KR101861394B1 - Composition for production of oxide thin films and method for producing oxide thin films by using said composition - Google Patents

Abstract

The present invention relates to a composition for preparing an oxide thin film and a method for producing an oxide thin film using the composition. More specifically, the present invention relates to (1) a composition for preparing a composite oxide thin film and a method for producing an oxide thin film using the composition (the first embodiment of the present invention), (2) a composition for preparing a zinc oxide thin film, (A second embodiment of the present invention), (3) a composition for preparing a zinc oxide thin film and a composition for preparing a zinc-doped zinc oxide thin film, and a method for producing a zinc oxide thin film using these compositions Third embodiment).

Description

TECHNICAL FIELD The present invention relates to a composition for preparing an oxide thin film and a method for producing an oxide thin film using the composition,

The present application is based on Japanese Patent Application No. 2010-235994 filed on October 20, 2010, (2) Japanese Patent Application No. 2010-235996, (3) Japanese Patent Application No. 2010-235478, (4) Japanese Patent Application No. 2010-235480 (5) Japanese Patent Application No. 2010-235962, and (6) Japanese Patent Application No. 2010-235992, all of which are hereby expressly incorporated by reference.

The present invention relates to a composition for preparing an oxide thin film and a method for producing an oxide thin film using the composition. More particularly, the present invention relates to (1) a composition for preparing a composite oxide thin film and a method for producing an oxide thin film using the composition (the first embodiment of the present invention), (2) a composition for preparing a zinc oxide thin film, (A second embodiment of the present invention), (3) a composition for preparing a zinc oxide thin film and a composition for preparing a zinc-doped zinc oxide thin film, and a method for producing a zinc oxide thin film using these compositions Third embodiment).

A first embodiment of the present invention is a composite oxide capable of being mixed with an oxide semiconductor film of IGZO or the like which has an average transmittance of 80% or more with respect to visible light and is used for a switching element (thin film transistor) of a liquid crystal display, a thin film electroluminescence display, The present invention relates to a composite oxide thin film composition capable of preparing a thin film, a composite oxide thin film using the composition, and a composite oxide thin film produced by using the composition.

By using the composition for preparing a composite oxide thin film of the first embodiment of the present invention, an organozinc compound and a Group 3B element compound are prepared as a raw material and have no ignitability and are easy to handle, and spin coats, dip coating raw materials, When used as a pyrolysis coating raw material, a composite oxide thin film having an average transmittance of 80% or more with respect to visible light can be provided.

The second mode of the present invention is a method for producing a transparent zinc oxide thin film having a high transmittance to visible light by heating at a pressure near atmospheric pressure and at a temperature not higher than 300 ° C to produce an organic zinc compound as a raw material, And a composition for preparing a zinc oxide thin film doped with a Group 3B element and a method for producing a zinc oxide thin film and a zinc oxide thin film doped with a Group 3B element using these compositions, An antistatic thin film, an ultraviolet ray blocking thin film, and a transparent electrode thin film manufactured by the method.

A transparent zinc oxide thin film or a zinc oxide thin film doped with a Group 3B element, which has high transparency to visible light, obtained in the second embodiment of the present invention can be used as a photocatalytic film, an ultraviolet ray blocking film, an infrared ray reflective film, a buffer layer of a CIGS solar cell, An electrode film of an increase and decrease solar cell, an antistatic film, and the like, and has a wide range of applications.

A third aspect of the present invention is to provide a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light and capable of preparing a zinc oxide thin film having a lower volume resistivity as the antistatic thin film, the ultraviolet ray blocking thin film, An antistatic thin film, an ultraviolet ray blocking thin film, and a transparent electrode thin film manufactured by using the composition and a method for producing the zinc oxide thin film using the composition.

By using the composition for preparing a zinc oxide thin film according to the third embodiment of the present invention, it is possible to prepare an organic zinc compound as a raw material without any ignitability and easy handling, and when used as a raw material for spin coating, dip coating application or spray pyrolysis coating , It is possible to provide a zinc oxide thin film having conductivity and an average transmittance of 80% or more with respect to visible light. The zinc oxide thin film has high transparency to visible light and the zinc oxide thin film having conductivity is used as an electrode of an FPD (flat panel display), an electrode of a resistive film type touch panel and a capacitive touch panel, It is widely used for solar cells and compounds (CdTe, CIS (2-selenide copper indium)) thin film solar cells, dye-sensitized solar cells, top electrodes of organic thin film solar cells, ultraviolet barrier film, antistatic film and infrared ray reflection film. I have.

As the first mode of the present invention, an oxide semiconductor film made of an oxide (IGZO) of In, Ga, and Zn, for example, is known as an oxide semiconductor film made of a metal composite oxide which is one of complex oxides. Si has a higher mobility than the Si film. Such an oxide semiconductor film is expected to be applied to a switching device (thin film transistor) such as a liquid crystal display device and a thin film electroluminescence display device because the electron mobility is higher than that of the amorphous Si film and the visible light transmittance is high It is attracting attention.

It is known that IGZO is a main component of a compound represented by InGaO ₃ (ZnO) _m (m is an integer of 1 to 20). As a method of forming the amorphous oxide film, a method of forming a thin film by treating a sintered body of IGZO in vacuum, such as a PVD method or a sputtering method, is generally known. It is known that an IGZO sputtering target is used for forming an amorphous oxide film (Patent Document 1).

On the other hand, in the formation of the oxide thin film, the film formation by the coating method is known. This coating method is advantageous in that the apparatus is simple and the film forming speed is fast because the productivity is high and the manufacturing cost is low and there is no restriction by the vacuum container because there is no need to use the vacuum container and therefore a large oxide thin film can be produced .

(Patent Document 2)), dip coating (Non-Patent Document 1), spray pyrolysis (non-patent document 2, non-patent document 3)) as a coating method for forming a general oxide thin film.

As a material for forming the coating oxide thin film, there is known a material for forming a zinc oxide thin film for the purpose of using a transparent conductive film or the like. Specifically, a zinc oxide thin film is formed by dissolving zinc diethylate in an organic solvent, , A composition obtained by partially hydrolyzing diethyl zinc, and the like.

Patent Document 2 and Non-Patent Documents 1 to 3 relate to a zinc oxide thin film, and a 3B group element such as In, Ga or the like is merely added in a small amount of about several weight% in order to impart conductivity. The inventors tried to form a film by the spin coating method, the dip coating method and the spray pyrolysis method by adjusting the composition of the above-described IGZO using the material of Patent Document 2, but it was difficult to obtain a transparent thin film.

On the other hand, the inventors of the present invention attempted to form a film by a spin coating method using a solution obtained by partially hydrolyzing diethyl zinc or a solution of a composition obtained by partial hydrolysis of diethyl zinc and a compound of Group 3B element, The zinc oxide thin film having an average transmittance equal to or higher than that of the zinc oxide thin film can be obtained. (Patent Document 3, Patent Document 4).

In the inventions of Patent Documents 3 and 4, in order to improve the conductivity of the zinc oxide thin film, a Group 3B element such as In and Ga coexist in the composition, but the molar ratio (composition ratio) of the Group 3B element to zinc is 0.005 To 0.1 and the application to a material such as IGZO in which the molar ratio of the mixture of the Group 3B elements to zinc exceeds 0.1 is considered to be necessary again.

Accordingly, a first aspect of the present invention is to provide a novel means capable of forming an oxide semiconductor film such as IGZO in a composition based on a partial hydrolyzate of an organic zinc compound such as diethylzinc or diethylzinc .

As a result of intensive researches to achieve the above object, the present inventors have found that a compound having a structure in which an alkyl group is bonded to a zinc or 3B group element, more specifically, an organic zinc compound such as diethyl zinc and an organic zinc compound such as diethyl zinc And a mixture of a product obtained by partial hydrolysis with water and a compound including a Group 3B element such as In and Ga in an organic zinc compound such as diethyl zinc and an organic zinc compound such as diethyl zinc, Even when the molar ratio of the Group 3B element in the mixture of the Group 3B elements such as In and Ga to the zinc in the product obtained by partial hydrolysis of the product exceeds 0.1, the IGZO or the like can be obtained as an average transmittance of 80% The oxide semiconductor film of the present invention can be easily obtained, thereby completing the first embodiment of the present invention.

In the second embodiment of the present invention, various methods are known as a method for producing a transparent zinc oxide thin film or a zinc oxide thin film doped with a Group 3B element (Non-Patent Document 4)). As a typical method of using an organic zinc compound as a raw material, there are a chemical vapor deposition (CVD) method (non-patent document 5) and a spray pyrolysis method (non-patent document 3)) and a spin coating method (patent document 5) (Non-Patent Document 2)).

However, in the chemical vapor deposition (CVD) method, it is necessary to use a large-sized vacuum container, and the film forming speed is very slow, so that the manufacturing cost is increased. Further, since the size of the zinc oxide thin film doped with the Group 3B element that can be formed by the size of the vacuum container is limited, there is a problem that a large-sized zinc oxide thin film can not be formed.

The coating method is simpler in apparatus than the chemical vapor deposition (CVD) method and has a higher film forming speed, resulting in higher productivity and lower manufacturing cost. In addition, since there is no need to use a vacuum container and there is no restriction by a vacuum container, there is an advantage that a zinc oxide thin film doped with a large 3B group element can be produced.

In the spray pyrolysis method, the zinc oxide thin film or the zinc oxide thin film coated with the zinc oxide thin film or the Group 3B element is obtained by heating the substrate at a temperature of 360 ° C or higher.

In the spin coating method and the dip coating method, a zinc oxide thin film or zinc oxide thin film coated with a zinc oxide thin film or a Group 3B element is obtained by drying the solvent after spin coating or dip coating and then heating the substrate temperature to 400 캜 or higher.

A transparent zinc oxide thin film or a zinc oxide thin film doped with a Group 3B element is formed on a plastic substrate. Therefore, it is necessary that the heating applied at the time of forming the transparent zinc oxide thin film or the zinc oxide thin film doped with the Group 3B element is carried out at a temperature not higher than the heat resistant temperature of the plastic substrate. However, in the spray pyrolysis method described in Non-Patent Document 3, the spin coat method disclosed in Patent Document 1, and the dip coating method described in Non-Patent Document 4, the heat resistance temperature of the plastic substrate (usually about 300 to 400 ° C , It is impossible to obtain a transparent zinc oxide thin film or a zinc oxide thin film doped with a Group 3B element. Considering the heat resistance temperature of the plastic substrate and the cost required for heating, it is preferable that the heating required for film formation is 300 DEG C or less.

The inventors of the present invention have found that a 3B group element compound used in the spray pyrolysis method described in Non-Patent Document 3 and an aqueous solution of zinc acetate, a 3B group element compound used in the spin coating method described in Patent Document 1, A solution made of a solvent or a solution made of an organic zinc compound and an organic solvent used in the dip coating method described in Non-Patent Document 2 was tried to form a film at a temperature of 300 ° C or lower. In either case, however, a zinc oxide thin film doped with a transparent Group 3B element could not be obtained, and only an opaque zinc oxide thin film could be obtained. The film formation at 300 DEG C or less was also attempted using the hexane solution of diethyl zinc described in Patent Document 5. [ However, zinc oxide thin films doped with the same transparent Group 3B element could not be obtained.

In addition, diethylzinc is a compound that has a flammability in the atmosphere and must devote a great deal of attention when stored and used. Therefore, it is practically difficult to use diethyl zinc in a spray pyrolysis method, a spin coating method, or the like, which is often carried out in an atmosphere in which water is present, without diluting it. On the other hand, in the state where the diethyl zinc is dissolved in an organic solvent, the danger such as ignitability can be reduced. As described in Patent Document 1, the risk can be reduced in the case of forming a zinc oxide thin film using diethylzinc which is dissolved while reacting with an alcohol-based organic solvent. However, in order to form a transparent film, heating at a high temperature of 400 ° C or more is required .

In order to improve this point, the inventors discovered that zinc dioxide can be formed at a low temperature by dissolving diethyl zinc in an electron donating solvent and spraying it by a film forming method as in Patent Document 6, and applied for a patent. When the solution for forming the zinc oxide thin film is formed by a coating method such as spin coating, although a thin film can be formed, diethyl zinc, which is an organic zinc compound, is volatile and has a low viscosity, There is a room for improvement such as an increase in the number of times of application for obtaining

Therefore, the object of the second aspect of the present invention is to provide a zinc oxide thin film which is prepared by using an organic zinc compound as a raw material but has no ignitability and is easy to handle, Which is capable of forming a thin zinc oxide thin film. It is also an object of the present invention to provide a plastic substrate which does not require heating at the time of film formation in view of the heat resistance temperature of the plastic substrate and the cost required for heating, And a method for obtaining a zinc oxide thin film or a zinc oxide thin film doped with a Group 3B element.

In the third embodiment of the present invention, as described in the second embodiment, various methods are known as a method for producing a zinc oxide thin film. Among them, the coating method is simple in apparatus and has a high film forming speed. There is no need to use a vacuum container which is high in cost and low in manufacturing cost, and there is no restriction by a vacuum container, and therefore it is advantageous that a large zinc oxide thin film can be produced.

As the material of the zinc oxide thin film for application, diethylzinc dissolved in the reaction with an organic solvent of zinc acetate or alcohol, a composition obtained by partially hydrolyzing diethyl zinc, and the like are used.

The inventors of the present invention have found that the film formation according to the spin coating method using the solution of the Group 3B element compound and the organic zinc compound described in Patent Document 5 and the film formation according to the dip coating method using the solution comprising the organic zinc compound and the organic solvent described in Non- , And a spray pyrolysis method using a solution of a Group 3B element compound and zinc acetate described in Non-Patent Documents 3 and 4 was tried. However, spin coating method, in the case of dip coating does not get out of the volume resistivity 1 × 10 ^-1 Ω · ㎝ zinc oxide thin films above, is also the volume resistivity to the spray pyrolysis 1 × 10 ^-3 Ω · ㎝ than the zinc oxide thin film only And no zinc oxide thin film could be obtained with low resistance for each.

Further, in both of the spin coating method, the dip coating method and the spray pyrolysis method, when the heating temperature of the substrate at the time of film formation is 300 DEG C or less, it is difficult to obtain a transparent zinc oxide thin film having a low resistance.

With respect to this point, as described in the first embodiment, the inventors of the Patent Documents 3 and 4 obtained a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light by film formation according to the spin coating method Lt; / RTI >

JP 2007-73312 A JPH7-182939A JP 2010-254481 A JP 2011-46566 A JPH7-182939A JP 2010-126402 A

 Y. Ohya, et al., J. Mater. Sci., 4099 (29), 1994  F. Paraguay D, et al., Hinsolid Films., 16 (366), 2000  L. Castaneda, et al., ThinSolid Films., 212 (503), 2006  Japan Society for the Promotion of Science, Transparent Oxide Optoelectronic Materials, Vol. 166, Technical Transparent Conductive Film, 2nd Edition (2006), pp. 165-173  K.Sorab, et al. Appl. Phys. Lett., 37 (5), 1 September 1980

Therefore, the third aspect of the present invention is to provide a process for producing a low-temperature film having a substrate temperature of 300 DEG C or less at the time of film formation from a composition based on a partial hydrolyzate of an organic zinc compound such as diethylzinc or diethylzinc, It is an object of the present invention to provide a new means for preparing a zinc oxide thin film having an average transmittance of 80% or more with respect to a light ray and a volume resistivity which is low enough to be usable in an antistatic thin film or the like.

As a result of intensive studies to achieve the above object, the present inventors have found that an organic zinc compound such as diethyl zinc is obtained by dissolving an organic zinc compound, such as diethyl zinc, in an organic solvent different from the electron- Products and products obtained by partial hydrolysis of an organic zinc compound such as diethyl zinc and water are mixed with an organic zinc compound dissolved in a solvent mixture of an electron-donating organic solvent and an electron-donating organic solvent other than the electron- It is possible to obtain a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light and a volume resistivity as low as that which can be used for an antistatic thin film or the like by applying a composition containing a partial hydrolyzate with water, 3 was completed.

 A first aspect of the present invention is as follows.

(1-1)

An organozinc compound represented by the following formula 1 or a partial hydrolyzate of the organic zinc compound with water and a partial hydrolyzate of a 3B group compound or a 3B group element compound by water are mixed so that the molar ratio of the Group 3B element to zinc is 0.1 By weight and less than 5% by weight based on the total weight of the composite oxide thin film.

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(1-2)

The composition according to (1-1), which further contains an organic solvent.

(1-3)

The partial hydrolyzate of the organic zinc compound with water is a product obtained by partially hydrolyzing at least the organic zinc compound by mixing the organozinc compound represented by the formula (1) and water in a molar ratio of 0.05 to 0.8 , The partial hydrolyzate of the 3B group element compound with water is a product obtained by partially hydrolyzing at least the 3B group element compound by mixing the 3B group element compound and water in a molar ratio of 0.05 to 0.8, (1-1) or (1-2).

(1-4)

The partial hydrolyzate of the organic zinc compound with water and the partial hydrolyzate of the 3B group compound with water are obtained by adding water to the organic zinc compound and the Group 3B element compound in such a manner that water is added to the sum of the organozinc compound and the Group 3B element compound (1-1) or (1-2), wherein the organic zinc compound and the Group 3B element compound are partially hydrolyzed by adding the organic zinc compound and the Group 3B element compound so that the molar ratio of the organic zinc compound and the Group 3B element compound is in the range of 0.05 to 0.8.

(1-5)

The composition according to any one of (1-1) to (1-4), wherein the Group 3B element compound is a Group 3B element compound represented by the following Chemical Formula 2 or 3:

Wherein M is a Group 3B element and R ² , R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, , Or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

(1-6)

The composition according to any one of (1-2) to (1-5), wherein the organic solvent comprises at least one of an electron donating solvent, a hydrocarbon solvent, and a mixture thereof.

(1-7)

The composition according to any one of (1-2) to (1-6), wherein the organic solvent has a boiling point of 230 占 폚 or less.

(1-8)

The electron donor solvent may be at least one selected from the group consisting of 1,2-diethoxytane, tetrahydrofuran, diisopropyl ether, dioxane, and a solvent containing at least one of hexane, heptane, octane, toluene, xylene, -6).

(1-9)

The composition according to any one of (1-1) to (1-8), wherein the organic zinc compound is diethylzinc.

(1-10)

Wherein the Group 3B element compound of Formula 2 is selected from the group consisting of trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trisacetylacetonatalluminium, trisacetylacetonatallarg, trisacetylacetonite And examples of the transition metal compound include indium, aluminum chloride, gallium chloride, indium chloride, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, (1-5) to (1-9), wherein the composition contains at least one of gallium and gallium.

(1-11)

The composition according to any one of (1-1) to (1-9), wherein the Group 3B element is Ga and In.

(1-12)

(1) to (1-11) is applied to the surface of a substrate in an inert gas atmosphere, and then the operation of heating the obtained coating film is performed at least once, A method for producing a composite oxide thin film having an average transmittance.

(1-13)

The production method according to any one of (1-12), wherein the inert gas atmosphere contains water vapor.

(1-14)

The production method according to (1-13), wherein the inert gas atmosphere containing water vapor has a relative humidity of 2 to 15%.

(1-15)

(1) to (1-11), which has an average transmittance of 80% or more with respect to visible light, including spraying the surface of a heated substrate in an inert gas atmosphere containing water vapor A method for producing a composite oxide thin film.

(1-16)

The method for producing a composite oxide thin film according to (1-15), wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure.

(1-17)

The method for producing a composite oxide thin film according to (1-15), wherein a heating temperature of the substrate surface is 400 占 폚 or less.

(1-18)

The method for producing a composite oxide thin film according to (1-16) or (1-17), wherein the supply amount of the water vapor is such that a molar ratio of water to zinc in the supplied composition is in a range of 0.1 to 5.

(1-19)

An oxide semiconductor film comprising a composite oxide thin film produced by the manufacturing method according to any one of (1-12) to (1-17).

By using the composition for preparing a composite oxide thin film of the first embodiment of the present invention, a useful composite oxide thin film such as an oxide semiconductor film such as IGZO can be easily formed by a coating method such as a spin coating method, a dip coating method, a spray pyrolysis method, And a composite oxide thin film having an average transmittance of 80% or more with respect to visible light can be produced. According to the method for producing a composite oxide thin film of the first embodiment of the present invention, a useful composite oxide thin film such as an oxide semiconductor film such as IGZO can be easily formed by a coating method such as a spin coating method, a dip coating method or a spray pyrolysis method And a composite oxide thin film having an average transmittance of 80% or more with respect to visible light can be produced.

A second aspect of the present invention is as follows.

(2-1)

(Hereinafter, also referred to as partial hydrolyzate 1) obtained by adding water to a solution obtained by dissolving the organic zinc compound represented by the general formula (1) in an electron-donating organic solvent to at least partially hydrolyze the organic zinc compound Wherein the amount of water added ranges from 0.05 to less than 0.4 in terms of the molar ratio to the organic zinc compound.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(2-2)

Water is added to a solution obtained by dissolving at least one kind of an organic zinc compound represented by the following general formula (1) and an electron-borne organic solvent represented by the following general formula (2) or (3) (Hereinafter, also referred to as partial hydrolyzate 2), wherein the molar ratio of the Group 3B element compound to the organic zinc compound is 0.005 to 0.3, and the addition amount of the water Wherein the molar ratio of the organic zinc compound and the Group 3B element compound to the total amount is in the range of 0.05 or more to less than 0.4.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(2)

Wherein M is a Group 3B element and R ² , R ³ and R ⁴ are independently hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a straight or branched alkoxy group having 1 to 7 carbon atoms, An acyl group or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)

(3)

M _c X _d揃 aH ₂ O

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

(2-3)

The composition according to (2-2), wherein the product comprises the hydrolyzate of the Group 3B element compound.

(2-4)

Water is added to a solution obtained by dissolving the organic zinc compound represented by the formula (1) in an electron-donating organic solvent to at least partially hydrolyze the organic zinc compound, and then the solution of the compound of the group 3B element (Hereinafter, also referred to as partial hydrolyzate 3), and the addition amount of the organic zinc compound is in the range of 0.005 to 0.3, Wherein the molar ratio to the compound is in the range of 0.05 or more to less than 0.4.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(2)

(Wherein M is a Group 3B element and R ² _, R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, An acyl group or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)

(3)

M _c X _d揃 aH ₂ O

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

(2-5)

The composition according to (2-4), wherein the product is substantially free of the hydrolyzate of the Group 3B element compound.

(2-6)

The composition according to any one of (2-1) to (2-5), wherein the concentration of the product is in the range of 1 to 30 mass%.

(2-7)

Wherein the organic zinc compound is a compound wherein R ¹ is an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms.

(2-8)

The composition according to any one of (2-1) to (2-7), wherein the organic zinc compound is diethylzinc.

(2-9)

In the composition described in any one of 2-1 to 8, the composition described in 2-1 is referred to as Composition 2A, which is referred to as Composition 2B described in 2-2, is referred to as Composition 2C described in 2-4, Wherein the coating film is applied to the surface of the substrate in an atmosphere of at least one time and then an operation of heating the obtained coating material is performed at least once.

(2-10)

The method for producing a zinc oxide thin film according to (2-9), wherein the inert gas atmosphere contains water vapor.

(2-11)

The method for producing a zinc oxide thin film according to (2-10), wherein the inert gas atmosphere containing water vapor has a relative humidity of 2 to 15%.

(2-12)

A method for producing a zinc oxide thin film according to (2-9), which comprises spraying a heated substrate surface under an inert gas atmosphere containing water vapor.

(2-13)

The method for producing a zinc oxide thin film according to (2-10), wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure.

(2-14)

Wherein the heating temperature of the substrate surface is 400 占 폚 or less.

(2-15)

(2-13) or (2-14) wherein the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5.

(2-16)

(2-1) to (2-12), wherein the electron-donating organic solvent has a boiling point of 230 占 폚 or less.

(2-17)

An antistatic thin film made of a zinc oxide thin film produced by the manufacturing method according to any one of (2-9) to (2-16).

(2-18)

An ultraviolet blocking thin film comprising a zinc oxide thin film produced by the manufacturing method according to any one of (2-9) to (2-16).

(2-19)

A transparent electrode thin film comprising a zinc oxide thin film produced by the manufacturing method according to any one of (2-9) to (2-16).

The composition for preparing a zinc oxide thin film of the second embodiment of the present invention and the composition for preparing a zinc oxide thin film doped with a Group 3B element are free from ignition and easy to handle and can also be used as a composition for preparing a zinc oxide thin film of the present invention, When a composition for preparing a doped zinc oxide thin film is used, a transparent zinc oxide thin film and a zinc oxide thin film doped with a Group 3B element can be produced even if the film is formed at a temperature of 300 ° C or lower.

According to the zinc oxide thin film production method of the second embodiment of the present invention, a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light can be produced for the spin coating method and the dip coating method. Further, according to the zinc oxide thin film production method of the present invention, in the spray pyrolysis method, a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light can be produced. Since the zinc oxide thin film thus produced has excellent transparency and conductivity as described above, it can be applied to an antistatic thin film, an ultraviolet ray blocking thin film, a transparent electrode thin film, and the like.

A third aspect of the present invention is as follows.

(3-1)

A composition for preparing a zinc oxide thin film, which is a solution obtained by dissolving an organic zinc compound represented by the following formula (1) in a mixed solvent of an electron-donating organic solvent and an electron-donating organic solvent.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(3-2) The mixed organic solvent contains 3 to 90% by weight of the electron-donating organic solvent, and the organic zinc compound represented by the formula (1) is contained in the mixed organic solvent at a concentration in the range of 4 to 12% (3-1).

(3-3)

A partial hydrolyzate obtained by at least partial hydrolysis of an organozinc compound represented by the following general formula (1) with water, and a mixed hydrogel of an organic solvent and an organic solvent different from the electron- Composition for producing a thin film.

Formula 1

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(3-4)

The composition according to (3-3), wherein the mixed organic solvent contains 3 to 90% by weight of an electron donative organic solvent.

(3-5)

The partial hydrolysis of the organic zinc compound represented by the general formula (1) can be carried out by dissolving the organic zinc compound represented by the general formula (1) in an organic solvent different from the electron-donating organic solvent, the electron-donating organic solvent, The composition according to (3-3) or (3-4), which is carried out by adding water to the solution.

(3-6)

A solution obtained by dissolving the organozinc compound represented by the formula (1) in an organic solvent different from the electron-donating organic solvent or the electron-donating organic solvent or an organic solvent mixed with them at a concentration ranging from 4 to 12 mass% The composition according to (3-5), which is hydrolyzed.

(3-7)

The composition according to (3-5) or (3-6), wherein the partial hydrolyzate is added by adding water such that the molar ratio of the partial hydrolyzate to the organic zinc compound is in the range of 0.05 to 0.8.

(3-8)

(3-1) to (3-7) in which the molar ratio of the Group 3B element compound represented by the following formula (2) or (3) to the organic zinc compound is in the range of 0.005 to 0.1 Compositions for preparing zinc oxide thin films.

(2)

(Wherein M is a Group 3B element and R ² _, R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, An acyl group or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)

(3)

M _c X _d揃 aH ₂ O

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

(3-9)

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

A partial hydrolyzate obtained by partial hydrolysis of the organic zinc compound with water, and a partial hydrolyzate obtained by partial hydrolysis of the organic zinc compound with water in a composition containing a Group 3B element compound represented by the following Chemical Formula 2 or 3 at a molar ratio of 0.005 to 0.09 to the organic zinc compound A composition comprising an organic solvent and an organic solvent mixed with an organic solvent different from the organic solvent.

(2)

Wherein M is a Group 3B element and R ² _, R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, , Or an acetylacetonate group, and L is a saturating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)

(3)

M _c X _d揃 aH ₂ O

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

(3-10)

The composition according to (3-9), wherein the mixed organic solvent contains 3 to 90% by weight of an electron donating organic solvent.

(3-11)

The partial hydrolysis may be carried out by adding an organic zinc compound represented by the formula (1) and a group 3B group represented by the formula (2) or (3) to an organic solvent different from the electron-donating organic solvent, A composition according to (3-9), which is carried out by adding water to a solution in which an elemental compound is dissolved.

(3-12)

The concentration of the organic zinc compound and the Group 3B element compound in an organic solvent different from that of the electron-donating organic solvent or the electron-donating organic solvent or an organic solvent containing them is in the range of 4 to 12 mass% (3-11).

(3-13)

The composition according to (3-11) or (3-12), wherein the partial hydrolysis is carried out by adding water so that the molar ratio to the organic zinc compound is in the range of 0.05 to 0.8.

(3-14)

The composition according to any one of (3-1) to (3-13), wherein the electron-donating organic solvent has a boiling point of 230 ° C or less.

(3-15)

(3-1) to (3-14), wherein the organic solvent different from the electron-donating organic solvent comprises at least one of a linear chain, a branched hydrocarbon compound, a cyclic hydrocarbon compound, an aromatic hydrocarbon compound, 0.0 > 1, < / RTI >

(3-16)

The composition according to any one of (3-1) to (3-15), wherein the organic solvent different from the electron-donating organic solvent comprises at least one of hexane, heptane, octane, toluene, xylene and cyclohexane.

(3-17)

The composition according to any one of (3-1) to (3-16), wherein the organic zinc compound is diethyl zinc.

(3-18)

Wherein the Group 3B element compound of Formula 2 is selected from the group consisting of trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trisacetylacetonatalluminium, trisacetylacetonatallarg, trisacetylacetonite And examples of the transition metal compound include indium, aluminum chloride, gallium chloride, indium chloride, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, (3-8) to (3-17), wherein the composition contains at least one of gallium arsenide and gallium arsenide.

(3-19)

(3-1) to (3-18), wherein the electron donating organic solvent comprises any one of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether and dioxane.

(3-20)

The composition according to any one of (3-1) to (3-19), except that the composition described in (3-1) is referred to as composition 3A, the composition according to (3-3) -8) is referred to as Composition 3C, and the composition described in (3-9) is applied to the substrate surface in an inert gas atmosphere called Composition 3D, and then the obtained coating film is heated at least once Wherein the zinc oxide thin film has an average transmittance of 80% or more with respect to visible light.

(3-21)

The method for producing a zinc oxide thin film according to (3-20), wherein the inert gas atmosphere contains water vapor.

(3-22)

The inert gas atmosphere containing water vapor has a relative humidity of 2 to 15% (3-21).

(3-23)

The composition according to any one of (3-1) to (3-19), except that the composition described in (3-1) is referred to as composition 3A, the composition according to (3-3) -8) is referred to as Composition 3C, the composition described in (3-9) is referred to as Composition 3D, and the composition is sprayed on a heated substrate surface in an inert gas atmosphere containing water vapor, % ≪ / RTI >

(3-24)

The method for producing a zinc oxide thin film according to (3-23), wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure.

(3-25)

(3-23) wherein the heating temperature of the substrate surface is 400 占 폚 or less.

(3-26)

The method for producing a zinc oxide thin film according to (3-24) or (3-25), wherein the supply amount of the water vapor is set so that a molar ratio of water to zinc in the supplied composition is in a range of 0.1 to 5.

(3-27)

An antistatic thin film made of a zinc oxide thin film produced by the manufacturing method according to any one of (3-20) to (3-26).

(3-28)

An ultraviolet blocking thin film comprising a zinc oxide thin film produced by the manufacturing method according to any one of (3-20) to (3-26).

(3-29)

A transparent electrode thin film made of a zinc oxide thin film produced by the manufacturing method according to any one of (3-20) to (3-26).

In the composition for preparing a zinc oxide thin film of the third embodiment of the present invention, it is possible to use other commonly used solvents such as hydrocarbon solvents other than electron-donating organic solvents, The application range in industrial use can be further widened. By using the composition of the present invention, a zinc oxide thin film having conductivity and an average transmittance of 80% or more with respect to visible light can be produced by the spin coating method or the dip coating method.

When the composition for preparing a zinc oxide thin film of the third embodiment of the present invention is used, a zinc oxide thin film having conductivity and having an average transmittance of 80% or more with respect to visible light can be produced by the spray pyrolysis method.

In the third embodiment of the present invention, it is possible to use other commonly used solvents such as hydrocarbon solvents other than electron-donating organic solvents in compositions for preparing zinc oxide thin films, The application range in industrial use can be further widened. By using the composition of the present invention, a zinc oxide thin film having conductivity and an average transmittance of 80% or more with respect to visible light can be produced by the spin coating method or the dip coating method.

In the third embodiment of the present invention, when the composition for preparing a zinc oxide thin film is used, a zinc oxide thin film having conductivity and an average transmittance of 80% or more with respect to visible light can be produced by the spray pyrolysis method. Since the zinc oxide thin film thus produced has excellent transparency and conductivity as described above, it can be applied to an antistatic thin film, an ultraviolet ray blocking thin film, a transparent electrode thin film, and the like.

INDUSTRIAL APPLICABILITY The present invention is useful in the field of manufacturing an oxide thin film. Particularly, the first embodiment of the present invention is useful in the field of manufacturing a composite oxide thin film containing an oxide of zinc oxide and a Group 3B element.

The second embodiment of the present invention is useful in the field of manufacturing a zinc oxide thin film or a dope zinc oxide thin film. The third embodiment of the present invention is useful in the field of manufacturing a zinc oxide thin film.

1 is a schematic view showing a spray-coating apparatus;
2 shows the NMR spectra of the composition obtained in Example 2-1 after vacuum drying;
3 is an XRD chart of the zinc oxide thin film obtained in Example 2-5;
4 is an XRD chart of the indium-doped zinc oxide thin film obtained in Example 2-8;
5 shows the NMR spectra of the composition obtained in Example 3-1 after vacuum drying;
6 is an XRD spectrum of the zinc oxide thin film obtained in Example 3-1;
7 is an XRD spectrum of the zinc oxide thin film obtained in Examples 3-12.

≪ First Aspect of Present Invention &

[Composition for preparing composite oxide thin film]

The composition for preparing a composite oxide thin film according to the present invention comprises an organic zinc compound represented by the following formula (1) or a partial hydrolyzate of a water-based partial hydrolyzate of the organic zinc compound and a water-based partial hydrolyzate of a 3B- And the molar ratio of the Group 3B element to zinc is in the range of more than 0.1 and not more than 5.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

The composition for preparing a composite oxide thin film of the present invention includes the following forms.

(i) a composition containing an organozinc compound represented by the above formula (1) and a Group 3B element compound (hereinafter also referred to as Composition 1)

(ii) a composition containing an organic zinc compound represented by the formula (1) and a partial hydrolyzate of a Group 3B element compound with water (hereinafter, also referred to as Composition 2)

 (iii) a composition containing an organic zinc compound represented by the formula (1), a partial hydrolyzate of a Group 3B element compound and a Group 3B element compound by water (hereinafter, also referred to as Composition 3)

(Iv) a composition containing the partial hydrolyzate of water and the Group 3B element compound of the organic zinc compound represented by Formula 1 (hereinafter, also referred to as Composition 4)

(V) a composition comprising a partial hydrolyzate of an organic zinc compound represented by the above formula (1) and a partial hydrolyzate of a Group 3B element compound by water (hereinafter, also referred to as Composition 5).

(Vi) a composition containing a partial hydrolyzate of an organic zinc compound represented by the formula (1), a 3B group element compound and a partial hydrolyzate of a 3B group element compound by water (hereinafter, also referred to as composition 6)

(Iii) A composition containing an organic zinc compound represented by the formula (1), a partial hydrolyzate of the organic zinc compound with water, and a Group 3B element compound (hereinafter, also referred to as Composition 7).

(Iii) a composition containing the organic hydroxides of the organic zinc compound represented by the formula (1), the partial hydrolyzate of the organic zinc compound with water and the partial hydrolyzate of the 3B group element compound by water (hereinafter, also referred to as Composition 8) .

(Iii) a composition containing the partial hydrolyzate of the organic zinc compound represented by the formula (1), the partial hydrolyzate of the organic zinc compound with water, the partial hydrolyzate of the 3B group element compound and the 3B group element compound ).

The present invention also encompasses the above composition, which further comprises an organic solvent.

In the present invention, the Group 3B element compound may be, for example, a Group 3B element compound represented by the following Chemical Formula 2 or 3.

(2)

Wherein M is a Group 3B element and R ² , R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, , Or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)

(3)

M _c X _d揃 aH ₂ O

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

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

(A) adding water to a solution obtained by dissolving an organic zinc compound represented by the formula (1) in an organic solvent to at least partially hydrolyze the organic zinc compound, And / or a product containing a mixture of a Group 3B element compound represented by the general formula (3) (hereinafter, also referred to as partial hydrolyzate 1).

(B) A solution prepared by dissolving a mixture of an organic zinc compound represented by the formula (1) and a Group 3B element compound represented by the following formula (2) and / or (3) containing at least one 3B group element in an organic solvent, (Hereinafter, also referred to as partial hydrolyzate 2) obtained by at least partial hydrolysis of at least the organic zinc compound.

Specific examples of the alkyl group represented by R ¹ in the organic zinc compound represented by the formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec- Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, 2-hexyl group and heptyl group. The compound represented by formula (1), R ¹ is a compound having 1, 2, 3, 4, 5, or 6 are preferred. The compound represented by the general formula (1) is preferably a diethylzinc compound in which R ¹ is 2 carbon atoms.

Specific examples of the metal represented by M in the Group 3B element compound represented by Formula 2 include B, Al, Ga, and In.

It is preferable that R ² , R ³ , and R ⁴ are hydrogen.

R ² , R ³ and R ⁴ are preferably an alkyl group. 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, a sec- , Pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, 2-hexyl group and heptyl group. It is also preferred that at least one of R ² , R ³ , and R ⁴ is hydrogen and the remainder is an alkyl group. Specific examples of the alkoxyl group include a methoxy group, an ethoxy group, an isopropoxide group, and a tert-butoxy group.

The ligand represented by L is at least one compound selected from the group consisting of trimethylamine, triethylamine, triphenylamine, pyridine, monophorine, N, N-dimethylaniline, N, N-diethylaniline, triphenylphosphine, And tetrahydrofuran. The 3B group element compound represented by the general formula (3) is preferably selected from the group consisting of diborane, borane tetrahydrofuran complex, borane trimethylamine complex, borane triethylamine complex, triethylborane, tributylborane, Ethylamine complex, trimethylaluminum, dimethylaluminum hydride, triisobutylaluminum, diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, trimethylindium, triethylindium, trimethoxyborane, triethoxyborane , Triisopropoxy indium, triisopropoxy gallium, triisopropoxy aluminum, tri-tert-butoxy indium, and tri-tert-butoxy gallium. From the viewpoint that the price is low and the availability is easy, it is preferable that triethyl aluminum, triisobutyl aluminum, trimethyl gallium, trimethyl indium, trimethoxyborane, triethoxyborane, triisopropoxy indium, triisopropoxy gallium, Particularly preferred are aluminum trioxide, tri-tert-butoxy indium, and tri-tert-butoxy gallium.

Specific examples of the metal represented by M in the 3B group element in the 3B group element compound and the 3B group element compound represented by the above-mentioned formula (3) include, for example, B, Al, Ga and In. Specific examples of the salt represented by X include fluorine, chlorine, bromine, iodine, acetic acid and sulfuric acid. The 3B group element compound represented by the general formula (2) is preferably selected from boron fluoride, boron chloride, aluminum chloride, aluminum chloride hexahydrate, aluminum acetate 9 hydrate, gallium chloride, gallium gallate hydrate, indium chloride, Hydrates.

In the present invention, an organic solvent may be used to dissolve the above-mentioned metal-containing compound. The organic solvent dissolves the zinc or the Group 3B element described above, and is not particularly limited as long as there is no problem in use. In general, an electron-donating organic solvent such as ether or the like, which is industrially used, or a hydrocarbon compound such as hexane or toluene Is preferably used. These organic solvents may be used alone or as a mixture with other solvents. By dissolving the composition of the present invention using these solvents and applying it to a substrate or the like, an oxide semiconductor film such as IGZO can be easily obtained with an average transmittance of 80% or more with respect to visible light.

Examples of the electron-donating organic solvent include ether compounds, amine compounds, and the like, and those having solubility in an organic zinc compound represented by the general formula (1) and water. Examples of preferred electron donor organic solvents include those having a boiling point of 230 占 폚 or lower. Examples thereof include di-n-butyl ether (boiling point 142.4 占 폚), dihexyl ether (boiling point 226.2 占 폚) Butyl ether (boiling point: 210.3 占 폚), pentyl phenyl ether (boiling point: 214 占 폚), methoxytoluene (boiling point: 171.8 占 폚), benzyl ethyl ether 1,2-diethoxyethane (boiling point 121 占 폚), 1,2-dibutoxyethane (boiling point 203.3 占 폚), and triethylamine (boiling point 258.3 占 폚), veratrol (2-methoxyethoxy) ether (boiling point: 162 占 폚), bis (2-ethoxyether) ether (boiling point: 188.4 占 폚), bis Bis (2-methoxyethoxy) ethane (boiling point 216 ° C), bis [2- (2-methoxyethoxyethyl)] ether (boiling point 275 ° C) ), And ether-based ones such as triglyme N, N-dimethylaniline (boiling point 193 DEG C), N, N-diethylaniline (boiling point 217 DEG C), tri-n-butylamine ° C), and pyridine (boiling point: 115.3 ° C). As the electron donative organic solvent, 1,2-diethoxyethane (boiling point 121 캜), which is a kind of glyme, is preferable from the viewpoints of both inhibition of the gel at the preparation of the composition and volatility of the solvent itself. The upper limit of the boiling point of the electron-donating organic solvent is not particularly limited, but it is preferably 230 ° C or lower from the viewpoint that the drying time when the solvent is removed after coating the obtained composition to become a coating film becomes relatively short.

In the present invention, a hydrocarbon compound can be used as a solvent.

The hydrocarbon compound is preferably a straight chain, branched hydrocarbon compound or cyclic hydrocarbon compound having 6 to 12 carbon atoms, more preferably 6 to 12 carbon atoms, more preferably 6 to 12 carbon aromatic hydrocarbon compounds having 5 to 20 carbon atoms, Can be exemplified.

Specific examples of these hydrocarbon compounds include pentane, n-hexane, heptane, isohexane, methylpentane, octane, 2,2,4-trimethylpentane (isooctane), n-nonane, , Aliphatic hydrocarbons such as eicosane, methylheptane, 2,2-dimethylhexane and 2-methyloctane, alicyclic hydrocarbons such as cyclopentane, cyclohexanemethylcyclohexane and ethylcyclohexane, aliphatic hydrocarbons such as benzene, toluene, xylene, cumene, Aromatic hydrocarbons such as trimethylbenzene, and hydrocarbon-based solvents such as mineral spirits, solvent naphtha, kerosene, and petroleum ether.

From the viewpoint that the drying time when the solvent is removed after coating the obtained composition to become a coating film is relatively short, there is no particular limitation on the upper limit of the boiling point of the organic solvent or the hydrocarbon compound of the kind other than the electron- It is preferably 230 deg. From the viewpoint of improving the stability of the metal-containing compound, it is preferable that the electron-donating compound is contained in the composition of the present invention.

The concentration of the compound represented by the formula (1) in the solution obtained by dissolving the compound represented by the formula (1) in the electron-donating organic solvent or the mixed organic solvent containing the electron-donating organic solvent is preferably 4 to 12 mass% Is preferably in the range of The concentration of the compound represented by the general formula (1) in the solution dissolved in the organic solvent is preferably in the range of 6 to 10 mass%.

The composition obtained by dissolving the compound or the partial hydrolyzate in an organic solvent may be a composition in which the composition is dissolved or reacted as described above. Alternatively, the composition may be obtained by, for example, a partial hydrolysis reaction, A compound such as an organic solvent may optionally be added and the composition thereof may be adjusted to prepare the composition of the present invention.

The amount of water to be added in the preparation of the partial hydrolyzate is, for example, in the range of 0.05 to 0.8 in terms of the molar ratio of the partial hydrolyzate 1 to the organic zinc compound, And the molar ratio of the compound to the total amount of the Group 3B element compound is preferably in the range of 0.05 to 0.8. Since the added amount of water is in this range, the reaction product containing the partial hydrolyzate obtained in the spin coating method, the dip coating method and the spray pyrolysis can form a transparent and conductive zinc oxide thin film. In the case of partial hydrolysis of the Group 3B element compound alone, it is preferable that the molar ratio of water to the Group 3B element compound is in the range of 0.05 to 0.8.

For example, when the molar ratio of water is 0.4 or more, partial hydrolysis of an organozinc compound is achieved by partially hydrolyzing the organozinc compound at a high yield of 90% or more based on the zinc contained in the raw material . As for the partial hydrolyzate 2, an appropriate amount of the Group 3B element compound is partially hydrolyzed. By setting the molar ratio to 0.4 or more, it is possible to suppress the residual amount of the organic zinc compound as the unreacted raw material in the case of the partial hydrolyzate 1 and the residual amount of the organic zinc compound and the 3B group compound in the case of the partial hydrolyzate 2 . In addition, by setting the molar ratio to 0.8 or less, generation of gel during the hydrolysis reaction can be suppressed. When the gel is generated during the hydrolysis reaction, the viscosity of the solution increases, and subsequent operations may become difficult. From the above viewpoint, the upper limit of the molar ratio of addition of water is preferably 0.8, more preferably 0.75.

Control of the addition amount of this water makes it possible to control the physical properties such as viscosity and boiling point of the composition. For example, the coating which is difficult to carry out the reaction such as the spin coat method can facilitate the film formation by increasing the addition amount of water. In addition, in the spraying method or the like, the present invention The film formation that reflects the reactivity of the organic zinc compound itself, such as the film formation at a low temperature, can be performed.

For products containing a mixture of an organozinc compound represented by the above formula (1) and a group 3B element, for example, a group 3B element represented by the above formula (2) and / or the above formula (3) The composition can be prepared by adding the organic zinc compound represented by the formula (1) and the 3B group compound of the formula (2) or (3) to an organic solvent or the like. The addition amount of the Group 3B element compound is preferably 0.1 to 5, and more preferably 5 or less based on the amount of the organic zinc compound.

In the partial hydrolyzate 1, since water is added to the organozinc compound and then the Group 3B element compound is added, the added water is consumed for hydrolysis of the organozinc compound, When added, the product usually does not include the hydrolyzate of the Group 3B element compound. The group 3B elemental compound is not hydrolyzed, is contained as a raw material, or the possibility that the organic group of the partial hydrolyzate of the organic zinc compound and the organic group (ligand) of the 3B group element are exchanged (ligand exchange) There is also. With regard to the partial hydrolyzate 3, water is added to a mixed solution of an organic zinc compound and a Group 3B element compound, so that the product generally includes the hydrolyzate of the above-mentioned Group 3B element compound. The hydrolyzate of the Group 3B element compound may be a partial hydrolyzate depending on the amount of water added and the like.

The addition of water may be carried out with water alone without mixing water with another solvent, or with a mixed solvent obtained by mixing water with another solvent. From the viewpoint of suppressing progress of local hydrolysis, it is preferable to use a mixed solvent. The content of water in the mixed solvent may be, for example, 1 to 50 mass%, preferably 2 to 20 mass% to be. The solvent which can be used for the mixed solvent with water can be, for example, the above electron-donating organic solvent. The electron-donating organic solvent may be an organic solvent having a boiling point of 110 ° C or higher or an organic solvent having a boiling point of lower than 110 ° C. However, it is preferable that the organic solvent has a boiling point of less than 110 캜 from the viewpoint that it is inactive to diethylzinc and needs to have high water solubility.

The addition of water depends on the scale of the reaction, but for example, it takes 60 seconds to 10 hours to carry out the reaction. It is preferable to add water or a mixed solvent of water with the organic zinc compound of the formula (1) as a raw material by dropping it from the viewpoint of good yield of the product. The addition of water can be carried out without stirring (in a stationary state) or with stirring a solution of the compound represented by the general formula (1) and the electron-donating organic solvent. The temperature at the time of the addition may be any temperature between -90 and 150 캜. -15 to 30 캜 is preferable in view of the reactivity of water and the organic zinc compound.

After the addition of water, the reaction between water and the compound represented by the formula (1) and the compound represented by the formula (2) or (3) or the reaction between water and the compound represented by the formula (1) Without stirring (in a stationary state) or stirring. The reaction temperature can be reacted at any temperature between -90 and 150 캜. The reaction temperature is preferably in the range of 5 to 80 캜 from the viewpoint of obtaining the partial hydrolyzate in high yield. The reaction pressure is not limited. Normally, it can be carried out at normal pressure (atmospheric pressure). The progress of the reaction between water and the compound represented by the formula (1) can be monitored by sampling the reaction mixture, analyzing the sample by NMR or IR, or sampling the generated gas, if necessary.

In the composition containing the composition of the present invention, for example, the partial hydrolyzate 1 and 2, the molar ratio of the organozinc compound represented by the formula 1 to the organozinc compound represented by the formula 2 or 3 is 3: , More than 0.1 and not more than 5 are suitable from the viewpoint of obtaining an oxide semiconductor film such as IGZO in which the effect of addition of the Group 3B element is adequately expressed. From the same viewpoint, the upper limit of the amount of the Group 3B element compound added is preferably 4.5, more preferably 4, still more preferably 2.5, still more preferably 2, still more preferably 0.95. For partial hydrolyzate 1, water is added to a solution containing an organic zinc compound to obtain a partial hydrolyzate, and then a Group 3B element compound is added at the above-mentioned molar ratio. With respect to the partial hydrolyzate 2, water is added to a solution containing the organozinc compound and the Group 3B element compound at the above-mentioned molar ratio to obtain a partial hydrolyzate.

The organic solvent, the organic zinc compound of Formula 1, and the mixed solvent with water or water can be introduced into the reaction vessel according to any conventional method. These reaction processes may be any one of a batch operation type, a semi-batch operation type and a continuous operation type, and there is no particular limitation, but a batch operation type is preferable.

By the reaction, the organozinc compound of the formula (1) and the group 3B element compound of the formula (2) or (3) or the organozinc compound of the formula (1) are partially hydrolyzed by water and the partial hydrolyzate Products can be obtained. When the organozinc compound of formula (1) is diethyl zinc, the analysis of the product obtained by the reaction with water has been carried out from the past, but the results differ depending on the report, and the composition of the product is not clearly specified. Further, the composition of the product may vary depending on the addition mole ratio of water, the reaction time, and the like.

For example, it is presumed that the partial hydrolyzate 1 or 2 is a compound represented by the following general formula (4), or a mixture of plural kinds of compounds having different p's.

(Wherein, R ¹ is the same as R ¹ in Chemical Formula 1, p is an integer of 2-20.)

In the present invention, the main component of the product is, for example, the compound obtained by combining the structural unit represented by the following general formulas (5) and (6) and the structural unit represented by the following general formula (7) for the partial hydrolyzate Lt; RTI ID = 0.0 > of a < / RTI >

(Wherein, R ¹ is the same as R ¹ in Chemical Formula 1, M is an integer of 2-20.)

(Wherein M is the same as M in the formula (2) or (3), and Q is X, R ² , R ³ , R ⁴ And M is an integer of 2 to 20.)

In the case of the partial hydrolyzate 1 in which the Group 3B element compound is not coexisted during the hydrolysis of the organic zinc compound, a Group 3B element compound such as 3B of the formula (2) or (3) The composition can be prepared by adding a group-III compound. As described above, the addition amount of the Group 3B element compound is preferably 0.1 to 5, and more preferably 5 or less based on the amount of the organic zinc compound added.

By using the composition of the present invention, it is possible to form an oxide semiconductor film made of oxide (IGZO) of In, Ga and Zn.

The composition for forming the IGZO film contains Ga and In as essential elements in the composition, as zinc and Group 3B elements. That is, the composition of the present invention makes it necessary to use Zn by using a product containing the organic zinc compound and the partial hydrolyzate of Formula 1, and further, it is necessary to use a 3B group compound such as 3B of Formula 2 and / Group compound, the use of the two components of In and Ga as a group 3B element is essential. It is possible to adjust the molar ratio of Zn, In, and Ga such that the composition ratio is the composition of the desired IGZO. The molar ratio of InGaZnO ₄ , In ₂ Ga ₂ ZnO ₇ , InGaZn ₅ O ₈ (M = an integer of 1 to 20), such as InGaO ₃ (ZnO) _m (m is an integer of 1 to 20), etc., and oxygen deficient compounds, and the other composition ratios are not limited to the constant ratios , It is possible to prepare an arbitrary composition by adjusting the addition amount of each element.

In particular, the composition of the present invention can be used as a compound containing zinc prepared as described above, which is obtained by partial hydrolysis of an organic zinc compound represented by the following formula (1) and an organic zinc compound such as diethyl zinc have. This addition is a hydrolysis of the composition in which the alkyl group R ¹ bonded to the product obtained by partial hydrolysis of an organozinc compound and an organozinc compound with water, wherein R ¹ is a linear or branched alkyl groups) Identification of hydrocarbon R ¹ H, mainly generated from, is confirmed by the amount. For example, in the case of diethylzinc, the main component of the gas produced by hydrolysis is ethane.

Further, the alkyl group R ¹ (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) bonded to the product obtained by the partial hydrolysis of the organic zinc compound and the organic zinc compound with water is a 3B (2), R ² , R ³ and R ⁴ (wherein R ² , R ³ and R ⁴ are independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms) represented by the formula .

After completion of the hydrolysis reaction, a part or the whole of the product can be recovered and purified by a general method such as filtration, concentration, extraction, or column chromatography. When a Group 3B element compound is added after completion of the hydrolysis reaction, a part or all of the product can be recovered and purified by filtration. When the organic zinc compound of the formula (1) or the group 3B element compound of the formula (2) or (3) remains in the reaction product, the compound may be recovered or recovered by the above method.

The solution prepared by the above method can be used as it is as a coating solution for forming a composite oxide thin film. Alternatively, it may be appropriately diluted or concentrated. However, from the viewpoint that the production process can be simplified, it is preferable that the solution prepared by the above method is a concentration that can be used as a solution for coating for forming an oxide complex oxide.

[Production method of composite oxide thin film]

The method for producing a composite oxide thin film of the present invention is a method for producing a composite oxide thin film which comprises applying a composition for forming a composite oxide thin film on a surface of a substrate under an inert gas atmosphere and then heating the obtained coating film at least once, A method for producing a zinc oxide thin film having an average transmittance of 80% or more. When the coating is performed by, for example, a spin coating method, a dip coating method, or a spray pyrolysis method, a composite oxide thin film having conductivity and an average transmittance of 80% or more with respect to visible light can be formed.

Application to the surface of the substrate can be carried out by conventional means such as dip coating method, spin coating method, spray pyrolysis method, ink jet method, and screen printing method.

The composition is applied to the surface of the substrate under an atmosphere of an inert gas such as nitrogen in an atmosphere of air containing a large amount of water vapor and a high relative humidity and in a reducing gas atmosphere such as hydrogen, Or in a mixed gas atmosphere thereof, under atmospheric pressure or under pressure.

The spin coating method or the dip coating method may be carried out under an inert gas atmosphere or by mixing an inert gas and water vapor in an atmosphere having a relative humidity of 2 to 15%.

The spray pyrolysis method is a method which can be carried out while heating the substrate. Therefore, the solvent can be dried in parallel with the application, and in some cases, heating for solvent drying is unnecessary. Depending on the conditions, the reaction of the composition of the present invention with the composite oxide may be at least partially proceeded in addition to the drying. For this reason, the composite oxide thin film can be formed more easily by heating to a predetermined temperature, which is a subsequent step. The heating temperature of the substrate may be, for example, in the range of 50 to 550 占 폚.

Fig. 1 shows a spray-coating apparatus usable by spray pyrolysis. In the figure, reference numeral 1 denotes a spray bottle filled with a coating liquid, 2 denotes a substrate holder, 3 denotes a spray nozzle, 4 denotes a pressure, 5 denotes a substrate, and 6 denotes a tube for introducing water vapor. In the spray application, the substrate is placed on the substrate holder 2, heated to a predetermined temperature using a heater if necessary, and thereafter compressed in a predetermined atmosphere from the spray nozzle 3 disposed above the substrate A composite oxide thin film can be formed on a substrate by simultaneously supplying an inert gas and a coating liquid and atomizing and spraying the coating liquid. The composite oxide thin film is formed by spray application without additional heating or the like.

Spraying of the coating liquid is carried out by discharging the coating liquid so that the size of the liquid droplets is in the range of 1 to 15 mu m in the spray nozzle and further performing the distance within 50 cm between the spray nozzle and the substrate, Is preferable from the viewpoint of being able to produce a composite oxide thin film.

Considering the adhesion to the substrate and the ease of evaporation of the solvent, it is preferable that the size of all liquid droplets ejected from the spray nozzle is in the range of 1 to 30 mu m. The size of the liquid droplet is more preferably in the range of 3 to 20 占 퐉.

The distance between the spray nozzle and the substrate is preferably within 50 cm, considering that the solvent evaporates slightly from the spray nozzle until reaching the substrate and the size of the droplet decreases. The distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint of enabling formation of the composite oxide thin film.

In the spray pyrolysis method, it is preferable from the viewpoint of forming a composite oxide thin film having a lower volume resistivity by promoting decomposition of the composition by introducing water vapor from the water vapor introduction tube 6 in an inert gas atmosphere. For example, the introduction amount of water vapor is preferably 0.05 to 5 in terms of a molar ratio with respect to the total amount of zinc and 3B group elements in the supplied composition, and from the viewpoint of obtaining a composite oxide thin film having high transparency, More preferable.

The method of introducing water vapor can be introduced into a composite oxide thin film production apparatus according to all common methods. The water vapor and the composition are preferably reacted in the vicinity of the heated substrate, and 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 from the tube.

After coating the coating liquid on the substrate surface, if necessary, the substrate is heated to a predetermined temperature, the solvent is dried and then heated to a predetermined temperature to form a composite oxide thin film.

The temperature at which the solvent is dried may be, for example, in the range of 20 to 200 占 폚, and may be set in a timely manner depending on the kind of coexisting organic solvent. The heating temperature for forming the complex oxide after solvent drying is, for example, in the range of 50 to 550 占 폚, preferably in the range of 50 to 500 占 폚. It is also possible to perform the solvent drying and the complex oxide formation at the same time by setting the solvent drying temperature to the same heating temperature for forming the complex oxide thereafter.

If necessary, the above heating is carried out in an atmosphere of an oxidizing gas such as oxygen under a reducing gas atmosphere such as hydrogen in a plasma atmosphere of hydrogen, argon, oxygen, or the like to promote the formation of zinc oxide, It is also possible to improve. The thickness of the composite oxide thin film is not particularly limited, but it is preferably in the range of 0.05 to 2 탆 in practical use. According to the above manufacturing method, in the case other than the spray pyrolysis method, the coating (drying) heating is repeated one or more times, so that a thin film having the film thickness within the above range can be suitably manufactured.

The composite oxide thin film formed by the above production method varies depending on the application method and subsequent drying conditions and heating conditions. The volume resistivity is the resistance per unit volume, which can be obtained by multiplying the surface resistance by the film thickness. The surface resistance is measured by, for example, the 4-probe method, and the film thickness is measured by, for example, SEM measurement, a stylus type step film thickness meter or the like. Since the volume resistivity changes (increases) by the degree of formation of the composite oxide upon application of the spray or after application, the volume resistivity is preferably controlled so that the volume resistivity of the thin film becomes a desired resistance value. Time) is preferably set.

The composite oxide thin film formed by the above production method preferably has an average transmittance of 80% or more with respect to visible light, and more preferably has an average transmittance of 85% or more with respect to visible light. The " average transmittance to visible light " is defined as follows and is also measured. The average transmittance to visible light is the average of the transmittance of light in the range of 380 to 780 nm and is measured by an ultraviolet visible spectrophotometer. The average transmittance to visible light can also be expressed by showing the transmittance of visible light at 550 nm. The transmittance to visible light is changed (increased) by the degree of formation of zinc oxide upon application of the spray or after coating, so that the transmittance of the thin film to visible light is considered to be 80% or more, It is preferable to set the post-heating condition (temperature and time).

The substrate to be used may be, for example, an alkali glass, an alkali-free glass, or a transparent base film, and the transparent base film may be a plastic film. Examples of the polymer forming the plastic film include polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), poly (meth) acrylate (for example, polymethyl methacrylate (PMMA) (PC), polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, cyclic polyolefin (COP), ethylene-vinyl acetate copolymer, polyurethane, triacetate and cellophane. , PET, PEN, PC, and P MMA are preferable. The transparent base film may be a non-oriented film or a stretched film depending on the type of polymer. For example, a polyester film, for example, a PET film, And the PC film, the triacetate film, the cellophane film, and the like are usually lead-free films, but the present invention is not intended to be limited to these examples. It may be used at any of the three types.

[Use of composite oxide thin film]

The composite oxide thin film produced by the above method has excellent transparency and mobility and can therefore be used as an antistatic film, an ultraviolet ray blocking film, a transparent conductive film, and the like. The antistatic film can be used, for example, in the field of building materials such as solid electric field capacitors, chemical amplification resistors, and glass windows. The ultraviolet screening film can be used in, for example, fields such as a front filter of an image display apparatus, an imaging apparatus such as a drive recorder, a lighting apparatus such as a high-pressure discharge lamp, a building material such as a cover glass for a clock, Further, the transparent conductive film may be formed of a material such as an FPD, a resistive film touch panel, a capacitive touch panel, a thin film silicon solar cell, a compound (CdTe, CIS) thin film solar cell, It is available in the field. Particularly, an oxide semiconductor film made of an oxide (IGZO) of In, Ga and Zn has a higher mobility than that of an amorphous Si film and is used as a switching element (thin film transistor) in a liquid crystal display device, a thin film electroluminescence display device, Can be used. Such a field effect transistor such as a thin film transistor (TFT) is widely used as a unit electronic element, a high frequency signal amplifying element, a liquid crystal driving element, and the like of a semiconductor memory integrated circuit. However, it is not intended to be limited to these fields.

≪ Second embodiment of the present invention &

[Composition for preparing zinc oxide thin film]

The composition for preparing a zinc oxide thin film of the present invention (Composition 2A) is prepared by adding water to a solution obtained by dissolving an organic zinc compound represented by the following formula (1) in an electron-donating organic solvent and at least partially hydrolyzing the organic zinc compound (Partial hydrolyzate 1), and the amount of the water added is in the range of from 0.05 or more to less than 0.4 in terms of the molar ratio with respect to the organic zinc compound.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

In the partial hydrolyzate 1, hydrolysis products can be obtained even if the amount of water added is increased to 0.4 or more and the degree of hydrolysis is advanced. However, the residual amount of diethylzinc having a high reactivity unreacted is small, and the reactivity at low temperatures There is a possibility that it can not be obtained.

[Composition for preparing zinc oxide thin film doped with Group 3B element]

The compositions (compositions B and C) for preparing a zinc oxide thin film doped with a Group 3B element of the present invention comprise (i) an organozinc compound represented by the following formula (1) and at least one of the Group 3B element compounds represented by the following formula (Partial hydrolyzate 2) obtained by at least partially hydrolyzing at least the above-mentioned organic zinc compound by adding water to a solution obtained by dissolving a species in an electron-donating organic solvent, or (ii) Water is added to a solution obtained by dissolving the organozinc compound in an electron donating organic solvent to at least partially hydrolyze the organozinc compound and then at least one species of the Group 3B element compound represented by the above Chemical Formula 2 or 3 (Hereinafter, also referred to as partial hydrolyzate 3). The composition containing partial hydrolyzate 2 is composition B and the composition including partial hydrolyzate 3 is composition C.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(2)

Wherein M is a Group 3B element and R ² , R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, , Or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)

(3)

M _c X _d揃 aH ² O

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

In the partial hydrolyzate 2, water is added to a mixed solution of an organic zinc compound and a Group 3B element compound, so that the product generally includes a hydrolyzate of the above-mentioned Group 3B element compound. The hydrolyzate of the Group 3B element compound may be a partial hydrolyzate depending on the amount of water added and the like. In addition, in the partial hydrolyzate 3, water is added to the organozinc compound and then the Group 3B element compound is added. Therefore, although the added water is consumed for hydrolysis of the organozinc compound, the amount of the Group 3B element When added to a compound, the product usually does not include the hydrolyzate of the Group 3B element compound. The group 3B elemental compound is not hydrolyzed, is contained as a raw material, or the possibility that the organic group of the partial hydrolyzate of the organic zinc compound and the organic group (ligand) of the 3B group element are exchanged (ligand exchange) There is also.

In the partial hydrolyzate 2, the molar ratio of the organic zinc compound to the total amount of the Group 3B element compound is set in the range of 0.05 or more to less than 0.4. For the composition for preparing a zinc oxide thin film or the partial hydrolyzate 3, the addition amount of the water is set to a range of 0.05 or more to less than 0.4 in terms of the organic zinc compound. The hydrolysis product can be obtained by increasing the addition amount of water by 0.4 or more and the degree of hydrolysis is increased. However, the residual amount of diethylzinc which is unreacted with high reactivity becomes small, and the possibility that reactivity at low temperature .

Hereinafter, the partial hydrolyzates 1 to 3 will be described.

The electron donating organic solvent may be any one having solubility in an organic zinc compound represented by Chemical Formula 1 and water for the partial hydrolyzate 1 and an organic zinc compound represented by Chemical Formula 1 for the partial hydrolyzate 2 and 3, It may be any compound which has solubility in the 3B group element compound represented by the general formula (2) or (3) and water. Examples of such electron-donating organic solvents include organic solvents such as 1,2-diethoxyethane, diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, Ether-based solvents such as triglyme, and amine-based solvents such as trimethylamine, triethylamine and triphenylamine. As a solvent having an electron donor, 1,2-diethoxyethane, tetrahydrofuran and dioxane are preferable.

The organozinc compound represented by Formula 1,

The Group 3B element compound represented by Formula 2 or 3 is the same as the organozinc compound represented by Formula 1 and the Group 3B element compound represented by Formula 2 or 3 in the first embodiment of the present invention, See the description in the first aspect of the present invention.

In the compositions (partial hydrolysates 2 and 3) of the present invention, the molar ratio of the organozinc compound represented by Formula 1 to the organozinc compound represented by Formula 2 or 3 is preferably 0.005 to 0.3 . If the amount of the Group 3B element compound to be added is too large, it tends to deteriorate the film characteristics as impurities, so that the ratio is preferably 0.005 to 0.1. However, in the partial hydrolyzate 2, water is added to a solution containing the organozinc compound and the Group 3B element compound at the above-mentioned molar ratio to obtain a partial hydrolyzate. In the partial hydrolyzate 3, water is added to a solution containing an organic zinc compound to obtain a partial hydrolyzate, and then a Group 3B element compound is added at the above-mentioned molar ratio.

The concentration of the compound represented by the formula (1) in the solution obtained by dissolving the compound represented by the formula (1) in the electron-donating organic solvent is appropriately determined in consideration of solubility in a solvent and the like, By mass to 50% by mass, and more preferably from 1% by mass to 30% by mass. The compound represented by the formula (1) and the compound represented by the formula (2) or (3) in the solution of the compound represented by the formula (1) and the compound of the group 3B element represented by the formula (2) The concentration of the total amount of the Group 3B element compound is appropriately determined in consideration of solubility in a solvent and the like, but is suitably in the range of, for example, 0.1 to 50 mass%.

When the organic zinc compound of Formula 1 is at least partially hydrolyzed and then the 3B element compound of Formula 2 or 3 is added (in the case of partial hydrolyzate 3), the compound of Formula 1 is reacted with the electron donating organic compound The concentration of the compound represented by the formula (1) in the solution dissolved in the solvent is suitably determined in consideration of the solubility in a solvent and the like, but is suitably in the range of, for example, 0.1 to 50 mass%.

The addition of water may be carried out without mixing water with another solvent or after mixing water with another solvent. The addition of water may depend on the scale of the reaction, but may be carried out over a period of, for example, 60 seconds to 10 hours. From the viewpoint that the yield of the product is good, it is preferable to add water by dropwise adding the organic zinc compound of the formula (1) as raw material. The addition of water can be carried out without stirring (in a stationary state) or with stirring a solution of the compound represented by the general formula (1) and the electron-donating organic solvent. The temperature at the time of the addition may be any temperature between -90 and 150 캜. -15 to 30 캜 is preferable in view of the reactivity of water and the organic zinc compound.

After the addition of water, the reaction of water with the compound represented by the formula (1) and the compound represented by the formula (2) or (3) or the reaction between water and the compound represented by the formula (1) Stir without stirring (in a stationary state) or stir. At the reaction temperature, the reaction can be carried out at any temperature between -90 and 150 ° C. And the temperature is preferably 5 to 80 DEG C from the viewpoint of obtaining the partial hydrolyzate at a high yield. The reaction pressure is not limited. Normally, it can be carried out at normal pressure (atmospheric pressure). The progress of the reaction between water and the compound represented by the formula (1) can be monitored by sampling the reaction mixture, analyzing the sample by NMR or IR, or sampling the generated gas, if necessary.

The organic solvent, the organic zinc compound of Formula 1 as a raw material, and water can be introduced into a reaction vessel according to all common methods, and can also be introduced as a mixture with a solvent. These reaction processes may be any one of a batch operation type, a semi-batch operation type, and a continuous operation type, and there is no particular limitation, but a batch operation type is preferable.

According to the above reaction, the organozinc compound of Formula 1 and the Group 3B element compound of Formula 2 or 3 or the organozinc compound of Formula 1 are at least partially hydrolyzed by water, and the partial hydrolyzate The product can be obtained. In the present invention, the main component of the product is a compound obtained by combining the structural units represented by the formulas (5) and (6) shown in the description of the first embodiment of the present invention with the structural unit represented by the formula (7) And m in formula (6) is a mixture of plural kinds of compounds different from each other.

The partial hydrolyzate 1 or the partial hydrolyzate 3 in the composition for preparing a zinc oxide thin film may be a compound represented by the formula 4 shown in the explanation of the first aspect of the present invention or a mixture of plural kinds of compounds having different p in the formula 4 .

In the composition for preparing a zinc oxide thin film doped with a Group 3B element, when the above-mentioned Group 3B element compound is not coexisted during the hydrolysis of the organic zinc compound, after the completion of the reaction, the 3B group compound of the above formula 2 or 3 is added A composition is prepared. The amount of the Group 3B element compound added is 0.005 to 0.3 based on the amount of the organic zinc compound added. From the viewpoint that the effect of addition of the Group 3B element compound can be reliably obtained, and since the amount of the added amount tends to deteriorate the film characteristics as impurities, it is particularly preferably 0.005 to 0.1.

After completion of the hydrolysis reaction, a part or the whole of the product can be recovered and purified by a general method such as filtration, concentration, extraction, or column chromatography. When a Group 3B element compound is added after completion of the hydrolysis reaction, a part or all of the product can be recovered and purified by filtration. When the organic zinc compound of the formula (1) remains in the reaction product, it may be recovered by the above-mentioned method.

The composition recovered from the electron-donating organic solvent by the above-described method may be dissolved in an organic solvent for forming a thin film other than the electron-donating organic solvent used for the reaction to prepare a coating solution. Alternatively, the reaction mixture may be left as it is or without being separated from the electron-donating organic solvent, or may be made into a coating solution by adjusting the concentration.

Examples of the organic solvent for forming a thin film include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane and petroleum ether, aromatic hydrocarbon solvents such as benzene, toluene, ethylbenzene and xylene, diethylether, diisopropylether , Ether solvents such as glyme, diglyme, triglyme, dioxane and tetrahydrofuran, amine solvents such as trimethylamine, triethylamine and triphenylamine. They may be used alone or in combination of two or more. Considering the solubility of the reaction product including the partial hydrolyzate of the organic zinc compound contained in the reaction product and the volatility of the organic solvent itself, examples of the organic solvent for forming the thin film include 1,2-diethoxyethane, 1,4 - dioxane, methyl monoglyme, ethyl monoglyme and methyl diglyme are preferable.

The solid concentration of the composition for forming a zinc oxide thin film or the composition for preparing a zinc oxide thin film doped with a Group 3B element may be arbitrarily selected within a range of 1 to 30 mass%. The higher the concentration is, the thinner can be produced with a smaller number of application, but it is preferably 1 to 12 mass% in consideration of the solubility of the reaction product including the partial hydrolyzate of the organic zinc compound and the ease of formation of the transparent zinc oxide thin film.

[Manufacturing method of zinc oxide thin film]

The method for producing a zinc oxide thin film of the present invention is characterized in that any one of the zinc oxide thin film forming compositions 2A to 2C of the present invention is applied to the surface of the substrate and then the obtained coated film is heated to 300 DEG C or less, Lt; / RTI > More specifically, the production method of the present invention includes a step of applying any one of the compositions 2A to 2C to the surface of a substrate in an inert gas atmosphere, and subsequently conducting an operation of heating the obtained coating at least once . The application and the heating operation of the obtained coating material can be appropriately carried out in order to obtain desired physical properties such as conductivity, but it is preferably 1 to 50 times, more preferably 1 to 30 times, more preferably 1 time To 10 times, and so on.

Application to the surface of the substrate can be carried out by conventional means such as dip coating method, spin coating method, spray pyrolysis method, ink jet method, and screen printing method. The spray pyrolysis method is a method which can be carried out while heating the substrate. Therefore, the solvent can be dried in parallel with the application, and in some cases, heating for solvent drying is not required in some cases. Depending on the conditions, the reaction of the partial hydrolyzate of the organic zinc compound to zinc oxide may proceed at least in part in addition to the drying. For this reason, the zinc oxide thin film can be formed more easily by heating to a predetermined temperature, which is a subsequent step. The spray pyrolysis method can be carried out using, for example, the apparatus shown in Fig. 1, and the heating temperature of the substrate can be, for example, in the range of 50 to 250 캜.

The composition is applied to the surface of the substrate under an atmosphere of an inert gas such as nitrogen in an atmosphere of air containing a large amount of water vapor and a high relative humidity and in a reducing gas atmosphere such as hydrogen, Or under several atmospheres under these mixed gas atmosphere, or under atmospheric pressure or pressurization. Since the product contained in the composition of the present invention reacts with moisture in the atmosphere and slowly decomposes, it is preferable to carry out the reaction in an inert gas atmosphere. The application in the method of the present invention can be carried out under reduced pressure, but it is also preferable that the application is carried out at atmospheric pressure on the apparatus.

After the application liquid is coated on the surface of the substrate, the substrate is heated to a predetermined temperature as required, the solvent is dried, and the substrate is heated to a predetermined temperature to form a zinc oxide thin film.

The temperature at which the solvent is dried may be, for example, in the range of 20 to 200 占 폚, and may be set in a timely manner depending on the kind of coexisting organic solvent. The heating temperature for zinc oxide formation after solvent drying is, for example, in the range of 20 to 300 캜, preferably in the range of 50 to 250 캜, and more preferably in the range of 100 to 200 캜. It is also possible to simultaneously perform solvent drying and zinc oxide formation by making the solvent drying temperature and the subsequent heating temperature for forming zinc oxide the same.

If necessary, the above heating is carried out in an atmosphere of an oxidizing gas such as oxygen in a reducing gas atmosphere such as hydrogen under a plasma atmosphere of hydrogen, argon, oxygen, or the like to promote the formation of zinc oxide, It is also possible to improve. The thickness of the zinc oxide thin film is not particularly limited, but it is preferably in the range of 0.05 to 2 탆 in practical use. According to the production method of the present invention, the coating (drying) heating is repeated one or more times to suitably produce a thin film having the above-mentioned film thickness.

The zinc oxide thin film formed by this production method preferably has an average transmittance of 80% or more with respect to visible light, and more preferably has an average transmittance of 85% or more with respect to visible light. The " average transmittance to visible light " is defined and measured as follows. The average transmittance for visible light is the average of the transmittance of light in the range of 380 to 780 nm and is measured by an ultraviolet visible spectrophotometer. The average transmittance to visible light can also be expressed by showing the transmittance of visible light at 550 nm. Since the transmittance to visible light changes (increases) with the application of the spray or with the degree of formation of zinc oxide by heating after coating, the transmittance of the thin film to visible light is preferably 80% or more, , Or the heating condition (temperature and time) after coating is preferably set.

Further, since the doped zinc oxide thin film formed by this manufacturing method is doped with a Group 3B element, the possibility of obtaining a low resistance film is increased by learning the film forming method again.

The material used as the substrate in the above production method may be the material in the first aspect of the present invention.

≪ Third embodiment of the present invention &

[Composition for preparing zinc oxide thin film]

The composition for preparing a zinc oxide thin film of the present invention includes the following five types (i) to (v).

(i) a product (solution) obtained by dissolving an electron-donating organic solvent represented by the following formula (1) in a mixed solvent of an electron-donating organic solvent and another kind of organic solvent box)

Specific examples of the composition 1 include the following composition (a).

Composition a:

The organic zinc compound represented by the following formula (1) is added to a mixed organic solvent containing an electron-donating organic solvent in an amount of 3 to 90% by weight for an organic solvent different from the electron-donating organic solvent and the electron- To 12% by mass of a solution obtained by dissolving the product

(ii) dissolving an organozinc compound represented by the following formula (1) in a solvent mixture of an electron-donating organic solvent and an electron-donating organic solvent and then dissolving the organic compound in an organic solvent of the group 3B element A product 2 obtained by adding at least one kind of compound (hereinafter also referred to as Composition 2) Composition 2 is included in Composition 3B.

Specific examples of the composition 2 include the following compositions b and c.

Composition b:

The electron donating organic solvent and the electron donating organic solvent may be added to a mixed organic solvent containing an electron donating organic solvent in an amount of 3 to 90% by weight based on the other organic solvent, and the organic zinc compound represented by the above formula Mass%, and then adding at least one of the Group 3B element compounds represented by the above general formula (2) or (3) to obtain a product

Composition c:

The organic zinc compound represented by the formula (1) and the organic zinc compound represented by the formula (1) in an organic solvent containing an electron donating organic solvent and an electron donating organic solvent in an amount of 3 to 90% 2 or 3 at a concentration in the range of 4 to 12 mass%, and the product obtained by dissolving at least one of the Group 3B element compounds represented by

(iii) adding water to a solution obtained by dissolving an organic zinc compound represented by the following formula (1) in an organic solvent different from that of an electron-donating organic solvent or an electron-donating organic solvent or an organic solvent in which these organic solvents are mixed, (Hereinafter, also referred to as partial hydrolyzate 1) obtained by at least partially hydrolyzing an organic solvent (hereinafter sometimes referred to as a partial hydrolyzate 1) and dissolving it in a mixed solvent with an organic solvent different from the electron-donating organic solvent (Composition 3B).

As a specific example of the partial hydrolyzate 1, the following composition d can be mentioned.

Composition d:

The organic zinc compound represented by the formula (1) is added to a mixed organic solvent containing 3 to 90% by weight of an electron donating organic solvent for an organic solvent different from the electron donating organic solvent and the electron donating organic solvent, To 12% by mass of the organic zinc compound in a molar ratio of water to the organic zinc compound of 0.05 to 0.8, and at least partially hydrolyzing the organic zinc compound.

(iv) adding water to a solution obtained by dissolving an organic zinc compound represented by the following formula (1) in an organic solvent different from that of an electron-donating organic solvent or an electron-donating organic solvent or an organic solvent in which these organic solvents are mixed, (Hereinafter, also referred to as partial hydrolyzate 2) obtained by at least partially hydrolyzing the compound and then adding at least one kind of the Group 3B element compound represented by the general formula (2) or (3) And an electron donating organic solvent in a mixed solvent of an organic solvent and another kind of organic solvent. This composition is also included in composition 3B.

As a concrete example of the partial hydrolyzate 2, the following composition e can be mentioned.

Composition e:

The organic zinc compound represented by the formula (1) is added to a mixed organic solvent containing 3 to 90% by weight of an electron donating organic solvent for an organic solvent different from the electron donating organic solvent and the electron donating organic solvent, The organic zinc compound is at least partially hydrolyzed, and then the organic zinc compound is added to the solution of the compound of Formula 2 or 3 And at least one kind of a Group 3B element compound represented by the following formula (1).

(v) reacting at least one of the organozinc compound represented by the following formula (1) and the group 3B element compound represented by the following formula (2) or (3) with an electron donating organic solvent, an organic solvent different from the electron donating organic solvent, (Hereinafter, also referred to as a partial hydrolyzate 3) obtained by at least partially hydrolyzing at least the organic zinc compound by adding water to a solution obtained by dissolving the organic zinc compound in a mixed organic solvent, In a mixed solvent with an organic solvent different from the organic solvent. This composition corresponds to composition 3D.

[Chemical Formula 1]

R ¹ -Zn-R ¹

(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)

(2)

Wherein M is a Group 3B element and R ² , R ³ and R ⁴ are independently hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a straight or branched alkoxy group having 1 to 7 carbon atoms, An acyl group or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)

(3)

M _c X _d揃 aH ₂ O

(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.)

In the composition of the present invention, an organic solvent mixed with an electron-donating organic solvent, an electron-donating organic solvent and another kind of organic solvent is used as the organic solvent.

The present inventors have found that by using such a solvent, a zinc oxide thin film having an average transmittance of 80% or more and having conductivity can be formed.

The content of the electron-donating organic solvent in the mixed organic solvent is preferably in the range of 3 to 90% by weight from the viewpoint of obtaining the effect of the present invention.

The electron-donating organic solvent preferably has a boiling point of 230 ° C or lower, and in addition to the composition 1, the electron-donating organic solvent has solubility in the organic zinc compound represented by the formula (1) Zinc compounds and 3B group element compounds represented by the general formulas (2) or (3); those having solubility in organic hydrocarbons represented by the general formula (1) and water, partial hydrolyzates 2 and 3 , The organic zinc compound, the group 3B element compound represented by the general formula (2) or (3), and water. Examples of such organic solvents include tetrahydrofuran (boiling point: 66 ° C), di-n-butyl ether (boiling point: 142.4 ° C), dihexyl ether (boiling point: 226.2 ° C), anisole (boiling point: 153.8 ° C) 172 ° C), butyl phenyl ether (boiling point 210.3 ° C), pentyl phenyl ether (boiling point 214 ° C), methoxy toluene (boiling point 171.8 ° C), benzyl ethyl ether (boiling point 189 ° C) Glycine such as trol (boiling point 206.7 占 폚), trioxane (boiling point 114.5 占 폚), 1,2-diethoxyethane (boiling point 121 占 폚) and 1,2- dibutoxyethane Diglyme such as bis (2-methoxy ether) ether (boiling point: 162 ° C), bis (2-ethoxy ether) ether (boiling point: 188.4 ° C) , Triglyme such as 2-bis (2-methoxyethoxy) ethane (boiling point 216 ° C) and bis [2- (2-methoxyethoxyethyl)] ether (boiling point 275 ° C) , Tri-n-propylamine (boiling point 150 to 156 占 폚), tri-n- Amine type solvents such as pentylamine (boiling point 130 캜), N, N-dimethylaniline (boiling point 193 캜), N, N-diethylaniline (boiling point 217 캜), and pyridine (boiling point 115.3 캜). As the electron donative organic solvent, 1,2-diethoxyethane (boiling point 121 캜), which is a kind of glyme, is preferable from the viewpoints of both inhibition of the gel at the preparation of the composition and volatility of the solvent itself. The upper limit of the boiling point of the electron-donating organic solvent is not particularly limited, but it is preferably 230 ° C or less from the viewpoint that the drying time is relatively short when the solvent is removed after coating the obtained composition to form a coating film.

In the present invention, the electron-donating organic solvent as the solvent is characterized by using an organic solvent different from the electron-donating organic solvent.

The organic solvent different from the electron-donating organic solvent is not particularly limited so long as it dissolves each component of the composition containing the compositions 1 and 2 and the partial hydrolyzate 1, 2 and 3 of the present invention, A hydrocarbon compound which is an organic solvent widely used can be used. The hydrocarbon compound is preferably a straight chain, branched hydrocarbon compound or cyclic hydrocarbon compound having 5 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, an aromatic hydrocarbon compound having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, For example.

Specific examples of these hydrocarbon compounds include pentane, n-hexane, heptane, isohexane, methylpentane, octane, 2,2,4-trimethylpentane (isooctane), n-nonane, , Aliphatic hydrocarbons such as eicosane, methylheptane, 2,2-dimethylhexane and 2-methyloctane, alicyclic hydrocarbons such as cyclopentane, cyclohexanemethylcyclohexane and ethylcyclohexane, aliphatic hydrocarbons such as benzene, toluene, xylene, cumene, Aromatic hydrocarbons such as trimethylbenzene, mineral spirits, absorbent naphtha, kerosene, petroleum ether and the like.

From the viewpoint that the drying time when the solvent is removed after coating the obtained composition to become a coating film is relatively short, there is no particular limitation on the upper limit of the boiling point of the organic solvent or the hydrocarbon compound of the kind other than the electron- It is preferably 230 deg.

The concentration of the compound represented by the formula (1) in the solution obtained by dissolving the compound represented by the formula (1) in the electron-donating organic solvent or the mixed organic solvent containing the electron-donating organic solvent is preferably 4 to 12 mass% Is preferably in the range of When the concentration of the compound represented by the above formula (1) is less than 4% by mass and more than 12% by mass even when using an electron donating organic solvent having a boiling point of 110 ° C or higher, formation of a zinc oxide thin film having desired transparency and conductivity It tends to be difficult. The concentration of the compound represented by the general formula (1) in the solution dissolved in the organic solvent is preferably in the range of 6 to 10 mass%.

In the compositions 1 and 2 of the present invention, the organic zinc compound and / or the Group 3B element compound are dissolved in a mixed solvent of an electron-donating organic solvent and an electron-donating organic solvent.

The composition containing the partial hydrolysates 1, 2 and 3 is a composition in which a partial hydrolyzate is dissolved in a mixed solvent of an electron-donating organic solvent and an electron-donating organic solvent and a different organic solvent. In these compositions, the electron-donating organic solvent is preferably 3 to 90% by weight. The content of the electron-donating organic solvent is more preferably 10 to 90% by weight from the standpoint of stability of the composition.

The composition in which the electron donating organic solvent and the electron donating organic solvent are dissolved in a mixed solvent with an organic solvent other than that of the electron donating organic solvent is not limited to a composition which is directly dissolved or reacted as described above, , Or after addition of the above-mentioned Group 3B element compound or the like to the partial hydrolyzate obtained by hydrolyzing the organozinc compound or water thereof with an organic solvent other than the electron-donating organic solvent and the electron-donating organic solvent, The composition of the present invention can be prepared by arbitrarily adding it to adjust its composition.

The molar ratio of the water to the organic zinc compound in the partial hydrolyzate 1 or 2 is in the range of 0.05 to 0.8, and in the partial hydrolyzate 3, the molar ratio of the organic zinc compound to the total amount of the 3B group compound is It is preferable that the thickness is in the range of 0.05 to 0.8. By setting the amount of water to be in this range, the reaction product containing the partial hydrolyzate obtained in the spin coating method, dip coating method and spray pyrolysis can form a transparent and conductive zinc oxide thin film.

For example, when the amount of water added is 0.4 or more, an organic zinc composition containing a product obtained by partially hydrolyzing an organic zinc compound at a high yield of 90% or more based on the zinc contained in the raw material can be obtained. In the partial hydrolyzate 3, an appropriate amount of the Group 3B element compound is partially hydrolyzed. The amount of water to be added is set to 0.4 or more at a molar ratio. In the case of the partial hydrolyzate 1 or 2, the residual amount of the organic zinc compound as the unreacted raw material is set to be the same as the amount of the organic zinc compound and the Group 3B element compound The residual amount can be suppressed. The addition of water at a molar ratio of 0.8 or less can suppress the generation of gel during the hydrolysis reaction. When a gel is generated during the hydrolysis reaction, the viscosity of the solution increases, and subsequent operations may become difficult. The upper limit of the molar ratio of addition of water is preferably 0.8, more preferably 0.75 from the above viewpoint.

Control of the addition amount of this water makes it possible to control the physical properties such as viscosity and boiling point of the composition. For example, the coating which is difficult to carry out the reaction such as the spin coating method can facilitate the film formation by increasing the addition amount of water. In addition, in the spraying method or the like, the present invention It is possible to perform film formation reflecting the reactivity of the organic zinc compound itself such as film formation at a low temperature.

As for the partial hydrolyzate 2, since water is added to the organozinc compound and then the Group 3B element compound is added, the added water is consumed for hydrolysis of the organozinc compound, and then the amount of the Group 3B element compound Is added, the product usually does not include the hydrolyzate of the 3B group element compound. The possibility that the group 3B elemental compound is not hydrolyzed, is contained as a raw material, or that the organic group of the organic hydrolyzate of the organic zinc compound and the organic group (ligand) of the Group 3B element compound are exchanged have. In the partial hydrolyzate 3, water is added to a mixed solution of the organozinc compound and the Group 3B element compound, so that the product usually includes a hydrolyzate of the 3B group element compound. The hydrolyzate of the Group 3B element compound may be a partial hydrolyzate depending on the amount of water added and the like.

The addition of the compound may be carried out using water alone without mixing the water with another solvent, or by using a mixed solvent obtained by mixing water with another solvent. From the viewpoint of suppressing the progress of local hydrolysis, it is preferable to use a mixed solvent. The content of water in the mixed solvent may be, for example, in the range of 1 to 50 mass%, preferably 2 to 20 mass% %to be. The solvent which can be used for the mixed solvent with water can be, for example, the above electron-donating organic solvent. The electron-donating organic solvent may be an organic solvent having a boiling point of 110 ° C or higher or an organic solvent having a boiling point of lower than 110 ° C. However, from the viewpoint of being inert to diethylzinc and having high water solubility, it is preferable that the organic solvent has a boiling point of less than 110 占 폚.

The addition of water depends on the scale of the reaction, but for example, it takes 60 seconds to 10 hours to carry out the reaction. From the viewpoint that the yield of the product is good, it is preferable to add the organic zinc compound of the formula (1) as a starting material by dropwise adding water or a mixed solvent with water. The addition of water can be carried out without stirring (in a stationary state) or with stirring a solution of the compound represented by the general formula (1) and the electron-donating organic solvent. The temperature at the time of the addition may be any temperature between -90 and 150 캜. -15 to 30 캜 is preferable in view of the reactivity of water and the organic zinc compound.

After the addition of water, the reaction of water with the compound represented by the formula (1) and the compound represented by the formula (2) or (3) or the reaction between water and the compound represented by the formula (1) Without stirring (in a stationary state) or stirring. At 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 캜 from the viewpoint of obtaining the partial hydrolyzate in high yield. The reaction pressure is not limited. Normally, it can be carried out at normal pressure (atmospheric pressure). The progress of the reaction between water and the compound represented by the formula (1) can be monitored by sampling the reaction mixture, analyzing the sample by NMR or IR, or sampling the generated gas, if necessary.

The organozinc compound represented by Formula 1,

The Group 3B element compound represented by Formula 2 or 3 is the same as the organozinc compound represented by Formula 1 and the Group 3B element compound represented by Formula 2 or 3 in the first embodiment of the present invention, See the description in the first aspect of the present invention.

In the compositions 2 and 3 and partial hydrolyzates 2 and 3 of the present invention, the molar ratio of the organozinc compound represented by the formula 1 to the organozinc compound represented by the formula 2 or 3 is preferably 0.005 - 0.1 is appropriate from the viewpoint of obtaining a zinc oxide thin film in which the effect of addition of the Group 3B element is adequately expressed. However, in the partial hydrolyzate 2, water is added to a solution containing an organic zinc compound to obtain a partial hydrolyzate, and the 3B group compound is further added at the above-mentioned molar ratio. In the partial hydrolyzate 3, water is added to a solution containing the organozinc compound and the Group 3B element compound at the above-mentioned molar ratio to obtain a partial hydrolyzate.

The organic solvent, the organic zinc compound of Formula 1 as a raw material, and the mixed solvent with water or water can be introduced into the reaction vessel according to any conventional method.

Such a reaction process may be any one of a batch operation type, a half batch operation type and a continuous operation, and is not particularly limited, but a batch operation type is preferable.

By the reaction, the organozinc compound of Formula 1, the Group 3B element compound of Formula 2 or 3, or the organozinc compound of Formula 1 are partially hydrolyzed by water and the product containing partial hydrolyzate Can be obtained.

It is presumed that the main component of the product is a compound represented by the formula 4 shown in the explanation of the first embodiment of the present invention in the partial hydrolyzate 1 or 2 or a mixture of a plurality of compounds having different p in the formula 4.

In the partial hydrolyzate 3, the compound represented by the formula (5) and the compound represented by the formula (6) shown in the first embodiment of the present invention may be combined with the structural unit represented by the formula (7) It is assumed to be a mixture.

In the case of the partial hydrolyzate 2 in which the 3B group element compound is not present at the time of hydrolysis of the organic zinc compound, after completion of the reaction, the composition is prepared by adding the 3B group compound of the above formula 2 or 3. The addition amount of the Group 3B element compound is suitably 0.005 to 0.09 with respect to the addition amount of the organic zinc compound as described above.

After completion of the hydrolysis reaction, a part or the whole of the product can be recovered and purified by a general method such as filtration, concentration, extraction, or column chromatography. When a Group 3B element compound is added after completion of the hydrolysis reaction, a part or all of the product can be recovered and purified by filtration. When the organic zinc compound of the formula (1) remains in the reaction product, it may be recovered or recovered by the above-mentioned method.

The solution prepared by the above method can be used as it is as a coating solution for forming a zinc oxide thin film. Alternatively, the solution may be diluted or concentrated appropriately. However, from the viewpoint of simplifying the production process, it is preferable that the solution prepared by the above method is a concentration that can be used as a coating solution for forming a zinc oxide thin film.

[Manufacturing method of zinc oxide thin film]

The zinc oxide thin film manufacturing method of the present invention is a method of applying the above composition 3A, 3B, 3C or 3D onto the surface of a substrate, and then heating the resulting coating film to obtain a zinc oxide thin film. More specifically, in the manufacturing method of the present invention, one of the compositions 3A to 3D is applied to the substrate surface in an inert gas atmosphere, and then the operation for heating the obtained coating is performed at least once . The application and the heating operation of the obtained coating material can be carried out appropriately in order to obtain desired physical properties such as conductivity, but it is preferably 1 to 50 times, more preferably 1 to 30 times, still more preferably 1 10 times, and so on. When the application is performed by, for example, a spin coating method, a dip coating method, or a spray pyrolysis method, a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light and having conductivity can be formed.

Application to the surface of the substrate can be carried out by conventional means such as dip coating method, spin coating method, spray pyrolysis method, ink jet method, and screen printing method.

The composition is applied to the surface of the substrate under an atmosphere of an inert gas such as nitrogen in an atmosphere of air containing a large amount of water vapor and a high relative humidity and in a reducing gas atmosphere such as hydrogen, Or in a mixed gas atmosphere thereof, or under atmospheric pressure or under pressure.

The spin coating method or the dip coating method may be carried out under an inert gas atmosphere or by mixing an inert gas and water vapor in an atmosphere having a relative humidity of 2 to 15%.

The spray pyrolysis method is a method which can be carried out while heating the substrate. Therefore, the solvent can be dried in parallel with the application, and in some cases, heating for solvent drying is unnecessary. Depending on the conditions, in addition to the drying, the reaction of the partial hydrolyzate of the organic zinc compound to zinc oxide may proceed at least partially. For this reason, the zinc oxide thin film can be formed more easily by heating to a predetermined temperature, which is a subsequent step. The heating temperature of the substrate may be, for example, in the range of 50 to 550 占 폚.

The spray pyrolysis method can be carried out by using the spray film forming apparatus shown in Fig. For the description of the drawings, see the first embodiment.

Spraying of the coating liquid is carried out by discharging the coating liquid so that the size of the liquid droplets is in the range of 1 to 15 mu m in the spray nozzle and further performing the distance within 50 cm between the spray nozzle and the substrate, Is preferable from the viewpoint of being able to produce a zinc oxide thin film.

Considering the adhesion to the substrate and the ease of evaporation of the solvent, it is preferable that the size of all droplets discharged from the spray nozzle is in the range of 1 to 30 mu m. The size of the droplet is more preferably in the range of 3 to 20 mu m.

The distance between the spray nozzle and the substrate is preferably within 50 cm, considering that the solvent evaporates slightly from the spray nozzle until reaching the substrate and the size of the droplet decreases. The distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint that the formation of the zinc oxide thin film can be favorable.

In the spray pyrolysis method, it is preferable from the viewpoint of forming a zinc oxide thin film having a lower volume resistivity to promote the decomposition of the composition by introducing water vapor from the water vapor introduction tube 6 in an inert gas atmosphere. For example, the amount of water vapor to be introduced may be different depending on whether the composition to be supplied contains partial hydrolyzate (partial hydrolyzate 1 to 3) or partial hydrolysis (composition 1 to 2) Is preferably from 0.1 to 5 in terms of the molar ratio to the zinc in the supplied composition and more preferably from 0.3 to 2 from the viewpoint of obtaining a zinc oxide thin film having a lower volume resistivity.

The method of introducing water vapor can be introduced into the zinc oxide thin film production container according to all the conventional methods. The water vapor and the composition are preferably reacted in the vicinity of the heated substrate, and for example, an inert gas containing water vapor produced by bubbling water with an inert gas is introduced from a pipe near the heated substrate.

After coating the surface of the substrate with a coating solution, the substrate is heated to a predetermined temperature as required, the solvent is dried and then heated to a predetermined temperature to form a zinc oxide thin film.

The temperature at which the solvent is dried may be, for example, in the range of 20 to 200 占 폚, and may be set in a timely manner depending on the kind of coexisting organic solvent. The heating temperature for zinc oxide formation after solvent drying is, for example, in the range of 50 to 550 占 폚, preferably in the range of 50 to 500 占 폚. It is also possible to perform solvent drying and zinc oxide formation simultaneously by making the solvent drying temperature and the subsequent heating temperature for forming zinc oxide the same.

If necessary, the above heating is carried out in an atmosphere of an oxidizing gas such as oxygen under a reducing gas atmosphere such as hydrogen in a plasma atmosphere of hydrogen, argon, oxygen, or the like to promote the formation of zinc oxide, It is also possible to improve. The thickness of the zinc oxide thin film is not particularly limited, but it is preferably in the range of 0.05 to 2 탆 in practical use. According to the above production method, in the case other than the spray pyrolysis method, the coating (drying) heating is repeated one or more times to appropriately produce a thin film having the above-mentioned film thickness.

The zinc oxide thin film formed by the above production method varies depending on the application method and subsequent drying conditions and heating conditions. The volume resistivity is the resistance per unit volume, which can be obtained by multiplying the surface resistance by the film thickness. The surface resistance is measured by, for example, the 4-probe method, and the film thickness is measured by, for example, SEM measurement, a stylus type step film thickness meter or the like. Since the volume resistivity varies (increases) with the degree of formation of zinc oxide upon application of the spray or after the application, the volume resistivity is preferably controlled so that the volume resistivity of the thin film becomes a desired resistance value, And time) is preferably set.

The zinc oxide thin film formed by the above production method preferably has an average transmittance of 80% or more with respect to visible light, and more preferably has an average transmittance of 85% or more with respect to visible light. The " average transmittance to visible light " is defined and measured as follows. The average transmittance for visible light is the average of the transmittance of light in the range of 380 to 780 nm and is measured by an ultraviolet visible spectrophotometer. The average transmittance to visible light can also be expressed by showing the transmittance of visible light at 550 nm. The transmittance to visible light changes (increases) by the degree of formation of zinc oxide upon application of the spray or after application, so that the transmittance of the thin film to visible light is 80% or more, It is preferable to set the post-heating condition (temperature and time).

The material used as the substrate may be that of the first embodiment.

[Use of zinc oxide thin film]

Since the zinc oxide thin film produced by the above method has excellent transparency and conductivity, it can be used as an antistatic film, an ultraviolet ray blocking film, a transparent conductive film or the like. The antistatic film can be used, for example, in the field of building materials such as solid electric field capacitors, chemical amplification resistors, and glass windows. The ultraviolet screening film can be used in, for example, fields such as a front filter of an image display apparatus, an imaging apparatus such as a drive recorder, a lighting apparatus such as a high-pressure discharge lamp, a building material such as a cover glass for a clock, Further, the transparent conductive film may be formed of a material such as an FPD, a resistive film touch panel, a capacitive touch panel, a thin film silicon solar cell, a compound (CdTe, CIS) thin film solar cell, It is available in the field. However, it is not intended to be limited to these fields.

(Example)

 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The preparation of the product including partial hydrolyzate from all the organic zinc compounds and the film formation using the same were carried out under a nitrogen gas atmosphere controlled in water, and all of the solvents were dehydrated and deaerated.

[Example 1-1]

1.5388 g of a 1,2-diethoxyethane solution in which 0.1879 g of indium triisopropoxide and 0.1579 g of gallium triisopropoxide were dissolved and a product obtained by hydrolysis of diethyl zinc and water at O / Zn = 0.6 (molar ratio) 1.0986 g of a 1,2-diethoxyethane solution (Zn = 3.85 wt%) was mixed at room temperature and further diluted with 6.2633 g of 1,2-diethoxyethane to prepare a composition so as to obtain IGZO as a composite oxide. The molar ratio of each element of the composition is In: Ga: Zn = 1: 0.99: 1.01. This composition is intended to form InGaZnO ₄ as IGZO from a generally constant ratio.

[Example 1-2]

1.5713 g of a 1,2-diethoxyethane solution in which 0.1807 g of indium triisopropoxide and 0.1612 g of gallium triisopropoxide were dissolved and a product obtained by hydrolyzing diethyl zinc and water at O / Zn = 0.6 (molar ratio) (Zn = 3.85 wt%) were mixed at room temperature, and further diluted with 6.3026 g of 1,2-diethoxyethane to prepare a composition so as to obtain IGZO as a composite oxide. The molar ratio of each element of the composition is In: Ga: Zn = 2: 2.16: 1. This composition is intended to form In ₂ Ga ₂ ZnO ₇ as IGZO from a generally constant ratio.

[Example 1-3]

0.9093 g of a 1,2-diethoxyethane solution in which 0.1280 g of indium triisopropoxide and 0.0933 g of gallium triisopropoxide were dissolved and 0.9093 g of a product obtained by hydrolyzing diethyl zinc and water with O / Zn = 0.6 (molar ratio) (Zn = 3.85 wt%) were mixed at room temperature, and further diluted with 3.6529 g of 1,2-diethoxyethane to prepare a composition so as to obtain IGZO as a composite oxide. The molar ratio of each element of the composition is In: Ga: Zn = 1: 0.86: 4.73. This composition is intended to form InGaZn ₅ O ₈ as IGZO from a generally constant ratio.

[Example 1-4]

1.576 g of a 1,2-diethoxyethane solution in which 0.1741 g of indium triisopropoxide and 0.1607 g of gallium triisopropoxide were dissolved and 1.5659 g of a product obtained by hydrolyzing diethyl zinc and water at O / Zn = 0.6 (molar ratio) 1.0816 g of a 1,2-diethoxyethane solution (Zn = 3.85 wt%) was mixed at room temperature and further diluted with 6.2927 g of toluene to prepare a composition so as to obtain IGZO as a composite oxide. The molar ratio of each element of the composition is In: Ga: Zn = 1: 1.09: 1.07. This composition is intended to form InGaZnO ₄ as IGZO from a generally constant ratio.

[Example 1-5]

1.5424 g of a 1,2-diethoxyethane solution in which 0.1724 g of indium triisopropoxide and 0.1583 g of gallium triisopropoxide were dissolved and a product obtained by hydrolysis of diethyl zinc and water at O / Zn = 0.6 (molar ratio) 0.5140 g of a 1,2-diethoxyethane solution (Zn = 3.85 wt%) was mixed at room temperature and again diluted with 6.2895 g of toluene to prepare a composition so as to obtain IGZO as a composite oxide. The molar ratio of each element of the composition is In: Ga: Zn = 1: 1.09: 0.51. This composition is intended to form In ₂ Ga ₂ ZnO ₇ as IGZO from a generally constant ratio.

[Example 1-6]

0.9112 g of a 1,2-diethoxyethane solution in which 0.1185 g of indium triisopropoxide and 0.0935 g of gallium triisopropoxide were dissolved and a product obtained by hydrolyzing diethyl zinc and water at O / Zn = 0.6 (molar ratio) (Zn = 3.85 wt%) were mixed at room temperature, and further diluted with 3.6729 g of toluene to prepare a composition so as to obtain IGZO as a composite oxide. The molar ratio of each element of the composition is In: Ga: Zn = 1: 0.93: 5.09. This composition is intended to form InGaZn ₅ O ₈ as IGZO from a generally constant ratio.

[Example 1-7]

1.9881 g of a 1,2-diethoxyethane solution in which 0.1746 g of indium triisopropoxide and 0.1511 g of gallium triisopropoxide were dissolved and 1.2981 g of a 1,2-diethoxyethane solution of zinc diethyl (Zn = 3.706 wt%) 1.2243 g were mixed at room temperature and again diluted with 4.4200 g of toluene to prepare a composition so as to obtain IGZO as a composite oxide. The molar ratio of each element of the composition is In: Ga: Zn = 1: 1.02: 1.16. This composition is intended to form InGaZnO ₄ as IGZO from a generally constant ratio.

[Example 1-8]

The product-containing coating liquid obtained in Example 1-1 was filtered with a membrane filter to be used for coating film formation. The solution obtained by filtration was a slightly yellowish almost colorless transparent solution. This product-containing coating solution was coated on the surface of a 18 mm square Corning 1737 glass substrate by a spin coat method. Thereafter, the substrate was heated at 300 DEG C for 5 minutes to dry the solvent and to form a composite oxide. The above operation was repeated five times again. The film thickness of the obtained thin film was 188 nm, and the total transmittance was 96% with respect to 550 nm, as compared with the analysis by SEM. In addition, the product-containing coating liquid was applied onto the surface of a Corning 1737 glass substrate of 18 mm square by a dipping method. Thereafter, the substrate was heated at 300 DEG C for 5 minutes to dry the solvent and to form a composite oxide. The above operation was repeated five times again. The transmittance of the obtained thin film was 94%.

[Example 1-9]

The solution obtained in Example 1-4 was coated by spin coating at 300 ° C in the same manner as in Example 1-8. The transmittance of the obtained thin film was 96% with respect to 550 nm.

[Example 1-10]

The solution obtained in Example 1-6 was coated by spin coating at 300 ° C in the same manner as in Example 1-8. The transmittance of the obtained thin film was 81% with respect to 550 nm. Observation of the obtained thin film by SEM revealed that the film thickness was 333 nm. X-ray diffraction analysis, and peaks at which 2? = 30 to 38 占 and 50 to 68 占 could be regarded as a wide amorphous substance were confirmed.

[Example 1-11]

The solution obtained in Example 1-7 was coated by spin coating at 300 ° C in the same manner as in Example 1-8. The transmittance of the obtained thin film was 84% with respect to 550 nm. The obtained thin film was observed by SEM, and the film thickness was found to be 207 nm. X-ray diffraction analysis was carried out to confirm peaks that can be considered to be amorphous over a wide range of 2? = 30 to 38 占 and 50 to 68 占.

[Comparative Example 1-1]

In Example 1-1, indium acetylacetonite was used instead of indium triisopropoxide, gallium acetylacetonate was used instead of gallium triisopropoxide, and zinc acetate was used in place of diethyl zinc, and 2-methoxyethanol , And ethanol amine as a preparation, and a coating liquid having the same composition was prepared.

The obtained coating liquid was subjected to film formation at 300 ° C in the same manner as in Example 1-8 to obtain a thin film. The visible light transmittance at 550 nm was 60% and only an opaque thin film having a transmittance of 80% or less could be obtained. Further, the obtained film was cloudy and uneven.

[Example 2-1]

To 30.0 g of 1,2-diethoxyethane, 2.60 g of diethyl zinc was added. After sufficiently stirring, it was cooled to 12 캜. A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of diethylzinc to water was 0.2. Thereafter, the temperature was raised to room temperature (22 ° C), the reaction was allowed to proceed at room temperature for 18 hours, and the reaction was carried out so as to have a molar ratio of 0.02 to the diethylzinc of trimethyl indium. The solution thus obtained was filtered with a membrane filter to obtain 33.1 g of a partial hydrolyzate solution containing indium (concentration: 7.9 mass%). NMR (THF-d8, ppm) measurement after removal of the solvent and the like by vacuum drying gave the spectrum of Fig.

The product-containing coating solution containing the partial hydrolyzate obtained as described above was applied onto the surface of a Corning 1737 glass substrate of 18 mm square by the spin coating method. Thereafter, the substrate was heated at 350 DEG C for 5 minutes to dry the solvent and to form zinc oxide. The above operation was repeated five times again. The analysis results of the formed thin film are shown in Table 1 (the same as Examples 2-1 to 2-8).

[Example 2-2]

To 30.0 g of 1,2-diethoxyethane, 2.60 g of diethyl zinc was added. After sufficiently stirring, it was cooled to 12 캜. A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of water to diethyl zinc was 0.39. Thereafter, the temperature was raised to room temperature (22 ° C), the reaction was allowed to proceed at room temperature for 18 hours, and the reaction was carried out so as to have a molar ratio of 0.02 to the diethylzinc of trimethyl indium. The solution thus obtained was filtered with a membrane filter to obtain 33.3 g of a partial hydrolyzate solution containing indium (concentration: 7.9 mass%). Using the product-containing coating solution containing the obtained partial hydrolyzate, a zinc oxide thin film was formed in the same manner as in Example 2-1.

[Examples 2-3, 2-4]

The products containing the partial hydrolyzate obtained in Examples 2-1 and 2-2 were each coated on the surface of a 18 mm square Corning 1737 glass substrate by the spin coating method, In the same manner, thin films of zinc oxide of Examples 2-3 and 2-4 were formed.

[Example 2-5]

To 30.0 g of 1,2-diethoxyethane, 2.60 g of diethyl zinc was added. After sufficiently stirring, it was cooled to 12 캜. A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of diethylzinc to water was 0.2. Thereafter, the temperature was raised to room temperature (22 ° C) and the reaction was allowed to proceed at room temperature for 18 hours. The obtained solution was filtered with a membrane filter to obtain 33.1 g of a partial hydrolyzate solution (concentration: 7.9 mass%).

The obtained coating liquid was filled into a spray bottle of the spray-coating apparatus shown in Fig. A Corning 1737 glass substrate of 18 mm square was placed in the substrate holder. Under a nitrogen gas atmosphere, the glass substrate was heated to 200 占 폚. Thereafter, the coating liquid was sprayed at a flow rate of 4 ml / min over the spray nozzle for 8 minutes. The XRD spectrum of the formed thin film is shown in Fig. The formation of zinc oxide was confirmed.

[Example 2-6]

The procedure of Example 2-5 was repeated except that the tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of water to diethylzinc was 0.39 to obtain a partial hydrolyzate solution (concentration: 7.9 mass%) of 33.1 g. NMR (THF-d8, ppm) measurement after removing the solvent and the like by vacuum drying gave a spectrum as shown in Fig. The obtained coating liquid was treated in the same manner as in Example 2-5 by using the spray film forming apparatus of Fig. 1 to obtain a thin film.

[Example 2-7]

To 30.0 g of 1,2-diethoxyethane, 2.60 g of diethyl zinc was added. After sufficiently stirring, it was cooled to 12 캜. A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of diethylzinc to water was 0.2. Thereafter, the temperature was raised to room temperature (22 ° C), and the reaction was carried out at room temperature for 18 hours. Then, the reaction was carried out at a molar ratio of 0.02 to diethylzinc in trimethyl indium. The solution thus obtained was filtered with a membrane filter to obtain 33.1 g of a partial hydrolyzate solution containing indium (concentration: 7.9 mass%).

The obtained coating liquid was operated in the same manner as in Example 2-5 by using the spray film forming apparatus of Fig. 1 to obtain a thin film.

[Example 2-8]

The procedure of Example 2-5 was repeated except that the tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of water to diethylzinc was 0.39, and a partial hydrolyzate solution containing indium (concentration of 7.9 Mass%).

The obtained coating liquid was treated in the same manner as in Example 2-5 by using the spray film forming apparatus of Fig. 1 to obtain a thin film. The XRD spectrum of the thin film is shown in Fig. The formation of zinc oxide was confirmed.

[Comparative Example 2-1]

To 24.12 g of 2-methoxyethanol was added 1.23 g of zinc acetate dihydrate and 0.34 g of ethanolamine as a coagent, and further adding trisacetylacetonate aluminum to the zinc acetate dihydrate at a molar ratio of 0.02, To obtain a coating liquid.

A thin film was obtained in the same manner as in Example 2-1 except that the thus obtained coating liquid was used in air. The visible light transmittance at 550 nm was 75% and only an opaque thin film having a transmittance of 80% or less could be obtained. Further, the film was non-uniform, and no peak derived from zinc oxide was observed in XRD (not shown).

[Comparative Example 2-2]

A coating liquid containing gallium was obtained in the same manner as in Comparative Example 1 except that trisacetylacetonate aluminum was changed to gallium chloride.

The thus obtained coating liquid was subjected to the same operation as in Comparative Example 2-1 to obtain a thin film. In addition, the visible light transmittance at 550 nm was 66%, and only an opaque thin film having a transmittance of 80% or less could be obtained. Further, the film was non-uniform, and no peak derived from zinc oxide was observed in XRD (not shown).

[Comparative Example 2-3]

A coating liquid containing indium was obtained in the same manner as in Comparative Example 2-1 except that trisacetylacetonate aluminum was changed to indium chloride tetrahydrate.

The thus obtained coating liquid was subjected to the same operation as in Comparative Example 2-1 to obtain a thin film. In addition, the visible light transmittance at 550 nm was 71%, and only an opaque thin film having a transmittance of 80% or less could be obtained. Further, the film was non-uniform, and no peak derived from zinc oxide was observed in XRD (not shown).

[Example 3-1]

(Equivalent to 8.0% by weight) of diethyl zinc was added to 51.7 g of a mixed solvent of 30% by weight of tetrahydrofuran and 70% by weight of n-hexane. After sufficiently stirring, trimethyl indium (TMI) was added at a molar ratio of 0.04 with respect to the diethyl zinc loaded, and the obtained solution was filtered with a membrane filter to obtain 56.4 g of a solution containing indium. The spectrum of FIG. 5 was obtained by NMR (THF-d8, ppm) measurement after removing the solvent and the like by vacuum drying.

The coating liquid obtained as described above was filled into a spray bottle of the spray-coating apparatus shown in Fig. A Corning 1737 glass substrate of 18 mm square was placed in the substrate holder. After the glass substrate was heated to 200 캜 in a nitrogen gas atmosphere, nitrogen gas bubbled at 35 캜 water at a rate of 10 ℓ per minute was introduced into the vicinity of the substrate by the water vapor introducing tube 6 to introduce water. Thereafter, the coating liquid was sprayed from the spray nozzle at 4 ml / min for 8 minutes. The size of the liquid droplet ejected from the spray nozzle was in the range of 3 to 20 占 퐉 and the distance between the spray nozzle and the substrate was 30 cm. The analytical results of the formed thin film are shown in Table 2 (same as in Examples 3-1 to 3-17). Further, it was confirmed by XRD (see Fig. 6) to be zinc oxide.

[Example 3-2]

The coating liquid obtained in Example 3-1 was formed in the same manner as in Example 3-1 except that the glass substrate was heated to 300 ° C to form a thin film.

[Example 3-3]

4.5 g (corresponding to 8.0 wt%) of diethyl zinc was added to 51.7 g of a mixed solvent containing 10 wt% of tetrahydrofuran and 90 wt% of n-hexane. After sufficiently stirring, trimethyl indium (TMI) was added at a molar ratio of 0.04 with respect to the diethyl zinc loaded, and the obtained solution was filtered with a membrane filter to obtain 56.4 g of a solution containing indium.

Using the obtained coating liquid, a spray film was formed in the same manner as in Example 3-1 to form a thin film.

[Example 3-4]

A spray film was formed in the same manner as in Example 3-3 except that the heating temperature of the glass substrate was changed to 300 캜 by using the coating liquid obtained in Example 3-3 to form a thin film.

[Example 3-5]

A solution containing 56.4 g of gallium was obtained in the same manner as in Example 3-3 except that trimethylgallium (TMG) was used instead of trimethyl indium (TMI).

Using the obtained coating liquid, a spray film was formed in the same manner as in Example 3-3 to form a thin film.

[Example 3-6]

A spray film was formed in the same manner as in Example 3-5 except that the heating temperature of the glass substrate was changed to 300 캜 by using the coating liquid obtained in Example 3-5 to form a thin film.

[Example 3-7]

An operation was carried out in the same manner as in Example 3-3 except that trimethyl indium (TMI) was replaced with gallium trichloride (GaCl ₃ ) to obtain 56.4 g of a solution containing gallium.

A spray film was formed in the same manner as in Example 3-2, except that the heating temperature of the glass substrate was changed to 300 캜 by using the obtained coating liquid to form a thin film.

[Example 3-8]

(Equivalent to 8.0% by weight) of diethyl zinc was added to 51.7 g of a mixed solvent of 10% by weight of 1,2-diethoxyethane and 90% by weight of n-hexane. After thoroughly stirring, the obtained solution was filtered with a membrane filter to obtain 56.2 g of a solution.

The obtained coating liquid was spray-formed in the same manner as in Example 3-1, except that the heating temperature of the glass substrate was 200 占 폚 to form a thin film.

[Example 3-9]

4.5 g (corresponding to 8.0 wt%) of diethylzinc was added to 51.7 g of a mixed solvent of 10 wt% of tetrahydrofuran and 90 wt% of toluene. After thoroughly stirring, the obtained solution was filtered with a membrane filter to obtain 56.2 g of a solution.

The obtained coating liquid was subjected to spray film formation at 200 DEG C in the same manner as in Example 3-1 to form a thin film.

[Example 3-10]

4.5 g (corresponding to 8.0 wt%) of diethyl zinc was added to 51.7 g of a mixed solvent containing 10 wt% of tetrahydrofuran and 90 wt% of n-hexane. After sufficiently stirring, it was cooled to 12 캜. A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of water to diethyl zinc was 0.3. Thereafter, the temperature was raised to room temperature (22 ° C), and the reaction was carried out at room temperature for 18 hours. Then, trimethyl indium (TMI) was added to the diethyl zinc in a molar ratio of 0.04, and the obtained solution was filtered with a membrane filter And 56.7 g of a solution containing indium were obtained.

The coating liquid obtained as described above was spray-formed in the same manner as in Example 3-1, except that the heating temperature of the glass substrate was 200 占 폚 to form a thin film.

[Example 3-11]

The coating liquid obtained in Example 3-10 was spray-formed in the same manner as in Example 3-2, except that the heating temperature of the glass substrate was 300 ° C to form a thin film.

[Example 3-12]

(Equivalent to 8.0% by weight) of diethylzinc was added to 51.7 g of a mixed solvent of 24% by weight of tetrahydrofuran and 76% by weight of n-hexane. After sufficiently stirring, it was cooled to 12 캜. A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of diethylzinc to water was 0.6. Thereafter, the temperature was raised to room temperature (22 DEG C) and the reaction was allowed to proceed at room temperature for 18 hours. Then, trimethyl indium (TMI) was added to the diethyl zinc to be added in a molar ratio of 0.04. The resulting solution was filtered with a membrane filter And 56.8 g of a solution containing indium were obtained.

The obtained product-containing coating liquid was applied on the surface of a Corning 1737 glass substrate of 18 mm square by a spin coating method. Thereafter, the substrate was heated at 500 DEG C for 5 minutes to dry the solvent and to form zinc oxide. The above operation was repeated five times again. The formed thin film was confirmed to be zinc oxide by XRD (see Fig. 7).

[Example 3-13]

4.5 g (corresponding to 8.0 wt%) of diethyl zinc was added to 51.7 g of a mixed solvent containing 10 wt% of tetrahydrofuran and 90 wt% of n-hexane. After sufficiently stirring, it was cooled to 12 캜. A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of water to diethyl zinc was 0.3. Thereafter, the temperature was raised to room temperature (22 ° C) and the reaction was allowed to room temperature for 18 hours. Then, the solution thus obtained was filtered with a membrane filter to obtain 56.5 g of a solution.

Using the obtained product-containing coating liquid, coating was performed in the same manner as in Examples 3-12 to form zinc oxide.

[Examples 3-14]

 The procedure of Example 3-13 was repeated except that the tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of water to diethylzinc was 0.6, and 56.6 g of a solution was obtained.

Using the obtained product-containing coating liquid, coating was performed in the same manner as in Examples 3-12 to form zinc oxide.

[Example 3-15]

A tetrahydrofuran solution containing 5.0% water was added dropwise so that the molar ratio of water to diethyl zinc was 0.8, and the procedure of Example 3-13 was repeated to obtain 56.8 g of a solution.

Using the obtained product-containing coating liquid, coating was performed in the same manner as in Examples 3-12 to form zinc oxide.

[Examples 3-16]

The procedure of Example 3-10 was repeated to obtain 56.5 g of a solution containing indium, except that the molar ratio of diethyl zinc to trimethyl indium (TMI) was 0.02.

Coating was carried out in the same manner as in Example 3-12 except that the heating temperature of the substrate was changed to 350 캜 by using the coating solution containing the obtained product to form zinc oxide.

[Example 3-17]

Using the product-containing coating liquid obtained in Example 3-16, coating was performed in the same manner as in Example 3-12 to form zinc oxide.

[Referential Example 3-1]

To 24.12 g of 2-methoxyethanol was added 1.23 g of zinc acetate dihydrate and 0.34 g of ethanolamine as a coagent, and further adding trisacetylacetonate aluminum to the zinc acetate dihydrate at a molar ratio of 0.02, To obtain a coating liquid.

A thin film was obtained in the same manner as in Example 3-1 except that the thus obtained coating liquid was used in air. The visible light transmittance at 550 nm was 75% and only an opaque thin film having a transmittance of 80% or less could be obtained. Further, the film was non-uniform, and no peak derived from zinc oxide was observed in XRD (not shown).

[Referential Example 3-2]

A coating liquid containing gallium was obtained in the same manner as in Comparative Example 1 except that trisacetylacetonate aluminum was changed to gallium chloride.

The thus obtained coating liquid was subjected to the same operation as in Reference Example 3-1 to obtain a thin film. In addition, the visible light transmittance at 550 nm was 66%, and only an opaque thin film having a transmittance of 80% or less could be obtained. Further, the film was non-uniform, and no peak derived from zinc oxide was observed in XRD (not shown).

[Referential Example 3-3]

A coating liquid containing indium was obtained in the same manner as in Reference Example 3-1 except that trisacetylacetonate aluminum was changed to indium chloride tetrahydrate.

The thus obtained coating liquid was subjected to the same operation as in Reference Example 3-1 to obtain a thin film. In addition, the visible light transmittance at 550 nm was 71%, and only an opaque thin film having a transmittance of 80% or less could be obtained. Further, the film was non-uniform, and no peak derived from zinc oxide was observed in XRD (not shown).

1: Spray bottle 2: Board holder (with heater)
3: Spray nozzle 4: Compressor
5: alkali-free glass substrate 6: tube for introducing water vapor

Claims (67)

An organozinc compound represented by the following formula 1 or a partial hydrolyzate of the organic zinc compound with water and a partial hydrolyzate of a 3B group compound or a 3B group element compound by water are mixed so that the molar ratio of the Group 3B element to zinc is 0.1 By weight and less than 5% by weight based on the total weight of the composite oxide thin film.
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms) The method according to claim 1,
Wherein the composition further comprises an organic solvent. The method according to claim 1 or 2,
The water partial hydrolyzate of the organic zinc compound is a product obtained by partially hydrolyzing at least the organic zinc compound by mixing the organozinc compound represented by the general formula (1) and water in a molar ratio of 0.05 to 0.8, The partial hydrolyzate of the 3B group element compound by water is a product obtained by partially hydrolyzing at least the 3B group element compound by mixing the 3B group element compound and water in a molar ratio of 0.05-0.8. . The method according to claim 1 or 2,
The water partial hydrolyzate of the organic zinc compound and the partial hydrolyzate of the 3B group element compound by water can be prepared by adding water to the organic zinc compound and the Group 3B element compound in a total amount of the organozinc compound and the Group 3B element compound Is in the range of 0.05 to 0.8, and the resultant product is obtained by partial hydrolysis of the organic zinc compound and the Group 3B element compound. The method according to claim 1 or 2,
Wherein the Group 3B element compound is a Group 3B element compound represented by the following Chemical Formula 2 or 3:
(2)

Wherein M is a Group 3B element and R ² , R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, , Or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)
(3)
M _c X _d揃 aH ₂ O
(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.) The method of claim 2,
Wherein the organic solvent comprises at least one of an electron donor solvent, a hydrocarbon solvent, and a mixture thereof. The method according to claim 2 or 6,
Wherein the organic solvent has a boiling point of 230 캜 or less. The method of claim 6,
The electron donor solvent is at least one selected from the group consisting of 1,2-diethoxytane, tetrahydrofuran, diisopropyl ether, dioxane, and hydrocarbon solvents such as hexane, heptane, octane, toluene, xylene and cyclohexane / RTI > The method according to claim 1 or 2,
Wherein the organozinc compound is diethylzinc. The method of claim 5,
Wherein the Group 3B element compound of Formula 2 is selected from the group consisting of trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trisacetylacetonatalluminium, trisacetylacetonatallarg, trisacetylacetonite And examples of the transition metal compound include indium, aluminum chloride, gallium chloride, indium chloride, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, Lt; RTI ID = 0.0 > gallium < / RTI > The method according to claim 1 or 2,
Wherein the Group 3B element is Ga and In. A composite oxide thin film having an average transmittance of 80% or more with respect to visible light, including a step of applying the composition according to claim 1 or 2 on the surface of a substrate in an inert gas atmosphere and then heating the obtained coating film at least once, ≪ / RTI > The method of claim 12,
Wherein the inert gas atmosphere contains water vapor. 14. The method of claim 13,
Wherein an inert gas atmosphere containing water vapor has a relative humidity of 2 to 15%. A method for producing a composite oxide thin film having an average transmittance of 80% or more with respect to visible light, including spraying the composition of claim 1 or 2 onto a heated substrate surface in an inert gas atmosphere containing water vapor. The method of claim 15,
Wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure. 16. The method of claim 15,
Wherein the heating temperature of the substrate surface is 400 占 폚 or less. 18. The method of claim 16,
Wherein the supply amount of the water vapor is such that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5. An oxide semiconductor film comprising a composite oxide thin film produced by the manufacturing method according to claim 12. (Hereinafter, also referred to as partial hydrolyzate 1) obtained by adding water to a solution obtained by dissolving an organic zinc compound represented by the formula (1) in an electron-donating organic solvent to at least partially hydrolyze the organic zinc compound And the amount of water added ranges from 0.05 to less than 0.4 in terms of the molar ratio of the organic zinc compound to the organic zinc compound.
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms) Water is added to a solution obtained by dissolving at least one kind of an organic zinc compound represented by the following general formula (1) and an electron-borne organic solvent represented by the following general formula (2) or (3) (Hereinafter, also referred to as partial hydrolyzate 2), wherein the molar ratio of the Group 3B element compound to the organic zinc compound is 0.005 to 0.3, and the addition amount of the water Wherein the molar ratio of the organic zinc compound and the Group 3B element compound to the total amount is in the range of 0.05 or more to less than 0.4.
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)
(2)

Wherein M is a Group 3B element and R ² , R ³ and R ⁴ are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, , Or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
(3)
M _c X _d揃 aH ₂ O
(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.) 23. The method of claim 21,
Wherein the product comprises a hydrolyzate of the Group 3B element compound. Water is added to a solution obtained by dissolving the organic zinc compound represented by the formula (1) in an electron-donating organic solvent to at least partially hydrolyze the organic zinc compound, and then the solution of the compound of the group 3B element (Hereinafter, also referred to as partial hydrolyzate 3), and the addition amount of the organic zinc compound is in the range of 0.005 to 0.3, Wherein the molar ratio to the compound is in the range of 0.05 or more to less than 0.4.
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)
(2)

(Wherein M is a Group 3B element and R ² _, R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, An acyl group or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
(3)
McXd · aH ₂ O
(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.) 24. The method of claim 23,
Wherein the product is substantially free of the hydrolyzate of the Group 3B element compound. The method according to any one of claims 20 to 24,
Wherein the concentration of said product ranges from 1 to 30 mass%. The method according to any one of claims 20 to 24,
Wherein said organic zinc compound is a compound wherein R < ¹ > is an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms. The method according to any one of claims 20 to 24,
Wherein the organozinc compound is diethylzinc. The composition according to any one of claims 20 to 24, wherein the composition according to claim 20 is referred to as composition 2A, the composition according to claim 21 is referred to as composition 2B, and the composition according to claim 23 is referred to as composition 2C) Wherein the coating film is applied to the surface of the substrate in an atmosphere of at least one time and then an operation of heating the obtained coating material is performed at least once. 29. The method of claim 28,
Wherein the inert gas atmosphere contains water vapor. 29. The method of claim 29,
Wherein the inert gas atmosphere containing water vapor has a relative humidity of 2 to 15%. 29. The method of claim 28,
A method for producing a zinc oxide thin film, which comprises spraying a heated substrate surface with an inert gas atmosphere containing water vapor. 32. The method of claim 31,
Wherein an inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure. 32. The method of claim 31,
Wherein the heating temperature of the substrate surface is 400 占 폚 or less. 33. The method of claim 32,
Wherein the supply amount of the water vapor is such that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5. 29. The method of claim 28,
Wherein the electron-donating organic solvent has a boiling point of 230 占 폚 or less. An antistatic thin film made of a zinc oxide thin film produced by using the manufacturing method according to claim 28. 29. A UV-blocking thin film comprising a zinc oxide thin film produced by the method of claim 28. A transparent electrode thin film comprising a zinc oxide thin film produced by the manufacturing method according to claim 28. delete delete A partial hydrolyzate obtained by partial hydrolysis of an organic zinc compound represented by the following formula (1) with water, and a mixed organic solvent of an electron-donating organic solvent and an electron-donating organic solvent and other kinds of organic solvents,
The partial hydrolysis of the organic zinc compound represented by the following formula (1) may be carried out by adding an organic zinc compound represented by the following formula (1) to an organic solvent different from the electron-donating organic solvent, And the water is added to the dissolved solution so that the molar ratio of the organic zinc compound to the organic zinc compound is in the range of 0.05 to 0.8 while stirring the solution.
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms) 42. The method of claim 41,
Wherein the mixed organic solvent contains 3 to 90% by weight of the electron-donating organic solvent. delete delete delete In one of the compositions described in the following compositions 3A and 41,
A composition for preparing a zinc oxide thin film, which is obtained by adding a Group 3B element compound represented by the following formula (2) or (3) so that the molar ratio to the organic zinc compound is 0.005 to 0.1.
(Composition 3A is a solution in which an organic zinc compound represented by the following general formula (1) is dissolved in a mixed solvent of an electron-donating organic solvent and an electron-donating organic solvent and a different organic solvent)
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R &^lt; 1 > is a straight or branched alkyl group having 1 to 7 carbon atoms)
(2)

(Wherein M is a Group 3B element and R ² _, R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, An acyl group or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
(3)
McXd · aH ₂ O
(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.) An organozinc compound represented by the following formula (1)
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R < ^{1 >} is a linear or branched alkyl group having 1 to 7 carbon atoms)
A partial hydrolyzate obtained by partial hydrolysis of the organic zinc compound with water, and a partial hydrolyzate obtained by partial hydrolysis of the organic zinc compound with water in a composition containing a Group 3B element compound represented by the following Chemical Formula 2 or 3 at a molar ratio of 0.005 to 0.09 to the organic zinc compound A composition comprising an organic solvent and an organic solvent mixed with an organic solvent different from the organic solvent.
(2)

(Wherein M is a Group 3B element and R ² _, R ³ and R ⁴ independently represent hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkoxyl group having 1 to 7 carbon atoms, An acyl group or an acetylacetonate group, and L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
(3)
M _c X _d揃 aH ₂ O
(Wherein M is a Group 3B element and X is a halogen atom, acetic acid or sulfuric acid, X is a halogen atom or acetic acid, c is 1, d is 3, X is sulfuric acid, c is 2, 3, and a is an integer of 0 to 9.) 48. The method of claim 47,
Wherein the mixed organic solvent comprises 3 to 90% by weight of an electron donating organic solvent. 48. The method of claim 47,
The partial hydrolysis may be carried out by adding an organic zinc compound represented by the formula (1) and a group 3B group represented by the formula (2) or (3) to an organic solvent different from the electron-donating organic solvent, Characterized in that the composition is carried out by adding water to a solution in which the elemental compound is dissolved. 55. The method of claim 49,
The concentration of the organic zinc compound and the Group 3B element compound in an organic solvent different from that of the electron-donating organic solvent or the electron-donating organic solvent or an organic solvent containing them is in the range of 4 to 12 mass% ≪ / RTI > 48. The method of claim 49 or 50,
Wherein the partial hydrolysis is carried out by adding water such that the molar ratio to the organic zinc compound is in the range of 0.05 to 0.8. 47. The method of any one of claims 41, 46 and 47,
Wherein the electron-donating organic solvent has a boiling point of 230 ° C or less. 47. The method of any one of claims 41, 46 and 47,
Wherein the organic solvent different from the electron-donating organic solvent includes at least one of a linear chain, a branched hydrocarbon compound, or a cyclic hydrocarbon compound, an aromatic hydrocarbon compound, and a mixture thereof. 47. The method of any one of claims 41, 46 and 47,
Wherein the organic solvent different from the electron-donating organic solvent includes at least one of hexane, heptane, octane, toluene, xylene, and cyclohexane. 47. The method of any one of claims 41, 46 and 47,
Wherein the organozinc compound is diethylzinc. 47. The method of claim 46 or 47,
Wherein the Group 3B element compound of Formula 2 is selected from the group consisting of trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trisacetylacetonatalluminium, trisacetylacetonatallarg, trisacetylacetonite And examples of the transition metal compound include indium, aluminum chloride, gallium chloride, indium chloride, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, Gt; gallium < / RTI > 47. The method of claim 46 or 47,
Wherein the electron donor organic solvent comprises any one of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, and dioxane. The composition according to any one of the following compositions 3A and 41, 46 and 47, wherein the composition according to claim 41 is referred to as composition 3B, the composition according to claim 46 is referred to as composition 3C, the composition according to claim 47 is referred to as composition 3D Which has an average transmittance of 80% or more with respect to visible light, including the step of coating the surface of the substrate under an inert gas atmosphere and then heating the obtained coating film at least once.
(Composition 3A is a solution in which an organic zinc compound represented by the following general formula (1) is dissolved in a mixed solvent of an electron-donating organic solvent and an electron-donating organic solvent and a different organic solvent)
[Chemical Formula 1]
R ¹ -Zn-R ¹
(Wherein R &^lt; 1 > is a straight or branched alkyl group having 1 to 7 carbon atoms) 64. The method of claim 58,
Wherein the inert gas atmosphere contains water vapor. 55. The method of claim 59,
Wherein the atmosphere of inert gas containing water vapor has a relative humidity of 2 to 15%. A process for producing a zinc oxide thin film having an average transmittance of 80% or more with respect to visible light, including spraying the composition 3A, 3B, 3C, or 3D according to claim 58 on a heated substrate surface in an inert gas atmosphere containing water vapor . 62. The method of claim 61,
Wherein an inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure. 62. The method of claim 61,
Wherein the heating temperature of the substrate surface is 400 占 폚 or less. 63. The method of claim 62,
Wherein the supply amount of the water vapor is such that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5. An antistatic thin film made of a zinc oxide thin film produced by using the manufacturing method according to claim 58. 58. A UV-blocking thin film comprising a zinc oxide thin film produced by the method of claim 58. A transparent electrode thin film made of a zinc oxide thin film produced by using the manufacturing method according to claim 58.

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