above compound by adding water to the total molar ratio of the compound in the range of 0.05 to 0.8.

(1-9)

The composition of any one of 1-1 to 1-8, which further contains an organic solvent.

(1-10)

A composition according to any one of the preceding claims, wherein said organic solvent comprises at least one of an electron donating solvent, a hydrocarbon solvent, and the like.

(1-11)

A composition according to 1-9 or 1-10, wherein the above organic solvent has a boiling point of 230 ° C or less.

(1-12)

A composition according to 1-10, wherein said electron donating solvent comprises one selected from the group consisting of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, and At least one of a group consisting of hexane, heptane, octane, toluene, xylene, and cyclohexane as a hydrocarbon solvent.

(1-13)

The composition of any one of 1-2 to 1-12, wherein the above organozinc compound is diethylzinc.

(1-14)

The composition of any one of 1-4 to 1-13, wherein the compound of the Group 3B element of the above formula (2) comprises a compound selected from the group consisting of trimethyl indium, triethyl indium, trimethyl gallium, and triethyl gallium. At least one of the group consisting of trimethylaluminum, triethylaluminum, trioctylaluminum, trimethylborane, and triethylborane.

(1-15)

The composition of any one of 1-1 to 1-14, wherein the Group 3B element is Al, Ga and In.

(1-16)

The composition of any one of 1-1 to 1-15, wherein the Group 4A element is Ti, Zr and Hf.

(1-17)

The composition of any one of 1-1 to 1-16, wherein the Group 4B element is Si, Ge and Sn.

(2-1)

A method for producing a composite oxide film having an average transmittance of visible light of 80% or more, the method comprising the steps of performing at least one of: a compound selected from the group consisting of a zinc-containing compound and a group 3B At least one compound of the group consisting of the compound of the element, a partial hydrolyzate of the above compound using water or the above-mentioned compound and the above-mentioned partial hydrolyzate, and a compound selected from the group consisting of a compound containing a group 4A element and a compound containing a group 4B element At least one of the compounds in the group, the partial hydrolyzate produced by the above-mentioned compound, or the above-mentioned compound and the partial hydrolyzate include at least one element selected from the group consisting of a zinc element and a group 3B element, and The composite oxide production composition selected from at least one of the group consisting of the Group 4A element and the Group 4B element is applied to the surface of the substrate in an inert gas atmosphere, and then the obtained coating film is heated.

(2-2)

The production method according to 2-1, wherein the compound containing a zinc element is an organozinc compound represented by the following formula (1), and R ¹ -Zn-R ¹ (1)

(wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms).

(2-3)

The production method of 2-2, wherein the partial hydrolyzate produced by the use of the organic zinc compound is mixed with the organic zinc compound represented by the formula (1) and water in a molar ratio of 0.05 to 0.8. A product obtained by partially hydrolyzing the above-mentioned organozinc compound.

(2-4)

The production method according to any one of the items 2-1 to 2-3, wherein the compound containing a Group 3B element is a compound of a Group 3B element represented by the following formula (2),

(wherein M is a Group 3B element, R ² , R ³ , and R ^{4 are} independently hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, and L is a coordinating organic group containing nitrogen, oxygen, or phosphorus. Compound, n is an integer from 0 to 9).

(2-5)

The production method of 2-4, wherein the partial hydrolyzate produced by using the water of the above-mentioned Group 3B element compound is such that the compound of the Group 3B element represented by the formula (2) and water have a molar ratio of 0.05 to 0.8. Mixing, at least a product obtained by partially hydrolyzing the above-mentioned Group 3B element compound.

(2-6)

The method of any one of 2-1 to 2-5, wherein the compound containing a Group 4A element and the compound containing a Group 4B element are a compound of Group 4A represented by the following formula (3) or (4) And 4B elemental compounds,

(wherein M is a Group 4A element or a Group 4B element, and R ⁵ , R ⁶ , R ⁷ , and R ^{8 are} independently hydrogen, a straight or branched alkyl group having a carbon number of 1 to 7, and a carbon number of 1 to 7; Chain or branched alkoxy group, decyloxy group, acetamyl acetonyl group, decylamino group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer from 0 to 9)

M _c X _d . a H ₂ O (4)

(wherein M is a Group 4A element or a Group 4B element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, and d is 3, and when X is sulfuric acid, c is 2, d is 3, and a is an integer from 0 to 9.)

(2-7)

A manufacturing method according to 2-6, wherein the partial hydrolyzate produced by using the water of the above-mentioned Group 4A element compound and Group 4B element compound is a ratio of the compound represented by the formula (3) or (4) to water in a molar ratio of 0.05. A product obtained by partially hydrolyzing at least the above-mentioned Group 4A element compound and Group 4B element compound in a range of ~0.8.

(2-8)

The method of any one of 2-1 to 2-7, wherein the partial hydrolysis by water is at least one selected from the group consisting of a compound containing a Group 4A element and a compound containing a Group 4B element. The partial hydrolyzate produced by using water and at least one compound selected from the group consisting of a compound containing a zinc element and a compound containing a group 3B element is selected from the group consisting of a compound containing a group 4A element and a group 4B. And at least one compound selected from the group consisting of a compound of the element and at least one compound selected from the group consisting of a compound containing a zinc element and a compound containing a group 3B element, and a molar amount relative to the total of the above compounds Water is added in such a manner as to be in the range of 0.05 to 0.8, and the product obtained by partially hydrolyzing the above compound is obtained.

(2-9)

The production method according to any one of 2-1 to 2-8, wherein the above composition further contains an organic solvent.

(2-10)

The manufacturing method of 2-9, wherein the organic solvent comprises at least one of an electron donating solvent, a hydrocarbon solvent, and the like.

(2-11)

A manufacturing method according to 2-9 or 2-10, wherein the organic solvent has a boiling point of 230 ° C or lower.

(2-12)

The manufacturing method of 2-10, wherein the electron donating solvent comprises a solvent selected from the group consisting of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, and At least one of a group consisting of hexane, heptane, octane, toluene, xylene, and cyclohexane as a hydrocarbon solvent.

(2-13)

The production method according to any one of 2 to 2, wherein the above-mentioned organozinc compound is diethylzinc.

(2-14)

The method of any one of 2-4 to 2-13, wherein the compound of the Group 3B element of the above formula (2) comprises a compound selected from the group consisting of trimethyl indium, triethyl indium, trimethyl gallium, and triethyl gallium. At least one of the group consisting of trimethylaluminum, triethylaluminum, trioctylaluminum, trimethylborane, and triethylborane.

(2-15)

The method of any one of 2-1 to 2-14, wherein the Group 3B element is Al, Ga, and In.

(2-16)

The method of any one of 2-1 to 2-15, wherein the Group 4A element is Ti, Zr and Hf.

(2-17)

The method of any one of 2-1 to 2-16, wherein the Group 4B element is Si, Ge, and Sn.

(2-18)

The method of any one of 2-1 to 2-17, wherein the inert gas atmosphere contains water vapor.

(2-19)

For example, in the manufacturing method of 2-18, the relative humidity of the inert gas atmosphere containing water vapor is in the range of 2 to 15%.

(2-20)

A method for producing a composite oxide film having an average transmittance of visible light of 80% or more, the method comprising the step of producing a composition for producing a composite oxide such as 2-1 in an inert gas containing water vapor The step of spray coating on the surface of the heated substrate in an environment.

(2-21)

For example, in the method for producing a composite oxide film of 2 to 20, an inert gas atmosphere containing water vapor is formed by supplying water vapor to the vicinity of the surface of the substrate under atmospheric pressure or under pressure.

(2-22)

For example, in the method for producing a composite oxide film of 2 to 20, the heating temperature of the surface of the substrate is 400 ° C or lower.

(2-23)

A method for producing a composite oxide film according to 2-21 or 2-22, wherein the amount of water vapor supplied is in a range of 0.1 to 5 with respect to the molar ratio of zinc in the supplied composition. The way to supply.

(2-24)

An oxide semiconductor film comprising a composite oxide film produced by the production method according to any one of 2-1 to 2-23.

By using the composition for producing a composite oxide film of the present invention, it is possible to form a film by a spin coating method, a dip coating method, a spray pyrolysis method or the like to form an oxide semiconductor film such as ZTO or ATO. A useful composite oxide film can produce a composite oxide film having an average transmittance of 80% or more for visible light.

1‧‧‧ spray bottle

2‧‧‧Substrate holder (with heater)

3‧‧‧ spray nozzle

4‧‧‧Compressor

5‧‧‧ Alkali-free glass substrate

6‧‧‧Water vapor introduction tube

Fig. 1 is a view showing a spray film forming apparatus.

[Composition for producing a composite oxide film]

The composition for producing a composite oxide film of the present invention contains at least one element selected from the group consisting of a zinc element and a group 3B element, and at least one selected from the group consisting of a group 4A element and a group 4B element. A composition for producing a composite oxide of a plurality of elements. The composition contains 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 produced by water of the above compound, or the above-mentioned compound and the above-mentioned partial hydrolyzate, and selected At least one compound selected from the group consisting of a compound of a Group 4A element and a compound containing a Group 4B element, a partial hydrolyzate produced by water of the above compound, or the above compound and the above partial hydrolyzate.

(1) Compounds containing zinc

The compound containing a zinc element is, for example, an organozinc compound represented by the following formula (1).

R ¹ -Zn-R ¹ (1)

(wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms)

Specific examples of the alkyl group represented by R ¹ in the organozinc compound represented by the above formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. Dibutyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. The compound represented by the formula (1) is preferably a compound wherein R ¹ is a carbon number of 1, 2, 3, 4, 5 or 6. The compound represented by the formula (1) is particularly preferably a diethyl zinc wherein R ¹ is a carbon number of 2.

(2) Compounds containing Group 3B elements

Examples of the compound containing a Group 3B element include a Group 3B element compound represented by the following formula (2).

(wherein M is a Group 3B element, and R ² , R ³ , and R ^{4 are} independently hydrogen, and a straight or branched alkyl group having 1 to 7 carbon atoms)

Specific examples of the metal represented by M in the group 3B element compound represented by the above formula (2) include B, Al, Ga, and In. Further, R ² , R ³ and R ^{4 are} preferably hydrogen or an alkyl group, and 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 second group. Butyl, tert-butyl, pentyl, isopentyl, neopentyl, third pentyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. The ligand represented by L may be exemplified by trimethylamine, triethylamine, triphenylamine, pyridine, Porphyrin, N,N-dimethylaniline, N,N-diethylaniline, triphenylphosphine, dimethylsulfide, diethyl ether, tetrahydrofuran. The compound represented by the formula (2) is particularly preferably a compound wherein R ² , R ³ and R ⁴ are a carbon number of 1, ² , ³ , 4, 5 or 6, and examples thereof include trimethyl aluminum and triisobutyl group. Aluminum, diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, trimethylindium, triethylindium, trimethylborane, triethylborane, and the like A coordination compound formed by a ligand, and the like.

(3) Compounds containing Group 4A elements and compounds containing Group 4B elements

Examples of the compound containing a Group 4A element and the compound containing a Group 4B element include a Group 4A element compound and a Group 4B element compound represented by the following formula (3) or (4).

(wherein M is a Group 4A element or a Group 4B element, and R ⁵ , R ⁶ , R ⁷ , and R ^{8 are} independently hydrogen, a straight or branched alkyl group having a carbon number of 1 to 7, and a carbon number of 1 to 7; Chain or branched alkoxy group, decyloxy group, acetamyl acetonyl group, decylamino group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer from 0 to 9)

M _c X _d . a H ₂ O (4)

(wherein M is a Group 4A element or a Group 4B element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, and d is 3, and when 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 above formula (3) include Ti, Zr, and Hf. The alkyl compound is usually unstable, and R ⁵ , R ⁶ , R ⁷ and R ⁸ in the formula are preferably an alkoxy group or a decyloxy group, an ethoxy group, an acetoacetone group or a decylamino group. A ligand for oxygen or nitrogen. Specific examples of such a ligand include alkoxy groups, ethoxylated groups, anthracenyloxy groups, acetamylacetone groups, decylamino groups and the like which are generally known. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a third butoxy group. Further, examples thereof include a decyloxy group such as an ethoxy group such as an ethoxy group, an acetaminophen group, a decylamino group such as trimethyl decylamine, triethyl decylamine, isopropyl decylamine or t-butyl decylamine.

Further, specific examples of the element represented by M in the group 4B element compound represented by the above formula (3) include Si, Ge, and Sn. Specific examples of such compounds include an alkyl group, an alkoxy group, a decyloxy group, an acetoacetone group, and an anthranyl group which are generally known. Specific examples of the alkyl group of 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 second butyl group and a third butyl group. Base, pentyl, isopentyl, neopentyl, third amyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a third butoxy group. Further, examples thereof include a decyloxy group such as an ethoxycarbonyl group, an acetaminophen group such as an acetamylacetone group, a trimethylguanamine, a triethylguanamine, an isopropylamine or a tributylamine.

The group 4B element compound represented by the formula (3) is particularly, for example, ethyl tin, butyl tin, methoxy ruthenium, ethoxy ruthenium, isopropoxy ruthenium, tert-butoxy ruthenium, methoxy ruthenium, Ethoxy ruthenium, osmium isopropoxide, ruthenium tert-butoxide, methoxy tin, ethoxy tin, isopropyl Oxytin, third butoxide, barium acetate, tin acetate, acenaphthylacetate, acetonyl acetonide, dimethyl guanamine oxime, diisopropyl guanamine oxime, dimethyl guanamine tin, two Isopropyl guanamine tin and the like.

Examples of the ligand represented by L in the group 4A and 4B element compounds represented by the formula (3) include trimethylamine, triethylamine, triphenylamine, and pyridine. Porphyrin, N,N-dimethylaniline, N,N-diethylaniline, triphenylphosphine, dimethylsulfide, diethyl ether, tetrahydrofuran. For example, the compound of the group 4A element represented by the formula (3) may, for example, be titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium butoxide, zirconium methoxide, zirconium ethoxide or the like. Zirconium propoxide, zirconium butoxide, cerium oxyhydroxide, cerium isopropoxide, zirconium butoxide, titanium acetate, zirconium acetate, cerium acetate, titanium acetylacetonate, zirconium acetonide, acetonide acetonide, Titanium dimethylamine, titanium titanium amide, titanium diisopropyl decylamine, titanium ditributy decylamine, zirconium dimethyl guanamine, zirconium diethyl guanamine, diisopropyl hydrazine Amine zirconium, zirconium dibutyl phthalamide, dimethyl guanamine oxime, diethyl guanamine oxime, diisopropyl guanamine oxime, ditributyl guanamine oxime, and the like .

Specific examples of the metal represented by M in the group 4A element compound represented by the above formula (4) include Ti, Zr, and Hf. Further, specific examples of the component forming a salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. For example, the group 4A element compound represented by the formula (4) may, for example, be titanium fluoride, zirconium fluoride, cesium fluoride, titanium chloride, zirconium chloride, cerium chloride, titanium nitrate, zirconium nitrate or cerium nitrate. And hydrates such as titanium sulfate, zirconium sulfate, barium sulfate and the like.

Specific examples of the metal represented by M in the group 4B element compound represented by the above formula (4) include Si, Ge, and Sn. Further, specific examples of the component forming a salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. For example, examples of the Group 4B element compound represented by the formula (4) include cesium fluoride, cesium fluoride, tin fluoride, cesium chloride, cesium chloride, tin chloride, tin bromide, cerium nitrate, and nitric acid. Tin, sulfuric acid, and the like, etc.

The composition for producing a composite oxide film of the present invention described above specifically includes the following aspects.

(i) an organic zinc compound represented by the above formula (1), a partially hydrolyzed product derived from water of the organozinc compound represented by the above formula (1), or an organic zinc represented by the above formula (1) The compound and the partial hydrolyzate produced by the use of water in the organozinc compound represented by the above formula (1) are added with the group 4A element compound and/or the group 4B element compound represented by the above formula (3) or (4). a product obtained by partially hydrolyzing a group 4A element compound and/or a group 4B element compound represented by the above formula (3) or (4), or a group 4A element represented by the above formula (3) or (4) A composition of a compound and/or a Group 4B element compound and a product obtained by partially hydrolyzing the compound.

(ii) a partial hydrolyzate produced by using water of a group 3B element compound represented by the above formula (2) and a group 3B element compound represented by the above formula (2), or represented by the above formula (2) a part of the hydrolyzate produced by using the water of the group 3B element compound and the group 3B element compound represented by the above formula (2), and the compound of the group 4A represented by the above formula (3) or (4) and/or a Group 4B element compound, a product obtained by partially hydrolyzing a Group 4A element compound represented by the above formula (3) or (4) and/or a Group 4B element compound, or a compound represented by the above formula (3) or (4) A composition of a Group 4A element compound and/or a Group 4B element compound and a product obtained by partially hydrolyzing the compound.

Furthermore, the group 4A element compound and/or the group 4B element compound represented by the above formula (3) or (4) are added to the following compositions 1 to 9, and the compound represented by the above formula (3) or (4) is added. a product obtained by partially hydrolyzing a Group 4A element compound and/or a Group 4B element compound, or a Group 4A element compound and/or a Group 4B element compound represented by the above formula (3) or (4), and partially hydrolyzing the compound The product obtained is a composition of a compound containing a Group 4A element and a compound containing a Group 4B element.

(i) a composition containing the organozinc compound represented by the above formula (1) and the group 3B element compound represented by the above formula (2) (hereinafter, sometimes referred to as composition 1)

(ii) a composition containing a partial hydrolyzate produced by water of the organozinc compound represented by the above formula (1) and the group 3B element compound represented by the above formula (2) (hereinafter, sometimes referred to as a composition) 2)

(iii) a portion derived from the use of water by the organozinc compound represented by the above formula (1), the group 3B element compound represented by the above formula (2), and the group 3B element compound represented by the above formula (2) Composition of hydrolyzate (hereinafter, sometimes referred to as composition 3)

(iv) a composition containing a partial hydrolyzate produced by water and a compound of a group 3B element containing the organozinc compound represented by the above formula (1) (hereinafter, sometimes referred to as composition 4)

(v) a composition containing a partial hydrolyzate produced by water and a partial hydrolyzate produced by using a water of a 3B group element compound containing the organozinc compound represented by the above formula (1) (hereinafter, sometimes referred to as composition 5) )

(vi) a partially hydrolyzed product derived from water containing the organozinc compound represented by the above formula (1), a compound of the group 3B represented by the above formula (2), and a group 3B represented by the above formula (2) A composition of an elemental compound using a partial hydrolyzate produced by water (hereinafter, sometimes referred to as composition 6)

(vii) a composition containing the organozinc compound represented by the above formula (1), the partially hydrolyzed product of the organozinc compound by water, and the group 3B element compound represented by the above formula (2) (hereinafter, Sometimes called composition 7)

(viii) an organic zinc compound represented by the above formula (1), a partially hydrolyzed product obtained by using the water of the organozinc compound, and a water-generating portion of the group 3B element compound represented by the above formula (2) Composition of hydrolyzate (hereinafter, sometimes referred to as composition 8)

(ix) a partial hydrolyzate produced by using the organozinc compound represented by the above formula (1) and the organozinc compound, and a group 3B element compound and a group 3B element compound represented by the above formula (2) A composition using a partial hydrolyzate produced by water (hereinafter, sometimes referred to as composition 9)

In the composition of the present invention, as the above zinc compound and as a formula other than the formula (1) As the compound, for example, a zinc compound represented by the following formula (5) or (6) can be added.

R ⁹ -MR ¹⁰ . (L)n (5)

(In the formula, M is a zinc element, and R ⁹ and R ^{10 are} independently hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms (except when R ⁹ and R ¹⁰ are both alkyl groups), and carbon number 1~ a linear or branched alkoxy group, a decyloxy group, an acetoacetone group or a decylamino group, and L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9)

M _c X _d . a H ₂ O (6)

(wherein M is a zinc element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, d is 2, and when X is sulfuric acid, c is 1, d Is 1, a is an integer from 0 to 9)

Specific examples of the zinc compound represented by the above formula (5) which can be added as a compound other than the formula (1) include, for example, a generally known alkyl group (in the above formula (5), R ⁹ And R ¹⁰ is a compound of an alkyl group, an alkoxy group, a decyloxy group, an acetamyl acetonyl group, and a decylamino group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a third butoxy group. Further, examples thereof include a decyloxy group such as an ethoxycarbonyl group, an acetaminophen group such as an acetamylacetone group, a trimethylguanamine, a triethylguanamine, an isopropylamine or a tributylamine.

The ligand represented by L in the above formula (5) may, for example, be trimethylamine, triethylamine, triphenylamine or pyridine. Porphyrin, N,N-dimethylaniline, N,N-diethylaniline, triphenylphosphine, dimethylsulfide, diethyl ether, tetrahydrofuran. For example, examples of the zinc compound represented by the formula (5) include zinc dimethoxide, zinc diethoxylate, zinc diisopropoxide, zinc zinc thirdoxide, zinc acetate, zinc acetylacetonate, and the like. Bis(dimethylamine) zinc, bis(diisopropylguanamine) zinc, and the like, and the like.

In the zinc compound represented by the above formula (6), specific examples of the component forming a salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. For example, examples of the zinc compound represented by the formula (6) include zinc fluoride, zinc chloride, zinc nitrate, and carbonic acid. Zinc, zinc sulfate and other hydrates thereof.

Furthermore, in the present invention, as the compound of the group 3B element and a compound other than the formula (2), for example, a compound of the group 3B represented by the following formula (7) or (8) may be added.

(wherein M is a Group 3B element, and R ¹¹ , R ¹² and R ^{13 are} independently hydrogen, and a straight or branched alkyl group having 1 to 7 carbon atoms (wherein R ¹¹ , R ¹² and R ¹³ are each an alkyl group) Except), a linear or branched alkoxy group having a carbon number of 1 to 7, a decyloxy group, an acetoacetone group or a decylamino group, and L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is 0. An integer of ~9)

M _c X _d . a H ₂ O (8)

(wherein M is a Group 3B element, X is a halogen atom, nitric acid or sulfuric acid, and 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, a is an integer from 0 to 9)

Specific examples of the metal represented by M in the group 3B element compound represented by the above formula (7) include B, Al, Ga, and In. Further, examples of R ¹¹ , R ¹² and R ¹³ include hydrogen or an alkyl group (except when R ¹¹ , R ¹² and R ¹³ are each an alkyl group), and specific examples of the alkyl group include a methyl group and an ethyl group. , propyl, isopropyl, butyl, isobutyl, t-butyl, tert-butyl, pentyl, isopentyl, neopentyl, third amyl, hexyl, isohexyl, second hexyl, Third hexyl, 2-hexyl, and heptyl. It is also preferred that at least one of R ² , R ³ and R ⁴ is hydrogen, and the balance is an alkyl group. Further, specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a third butoxy group. Further, examples thereof include a decyloxy group such as an ethoxycarbonyl group, an acetaminophen group, an acetamino group such as trimethyl decylamine, triethyl decylamine or isopropyl decylamine.

The ligand represented by L in the above formula (7) may, for example, be trimethylamine, triethylamine, triphenylamine or pyridine. Porphyrin, N,N-dimethylaniline, N,N-diethylaniline, triphenylphosphine, dimethylsulfide, diethyl ether, tetrahydrofuran. Specific examples of the Group 3B element compound represented by the formula (7) include diborane, borane-tetrahydrofuran complex, borane-trimethylamine complex, borane-triethylamine complex, Triethylborane, tributylborane, aluminum hydride-trimethylamine complex, aluminum hydride-triethylamine complex, trimethylaluminum, dimethylaluminum hydride, triisobutylaluminum , diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, trimethylindium, triethylindium, trimethoxyborane, triethoxyborane, triisopropoxy Indium, triisopropoxy gallium, triisopropoxy aluminum, tri-tert-butoxy indium, tri-tert-butoxy gallium. In terms of low cost and easy availability, it is especially preferred to be triethyl aluminum, triisobutyl aluminum, trimethyl gallium, trimethyl indium, trimethoxyborane, triethoxyborane, triiso Indium propoxide, gallium triisopropoxide, aluminum triisopropoxide, indium trisuccinate, and tris-butoxy gallium.

Specific examples of the metal represented by M in the Group 3B element of the Group 3B element compound and the Group 3B element compound represented by the above formula (8) include B, Al, Ga, and In. Further, specific examples of the component forming a salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. Examples of the Group 3B element compound represented by the formula (8) include boron fluoride, boron chloride, aluminum chloride, aluminum chloride hexahydrate, aluminum nitrate nonahydrate, gallium chloride, and gallium nitrate hydrate. Indium chloride, indium chloride tetrahydrate, indium nitrate pentahydrate, and the like.

Further, the compound represented by the formulae (1) and (2) has a linear or branched alkyl group having a carbon number of 1 to 7 by R ⁵ , R ⁶ , R ⁷ and R ^{7 in the} formula (3). The alkyl compound of the group 4A element compound or the group 4B element compound and the zinc compound represented by the formula (5) or (6), the group 3B element compound represented by the formula (7) or (8), and the like A case where a substituent exchange reaction between compounds other than an alkyl group is carried out in a solution of the composition. The compositions of the present invention also comprise a composition comprising a compound formed by such a substituent exchange reaction.

Further, the present invention includes the above composition further containing an organic solvent.

More specific examples of the composition of the present invention include the following. However, it is not intended to be limited to these.

(A) A solution containing the group 4A element represented by the above formula (3) and/or formula (4) in a solution obtained by dissolving the organozinc compound represented by the above formula (1) in an organic solvent. And/or a composition of a product of a Group 4B element compound (hereinafter, sometimes referred to as Mixture 1).

(B) The solution obtained by dissolving the 3B element compound represented by the above formula (2) in an organic solvent contains the group 4A element represented by the above formula (3) and/or formula (4). A composition of a compound and/or a product of a Group 4B element compound (hereinafter sometimes referred to as Mixture 2).

(C) adding water to a solution obtained by dissolving the organozinc compound represented by the above formula (1) in an organic solvent, and at least partially hydrolyzing the organozinc compound, and containing and containing at least one group 3B element a mixture of the compound of the group 3B element represented by the above formula (2) and/or formula (7) and a compound of the group 4A element and/or 4B represented by the above formula (3) and/or formula (4) A composition of a product of a group element compound (hereinafter, sometimes referred to as partial hydrolyzate 1).

(D) adding water to a solution obtained by dissolving the Group 3B element compound represented by the above formula (1) in an organic solvent to at least partially hydrolyze the above-mentioned Group 3B element compound, and containing the above formula (3) And/or a composition of a Group 4A element compound and/or a Group 4B element compound represented by the formula (4) (hereinafter sometimes referred to as a partial hydrolyzate 2).

(E) A mixture of an organozinc compound represented by the above formula (1) and a group 3B element compound represented by the following formula (2) containing at least one group 3B element is dissolved in an organic solvent. Water is added to the solution to at least partially hydrolyze the above-mentioned organozinc compound to obtain a product (hereinafter, sometimes referred to as a partial hydrolyzate 3), that is, to contain the above product and to contain the above formula (3) and/or formula (4). A composition of a product of a Group 4A element compound and/or a Group 4B element compound.

(F) an organozinc compound represented by the above formula (1), containing at least one 3B group The element of the group 3B element represented by the following formula (2) of the element, and the product of the compound of the group 4A element and/or the compound of the group 4B element represented by the above formula (3) and/or the formula (4) Water is added to the solution in which the mixture is dissolved in an organic solvent, and at least a part of the above-mentioned organozinc compound is hydrolyzed to obtain a product (hereinafter, sometimes referred to as a partial hydrolyzate 4), that is, a composition containing the above product.

In the present invention, an organic solvent can be used in order to dissolve the metal-containing compound described above. The organic solvent is not particularly limited as long as it dissolves the zinc or a group 3B element, a group 4A element, a group 4B element, or a partial hydrolyzate of the compound, and is not particularly limited in use. An electron-donating organic solvent such as an ether used in the industry or a hydrocarbon compound such as hexane or toluene is used. These organic solvents may be used singly or in the form of a mixture with other solvents. By using such a solvent to dissolve the composition of the present invention and apply it to a substrate or the like, an oxide film such as ZTO or ATO having an average transmittance of 80% or more with respect to visible light can be easily obtained.

Examples of the electron-donating organic solvent include an ether compound, an amine compound, and the like, and may be those having a solubility in a raw material compound such as an organozinc compound represented by the formula (1) and water. Examples of preferred electron-donating organic solvents include those having a boiling point of 230 ° C or lower, and examples thereof include di-n-butyl ether (boiling point: 142.4 ° C), dihexyl ether (boiling point: 226.2 ° C), and anisole (boiling point: 153.8). °C), phenylethyl ether (boiling point 172 ° C), butyl phenyl ether (boiling point 210.3 ° C), amyl phenyl ether (boiling point 214 ° C), methoxy toluene (boiling point 171.8 ° C), benzyl ether (boiling point 189 ° C), Diphenyl ether (boiling point 258.3 ° C), 1,2-dimethoxybenzene (veratrol) (boiling point 206.7 ° C), three Alkane (boiling point 114.5 ° C), and ethylene glycol dimethyl ether such as 1,2-diethoxyethane (boiling point 121 ° C), 1,2-dibutoxyethane (boiling point 203.3 ° C), and double ( 2-methoxyethyl)ether (boiling point 162 ° C), bis(2-ethoxyethyl)ether (boiling point 188.4 ° C), bis(2-butoxyethyl)ether (boiling point 254.6 ° C), etc. Ethylene glycol dimethyl ether, further 1,2-bis(2-methoxyethoxy)ethane (boiling point 216 ° C), bis[2-(2-methoxyethoxyethyl)]ether ( An ether solvent such as a boiling point of 275 ° C) such as triethylene glycol dimethyl ether; tri-n-propylamine (boiling point 150 to 156 ° C), tri-n-pentylamine (boiling point 130 ° C), N,N-dimethylaniline ( An amine solvent such as a boiling point of 193 ° C), N,N-diethylaniline (boiling point: 217 ° C), or pyridine (boiling point: 115.3 ° C). As the electron-donating organic solvent, in view of the inhibition of the gel at the time of preparation of the composition and the volatility of the solvent itself, it is preferably 1,2-diethoxy as a kind of ethylene glycol dimethyl ether. Ethylethane (boiling point 121 ° C). The boiling point of the electron-donating organic solvent is not particularly limited. However, from the viewpoint of drying the solvent after coating the obtained composition and removing the solvent to form a coating film, the drying time is preferably 230 ° C or lower.

Further, a hydrocarbon compound can be used as a solvent in the present invention. The hydrocarbon compound may be a linear, branched hydrocarbon compound or a cyclic hydrocarbon compound having a carbon number of 5 to 20, more preferably 6 to 12 carbon atoms, and a carbon number of 6 to 20, more preferably a carbon number of 6 to 12. A mixture of aromatic hydrocarbon compounds and the like.

Specific examples of the hydrocarbon compound include pentane, n-hexane, heptane, isohexane, methylpentane, octane, 2,2,4-trimethylpentane (isooctane), and An aliphatic hydrocarbon such as decane, n-decane, n-hexadecane, octadecane, eicosane, methyl heptane, 2,2-dimethylhexane or 2-methyloctane; cyclopentane, An alicyclic hydrocarbon such as cyclohexane, methylcyclohexane or ethylcyclohexane; an aromatic hydrocarbon such as benzene, toluene, xylene, cumene or trimethylbenzene; mineral spirits, solvent naphtha, A hydrocarbon solvent such as kerosene or petroleum ether.

There is no particular upper limit on the boiling point of the organic solvent or hydrocarbon compound which is different from the above-mentioned electron-donating organic solvent, but the drying time when the coating composition is removed and the solvent is removed to form a coating film becomes relatively short. The same as the electron-donating compound is preferably 230 ° C or lower. Further, from the viewpoint of improving the stability of the metal-containing compound, it is preferred to contain an electron-donating compound in the composition of the present invention.

The above formula (1) to (4) and the like are obtained by dissolving the compound represented by the above formula (1) in a solution obtained by dissolving the above-mentioned electron-donating organic solvent or a mixed organic solvent containing the electron-donating organic solvent; The concentration of the raw material compound is preferably in the range of 4 to 12% by mass. An original expressed by the general formulae (1) to (4) dissolved in a solution obtained by the above organic solvent The concentration of the compound is preferably in the range of 6 to 10% by mass.

The composition obtained by dissolving the above-mentioned compound or a partially hydrolyzed product in an organic solvent is dissolved or reacted as described above to form a composition directly, or after obtaining a product by, for example, a partial hydrolysis reaction, an electron-donating organic compound is optionally added. The composition of the present invention can be prepared by adjusting the composition of an organic solvent such as a solvent or a hydrocarbon compound.

With respect to the amount of water to be added in the preparation of the above partial hydrolyzate, for example, for the partial hydrolyzate 1, it is preferred to set the molar ratio of the organozinc compound of the above formula (1) to a range of 0.05 to 0.8. The partial hydrolyzate 2 preferably has a molar ratio of 0.05 to 0.8 in terms of a total amount of the compound of the group 3B element. The partial hydrolyzate 3 preferably has a molar ratio of 0.05 to 0.8 with respect to the total amount of the organozinc compound and the 3B group element compound. Further, the organozinc compound and the group 3B element compound may be further coexisted with the group 4A element compound and/or the group 4B element compound as in the partial hydrolyzate 4, and water may be added to carry out hydrolysis. In this case, it is preferred that the molar ratio of the total amount of the organozinc compound and the group 3B element compound is in the range of 0.05 to 0.8, but if the group 4A element compound or the group 4B element compound is also hydrolyzed, Further, water having a molar ratio of 0.01 to 0.8 in terms of a total amount of the organic zinc compound or the compound of the 3B group element may be added within a range not affecting the reaction of the organozinc compound or the compound of the 3B group element.

The reaction product containing the partially hydrolyzed product obtained by adding the amount of water to the range can form a transparent and conductive zinc oxide thin film by a spin coating method, a dip coating method, and spray thermal decomposition. Further, in the case where the component of the group 3B element is partially hydrolyzed, it is also preferred to set the molar ratio of water to the compound of the group 3B element to be in the range of 0.05 to 0.8.

For example, when the organic zinc compound is partially hydrolyzed by setting the molar ratio of water to 0.4 or more, partial hydrolysis of the organozinc compound can be obtained in a high yield of 90% or more based on the zinc contained in the raw material. Part of the hydrolyzate. Further, in the partial hydrolyzate 2, the compound of the 3B group element may be partially hydrolyzed in an appropriate amount. By setting the molar ratio to 0.4 In the case of the partial hydrolyzate 1, the residual amount of the organozinc compound which is an unreacted raw material can be suppressed, and in the case of the partial hydrolyzate 2, the residual amount of the organozinc compound and the 3B group element compound can be suppressed. Further, by setting the molar ratio to 0.8 or less, generation of a gel in the hydrolysis reaction can be suppressed. When a gel is generated in the hydrolysis reaction, the viscosity of the solution rises, and the subsequent operation becomes difficult. The upper limit of the molar ratio of water added to the molar ratio is preferably 0.8, more preferably 0.75.

By controlling the amount of water added, physical properties such as viscosity or boiling point of the composition can be controlled. For example, when it is difficult to apply a coating such as a spin coating method, it is possible to easily form an oxide by increasing the amount of water added. In addition, it is possible to easily form a film at a low temperature by using a composition of the present invention obtained by using a compound which is not hydrolyzed by a spray method or the like or a part of a hydrolyzate which is reduced in water addition.

In the partial hydrolyzate 1, since a 3B group element compound or the like is added after adding water to the organozinc compound, depending on the amount of water added, etc., the added water is consumed by the hydrolysis of the organozinc compound, and the 3B group element is added. In the case of a compound or the like, the above product usually does not contain a hydrolyzate of the above-mentioned Group 3B element compound or the like. The Group 3B element compound or the like is also contained as a raw material without being hydrolyzed, or is an organic group (coordination) exchange of an organic group having a partial hydrolyzate of an organozinc compound with a compound of a Group 3B element (coordination) Exchange) the possibility of being a winner. In the partial hydrolyzate 3, since water is added to the mixed solution of the organozinc compound and the group 3B element compound or the like, the above product usually contains a hydrolyzate such as the above-described group 3B element compound. The hydrolyzate of the Group 3B element compound or the like may be a partial hydrolyzate depending on the amount of addition of water or the like.

The addition of water may be carried out by mixing only water with other solvents, and may be carried out by using a mixed solvent obtained by mixing water with another solvent. From the viewpoint of suppressing the progress of the local hydrolysis, it is preferred 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 which can be used in the mixed solvent with water can be, for example, the above-mentioned electron-donating organic solvent. Further, as an electron-donating organic The 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, from the viewpoint of being inert to diethyl zinc and having high solubility in water, an organic solvent having a boiling point of less than 110 ° C is preferred.

The addition of water also depends on the scale of the reaction, for example, it can take between 60 seconds and 10 hours. In view of the fact that the yield of the product is good, it is preferably added by dropwise adding water or a mixed solvent of water to the organozinc compound of the above formula (1) as a raw material. The addition of water can be carried out by stirring the solution of the compound represented by the formula (1) and the electron-donating organic solvent without stirring (in a state of standing) or while stirring. The temperature at the time of addition can be selected from any temperature between -90 and 150 °C. From the viewpoint of reactivity of water with an organic zinc compound, it is preferably from -15 to 30 °C.

The hydrolysis of the compound of the Group 3B element of the formula (2) is slightly more severe than the reaction of the organozinc compound of the formula (1), but can be carried out by the same method as the reaction of the organozinc compound of the above formula (1), and the reaction conditions. The above reaction conditions are also appropriately selected, whereby the reaction can be controlled in the same manner. With respect to the Group 4A element compound or the Group 4B element compound of the formula (3) and the formula (4), the zinc compound of the formula (5) and the formula (6), the formula (7) and the formula (8) The hydrolysis of the 3B group element compound is also the same.

After the addition of water, in order to carry out the reaction of water, the compound represented by the formula (1), and the compound represented by the formula (2) to (4) or water with the compound represented by the formula (1), For example, it is left to stand or stir for 1 minute to 48 hours without stirring (in a state of standing). Regarding the reaction temperature, the reaction can be carried out at any temperature between -90 and 150 °C. The reaction temperature is preferably in the range of 5 to 80 ° C from the viewpoint of obtaining a partial hydrolyzate in a high yield. There is no limit to the reaction pressure. It can usually be carried out under normal pressure (atmospheric pressure). The reaction of the water with the compound represented by the formula (1) may be carried out by sampling the reaction mixture as needed, and the sample may be analyzed by NMR (nuclear magnetic resonance) or IR (infrared ray) or the like. The generated gas is sampled for detection.

The above organic solvent, the organozinc compound of the above formula (1), the group 3B element compound of the formula (2), the compound of the formula (3) and the group 4A element of the formula (4) or the group 4B element as a raw material The compound, the zinc compound of the formula (5) and the formula (6), the compound of the formula (7) and the group 3B element of the formula (8), and the mixed solvent of water or water can be introduced into the reaction according to all conventional methods. In the container. The reaction steps may be any of batch operation mode, semi-batch operation mode, and continuous operation mode, and are not particularly limited, but are preferably batch operation type.

By the above reaction, the organozinc compound of the above formula (1) or the compound of the group 3B of the above formula (2) and the like can be partially hydrolyzed by water to obtain a product containing a partial hydrolyzate. In the case where the organozinc compound of the formula (1) is diethylzinc, the analysis of the product obtained by the reaction with water has been performed previously, but the results vary according to different reports, and it is not clear Specify the composition of the product. Further, the composition of the product may vary depending on the molar ratio of water added to the molar ratio or the reaction time.

For example, the partial hydrolyzate 1 is presumed to be a mixture of a compound represented by the following formula (9) or a plurality of compounds different in p.

R ¹ -Zn-[O-Zn] _p -R ¹ (9)

(wherein R ^{1 is the} same as R ¹ in the formula (1), and p is an integer of 2 to 20)

Further, the partial hydrolyzate 2 is estimated to be a mixture of a compound represented by the following formula (10) or a plurality of compounds having different p.

(wherein M is the same as M in the formula (2), and Q is the same as any of R ² , R ³ and R ⁴ in the formula (2), and m is an integer of 2 to 20)

In the present invention, the main component of the product, for example, the partial hydrolyzate 3, is inferred to combine the structural unit represented by the following general formulae (11) and (12) with the structural unit represented by the above general formula (10). A mixture of compounds, or a plurality of compounds of different m.

(R ₁ -Zn)- (11)

-[O-Zn] _m - (12)

(wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20)

In the composition for producing a composite oxide film containing a zinc element (Zn), a group 3B element (3B), a group 4A element (4A), and a group 4B element (4B), it is used to form Zn-4A, Zn-4B. a composite oxide of a combination of elements of Zn-4A-4B, 3B-4A, 3B-4B, 3B-4A-4B, Zn-3B-4A, Zn-3B-4B, and Zn-3B-4A-4B The ratio of the composition of each element of Zn~4B in the composition can be arbitrarily adjusted to the formula used in the present invention in such a manner that the composition of the oxide of the composite oxide of the combination of the elements of the present invention is required. 1) The molar ratio of each compound of ~(8). The molar ratio can be adjusted by obtaining the usual composition of the reported composite oxide or its oxygen vacancy compound, etc., and other composition ratios are not limited to the integer ratio, and can be prepared by preparing the addition amount of each element. Any of the constituents.

For example, a composition for the film formation of the above ZTO or ATO is one in which the composition contains Sn as a Group 4B element in addition to zinc or aluminum. The ratio of the composition can arbitrarily adjust the molar ratio of Zn to Sn and Al to Sn in such a manner as to include the composition of the oxide of ZTO or ATO. The molar ratio can be adjusted in such a manner that the usual composition of the reported ZTO or ATO or its oxygen vacancy compound, etc., and other composition ratios are not limited to the integer ratio, and can be prepared by adjusting the addition amount of each element. Any of the constituents.

The composite oxide containing a zinc element (Zn), a Group 3B element (3B), a Group 4A element (4A), and a Group 4B element (4B) obtained by using the composition of the present invention can be exemplified by the following oxides and inclusions. Its oxides.

Examples 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 et al; examples of Zn-4B: Zn _x Sn _y O _t , Zn _x Ge _y O _t , Zn _x Si _y O _t , Zn _x Sn _y Si _y O _t , Zn _x Ge _y Sn _y O _t , Zn _x Si _y Ge _y O _t et al; Examples 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 ,} etc., 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 ; Examples of 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 Zr _y Hf _y O _t , Ga _x Hf _y Ti _y O _t , In _x Al _x Ti _y O _t , In _x Al _x Zr _y O _t , In _x Al _x Hf _y O _t , In _x Al _x Ti _y Zr _y O _t , Ga _x Al _x Ti _y Zr _y O _t , In _x Al _x Zr _y Hf _y O _t , In _x Al _x Hf _y Ti _y O _t , Ga _x In _x Al _x Hf _y Ti _y O _{t ,} etc.; Examples of 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 Sn _y Si _y O _t , In _x Ge _y Sn _y O _t , In _x Si _y Ge _y O _t , In _x Al _x Sn _y O _t , In _x Al _x Ge _y O _t , In _x Al _x Si _y O _t , In _x Al _x Sn _y Ge _y O _t , Ga _x Al _x Sn _y Ge _y O _t , In _x Al _x Ge _y Si _y O _t , In _x Al _x Si _y Sn _y O _t , Ga _x In _x Al _x Sn _y Ge _y O _t et al; Examples 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 _y O _t , Ga _x Sn _y Hf _y O _t Ga _x Sn _y Ti _y O _t , Ga _x Sn _y Ge _y Zr _y Hf _y O _t , In _x Sn _y Zr _y O _t , In _x Ge _y Zr _y O _t , In _x Si _y Zr _y O _t, etc. , In _x Sn _y Zr _y Hf _y O _t , In _x Sn _y Zr _y Si _y O _t , In _x Sn _y Hf _y O _t , In _x Sn _y Ti _y O _t , Zn _x In _y Ge _y Zr _y Hf _y O _t or the like, In _x Al _x Zn _x Sn _y Zr _y O _t , In _x Ga _x Ge _y Zr _y O _t , In _x Ga _x Sn _y Zr _y Hf _y O _t , Al _x Ga _x Sn _y Zr _y Si _y O _t , In _x Ga _x Sn _y Hf _y O _t , In _x Al _x Sn _y Ti _y O _t , Al _x Ga _x Sn _y Ge _y Zr _y Hf _y O _{t ,} etc.; 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 In _x Ti _y O _t , Zn _x In _x Zr _y O _t , Zn _x In _x Hf _y O _t , Zn _x In _x Ti _y Zr _y O _t , Zn _x In _x Zr _y Hf _y O _t , Zn _x In _x Hf _y Ti _y O _t , Zn _x In _x Al _x Ti _y O _t , Zn _x In _x Al _x Zr _y O _t , Zn _x In _x Al _x Hf _y O _t , Zn _x In _x Al _x Ti _y Zr _y O _t , Zn _x In _x Al _x Zr _y Hf _y O _t , Zn _x In _x Al _x Hf _y Ti _y O _t , Zn _x In _x Ga _x Ti _y O _t , Zn _x Ga _x Al _x Zr _y O _t , Zn _x In _x Ga _x Hf _y O _t , Zn _x Ga _x Al _x Ti _y Zr _y O _t , Zn _x Ga _x In _x Al _x Zr _y Hf _y O _t , Zn _x In _x Ga _x Hf _y Ti _y O _{t ,} etc.; examples 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 Sn _y Si _y O _t , Zn _x In _x Sn _y O _t , Zn _x In _x Ge _y O _t , Zn _x In _x Si _y O _t , Zn _x In _x Sn _y Ge _y O _t , Zn _x In _x Ge _y Si _y O _t , Zn _x In _x Si _y Sn _y O _t , Zn _x Al _x Sn _y O _t , Zn _x Al _x Ge _y O _t , Zn _x Al _x Si _y O _t , Zn _x Al _x Sn _y Si _y O _t , Zn _x Al _x Ge _y Sn _y O _t , Zn _x Al _x Si _y Ge _y O _t , Zn _x In _x Al _x Sn _y O _t , Zn _x In _x Sn _x Ge _y O _t , Zn _x In _x Al _x Sn _y O _t , Zn _x In _x Al _x Sn _y Ge _y O _t , Zn _x In _x Al _x Sn _y Sn _y O _t , Zn _x In _x Al _x Sn _y Si _y O _t , Zn _x In _x Ga _x Sn _y O _t , Zn _x Ga _x Al _x Ge _y O _t , Zn _x In _x Ga _x Si _y O _t , Zn _x Ga _x Al _x Sn _y Ge _y O _t , Zn _x Ga _x In _x Al _x Sn _y Ge _y O _t , Zn _x In _x Ga _x Sn _y Si _y O _t et al; Examples 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 et al.

The elements of 3B, 4A and 4B described above may contain one type or two or more types. Here, x, y, z, s, and t which are ratios of the respective elements are not particularly limited insofar as the oxide can be obtained, and the composite oxide may be any number as required, but usually 0.1 to 5 The composition is set within the range, and the molar ratio of each of the compounds of the above formulas (1) to (8) can be adjusted in such a manner that a desired composite oxide can be obtained. The composite oxide can be prepared in such a manner as to obtain an oxygen vacancy compound or the like, and the other composition ratio is not limited to the integer ratio, and any component can be prepared by preparing the addition amount of each element.

By using the composition of the present invention, an oxide film of Zn, Sn oxide (ZTO) or Al, Sn oxide (ATO) or the like can be formed. Further, the alkali metal of the Group 1A element in the elements other than Zn3B, 4A and 4B of the present invention is an alkaline earth metal of a Group 2A element, a rare earth such as a lanthanoid series or a lanthanide group, and 3A, 5A, 6A, and 7A The element may be a noble metal or a transition metal of a group 8 element, a metal compound which forms an oxide such as a group 5B element, or a composition which can form a composite oxide containing an element other than the element of Zn-4B and the like. .

In particular, the composition of the present invention can be obtained by using the organozinc compound represented by the following formula (1) and a product obtained by partial hydrolysis of an organic zinc compound such as diethylzinc with water as described above. A compound containing zinc. This addition allows the composition to be hydrolyzed, whereby the alkyl group R ¹ bonded to the product obtained mainly from the organozinc compound and the partial hydrolysis of the organozinc compound with water (here, R ¹ is a carbon number) The identification and quantification of the hydrocarbon R ¹ H produced by the linear or branched alkyl group of 1 to 7 is confirmed. For example, in the case of diethylzinc, the main component of the gas formed by hydrolysis becomes ethane.

Further, the organozinc compound and the alkyl group R ¹ bonded to the product obtained by partial hydrolysis of the organozinc compound and water (wherein R ¹ is a linear or branched alkane having a carbon number of 1 to 7) R ² , R ³ , R ⁴ (R ² , R ³ , R ⁴ independently represented by the formula (2) which is also a compound of a group 3B element coexisting is hydrogen, and the carbon number is 1 to 7 The case where an exchange reaction of a chain or a branched alkyl group is carried out.

The solution prepared by the above method can be directly used as a coating solution for forming a composite oxide film. Alternatively, it may be suitably diluted or concentrated. However, from the viewpoint of simplifying the production steps, it is preferred that the solution prepared by the above method is a concentration which can be directly used as a coating solution for forming a composite oxide.

[Manufacturing method of composite oxide film]

A method of producing the composite oxide film of the present invention will be described. The method for producing a composite oxide film of the present invention is a method for producing a composite oxide film using the composition for forming a composite oxide film of the present invention. In the production method, the composite oxide film-forming composition of the present invention is applied onto the surface of a substrate, and then the obtained coating film is heated to obtain a composite oxide film.

The application to the surface of the substrate can be carried out by a conventional method such as a dip coating method, a spin coating method, a spray pyrolysis method, an inkjet method, or a screen printing method. When the coating is carried out by, for example, a spin coating method, a dip coating method, or a spray pyrolysis method, a composite oxide film having an average transmittance of 80% or more with respect to visible light can be formed. In other words, from the viewpoint of forming a composite oxide film having an average transmittance of visible light of 80% or more, the coating method is preferably carried out, for example, by a spin coating method, a dip coating method, or a spray pyrolysis method.

The coating on the surface of the substrate can be applied under an inert gas atmosphere such as nitrogen, an air environment, an air environment containing a relatively high relative humidity of water vapor, an oxidizing gas atmosphere such as oxygen, or a reducing gas atmosphere such as hydrogen. Or under any environment such as a mixed gas atmosphere and under atmospheric pressure or under pressure.

The coating of the composition on the surface of the substrate is preferably carried out under an inert gas atmosphere such as nitrogen. The pressure applied to the film forming environment can be carried out under atmospheric pressure or under pressure, or under reduced pressure. Moreover, in the inert gas environment, a trace amount of oxygen or moisture is used as an oxide. In the case where an oxygen source necessary for the formation is formed, the inert gas may contain a gas component containing oxygen such as oxygen or moisture in a range which does not affect the film quality of the film.

The spin coating method and the dip coating method can be formed in an inert gas atmosphere, or can be carried out in an environment where the inert gas and the steam are mixed to have a relative humidity of 2 to 15%.

The spray pyrolysis method is a method in which the substrate is heated while being heated, so that the solvent can be dried in parallel with the coating, and there is a case where heating by solvent drying is not required depending on the conditions. Further, depending on the conditions, at least a part of the reaction of the composition of the present invention to the composite oxide in addition to drying may be carried out. Therefore, it is also possible to more easily perform the formation of a composite oxide film which is heated at a specific temperature as a later step. The heating temperature of the substrate may be, for example, in the range of 50 to 550 °C.

Fig. 1 shows a spray film forming apparatus which can be used in the spray pyrolysis method. In the figure, 1 denotes a spray bottle filled with a coating liquid, 2 denotes a substrate holder, 3 denotes a spray nozzle, 4 denotes a compressor, 5 denotes a substrate, and 6 denotes a water vapor introduction pipe. The spray coating system is provided on the substrate holder 2, and is heated to a specific temperature by using a heater as needed, and then the compressed inert gas is simultaneously supplied from the spray nozzle 3 disposed above the substrate in a specific environment. The coating liquid is atomized and sprayed with the coating liquid, whereby a composite oxide film can be formed on the substrate. The composite oxide film can be formed by spray coating without additional heating or the like.

With regard to the spray coating of the coating liquid, from the viewpoint of producing a composite oxide film having good film properties, it is preferred that the coating liquid is applied from the spray nozzle so that the droplet size is in the range of 1 to 15 μm. The method was carried out, and the distance between the spray nozzle and the substrate was set to be within 50 cm.

In consideration of the adhesion to the substrate, the easiness of evaporation of the solvent, etc., it is preferable that the size of the droplets ejected from the spray nozzle is in the range of 1 to 30 μm. The size of the droplets is more preferably in the range of 3 to 20 μm.

The distance between the spray nozzle and the substrate is preferably within 50 cm, considering that the solvent is slightly evaporated before the spray nozzle reaches the substrate and the droplet size is reduced. The distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint of forming a composite oxide film.

In the spray pyrolysis method, from the viewpoint of forming a composite oxide film having excellent film properties, it is preferred to introduce water vapor from the water vapor introduction pipe 6 in an inert gas atmosphere to promote decomposition of the composition. For example, the introduction amount of the water vapor is preferably 0.05 to 5 with respect to the molar ratio of the total amount of the zinc, the 3B group element, the 4A group element, and the 4B group element in the supplied composition, thereby obtaining a high transparency. From the viewpoint of the composite oxide film, it is further preferably 0.1 to 3.

The method of introducing the water vapor can be introduced into the composite oxide film manufacturing apparatus in accordance with all conventional methods. The water vapor and the composition are preferably reacted in the vicinity of 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 by a tube.

After applying the coating liquid to the surface of the substrate, the substrate is set to a specific temperature as necessary, and after drying the solvent, the substrate is heated at a specific temperature to form a composite oxide film.

The temperature at which the solvent is dried may be, for example, in the range of 20 to 200 ° C, and may be appropriately set depending on the type of the organic solvent to be coexisted. The heating temperature for forming the composite oxide after drying the solvent is, for example, in the range of 50 to 550 ° C, preferably in the range of 50 to 500 ° C. It is also possible to make the solvent drying temperature the same as the heating temperature for forming the composite oxide, and to perform solvent drying and composite oxide formation.

If necessary, the above heating may be carried out in an oxidizing gas atmosphere such as oxygen or a reducing gas atmosphere such as hydrogen gas or a plasma atmosphere such as hydrogen gas, argon gas or oxygen gas to promote the formation of zinc oxide or to improve crystallinity. The film thickness of the composite oxide film is not particularly limited, and is preferably in the range of 0.05 to 2 μm in practical use. According to the above production method, in the case other than the spray pyrolysis method, the coating (drying) heating is performed one or more times in a repeated manner. A film having a film thickness in the above range can be suitably produced.

The composite oxide film formed by the above production method varies depending on the coating method and subsequent drying conditions or heating conditions. The volume resistivity is a resistance per unit volume and can be obtained by multiplying the surface resistance by the film thickness. The surface resistance can be measured by, for example, a four-probe method, and the film thickness can be measured by, for example, SEM (scanning electron microscope), a stylus type film thickness meter, or the like. The volume resistivity is changed (increased) depending on the degree of formation of the composite oxide by heating at the time of spray coating or after application, and therefore it is preferable to consider the volume resistivity of the film to be a desired resistance value. The heating conditions (temperature and time) at the time of spray coating or after coating were set.

The composite oxide film formed by the above-described production method preferably has an average transmittance of 80% or more for visible light, and more preferably 85% or more for visible light. "Average transmittance to visible light" is defined and measured as follows. The average transmittance for visible light refers to the average of the transmittance of light in the range of 380 to 780 nm, which can be measured by an ultraviolet-visible spectrophotometer. Furthermore, the average transmittance of visible light can also be expressed by indicating the transmittance of visible light at 550 nm. The transmittance to visible light varies (increases) depending on the degree of formation of heated zinc oxide during spray coating or after application. Therefore, it is preferred that the transmittance of the film to visible light is 80% or more. The heating conditions (temperature and time) at the time of spray coating or after coating are set in consideration of the method.

As the substrate, for example, it may be an alkali glass, an alkali-free glass, or a transparent substrate film, and the transparent substrate film may be a plastic film. However, it is not intended to be limited to such exemplified materials.

[Use of composite oxide film]

The composite oxide film produced by the above method has excellent transparency and mobility, and thus can be used as an antistatic film, an ultraviolet cut film, a transparent conductive film, or the like. The antistatic film can be used, for example, in fields such as solid electric field capacitors, chemically amplified resists, and building materials such as window glass. The ultraviolet ray-off film can be used, for example, in a front filter of an image display device, an image pickup device such as a drive recorder, a high pressure discharge lamp, or the like. In the fields of lighting appliances, building materials such as cover glass and window glass. Further, the transparent conductive film can be used, for example, in an FPD (flat panel display), a resistive touch panel, a capacitive touch panel, a thin film, a solar cell, and a compound (CdTe, CIS (copper indium diselenide). Selenium)) is a thin film solar cell, a dye-sensitized solar cell, an organic thin film solar cell, and the like.

In particular, a composite oxide such as ZTO or ATO is used as an oxide semiconductor film including the same, and an oxide semiconductor film containing an oxide of In, Ga, and Zn (IGZO) is more likely to have a mobility higher than that of the amorphous Si film. The characteristics can be utilized in the field of switching elements (thin film transistors) such as liquid crystal display devices, thin film electroluminescence display devices, and the like. The electric field effect type transistor such as a thin film transistor (TFT) is widely used as a unit electronic component of a semiconductor memory bulk circuit, a high frequency signal amplifying element, a liquid crystal driving element, etc., and is currently the most widely used electronic device. However, it is not intended to be limited to such fields.

Example

The invention is illustrated in more detail below by way of examples, but these examples are not intended to limit the invention. The preparation of a product containing all of the hydrolyzate derived from the organozinc compound and the film formation using the same are carried out under a nitrogen atmosphere for controlling moisture, and all of the solvent is dehydrated and degassed.

[Example 1]

6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetrakis(t-butoxy)tin was dissolved and a solution of 1,2-diethoxyethane in which 0.2 g of diethylzinc was dissolved was 2.0. g was mixed at room temperature to prepare a composition in such a manner that ZTO can be obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn = 1:1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTO ZnSnO _x (x is an arbitrary number depending on film formation conditions).

[Embodiment 2]

5.3 g of a solution of 0.53 g of 1,2-diethoxyethane dissolved in tetrakis(tert-butoxy)tin and hydrolyzed diethylzinc with water at O/Zn=0.6 (mole ratio) were obtained. A solution of 1,2-diethoxyethane (Zn = 4.24 wt%) of 2.0 g of the product was mixed at room temperature to prepare a composition in such a manner that ZTO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn=. According to the approximate existence ratio, the composition is intended to be a film-former of ZTO ZnSnO _x (x is an arbitrary number depending on film formation conditions).

[Example 3]

7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetrakis(t-butoxy)tin was dissolved and a solution of 1.2 g of 1,2-diethoxyethane in which 0.2 g of triethylaluminum was dissolved. The composition was prepared by mixing at room temperature in such a manner that ATO can be obtained as a composite oxide. The molar ratio of each element of the composition is Al: Sn = 1:1. The composition is intended to be a film-forming person of AlSnO _x (where x is an arbitrary number depending on film formation conditions) of ATO according to the approximate existence ratio.

[Example 4]

6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetrakis(t-butoxy)tin was dissolved, and a solution of 0.0092 g of 1,2-diethoxyethane in which triethylaluminum was dissolved in a solution of 0.092 g. And 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of diethyl zinc was dissolved was mixed at room temperature to prepare a composition in such a manner that ZTAO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn:Al = 1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTAO Zn ₁₀ Sn ₁₀ AlO _x (x is an arbitrary number depending on film formation conditions).

[Example 5]

6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetrakis(t-butoxy)tin was dissolved, and 0.25 g of a 1,2-diethoxyethane solution in which 0.025 g of triethylgallium was dissolved. And 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of diethyl zinc was dissolved was mixed at room temperature to prepare a composition in such a manner that ZTGO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn:Ga = 1:1:0.1. The composition is intended to be a film-former of Zn ₁₀ Sn ₁₀ GaO _x (x is an arbitrary number depending on film formation conditions) of ZTGO, based on a substantially integer ratio.

[Embodiment 6]

6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetrakis(t-butoxy)tin was dissolved, and a solution of 1,2-diethoxyethane in which 0.36 g of trimethylindium was dissolved was 0.26 g. And 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of diethyl zinc was dissolved was mixed at room temperature to prepare a composition in such a manner that ZTIO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn:In=1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTIO Zn ₁₀ Sn ₁₀ InO _x (x is an arbitrary number depending on film formation conditions).

[Embodiment 7]

6.6 g of a 1,2-diethoxyethane solution in which tetrakis(t-butoxy)tin was dissolved in 0.66 g, and 1,62 g of 1,2-diethoxyB in which tetrazedoxy zirconium was dissolved. A composition of 0.62 g of an alkane solution and 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of diethylzinc was dissolved was mixed at room temperature to obtain a composition in which ZTZrO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn:Zr=1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTZrO Zn ₁₀ Sn ₁₀ ZrO _x (x is an arbitrary number depending on film formation conditions).

[Embodiment 8]

5.3 g of a 1,2-diethoxyethane solution in which 0.43 g of tetrakis(t-butoxy)tin was dissolved, and a solution of 0.14 g of 1,2-diethoxyethane in which triethylaluminum was dissolved in 0.0074 g. And a solution of 1,2-diethoxyethane (Zn=4.24 wt%) 2.0 g of a product obtained by hydrolyzing diethylzinc with water at O/Zn=0.6 (mole ratio) at room temperature The composition is prepared in such a manner that ZTAO can be obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn:Al = 1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTAO Zn ₁₀ Sn ₁₀ AlO _x (x is an arbitrary number depending on film formation conditions).

[Embodiment 9]

5.3 g of a 1,2-diethoxyethane solution in which 0.43 g of tetrakis(t-butoxy)tin was dissolved, and 0.20 g of a solution of 1,2-diethoxyethane in which triethylgallium (0.020 g) was dissolved. And a solution of 1,2-diethoxyethane (Zn=4.24 wt%) 2.0 g of a product obtained by hydrolyzing diethylzinc with water at O/Zn=0.6 (mole ratio) at room temperature The composition is prepared in such a manner that ZTGO can be obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn:Al = 1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTGO Zn ₁₀ Sn ₁₀ GaO _x (x is an arbitrary number depending on film formation conditions).

[Embodiment 10]

5.3 g of a 1,2-diethoxyethane solution in which 0.43 g of tetrakis(t-butoxy)tin was dissolved, and 0.62 g of a 1,2-diethoxyethane solution in which 0.062 g of trimethylindium was dissolved. And a solution of 1,2-diethoxyethane (Zn=4.24 wt%) 2.0 g of a product obtained by hydrolyzing diethylzinc with water at O/Zn=0.6 (mole ratio) at room temperature The composition was prepared in such a manner that ZTIO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn:Sn:In=1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTIO Zn ₁₀ Sn ₁₀ InO _x (x is an arbitrary number depending on film formation conditions).

[Example 11]

5.3 g of a 1,2-diethoxyethane solution in which 0.43 g of tetrakis(t-butoxy)tin was dissolved, and 1,2-diethoxy B in which tetrakis. 0.50 g of an alkane solution and a solution of 1,2-diethoxyethane (Zn = 4.24 wt%) of 2.0 g of a product obtained by hydrolyzing diethylzinc with water at O/Zn = 0.6 (mole ratio) The composition was prepared in such a manner that ZTZrO can be obtained as a composite oxide by mixing at room temperature. The molar ratio of each element of the composition is Zn:Sn:Zr=1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of ZTZrO Zn ₁₀ Sn ₁₀ ZrO _x (x is an arbitrary number depending on film formation conditions).

[Embodiment 12]

7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetrakis(t-butoxy)tin was dissolved, and a solution of 1,2-diethoxyethane in which 0.22 g of diethylzinc was dissolved was 0.27. g and 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of triethylaluminum was dissolved were mixed at room temperature to prepare a composition in such a manner that ATZO was obtained as a composite oxide. The molar ratio of each element of the composition is Al:Sn:Zn = 1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of AT ₁₀ Al ₁₀ Sn ₁₀ ZrO _x (x is an arbitrary number depending on film formation conditions).

[Example 13]

7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetrakis(t-butoxy)tin was dissolved, and 0.27 g of a solution of 1,2-diethoxyethane in which triethylgallium (0.027 g) was dissolved. And 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of triethylaluminum was dissolved was mixed at room temperature to prepare a composition in such a manner that ATGO was obtained as a composite oxide. The molar ratio of each element of the composition is Al:Sn:Ga = 1:1:0.1. The composition is intended to be a film-forming person of Al ₁₀ Sn ₁₀ GaO _x (x is an arbitrary number depending on film formation conditions) of ATGO, based on the approximate existence ratio.

[Embodiment 14]

7.2 g of a 1,2-diethoxyethane solution in which 0.42 g of tetrakis(t-butoxy)tin was dissolved, and a solution of 1,28-diethoxyethane in which 0.028 g of trimethylindium was dissolved was 0.28 g. And 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of triethylaluminum was dissolved was mixed at room temperature to prepare a composition in such a manner that ATIO was obtained as a composite oxide. The molar ratio of each element of the composition is Al:Sn:In=1:1:0.1. According to the approximate existence ratio, the composition is intended to be a film-former of Al ₁₀ Sn ₁₀ InO _x (x is an arbitrary number depending on film formation conditions) of ATIO.

[Example 15]

7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetrakis(t-butoxy)tin was dissolved, and 1,067 g of 1,3-diethoxyB, which was dissolved in tetrakis-butoxyzirconium 0.67 g of an alkane solution and 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of triethylaluminum was dissolved were mixed at room temperature to prepare a composition in such a manner that ATZrO was obtained as a composite oxide. The molar ratio of each element of the composition is Al:Sn:Zr=1:1:0.1. The composition is intended to be a film-forming person of Al ₁₀ Sn ₁₀ ZrO _x (where x is an arbitrary number depending on film formation conditions) of ATZrO, based on the approximate existence ratio.

[Example 16]

The transparent clarified solution portion of the composition obtained in Example 1 which is intended to form a film of ZnSnO _x (x is an arbitrary number depending on the film formation conditions) (using 0.2 μm of PTFE (Polytetrafluoroethene, polytetrafluoroethylene) The ethylene (filter) filter was used as a coating liquid for coating film formation. The product-containing coating liquid was applied onto a glass substrate surface of 18 mm square EAGLE XG ^(R) (manufactured by Corning) at room temperature by a spin coating method under a nitrogen atmosphere.

Thereafter, the substrate was heated at 150 ° C for 5 minutes to dry the solvent, and further heated at 200 ° C for 5 minutes. The film formed into the film is taken out into the air.

The obtained film was transparent and the transmittance was 93% at 550 nm. Further, the film was analyzed by FT-IR (fourier transform infrared spectroscopy), and it was confirmed that the peaks belonging to the respective vibrations of CH derived from the raw material, such as the third butoxy group or the ethyl group, disappeared. Further, the film was analyzed by XRD (X ray diffraction, X-ray diffraction measurement), and it was confirmed that there was no peak of crystal.

[Example 17]

The same operation as in Example 16 was repeated three times. The film formed into the film is taken out into the air. The obtained film was transparent and had a transmittance of 89% at 550 nm. Further, the film was analyzed by FT-IR, and the disappearance of the peak attributed to each of the vibrations of the CH derived from the third butoxy group or the ethyl group derived from the raw material was confirmed.

[Embodiment 18]

The same operation as in Example 16 was repeated five times. The film formed into the film is taken out into the air. The obtained film was transparent and had a transmittance of 85% at 550 nm.

[Examples 19 to 32]

Using the composition obtained in each of Examples 2 to 15 as a coating liquid, a film was formed by coating once in the same manner as in Example 16 to form a composite oxide film. Each of the compositions used a transparent clear solution portion or 0.2 μm in the same manner as in Example 1. The PTFE filter was used for filtration. The film formed into the film is taken out into the air. The appearance and transmittance of the obtained film are shown in Table 1.

[Examples 33 to 46]

Using the composition obtained in each of Examples 2 to 15 as a coating liquid, a film was formed by coating three times in the same manner as in Example 17 to form a composite oxide film. The film formed into the film is taken out into the air. The appearance and transmittance of the obtained film are shown in Table 2.

[Examples 47 to 60]

Using the composition obtained in each of Examples 2 to 15 as a coating liquid, a film was formed by coating five times in the same manner as in Example 18 to form a composite oxide film. The film formed into the film is taken out into the air. The appearance and transmittance of the obtained film are shown in Table 3.

[Examples 61 to 72]

The composition obtained in the above examples was used as a coating liquid to form a film, and the composite oxide film obtained in Examples 47 to 60 was subjected to a nitrogen atmosphere, followed by 5 minutes at 300 ° C and 400 ° C. The heat treatment was carried out under the conditions of 5 minutes at 500 ° C for 5 minutes. plus The hot film is taken out into the air. The transmittance of the obtained film is shown in Tables 4, 5 and 6.

[Example 95]

The portion of the transparent clear solution of each of the product-containing coating liquids obtained in Example 2 was used for coating into a film. The product-containing coating liquid was applied onto the surface of a 18 mm square quartz glass substrate by a spin coating method under a nitrogen atmosphere at room temperature. Thereafter, the substrate was heated at 150 ° C for 5 minutes, whereby the solvent was dried. In the film formation, baking is simultaneously performed at the drying temperature of the solvent and during the drying period. This operation was repeated three times in total, and coating was repeated to form a film. The film formed into the film is taken out into the air.

The film obtained was transparent and had a transmittance of 94% at 550 nm. Further, the film was analyzed by FT-IR, and the disappearance of the peak attributed to each of the vibrations of the CH derived from the third butoxy group or the ethyl group derived from the raw material was confirmed.

[Examples 96 to 99]

Using the coating liquids obtained in Examples 8, 9, 10 and 11, the same film formation and physical property evaluation as in Example 95 were carried out. The film properties and physical properties obtained are shown in Table 7.

[Example 100]

Using a RTA (Rapid Thermal Annealing) apparatus, the film obtained in Example 98 was heat-treated at 300 ° C, 400 ° C, 600 ° C, and 800 ° C for 30 minutes in an air atmosphere before heat treatment. XRD was used to confirm the structural change of the oxide at each temperature. Before the heat treatment, no peak of the crystal was observed under the above heat treatment conditions, and a broad peak which was considered to be amorphous was confirmed at 2θ=26 to 40°. Further, by performing heat treatment at 800 ° C for 1 hour, peaks of crystals corresponding to oxides of zinc and tin were confirmed in the vicinity of 2θ = 26°, 32°, 34°, and 52°.

[Example 101]

The film obtained in Example 99 was heat-treated at 200 ° C, 400 ° C, 600 ° C, and 800 ° C for 30 minutes in an air atmosphere before heat treatment using an RTA (Rapid Thermal Annealing) apparatus. XRD was used to confirm the structural change of the oxide at each temperature. Before the heat treatment, no peak of the crystal was observed under the above heat treatment conditions, and a broad peak which was considered to be amorphous was confirmed at 2θ=26 to 40°. Further, in the heat treatment at 800 ° C, peaks of crystals corresponding to oxides of zinc and tin were confirmed in the vicinity of 2θ=26°, 32°, 34°, and 52°.

[Comparative Example 1]

In Example 1, bis(acetonitrile) tin was used instead of tetrakis(t-butoxy)tin, and used. Zinc acetate was used instead of diethylzinc, and 2-methoxyethanol was used as a solvent, and ethanolamine was used as an auxiliary agent to prepare a coating liquid having the same composition.

The coating liquid obtained was subjected to film formation at 200 ° C in the same manner as in Example 18 to obtain a film. The visible light transmittance at 550 nm is 60%, and only a film having a low transmittance is obtained.

[Comparative Example 2]

In Example 3, tin chloride was used instead of tetrakis(t-butoxy)tin and aluminum acetate was used instead of triethylaluminum, 2-methoxyethanol was used as a solvent, and ethanolamine was used as an auxiliary to prepare the same composition. Coating solution.

The coating liquid obtained was subjected to film formation at 200 ° C in the same manner as in Example 18 to obtain a film. The visible light transmittance at 550 nm is 65%, and only a film having a low transmittance is obtained.

[Industrial availability]

The present invention is useful in the field of manufacturing a composite oxide film containing an oxide of a zinc, a Group 3B element, a Group 4A element, and/or a Group 4B element.

1‧‧‧ spray bottle

2‧‧‧Substrate holder (with heater)

3‧‧‧ spray nozzle

4‧‧‧Compressor

5‧‧‧ Alkali-free glass substrate

6‧‧‧Water vapor introduction tube

Claims (23)

A composition for producing a composite oxide, comprising at least one element selected from the group consisting of a zinc element and a group 3B element, and at least one element selected from the group consisting of a group 4A element and a group 4B element And the composition contains 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 produced by water of the above compound, or the above-mentioned compound and the above-mentioned partial hydrolyzate, And at least one compound selected from the group consisting of a compound containing a Group 4A element and a compound containing a Group 4B element, a partial hydrolyzate produced by using the above compound, or the above compound and the above partial hydrolyzate. The composition of claim 1, wherein the compound containing a zinc element is an organozinc compound represented by the following formula (1), R ¹ -Zn-R ¹ (1) (wherein R ¹ is a carbon number of 1) ~7 straight or branched alkyl). The composition of claim 2, wherein the partial hydrolyzate produced by using the water of the organozinc compound is obtained by mixing the organozinc compound represented by the formula (1) with water in a molar ratio of 0.05 to 0.8. A product obtained by partially hydrolyzing the above-mentioned organozinc compound. The composition according to any one of claims 1 to 3, wherein the compound containing a Group 3B element is a compound of a Group 3B compound represented by the following formula (2), (wherein M is a Group 3B element, R ² , R ³ , and R ^{4 are} independently hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, and L is a coordinating organic group containing nitrogen, oxygen, or phosphorus. Compound, n is an integer from 0 to 9). The composition of claim 4, wherein the above-mentioned Group 3B element compound is produced by using water The partial hydrolyzate is a product obtained by mixing a compound of the Group 3B element represented by the formula (2) with water so as to have a molar ratio of 0.05 to 0.8, and at least partially hydrolyzing the compound of the above Group 3B element. The composition according to any one of claims 1 to 5, wherein the compound containing a Group 4A element and the compound containing a Group 4B element are a Group 4A element compound represented by the following formula (3) or (4) and 4B Group element compound, (wherein M is a Group 4A element or a Group 4B element, and R ⁵ , R ⁶ , R ⁷ , and R ^{8 are} independently hydrogen, a straight or branched alkyl group having a carbon number of 1 to 7, and a carbon number of 1 to 7; Chain or branched alkoxy group, decyloxy group, acetamyl acetonyl group, decylamino group, L is a complex organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer from 0 to 9) M _c X _d . a H ₂ O (4) (wherein M is a Group 4A element or a Group 4B element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, and d is 3, When X is sulfuric acid, c is 2, d is 3, and a is an integer of 0-9. The composition of claim 6, wherein the partial hydrolyzate produced by using the water of the above-mentioned Group 4A element compound and Group 4B element compound has a molar ratio of 0.05 to 0.05 by weight of the compound represented by the formula (3) or (4). A product obtained by partially hydrolyzing at least the above-mentioned Group 4A element compound and Group 4B element compound in a range of ~0.8. The composition according to any one of claims 1 to 7, wherein the partial hydrolyzate produced by using water, at least one compound selected from the group consisting of a compound containing a Group 4A element and a compound containing a Group 4B element, And a benefit of at least one compound selected from the group consisting of a compound containing a zinc element and a compound containing a group 3B element The partial hydrolyzate produced by using water is at least one compound selected from the group consisting of a compound containing a Group 4A element and a compound containing a Group 4B element, and a compound selected from the group consisting of a compound containing a zinc element and a compound containing a Group 3B element. In at least one of the compounds of the composition, the product obtained by partially hydrolyzing the above compound is obtained by adding water so that the molar ratio of the total of the above compounds is in the range of 0.05 to 0.8. The composition of any one of claims 1 to 8, which further contains an organic solvent. The composition of claim 9, wherein the organic solvent comprises at least one of an electron donating solvent, a hydrocarbon solvent, and the like. The composition of claim 9 or 10, wherein the organic solvent has a boiling point of 230 ° C or less. The composition of claim 10, wherein the electron donating solvent comprises one selected from the group consisting of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, and At least one of a group consisting of hexane, heptane, octane, toluene, xylene, and cyclohexane as a hydrocarbon solvent. The composition of any one of claims 2 to 12, wherein the organozinc compound is diethylzinc. The composition according to any one of claims 4 to 13, wherein the compound of the Group 3B element of the above formula (2) comprises a compound selected from the group consisting of trimethyl indium, triethyl indium, trimethyl gallium, triethyl gallium, and three. At least one selected from the group consisting of methyl aluminum, triethyl aluminum, trioctyl aluminum, trimethyl borane, and triethyl borane. The composition according to any one of claims 1 to 14, wherein the Group 3B element is Al, Ga and In, the Group 4A element is Ti, Zr and Hf, and the Group 4B element is Si, Ge and Sn. Method for producing composite oxide film, the composite oxide film is visible light The line has an average transmittance of 80% or more, and the production method comprises applying the composition for producing a composite oxide according to any one of claims 1 to 15 to the surface of the substrate in an inert gas atmosphere at least once, and then The obtained coating film is subjected to a heating operation. The method of claim 16, wherein the inert gas atmosphere contains water vapor. The method of claim 17, wherein the relative humidity of the inert gas atmosphere containing water vapor is in the range of 2 to 15%. A method for producing a composite oxide film having an average transmittance of visible light of 80% or more, the method comprising the composition for producing a composite oxide according to claim 1 in an inert gas containing water vapor The step of spray coating on the surface of the heated substrate in an environment. The method for producing a composite oxide film according to claim 19, wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor to the vicinity of the surface of the substrate under atmospheric pressure or under pressure. The method for producing a composite oxide film according to claim 19, wherein the heating temperature of the surface of the substrate is 400 ° C or lower. The method for producing a composite oxide film according to claim 20 or 21, wherein the supply amount of the water vapor is performed in such a manner that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5. supply. An oxide semiconductor film comprising a composite oxide film produced by the production method according to any one of claims 16 to 22.