TW201109279A - Composition for forming doped or non-doped zinc oxide thin film, and method for producing zinc oxide thin film using same - Google Patents

Abstract

Disclosed is a composition for forming a zinc oxide thin film, which contains an organic zinc compound as a starting material, is not ignitable, and can be easily handled. The composition for forming a zinc oxide thin film is capable of forming a transparent zinc oxide thin film which is not doped or doped with a group 3B element by being heated at 300 DEG C or less. Also disclosed is a method for obtaining a transparent zinc oxide thin film, which is not doped or doped with a group 3B element, using the composition. Specifically, the composition for forming a zinc oxide thin film contains a product which is obtained by partially hydrolyzing an organic zinc compound by adding water to the organic zinc compound or a solution of the organic zinc compound and a group 3B element compound. In cases when a group 3B element compound is contained, the molar ratio of the group 3B element compound to the organic zinc compound is within the range of 0.005-0.3. The composition is applied to a substrate surface and then heated, thereby forming a zinc oxide thin film which is doped with the group 3B element.

Description

201109279 VI. Description of the Invention: [Technical Field] The present invention relates to a composition for producing an oxidized film which is prepared by using an organic zinc compound as a raw material, which is non-flammable and easy to handle, and is used for money. The invention relates to a method for producing an oxidized film, which is capable of forming a transparent oxidation having high transmittance to visible light by heating at a temperature τ of about 纟 atmospheric pressure and at a temperature of 3 以下 or less. A composition for producing an oxide film of a film and a method for producing a zinc oxide film using the composition. Further, the second aspect of the present invention relates to a composition for producing an oxidized film which is prepared by using an organic zinc compound as a raw material, is non-flammable, and is easy to handle, and is doped with A method for producing a zinc oxide film of a steroid element. In particular, the present invention relates to an oxidation of a Group 3B-doped element of a transparent zinc oxide film having a high transmittance for visible light by heating at a pressure of about 3 Torr and a temperature of about 3 Torr. A composition for producing a film and a method for producing a zinc oxide film doped with a Group 3B element using the composition Ο. Further, the third aspect of the present invention relates to a low volume resistivity which can produce an average transmittance of 80% or more for visible light and has a degree of use for an antistatic film, an ultraviolet cut thin film, a transparent electrode film, or the like. A composition for producing a zinc oxide thin film of a zinc oxide film. The composition for producing a zinc oxide thin film of the present invention is prepared by using an organic compound as a raw material, has no ignitability and is easy to handle, and can be provided with a volume resistivity of less than 8xl when used as a spin coating or dip coating raw material.氧化-2 Characteristics of Zinc Oxide Thin Film 147876.doc 201109279 Membrane, when used as a spray pyrolysis coating material, provides a zinc oxide film having a volume resistivity of less than lxio-3. The fourth aspect of the present invention relates to a zinc oxide film having a low volume resistivity of an extent of having an average transmittance of 8% or more for visible light and having an antistatic film, an ultraviolet cut film, a transparent electrode film, or the like. The manufacturing method is further related to an antistatic film, an ultraviolet cut film, and a transparent electrode film produced by using the production method. According to the manufacturing method of the fourth aspect of the present invention, in the case of spin coating or immersion, an oxidized film having a volume resistivity of less than 8 x 1 〇 - 2 〜 m can be obtained, and when it is decomposed by spray heat, it can be obtained. A zinc oxide film having a volume resistivity of less than 1 x 10 3 n.cm. A fifth aspect of the invention relates to a composition for doping a zinc oxide thin film and a method for producing a doped zinc oxide thin film. More specifically, the fifth aspect of the present invention relates to a composition for forming a oxidized film which is doped with a Group 3B element, and a method for producing an oxidized film doped with a Group 3B element. [Prior Art] A transparent zinc oxide film doped with a 3B element or an undoped film having high transmittance for visible light can be used for a photocatalytic film, an ultraviolet cut film, an infrared reflective film, cIGS (copper Indium Ganium Se(6)^, copper indium Magnetic) The buffer layer of a solar cell, an electrode film of a dye-sensitized solar cell, an antistatic film, a compound semiconductor light-emitting element, a thin film transistor, etc., has a wide range of uses. As a method for producing a doped or undoped transparent zinc oxide thin film, various methods (Non-Patent Document 1) are known as 147876.doc 201109279, and as a representative method for using an organic compound as a raw material, there is chemical vapor deposition. (CVD, chemicai V邛deposition) method (Non-Patent Document 2), spray pyrolysis method (Non-Patent Document 3), spin coating method (patent document 丨), dip coating method (non-patent literature sentence coating, etc.) • However, in the chemical vapor deposition (CVD) method, there are the following problems: It is necessary to use a large vacuum container, and the film formation speed is very slow, so that it is manufactured, improved, and, because of the size of the vacuum container. The size of the formed oxidized ruthenium film is limited, and thus it is impossible to form a large one. Compared with the above chemical vapor deposition (CVD) method, the above coating method has the following advantages: high productivity due to simple device and high film formation speed Moreover, the manufacturing cost is also low. Moreover, since it is not necessary to use a vacuum container and is not restricted by the vacuum container, a larger oxidized film can also be produced. In the thermal decomposition method, the solvent is dried while spraying, and then the substrate temperature is heated to 3 6 01 or more to obtain a zinc oxide film coating film. In the above spin coating method or dip coating method, spin coating or dip coating After the solvent is dried, the substrate temperature is heated to 400 t or more, whereby the oxidized film coating film is obtained. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 7-182939 [Non-Patent Document] [Non-Patent Document 1] Japanese Society for the Promotion of Science, Transparent Oxide, Electronic Materials, No. 147876.doc 201109279 166 Committee, Technical Revision of Transparent Conductive Films, 2nd Edition (2006), pl65~173 [Non-Patent Document 2] K. Sorab, Et al. Appl_ Phys. Lett., 37(5), 1 September 1980 [Non-Patent Document 3] J. Aranovich, et al. J. Vac. Sci. Technol., 16(4), July/August 1979 [Non Patent Document 4] Y. Ohya, et al. J. Mater Sci., 4099 (29), 1994 [Disclosure] [The problem to be solved by the invention] Doped or undoped transparent zinc oxide film uses plastic The substrate serves as a substrate. Therefore, the transparent zinc oxide film is used in formation. The heating is carried out at a temperature lower than the heat-resistant temperature of the plastic substrate. However, the above-mentioned non-patent document 3 includes a spray pyrolysis method, a spin coating method described in the patent document, and a dip coating method described in Non-Patent Document 4. The transparent zinc oxide film cannot be obtained by heating below the temperature resistance of the plastic substrate. If the heat resistance temperature of the plastic substrate and the cost required for heating are taken into consideration, the heating required for film formation is desirably below 300 °C. . According to the researcher of the present inventors, the research and development of the temple, and the use of the non-patent document 3, the aqueous solution of acetic acid, and the patent document 1. The dip 4 solution used in the spin coating method, or the non-patent literature 4"\= zinc compound and organic solvent zinc compound and organic, solvent, dip coating method, including organically obtained ml In the following film formation, the method is as follows: a transparent zinc oxide film is obtained, and only an opaque film is obtained. Patent Document 1 also discloses an emulsified (tetra) film. There is a method of using a solution of ethyl zinc in a hospital solution 147876.doc 201109279 Using the solution I tried to make a film below 300t, but I still can't get a transparent oxidized film. In addition, the diethylzinc is a compound that is flammable in the atmosphere and must be paid attention to during storage and use. Therefore, in practical applications. In addition, it is difficult to dilute the diethylation, etc., and it is often used in the environment of the presence of water, which is often used in the hot melt decomposition method of the nozzle, the spin coating method, etc. The diethyl group is used for cold solution in an organic solvent. In this case, it is necessary to reduce the risk of ignitability, etc., but it is necessary to form a film of an oxidized film in which an alcohol-based organic solvent = diethylzinc is dissolved while using a reaction as described in Patent Document 1 Yu Che c. Heating at a temperature higher than the above temperature. It is an object of the present invention to provide a composition for producing an oxidized film which is prepared by using an organic compound as a raw material, but which is ignitable and easy to handle, and can be heated even if heating is required. The transparent oxide film doped with a group 3B element or undoped is formed by heating below 〇〇t. Further, the present invention is to provide a method of using the composition in consideration of the heat resistant temperature of the plastic substrate and The cost of carrying and heating, etc., it is not necessary to add ^ or to heat up to 3 〇〇 t or less to obtain a transparent oxidized thin yttrium. [Technical means for solving the problem] The first aspect of the invention relates to a product for producing a oxidized film, comprising adding water to the solution 81 or the solution 82, and at least hydrolyzing the following organic portion, and the above-mentioned solution (10) The above-mentioned solution 82 is obtained by dissolving the organic compound represented by the following 2 (1) in an electron-donating organic solvent. The organic compound represented by the following formula (1) is 147876.doc 201109279 At least one of the compound and the group 3B element compound represented by the following formula (2) or the following formula (3) is dissolved in an electron-donating organic solvent: R^Zn-R1 (1) (wherein 'R1 is a linear or branched alkyl group with a carbon number of 1 to 7)

McXd.aHaO (2) (wherein, Μ is a Group 3B element, X is a halogen atom, nitric acid or sulfuric acid, and when χ is a functional atom or nitric acid, the lanthanum is 丨, 4 is 3, and when χ is sulfuric acid, cA 2, d is 3, a is an integer of 〇~9) R2TMM-R3 (wherein, Μ is a group 3B element, and R2, R3, and R4 are independently hydrogen or a straight or branched alkyl group of carbon number 7 a linear or branched alkoxy group having a carbon number of 1 to 7, a carboxylic acid group or an acetoacetone group, and further L is a coordinating organic compound containing nitrogen, oxygen or a dish, and η is an integer of 0 to 9) . The first aspect of the present invention is roughly divided into three aspects. The first aspect is a composition for producing an undoped oxidized film and a method for producing a zinc oxide film using the composition. The fl state is obtained by adding the above solution S1, and adding water to the solution S1 in such a manner that the molar ratio of the organic compound is in the range of the money 9 and containing at least partially hydrolyzing the above organic compound. A composition of the product. The composition of the i-th aspect is described below, and the manufacturing method of the correction state is as described in the following b 8 to 1-9. [1-1] A composition for producing a zinc oxide thin film comprising a product produced by the following method 147876.doc 201109279, that is, an organic zinc compound represented by the following formula (1) is dissolved in an electron-donating organic compound In the solution obtained by dissolving the sword, water is added in such a manner that the molar ratio of the organic compound is 0.6 to 〇.9, and the above organic compound is at least partially hydrolyzed: R^Zn-R1 (1) ( Wherein R1 is a linear or branched alkyl group having a carbon number of 丨7 to 7; [1-2] a composition comprising the above-mentioned oxime H separated from the above organic solvent and the above-mentioned electron donating The film having a different organic solvent forms a solution obtained by using an organic solvent. [1-3] The composition of [丨2] wherein the concentration of the above product is in the range of 3 to 12% by mass. [1-1] The composition according to any one of [1-3], wherein the above organic compounding

The compound R1 is a compound having an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. [1-5] The composition according to any one of [1-1] to [1-4] wherein the above organic compound is diethyl zinc. [1-6] The composition according to any one of [1-1] to [1-5], wherein the electron-donating organic solvent is tetrahydronaphthol. [1-7] The composition according to any one of [1-2] to [1-6] wherein the above film is formed using 147876.doc 201109279 The organic solvent is 1,4-dioxane. [1-8] A method for producing an oxidized film, comprising: applying a composition according to any one of [1_1] to [1-7] to a surface of a substrate, and then applying the obtained coating film to 300 C or less Heating is performed at a temperature to form a zinc oxide film. [1-9] The production method according to [1-8], wherein the zinc oxide film has an average transmittance of 80% or more for visible light. The second aspect is a composition for producing an oxidized film doped with a Group 3B element, and a method for producing an oxidized film using the composition. The second aspect is a composition comprising the above product, wherein the addition ratio of the elemental compound in the solution S2 is in the range of 0.005 to 〇·3 with respect to the molar ratio of the above organic compound. And the organic compound is obtained by hydrolysis to the upper part. The composition of the second aspect is described in the following 2_丨~2_1 2 'the second aspect of the production method as described in the following 2-1 3 to 2-14. [2-1] A composition for the production of a doped oxidized film, which comprises a zinc compound of the following formula (1), and a steroid element of the following formula (7) or the following formula (3) At least one of the compounds is dissolved in an electron-donating organic solvent, and water is added to the solution to at least partially hydrolyze the organozinc compound, and the above-mentioned 3 lanthanum compound is relative to the organic compound. The ratio of the ear to 〇〇〇5 to 0 3 is: R 丨-Zn-Ri (1) (wherein R is a linear or branched alkyl group having a carbon number of 77) 147876.doc •10· 201109279

McXd*aH20 (2) (wherein M is a Group 3B element, X is a halogen atom, nitric acid or sulfuric acid. When X is a halogen atom or nitric acid, c is 1, d is 3, and when X is sulfuric acid, c is 2, d is 3, a is an integer from 0 to 9)

I R4 〇 (wherein M is a Group 3B element, R 2 , R 3 , and R 4 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, or a linear or branched alkoxy group having 1 to 7 carbon atoms; And a carboxylic acid group or an acetoacetone group and further L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and η is an integer of 0 to 9). [2-2] The composition according to [2-1], wherein the above product contains the hydrolyzate of the above steroid element compound. [2-3] The composition of [2-1] or [2-2], wherein the amount of water added is relative to the upper layer (3)

The range of 〇.4 to 0.9 in the total amount of the organic compound and the three steroidal compound. [2] A composition for the production of a doped zinc oxide film, which comprises a product of the formula, that is, a solution obtained by supplying an organic solvent to the organic organic solvent represented by the formula (1) After the addition of the complex solution to at least partial hydrolysis of the compound, at least one of the 3 steroid element compounds of the general formula: 5 is added so as to be in a ratio of 〇 to 〇·3 with respect to the above-mentioned machine-zincification ratio. : ) or 147876.doc (i) 201109279 R丨-Zn-R丨 represented by the formula (3) (wherein R1 is a linear or branched alkyl group having 1 to 7 carbon atoms)

McXd.aH20 (2) (wherein Μ is a group 3B element 'X is a halogen atom, nitric acid or sulfuric acid, when X is a halogen atom or a certain acid, 'c is 1, d is 3, when X is sulfuric acid, c 2, d is 3, a is an integer of 0 to 9) R8-M-R3 I * (L) n (3) R4 (wherein Μ is a group 3B element 'R2, R3, R4 are independently hydrogen, carbon a linear or branched alkyl group of 7 or a straight or branched alkoxy group having a carbon number of 1 to 7, a carboxylic acid group or an acetoacetone group, and further L is a complex containing nitrogen, oxygen or phosphorus. The organic compound 'η is an integer from 0 to 9). [2-5] The composition of [2-4] wherein the above product is substantially free of the hydrolyzate of the above-mentioned group element compound. [2-6] The amount is relative to a composition such as U-4] or [2_5], wherein the addition of the above water to the organic zinc compound has a molar ratio of 〇 4 to Q.9. [2-7] The composition of any one of [2 1] to [2-6], 叱, 叱-丹甲上4, and the content of the organic zinc compound is 〇5 mass% [2-8] ] Bu. The composition according to any one of [1] to [2-7], which is obtained by forming a film different from the above-mentioned i-electron organic solvent, and is formed in Table I47876.doc •12·201109279 Solution. [2-9] The composition according to any one of [2-1] to [2-8] wherein the concentration of the above product is in the range of 1 to 30% by mass. [2] The composition according to any one of [2-1] to [2-9] wherein the above-mentioned organozinc compound R1 is a carbon group having 1, 2, 3, 4, 5 or 6 carbon atoms. compound of. [2-11]

The composition of any one of [2-1] to [2-1], wherein the above organic compound is diethyl zinc. [2] The composition according to any one of [2-1] to [2-11] wherein the electron-donating organic solvent is 1,4-bisaki. [2-13] A method for producing a doped zinc oxide film, comprising: applying a composition according to any one of [2-12] to a surface of a substrate, and then applying the obtained coating film to the following Heating is performed at a temperature to form a zinc oxide thin film doped with an element. [2-14] Light has an average transmittance of 80% or more. The third aspect is doped with a composition of 3 lanthanide emulsified fresh ruthenium film. The composition comprising the following products is a product having a boiling point of 110 CU. Electronic organic solvent

A 3 has a boiling point of 1 l 〇 ° C 147876.doc -13- 201109279 The above supply is obtained as power supply. [3-1]

The electronic organic solvent is used as the A-organic organic solvent, and the mixed organic solvent is used to at least partially hydrolyze the organozinc compound. The composition is as described in the following 3-1 to 3-10. The following two products contain a product obtained by dissolving: b) an organic zinc compound having a boiling point of 110. . The above organic solvent point is a concentration of (10) or more in the range of the electron donating range, and the organic solvent is formed in a liquid mixture of 4 to 12% by mass, based on the above-mentioned organic zinc compound. Water is added in a manner of a range of 0.8, and at least the above-mentioned compound is partially hydrolyzed:

Rl; Zn-R, (1) (wherein R is a linear or branched alkyl group having a carbon number of 1 to 7). [3-2] A composition in which the following formula is added in a composition such as [3 - oxime] in such a manner that the molar ratio of the above organozinc compound becomes 0.005 to 〇·1 ( 2) The organic group 3B element compound is obtained: R2—M—R3 ί * (L) n ¢2) R4 (wherein, Μ is a group 3B element, and R2, R3, and R4 are independently hydrogen, carbon number 1 a straight or branched alkyl group of ～7, a linear or branched alkoxy group of carbon number 7, a carboxylic acid, or an acetoacetone group, and L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus. η is an integer of 〇~9). [3-3] J47876.doc -14- 201109279 A composition comprising a product obtained by the following method, that is, an organozinc compound represented by the following formula (1),

Ri-Zn-R1 (1) (wherein, R1 is a linear or branched alkyl group having 1 to 7 carbon atoms), and the following formula (2) is a ratio of the molar ratio of 0.003 to 0.09 with respect to the above organozinc compound. Or the organic 3B group compound shown in (3)

—M—R 3 (L5 η (2) Ο

(wherein, Μ is a 3 steroid element, R 2 , R 3 , and r 4 are independently hydrogen, a linear or branched alkyl group of carbon number 7, a linear or branched alkoxy group having 1 to 7 carbon atoms, a carboxylic acid, Or a acetonyl group, L is a coordinating organic compound containing nitrogen, oxygen, or a can, and η is an integer of 〇~9)

McXd-aH2〇(3) (wherein, Μ is a Group 3B element, X is a halogen atom, a sulphuric acid or a sulfuric acid, and when χ is a Nansin atom or a sulphuric acid, c is i and d is 3, in 乂In the case of sulfuric acid, 2, d is 3, and a is an integer of 〇~9). The total concentration of the organic compound and the organic lanthanum compound is 4, which is dissolved in an electron-donating organic solvent having a boiling point of llGt or more or a mixed-electrolyte solvent containing an electron-donating organic solvent having a point of (10) or more as a main component. In the solution in the range of ～12% by mass, water is added in a range of 4 to G.8 with respect to the molar ratio of the zinc compound, and the organic compound is partially hydrolyzed to J. [3-4] The composition having the above electron donating property as in any one of [3-1] to [3-3] 147876.doc -15- 201109279 The solvent of the solvent is 2303⁄4 or less. [3-5] The composition of any one of [1] to [3, wherein the above organic compound is diethyl. [3-6] The composition of any one of [3-2] to [3_5], wherein the organic Group 3B element compound of the above formula (7) is trimethylindium. [3] The composition according to any one of [2] to [3] wherein the organic 3B group halogen compound of the above formula (2) is aluminum triacetate, gallium triacetate, triethyl S& [3-8] The composition according to any one of [3-2] to [3_5], wherein the organic warfare 70 compound is gasified aluminum, gallium chloride or indium chloride. [3-9] The composition according to any one of [3-1] to [3-8] wherein the electron-donating organic solvent is 1,2-diethoxyethane. [3-10] wherein the above mixed organic solvent is mixed. The composition of any one of [3-1] to [3-8] is 1,2-ethoxylated and tetrahydro-alpha, and the second aspect of the invention is the first aspect of the present invention. A method for producing a 4-state oxide film. In the method for producing a zinc oxide thin crucible according to the second aspect (fourth aspect) of the present invention, the composition of the third aspect of the invention described above is used. The manufacturing method of the second aspect (fourth aspect) of the present invention is as described in 4^: 147876.doc 16-201109279 ι. [4-1] In the above method, the zinc oxide film is visible to the visible light. The manufacturing method includes: i the second resistivity is less than 8 χι°·2

The BiC is operated in the following manner: The following composition of the composition of the eighth, B or C is heated on the inert gas ring coating film; U is applied to the surface of the substrate to obtain the composition A:

The composition contained the product obtained in the following manner, and was dissolved in a boiling point of 110 by the following organic compound. (: The above-mentioned power supply: an organic solvent or a mixed organic solvent containing an electron-donating organic hexaphyrin having a boiling point of H 〇 ° C or more as a main component, and further in the range of 4 to 12% by mass Adding water in such a manner that the molar ratio of the above organozinc compound becomes 〇.40'8, and at least partially hydrolyzing the above organic compound,

Rl-Zn~Rl (1) (wherein R is a linear or branched alkyl group having 1 to 7 carbon atoms); Composition B: 5H composition is in the above composition A to be relative to the above organic The organic group 38 element compound represented by the following formula (2) is added in such a manner that the molar ratio of the zincation & substance is 0.005 to 0.1, and *(L) η (2) R4 (wherein Μ Is a group 3B element, R2, R3, and R4 are independently hydrogen, and the number of carbons is 147876.doc -17- 201109279 linear or branched alkyl group, linear or branched alkoxy group having a carbon number of 77, carboxyl Acid, or acetamyl acetonate, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus 'n is an integer of 〇~9); Composition C: The composition comprises a product obtained in the following manner, ie, An organozinc compound represented by the following formula (1), R 丨-Zn-Ri (1) (wherein R 1 is a linear or branched alkyl group having 1 to 7 carbon atoms), relative to the above organozinc compound The organic 3B group compound M-R3 represented by the following formula (2) or (3) in which the molar ratio is 〇〇〇5 to 〇〇9 (wherein Μ is a 3B group 7C, R2 R3 and R4 are independently hydrogen or carbon number 7 straight chain or a branched alkyl group, a linear or branched alkoxy 'carboxylic acid having a carbon number of 丨7 or a acetylacetone group 'L is a coordinating organic compound containing nitrogen, oxygen, or scales, and η is 〇~9 Integer)

McXd*aH20 (7), nitric acid or sulfuric acid, when X is sulfuric acid for X, C is (wherein, Μ is a group 3B element, and X is a halogen atom or a nitric acid, c is 1, d is 3, 2, d is 3, a is an integer from 0 to 9). The total concentration of the organic zinc compound and the organic warfare element compound is determined by being dissolved in an electron-donating organic solvent having a boiling point of (10) or more, or a mixed organic solvent containing an electron-donating organic solvent having an atomic point of not more than the above. In the solution in the range of 4 to 12% by mass, water is added in such a manner that the molar ratio of the zinc compound of 147876.doc -18 to 201109279 is 0.448, and at least the above organozinc compound is partially hydrolyzed. [4-2] The above-mentioned inert gas ring, such as the zinc oxide film of [4-1], contains water vapor. [4-3] The gas environment is a manufacturing method according to [4-2], wherein the inert humidity of the water vapor is in the range of 2 to 1.5%.

[4-4] A method for producing an oxidized film, the oxidized film having an average transmittance of more than 嶋 for visible light and a volume resistivity of less than 1×10.3 n.cm, the method of manufacturing comprising: combining the compositions A and 8 or. Spraying on the surface of the heated substrate in an inert gas atmosphere containing water vapor; Composition A: The composition contains the product obtained in the following manner, and is expressed in the following formula (1) The compound is dissolved in a power supply having a boiling point of 1 UTC or more: an organic solvent, or a mixed organic solvent containing an electron-donating organic/grain agent having a point of 11 G ° C or more as a main component, and is in the range of 4 to 12% by mass. In the solution, water is added in such a manner that the molar ratio of the above organic compound is in the range of 〇.4 to 0.8, and at least the above organozinc compound is partially hydrolyzed, R^Zn-R1 (1) (wherein R1 is carbon a linear or branched alkyl group of ～7; Composition B: 147876.doc • 19-201109279 The composition is in the above composition A, and becomes 〇〇 with respect to the molar ratio of the above organozinc compound. Adding the ratio of 〇5 to 〇1 as an organic 3B group compound represented by the following formula (2), and obtaining R2 to M~R;

R (L) η ¢2) (wherein, Μ is a 3 steroid element, r2, R3, and R4 are independently hydrogen, a linear or branched alkyl group having a carbon number of 丨7, a linear chain having a carbon number of 丨7 or a branched alkoxy group, a carboxylic acid, or an acetoacetone group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and η is an integer of 〇~9); Composition C: The composition is as follows The product obtained by the method is an organic compound represented by the following formula (1), R'-Zn-R1, (1) (wherein R1 is a linear or branched alkyl group having 1 to 7 carbon atoms) An organic 3B group compound (2) represented by the following formula (2) or (3) in which the molar ratio of the above organic compound is 〇〇〇5 to 〇〇9

R (L) η (wherein 'Μ is a 3 Β element, r2, r3, is a nitrogen, a carbon number η is a straight or branched chain alkyl group, a carbon number is 7 straight or branched chain oxy, rebellion Acid 3, brewing acetone SL is a complex organic compound containing nitrogen, oxygen, or a mixture. The substance 'η is an integer of 〇~9)

McXd*aH2〇(,, > (3) "' Μ is a 3B group element, χ is a halogen atom, nitric acid or sulfuric acid, at: 147876.d〇c •20- 201109279 when it is a halogen atom or nitric acid, 'C is 1, d, 2, dh. d is 3, when X is sulfuric acid, c is 2 d is 3, a is an integer of 〇~9). The above-mentioned organic compound is dissolved in a power supply having a boiling point of 1 HTC or more, a *electrolytic organic solvent, or a mixed organic solvent containing an electron-donating organic solvent as a main component at a concentration of 11 〇 ° C or higher. In the solution of the range of 4 to 12% by mass of the human body, * # a /, organic 3 ugly compound, the molar ratio of the compound is 〇.4~〇乂„ Water is added in a manner of Nu, , and 8, and the above organic compound is partially hydrolyzed by Ο 乂 to 。. [4-5] A method for producing an oxidized film containing water vapor and an inert gas containing water vapor The environment is formed by supplying water vapor to the vicinity of the surface in the atmosphere or under the enthalpy. 攸[4-6] The temperature of the manufacturing of the zinc oxide thin layer is 40 (TC or less. ^The heating of the surface of the board [4 -7] a method for producing a zinc oxide thin smear according to [4·5] or [4·6], wherein the supply of the water sputum gas is based on the supplied water in the above composition The ratio of zinc is in the range of 0.1 to 5. [4-8] As in [4 1] to [4·7], the zinc oxide thin In the production method, the electron-donating organic solvent has a hysteresis of 23 or less. [8-9] The composition of the cup-τ5 in [4-1] to [4-8], wherein the organic辞合合147876.doc •21· 201109279 The substance is diethyl. [4-1〇] The organic 3B group of any of the above formula (2) [4-1] to [4-9] [4- 11) The method for producing a zinc oxide film, wherein the elemental compound is trimethyl indium. The organic 3B group of the general formula (2) of the oxidized film of any one of [4-Π to [4-9] The elemental compound is gallium acetyl acetonate or indium acetoacetate. The method for producing the zinc oxide film of any of the three items: The method for producing the above-mentioned organic group 3B element compound is a method for producing a zinc oxide film of gasification|g, gallium hydride, or galvanic acid [4-13], such as [4-!] to [4_12] The above-mentioned electron-donating organic solvent is U-diethoxyethane. Human [4-14] The mixed organic solvent in any one of [4-1] to [4-12] is hydrazine, 2- Solvent. Method for producing zinc oxide film, diethoxyethane and tetrahydrofuran Any one of [4-15], an electrostatic film comprising a zinc oxide film produced by using the manufacturing method of [Call to [14]. [4-16] An ultraviolet (C) film comprising A zinc oxide film produced by the method of manufacturing the article, i.S., pp. -22, 201109279 [4-17] A transparent electrode film comprising the use of /, I 3 1 such as [44] to [414 A zinc oxide film produced by the manufacturing method of any one of the methods. The third aspect of the present invention is a method for producing a zinc oxide thin film forming composition according to the fifth aspect of the present invention, and a zinc-based zinc thin film doped with a 3B group element. The zinc oxide thin film-forming composition of the third aspect (the fifth aspect) of the present invention and the method for producing a zinc oxide thin film doped with a three-lane element are as described in the following % 1 to 5-11. 5-1 [5-1] A composition for forming an oxidized film, which comprises an organozinc compound represented by the following formula (1) and a formula (20) represented by the following formula (20) in an organic solvent having electron-donating properties. An organic 3 steroid element compound, and the molar ratio of the above organic 3 lanthanum element compound to the above organozinc compound is 0.001 to 0.3; R^Zn-R1 (1)

(wherein 'R1 is a linear or branched thio group having 1 to 7 carbon atoms)

Rzo-M-R30 (2 0)

I R40 (wherein Μ is a Group 3B element, r2〇, r3〇&r4〇 is independently a 氲' or a linear or branched alkyl group having a carbon number of 1 to 7). [5-2] The composition of [5-1], wherein the above 3] group 3 element is B, A 仏 or In 〇 [5-3] 147876.doc -23- 201109279, such as [5-1] or [5-2] The composition of the above-mentioned organozinc compound, wherein is an ethyl group, the compound of the above organic group 3B element, wherein μ is aluminum, and R 2 〇, r30 and R40 are each an ethyl group. [5-4] The composition of [5-1] or [5-2] wherein, in the above organozinc compound, ^ is ethyl', the above organic group 3B element compound, M is gallium, r2〇, r3〇 And R40 is a methyl group. [5-5] The composition of [5-^15-2] wherein, in the above organic compound, ^ is an ethyl group, and in the above organic group 3B element compound, M is indium, and r2〇 and R40 are both methyl groups. . [5-6] wherein the above organic zinc compound is 15 mass. /. the following. The composition of the combination of any one of [5-1] to [5-5] and the organic Group 3B compound in a concentration of [5-7], such as [5-1] to [5-6 Any one of isopropyl _. Wherein the above organic solvent is a method for producing a film of [5-8], characterized in that a zinc oxide doped with a Group 3B element is: under atmospheric pressure or under pressure,

The following beauty, "庳nr 隹 隹 衩 衩 、 、 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 且 TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC TC Forming a doped material 5.9堂 [5.9] $常常之#U匕 zinc film. As in [5_8] manufacturing method, the coating composition of the above composition will be 147876.doc -24- 201109279 from the spray nozzle When the droplet size is in the range of 1 to 30 μm, the distance between the spray nozzle and the substrate is set to be within 50 cm. [5-10] Manufactured as [5-8] or [5-9] The method wherein the ambient temperature of the mouth coating is 40 ° C or less. [5-11] The manufacturing method of any one of [5_8] to [5-10], the table & The film has an average transmission of 80% or more for visible light, and has a surface resistance of Ιχίο5 Ω/□ or less. [Effect of the Invention] The zinc oxide film of the first aspect of the present invention is free from ignitability. It is easy to handle, and if the composition for producing a oxidized film of the present invention is used, the film can be formed at a temperature of 300 ° C or less and under the sound of ▲ 。 A transparent oxide film can be produced. The composition for producing a zinc oxide film doped with a working element of the second aspect of the present invention is non-flammable, easy to handle, and is oxidized by using the 3B group halogen of the present invention. Zinc film system

Looking for a joint exhibition & use composition, even at 300 〇C to resign the film. The composition of the zinc oxide film for the third aspect of the present invention is oxidized by a transparent doping element, and the composition for producing a zinc oxide film according to the third aspect of the present invention has an average of 80% or more for visible light in the spin coating method or the dip coating method. The oxidized film having a transmittance of I# _ Φ I and a soil resistivity of less than 8χ1〇-2 Ω·ειη. In addition, if the composition for the production of the oxidized film produced by Estonia is used in the spray pyrolysis method, the transmittance of the film is 80% or more for the visible light, and the transmittance of the sentence is 80% or more. And a zinc oxide film having a volume resistivity not exceeding the characteristics of W_3. The method for producing a zinc oxide film according to the fourth aspect of the present invention can produce an average transmittance of visible light and a volume resistivity of less than 8 χΐ〇 2 in the spin coating method. The zinc oxide thin film according to the present invention, in the spray pyrolysis method, can produce an average transmittance of more than 8% by weight for visible light and has a volume resistivity of less than lxl0-3n. Oxidation film of the characteristics of cm. The emulsified zinc film of ITO and ITO is excellent in transparency as described above, and can be applied to an antistatic film, an ultraviolet cut film, a transparent electrode film, and the like. The inventors have attempted to use a film such as a τ method: the patent document contains a solution of a compound of a group 3B element and an organic zinc compound == 丨 Non-patent document 2 contains a solution containing an organic compound and a solution of (4) The coating method and the non-patent documents 3 and 4 use the compound of the group (qua) group element and the solution of acetic acid to thermally decompose A1. ^, when using the spin coating method, dip coating method, only the volume resistivity can be obtained: the zinc oxide film of the second or wider, and only the volume resistivity can be obtained in the nozzle thermal decomposition method. Thin: The method obtains a thin film of oxidation with a lower resistance. Further, in the spray pyrolysis method, when the system is produced, only the volume resistivity is two: the film: the oxidation resistance is lower than the lower resistance: Attempts have been made to prepare media using a spin coating method using a solution in which a diethylation is partially hydrolyzed to a composition of 147876.doc -26 - 201109279 or a composition of a 3 steroidal elemental synthesis:::::::: : : A zinc oxide film having an average transmittance above 嶋 (Second aspect 2: The volume resistivity of the oxidized film obtained in the examples is lx10: cm or more 'in order to obtain a zinc oxide film having a lower electric resistance, A hydrazine containing a partial hydrolyzate prepared by partial hydrolysis of diethyl = organozinc compound in an organic solvent higher than the organic solvent of the second aspect

And , and an oxidized sputum film having an average transmittance of 8% or more for visible light, and a low volume resistivity which can be used for an antistatic film or the like, according to the fifth aspect of the present invention. For example, a doped zinc oxide thin film forming composition capable of obtaining a zinc oxide thin film doped with a 3 lanthanum halogen having a mean transmittance to visible light can be provided. 8透明% or more of transparency and surface resistance of 1XU) 5 Ω/□ or less. Further, according to the present invention, the following method can be provided. The composition can be obtained by the following method: no heating is required for film formation, or heating can be carried out by heating to produce an oxidation word of a doped 3 lanthanum element having the above transparency and low electrical resistance. film. [Examples] [The composition for producing a zinc oxide thin film (first aspect)] The composition for producing a zinc oxide thin film of the present invention contains a product (hereinafter sometimes referred to as a partially hydrolyzed product) which is produced by the following method. The zinc oxide film is made of 2D', and the organozinc compound represented by the general formula (1) is dissolved in the electron-distributing organic solvent, in order to reversal with respect to organic 147876.doc -27- 201109279 The organic zinc compound is at least partially hydrolyzed by adding water in such a manner that the molar ratio of the compound becomes 〇·6 to 〇9:

Rl'Zn-Rl (1) (wherein R1 is a linear or branched alkyl group having 1 to 7 carbon atoms). The organic compound represented by the formula (1), for example, Shisen Mianyang, Takeda Shingen, Tsuruta Fu 1 Gonghua 964〇66), 1967, Japanese Patent Special Day (4)-fine 99, Japanese Patent (4) (4)·66 Office Use it: % oxypropylene burning polymerization catalyst. When used as a polymerization catalyst for epoxidizing, the organic zinc composition is added with water to form a partial hydrolyzate so that the molar ratio of the organozinc compound is 1 Torr or more. However, in the above document, 'the reaction product of the compound obtained by adding water in such a manner that the molar ratio of the organic morphing person becomes 0.6 to 〇·9 is less than 縦〇 Under the addition of temperature; the transparent emulsified film 'is neither documented nor implied. As a result of research by the inventors et al., it is clear that as long as the water is in the range of 0.6 to 0.9 with respect to the organic rheme and the molar ratio, the obtained partially-read 2^ product can be shaped under the heating of the following temperature: Word film. By making the molar ratio 〇.6 based on the rolling word, the high-yield (4) or higher can be used to form the π»-semi-organic organozinc composition contained in the raw material, and the unreacted raw material is a general formula. (1) The residue of the organic compound can be inhibited by making the molar ratio 〇·9 or less and suppressing the generation of gel in the reaction. The electron-donating organic solvent is soluble in the organic substance and water. Yes, as an example, η 不 的 辞 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二 二An ether solvent such as dimethyl ether or triethylene glycol dimethyl ether; an amine solvent such as dimethylamine, triethylamine or triphenylamine. As the solvent having electron donating property, tetrahydrofuran is preferred. Specific examples of the alkyl group represented by R1 of the compound represented by the above formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group; a base group; a second butyl group; Third butyl, pentyl, isopentyl, neopentyl, third pentyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and anthracene

G heptyl. The compound represented by the formula (1) is preferably a compound wherein the carbon number of r1 is 2, V4, 5 or 6. The compound represented by the formula (1) is particularly preferably an ethyl group. The composition of the present invention comprises a partial hydrolyzate produced by the following method, that is, a solution of the compound represented by the formula (1) and an electron-donating organic solvent, and the above-mentioned molars are added. The above compound is at least partially hydrolyzed. The concentration of the chemical compound of the formula (1) and the solution of the compound of the formula (1) in the solution of the electron-donating organic solvent is appropriately determined in consideration of the solubility in the solvent, etc., for example, suitably 2 to 50% by mass. range. will! The addition of = can be carried out without mixing water with other solvents, or by mixing other solvents in the mold water. The addition of water can also be carried out, for example, from the viewpoint of a good yield of 6 sec to 10 hours. In the case of the organozinc compound of the formula (1); the compound & τ represented by the above formula (1) as a raw material is not used (stirring of the solution of the organic solvent in a standing state) It can be carried out on one side. When adding, the degree of dish can be selected from _90 to 15 (arc. Any temperature.) From the viewpoint of the reactivity of water with organozinc I47876.doc •29·201109279, it is preferable that - 15~5t. After the addition of water, in order to carry out the reaction between water and the compound represented by the formula (1), for example, in the case of residual mixing (in a state of standing), it is left for 1 minute, or when it is mixed. It can be reacted at any temperature ≤ between rc. From the viewpoint of obtaining a partial hydrolyzate in a high yield, it is preferably 5 to 80 ° C. The reaction pressure is not limited. Regarding water and the formula (1) The reaction of the illustrated compound can be carried out as needed by the reaction of the fiber (one nucleus magnetic resonance:: infrared spectroscopy, or by sampling the generated gas. The above organic solvent, An organic reincarnation person of the above formula (1) as a raw material, And the water can be introduced according to all conventional methods, and is also introduced as a mixture with a solvent. The reaction steps can be any one of a batch operation type, a semi-batch operation type, and a continuous operation type, and are not particularly limited. Preferably, the batch operation formula is obtained by the above reaction, wherein the organozinc compound of the above formula (1) is at least partially hydrolyzed by water to obtain a product comprising a partial hydrolyzate. In the case of ethyl zinc, the analysis of the product obtained by the reaction with water has been carried out since the beginning, but the results vary from report to report, and the composition of the product is not clearly determined. The addition of the water to the molar ratio, the reaction time, etc., is presumed to be a mixture of 1 to several of the compounds of the compound represented by the following formula (2) in the present invention: (2) R^-Zn-CO-ZnJm-R1 147876.doc •30- 201109279 (wherein R is the same as R1 in the general formula (1), m is an integer from 2 to 20). From (4), concentration, extraction, column chromatography, etc. % can be partially recovered or purified from the above-mentioned product. The organic compound 2 of the formula (1) remaining as a raw material in the reaction product can also be recovered by the above method, preferably by recovery. The composition recovered by the above method from the electron-donating organic solvent can also be dissolved in a thin layer different from the electron-donating organic solvent used in the reaction.

G film formation is performed with an organic solvent to prepare a coating solution. Further, it is also possible to form a coating solution by directly or appropriately adjusting the reaction mixture to the mixture of the power supply organic solvent without using the surface. The film-like organic solvent which is different from the organic solvent to be used in the reaction is, for example, preferably a solvent of the above. The reason is that since the Buddha's point is relatively high, the volatility is low, so that the solvent can be evaporated during the cloth operation, and the coating film becomes dry, which deteriorates the workability. Examples of Luozhizhi include aliphatic pentane solvents such as pentane, hexanehexane, octane, and petroleum hydrazine, and benzene, toluene, and aristocracy. Light, ethyl alcohol di- gamma ether, diethylene dimethyl ether, diethylene glycol dimethyl ether, diazane 'tetrahydrofuran and other ether solvents, = face look - methylamine, triethylamine, triphenyl The base 2 η can be used alone or in combination. ^ ^ ^ ^ ^ Α Right, considering the solubility of the reaction product of the Hu boring hydrolyzate in the portion containing the above-mentioned reaction product 3, and the volatility of the organic granule itself, as an organic solvent for film formation I47876.doc 201109279 Preferred is 1,4-dioxane, methyl monoethylene glycol dioxime ether, ethyl monoethylene glycol monomethyl ketone 'methyl diethylene glycol dimethyl hydrazine. The solid content concentration of the composition for forming a zinc oxide thin film can be arbitrarily selected in the range of 1 to 30% by mass. The higher the concentration, the smaller the number of times the coating can be produced. If the solubility of the reaction product containing the partial hydrolyzate of the organic compound and the ease of formation of the transparent zinc oxide film are considered, it is preferably 3~ 12% by mass. [Method for Producing Zinc Oxide Thin Film (First Aspect)]

The present invention relates to a method of producing an oxidized film. This production method includes applying the composition for forming a zinc oxide thin film of the present invention to the surface of a substrate, and then heating the obtained coating film to a temperature of 3 Torr (>c or less to form an oxidized film. , -, in the soil / A ^ ^ / 3⁄4. Shell powder method of inkjet method 'screen printing method and other conventional methods to implement. Spray heat can Φ heating the substrate _ surface coating method can therefore be at the same time The solvent is dried, and the root 摅 is very conditional, and there is also no need to dry after coating; the heating of the granules is >&

And, depending on the conditions, there is also a case where, in addition to drying, at least part of the reaction of the partial hydrolyzate of the organozinc compound is pushed. Since m m ^ 1 is also easier to carry out the post-step heating with a specific temperature & S ^ φ 7 into a thin film of zinc oxide. The twisting temperature of the substrate in the spray solution is also in the range of 5 〇 to 250 ° C, for example. And s things in the air environment of the substrate surface, containing a large nitrogen gas (four) gas environment, the relative humidity of the water vapor, oxygen and other oxidizing gas environment u,, the degree of work ^ wind 荨 荨 reducing gas environment 147,876 .do<-32- 201109279 These are mixed gas environments, etc., under ambient conditions and at atmospheric pressure or under pressure. The product of the composition of the present invention reacts slowly with the moisture in the environment and is therefore preferably decomposed in an inert gas atmosphere free of moisture. Further, the coating in the method of the present invention can also be carried out under reduced pressure, but it is also simpler in terms of equipment at atmospheric pressure, and thus is preferable. After coating the coating liquid on the surface of the substrate, set the substrate to a specific temperature as needed.

The solvent is dried and then heated at a specific temperature to form a zinc oxide film. The temperature at which the solvent is dried may be, for example, 2 G to fine. The range of c can be set as appropriate according to the type of organic solvent that is present. After the solvent is dried, it is used for the shape: the heating temperature of the emulsification is, for example, 20 to fan. The range of C is preferably in the range of 50 to 25 〇C, more preferably 10 〇 to 200. . The scope. It is also possible to make the solvent drying temperature the same as the heating temperature for forming the oxidized word, while performing solvent drying and zinc oxide formation. If necessary, the above addition may be carried out by using an oxidizing gas such as oxygen, a chlorine gas = a reducing gas atmosphere, hydrogen, argon, oxygen or the like (4): promoting zinc oxide formation or improving crystallinity. The film of zinc oxide film According to the special system of the road, it is better to use the range of 〇·05~2(4). The film of the film thickness in the above range can be suitably produced by repeating the above coating (drying) heating by 1 ^. The oxidized film formed by the production method of the present invention preferably has an average transmittance of more than 85 Å, more preferably an average transmittance of visible light. The "average transmission of visible light 147876.doc -33·201109279 rate" is defined and measured as follows. The average transmittance for visible light refers to the average transmittance of light in the range of 380 to 780 nm, which can be measured by an ultraviolet-visible spectrophotometer. Furthermore, the average transmittance of visible light can also be expressed by the transmittance of visible light of 5 5 〇 nm. Since the transmittance to visible light varies (increases) depending on the degree of formation of zinc oxide due to heating during spraying or after coating, it is preferable to make the transmittance of the film to visible light 8 〇. The heating conditions (temperature and time) at the time of spraying or after coating are set at % or more. In the first aspect of the present invention, for example, a substrate can be used as a transparent substrate film, and the transparent substrate film can be a plastic film. The polymer forming the plastic film can be exemplified by polyester (for example, polyethylene terephthalate (pET), polyethylene naphthalate (PEN), poly(methyl) propionate (for example, polydecyl). Methyl acrylate (PMMA), polycarbonate (PC), polystyrene, polyvinyl alcohol, polyethylene, polyvinylidene chloride, polyethylene, cyclic polyolefin (c〇p), ethylene vinyl acetate Ester copolymer, polyurethane, triacetate, celecoxime. Among them, PET, PEN, Pc, PMMA are preferred. The transparent substrate film may be non-extended depending on the type of polymer. The film may also be a stretched film. For example, a 1 Θ θ film such as a PET film is usually a biaxially stretched film, and a ruthenium film, a acetamidine film, a cellophane film or the like is usually a non-stretched film. (3) A composition for producing a zinc oxide thin film of a ternary element, wherein the composition for producing a zinc oxide thin film doped with a three-dimensional element of the second aspect of the invention includes: (1) an organic compound represented by the following formula (1), a solution 82 in which at least one of the compounds of the Group 3B element represented by the following formula (7) or (7) is dissolved in an electron-donating organic solvent a product obtained by at least partially hydrolyzing the above-mentioned organic compound l47S76.doc-34-201109279 (hereinafter sometimes referred to as partial hydrolyzate 1); or (ii) by using the above formula (1) The organic compound compound is dissolved in a solution towel made of an electron-donating organic solvent, and the organic zinc compound is at least partially hydrolyzed by adding water, and then the group 3B element represented by the above formula (2) or (3) is added. A product obtained by at least a compound of the compound (hereinafter sometimes referred to as a partial hydrolyzate 2): R^Zn-R1 (1) Ο 〇 (wherein, R is a linear or branched alkyl group having 1 to 7 carbon atoms)

McXd.aH20 (7) (弋中Μ is 3 B known element, X is a halogen atom, acid or sulfuric acid, when X is a south atom or nitric acid, (: is 1, (1 is 3, when χ is sulfuric acid, £ is 2, d is 3 ' a is an integer from 0 to 9) H2~M~R3 ' *(L) b (8) (wherein, Μ is a 3B group element, and R2, R3, and R4 are independently hydrogen and carbon number a linear or branched alkyl group of 7 or a linear or branched alkoxy group having a carbon number of 丨7, a carboxylic acid group, or an acetoacetone group, and further [coordination containing any one of nitrogen, oxygen, and phosphorus The organic compound, b is an integer of 〇~9.) In the case of the partial hydrolyzate 1, since the water is added to the mixed solution of the organozinc compound and the 3b-based halogen compound, the above product usually contains the above-mentioned Group 3B element. a hydrolyzate of the compound. The hydrolyzate of the compound of the 3B group element may be a partial hydrolyzate depending on the amount of addition of water, etc. Further, in the case of the partial hydrolyzate 2, a 3B group element is added after adding water to the organozinc compound. a compound, so it depends on the amount of water added, etc., and the water added by 147876.doc •35- 201109279 is hydrolyzed by the organic compound In the case where a compound of a 3B group element is added later, the above product usually does not contain the hydrolyzate of the above-mentioned 3B group octyl compound. The 3B group element compound may also have the following possibility: without the hydrolysis, it may be contained in the state of the raw material. The organic group (coordination) of the 3B group octyl I compound and the organic hydrazine exchange (coordination exchange) of the partial hydrolyzate of the organozinc compound. In the case of partial hydrolysis, the molar ratio of the above-mentioned organic zinc compound to the compound of the compound is set to be in the range of .4 to .9. Further, in the partial hydrolyzate; When the amount of the water added is in the range of 0.4 to 0.9 with respect to the organic compound compound, it is preferred to combine the water with respect to the organic compound and the organic 3β group element. Or the molar ratio of the addition of the organozinc compound is limited to "the range of two. By setting the molar ratio to 0.4 or more, the zinc contained in the raw material can be obtained in a high yield of 90% or more based on the zinc contained in the raw material. The organic zinc composition of the product obtained by partial hydrolysis of the compound. Further, in the case of partial hydrolysis, the '3 B group elemental character, the θθ a I mouth is also partially hydrolyzed. When the ratio is 0.4 or more, when the partial hydrolyzate E is dissolved in a clear form, the residual amount of the unreacted raw material, that is, the organic zinc compound, and the 3B private compound can be suppressed, and in the case of the partial hydrolyzate 2 The residual amount of the organic zinc compound can be permanently preserved, and as a result, a safely operable tool, an "organic zinc composition" can be obtained. Further, by making the molar ratio 0.9 or less, it is possible to shoot a report, and the gentleman l The gel is inhibited in the hydrolysis reaction. If a gel is produced in the hydrolysis reaction, there is a case where the solubility rises and the subsequent operation becomes difficult. The addition of water to the molars is better in the range of 〇.6~0.8, and better 147876.doc -36- 201109279 is the range of 0.6~0.75. The organic solvent is an organic compound represented by the formula (1): a compound of the formula (7) or (7), a compound of the group 3B and water, and is exemplified by diethyl ether and N-propyl ether, diisopropyl sulphate: dibutyl hydrazine, tetrahydro hydrazine, second burning, ethylene glycol dimethyl diene, diethylene glycol monomethyl ether, diethylene glycol dimethyl mystery and other key solvent, three An amine solvent such as methylamine, triethylamine or triphenylamine. As the solvent having electron donating property, tetrahydrogenated biting and two punctures are preferred.有机 有机 The organozinc compound represented by the above formula (1) is the same as those described in the above-mentioned work-bearing bear of the present invention. μ As a specific example of the metal represented by (10) in the compound of the third element represented by the above formula (2), B'.Ga, In can be mentioned. Specific examples of the salt represented by the shirt include chlorine, bromine, iodine, nitric acid, sulfuric acid, and scaly acid. Specific examples of the Group 3B element compound represented by the formula (2) include boron chloride, aluminum chloride hexahydrate, aluminum nitrate nonahydrate, gallium chloride, gallium nitrate hydrate, and indium chloride tetrahydrate. Indium nitrate pentahydrate. Specific examples of the metal represented by M in the group 3B element compound represented by the above formula (3) include B, A, Ga, and In. Further, R2, Rs, and Rule 4 are preferably hydrogen. Or R2, R3, and the ruler 4 are also preferably a specific example of the alkane, which may be exemplified by methyl, ethyl, propyl, isopropylisobutyl, t-butyl, tert-butyl, pentyl, Isoamyl, neopentyl, third amyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. It is also preferred that at least R 2 , R 3 , and 4 are hydrogen, and the rest are alkyl. As a ligand represented by L, there can be mentioned: dimethyl 147876.doc -37- 201109279 amine, triethylamine, triphenylamine, η than bite, imiline, N, N-dimethylamine , N,N-diethylaniline, triphenylphosphine, dimercaptosulfur, diethyl ether, tetrafuran. The compound of the Group 3B element represented by the formula (3) is particularly exemplified by: a sinter, a sinter-tetrahydrocarbamate complex, a borax-trimethylamine complex, and a roast-triethylamine. Complex, triethylborane, tributylborane, hydrogenated-trimethylamine complex, aluminum hydride-triethylamine complex, trimethylaluminum, hydrogenated dimethylaluminum, three Isobutyl aluminum, diisobutyl aluminum hydride, trimethyl gallium, triethyl gallium, trimethyl indium, triethyl indium. Particularly preferred in terms of being inexpensive and readily available are triethyl aluminum, triisobutyl aluminum, trimethyl gallium, and trimethyl indium. In the composition of the present invention, the organic compound represented by the above formula (1) and the compound of the above formula (2) or the group 3B are added to the k3B of the above formula (7) or (3). The molar ratio of the group element compound to the organic compound is 〇.005~〇3. When the amount of the Group 3B element compound added is too large, the film properties tend to be deteriorated as an impurity, and therefore the ratio is preferably a ratio. The partial hydrolyzate is obtained by adding water to the solution containing the organic compound and the cyclamate compound. Further, in the case of a part of water (4), water is added to a solution containing an organozinc compound to obtain a P-knife hydrolyzate, and a decarbamate compound is added in the above molar ratio. a compound represented by the above formula (1) and a compound represented by the above formula (7) or (3) in which the compound is dissolved in the electron-donating organic solvent, and the compound represented by the formula 3B is represented by the formula (1) The total concentration of the group-primary compounds represented by the formula (2) or (3) is determined by the dissolution of 147876.doc-38·201109279, etc., as appropriate. (4) The composition is at least surrounded by the organozinc compound of the above formula (1). After the hydrolysis of the 3B7t compound of the above formula (7) or (7) is carried out, the compound shown is dissolved in the above-mentioned electron-donating organic: = liquid, and sincerely? 1. π - W is dissolved, and - solution (4) The concentration of the compound is not considered in the solvent.适 0.1 50 0.1 to 50% by mass of the 关于 About the addition of water, can not ^ This Ο 〇 J does not mix water with other solvents: water and other solvents mixed. The addition of water also depends on: the inverse:: mode, for example, can take between 60 seconds and 10 hours. In view of the fact that the yield of the product is good, it is preferable that "(1), a good squid is added by adding water to the organic compound of the above formula () as a raw material. The addition of water may be incorrect. It is carried out with a solution of an electron-donating organic solvent (four), or it can be carried out while mixing. When adding, the dish can be selected at any temperature between .Hot. The reactivity of water with organic chemistry & In view of the above, it is preferred that _丨5~3 is dying. After the addition of water, in order to carry out water and the compound represented by the formula (1) and the compound represented by the formula (7) or (3), or water and The reaction of the chemical substance represented by the formula (1), for example, is left without stirring (in a state of standing) for i minutes to 48 = or stirring. The reaction temperature may be any temperature between _9 〇 and 15 〇. The reaction is preferably from 5 to 80 ° C in terms of obtaining a partial hydrolyzate in a high yield. The reaction pressure is not limited. It can be usually carried out under normal pressure (atmospheric pressure). About water and formula (1) The reaction of the indicated compound = row, the reaction mixture can be sampled if necessary, by *N Ml^iiR et al. 147876.doc •39· 201109279 samples were analyzed and controlled. Or by sampling the generated gas, the organic solvent was supervised, and the oxygen was used to make the above formula (1). The organic zincified person and the water can be introduced into the reaction vessel according to all the conventional sigma and the method used by the force member, and the mixture of the solvent and the solvent can be used as a batch operation method. The semi-batch is selected as + 'φ ΛΛ, , σ . Any one of the man-made and continuous operation modes, and is particularly limited, and is preferably a batch operation type. And... By the above reaction, the organic compound of the above formula (1) The zinc compound and the steroidal element of the above formula (2) or (3) a 铷 通 通 通 Ιέά 或者 或者 或者 或者 或者 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或 或Obtaining a product containing a partial hydrolyzate. When the organic compound of the formula (1) is a diethyl group, the analysis of the product obtained by the reaction with water starts from a very early stage, but the cause report is different. Different, not clear. The group of broken hibiscus products Further, the composition of the product may also vary depending on the molar ratio of water added to the molar ratio, the reaction time, etc. In the present invention, the main component of the partially hydrolyzed product is the following general formulae (4) and (5). A mixture of a structural unit and a structural unit represented by the following formula (6): or a mixture of a plurality of compounds: (4) (5) m is an integer of 2 to 20) (6) - [0 -Zn]m- (wherein 'R is the same as ri in the general formula (1) - [Ο-Μ]-

I

Q

(wherein X, RM are the same as any of the μ phase, R3, and R4 in the formula (2) or (3), and the same as in the Q and the formula (2) or (3), m is 2 to 20 The integer). 147876.doc -40- 201109279 With respect to the partial hydrolyzate 2, it is presumed that the main component of the product is a mixture of a compound represented by the following formula (8) or a plurality of compounds different in m. R1-Zn-[〇-Zn]p-R, (8) (wherein R1 is the same as Ri in the formula (1), and 卩 is an integer of 2 to 2 Å). When the above-mentioned organometallic compound is hydrolyzed, the above-mentioned Group 3B element compound does not coexist, and after the completion of the reaction, the compound of Group 3B of the above formula (2) or (3) is added to thereby produce a composition. The amount of the above-mentioned Group 3B element compound to be added is 〇〇〇5 to 〇3 with respect to the above-mentioned organic compound. In view of the fact that the addition effect of the compound of the 3B group element is obtained in abundance, and the amount of addition is large, the film property tends to deteriorate as an impurity, and it is particularly preferably 0.005 to 0.1. After completion of the hydrolysis reaction, part or all of the above product may be recovered and purified by a usual method such as filtration, concentration, extraction, column chromatography or the like. Further, when a group 38 element compound is added after completion of the hydrolysis reaction, part or all of the above product may be recovered by filtration and purified by filtration. When the organozinc compound of the formula (1) as a raw material remains in the reaction product, it can be recovered by the above method, and it is preferred to carry out the recovery. The reaction product obtained by recovering the remaining raw material by these methods is preferably one which does not contain the organozinc compound represented by the formula (1), and is preferably, for example, an organic compound represented by the formula (1). The content is 〇5% by mass or less. When the composition of the present invention is used as a coating liquid, a uniform film is formed, and it is preferred that the composition is not contained in the organozinc compound represented by the formula (1) which remains unreacted. The composition recovered by the above method from the separation of the electron-donating organic solvent 147876.doc -41 - 201109279 can also be combined with the right-handed w for forming a film in the reaction, "a thin material different from the electron-donating organic solvent" The organic solution (4) is made into a coating solution. Further, the organic solvent is separated, and the mixture is not directly supplied to the reaction mixture to form a coating solution directly or at a suitable concentration. 35 Fei Zhoutian adjustment The so-called organic organic solvent which is different from the organic solvent used in the reaction is a solvent for the formation of an organic binder, for example, a good eyebrow is 85 c or more. The reason is that since the boiling point is opposite to each other and the printing dots are relatively oriented, the squeezing of the squeezing sword in the coating operation can be avoided, and the evaluation can be avoided. (4) The work-like dysfunction caused by the drying of the coating film is an example of a mixture of the above-mentioned film formations, and examples thereof include: -: an aliphatic hydrocarbon solvent such as diheptane, octane or petroleum. Aromatic flue-curing solvents such as benzene, toluene, and xylene, diacetyl, diisopropyl hydrazine, ethyl methyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, diterpene pit, tetrahydrofuran An ether solvent, bis-_^^-t-amine, diethylamine, triphenylamine, #amine-based solvent, and the like. In addition, the company can be used alone or in combination with two or more types. On the right, considering the solubility of the reaction product containing the partial hydrolyzate of the zinc compound of the above reaction product, and the volatility of the machine itself, it is used as an organic solvent for film formation, and it is also good that , methyl monoethyl m ethyl monoethylene glycol dimethyl ether, ▼ diethylene glycol dioxime ether. The concentration of the solid content of the composition for forming a film of the emulsion can be arbitrarily selected. * * The range of the amount of bar/〇. The higher the degree of the coating, the smaller the number of times the coating can be made. The solubility of the reaction product containing the partial hydrolyzate of the organozinc compound and the ease of formation of the transparent zinc oxide film are compared with (4) 147876.doc • 42 - 201109279 is 3 to 12% by mass. [Method for Producing Zinc Oxide Thin Film (Second Aspect) The present invention relates to a method for producing a zinc oxide thin film. The production method comprises applying the composition for forming a zinc oxide thin film of the present invention to a surface of a substrate, and then The obtained coating film is heated at a temperature of rc or less to form a zinc oxide film. The coating on the surface of the substrate can be applied by dip coating, spin coating, spray pyrolysis, or ink jet method. It is carried out by a conventional method such as a screen printing method. The spray pyrolysis method is a method in which the substrate-surface is coated by a surface-heating method. Therefore, the solvent can be dried while being applied, and there is no need to apply depending on the conditions. In the case of heating for drying the solvent in the following, depending on the conditions, in addition to drying, at least part of the reaction of the partial hydrolyzate of the organozinc compound to the oxidation is carried out. Therefore, it is easier to use the latter step. A case where a zinc oxide film is formed by heating at a specific temperature. The heating temperature of the substrate in the spray pyrolysis method may be, for example, in the range of 5 Å to 25 (rc). The composition is coated on the surface of the substrate. It can be used in an inert gas atmosphere such as nitrogen, in an air environment, in an air environment containing a relatively large amount of water vapor, in an oxidizing gas atmosphere such as oxygen, in a reducing gas atmosphere such as hydrogen, or in a mixed gas atmosphere. In any of the environments, and under atmospheric pressure or under pressure, the product contained in the composition of the present invention reacts slowly with water in the environment to decompose slowly, and therefore is preferably carried out in an inert gas atmosphere containing no moisture. Furthermore, the coating in the method of the present invention can also be carried out under reduced pressure, but it is also simpler in terms of equipment at atmospheric pressure, so it is preferable. 147876.doc •43- 201109279, plate surface coating After the coating liquid, the substrate is set to a specific temperature & and the agent is dried, and then heated at a specific temperature, thereby forming an oxidized thin sputum. The temperature at which the granule is dried may be, for example, 2 〇. The range of ~2 〇〇 can be set according to the type of the common organic ridge A. The heating temperature for forming zinc oxide after the solvent is dried is, for example, a range of 20 to bribe, preferably 〇 The dry circumference of 250 C is more preferably in the range of 100 to 200 ° C. The drying temperature of the solvent may be the same as the heating temperature for forming zinc oxide, and the solvent drying and zinc oxide formation are simultaneously performed. Further, the heating may be carried out in an oxidizing gas atmosphere such as oxygen, a reducing body % under hydrogen or the like, hydrogen, argon, oxygen or the like (4) to promote the formation of zinc oxide or to improve crystallinity. The thickness of the film is not particularly limited. It is preferably a range in which G.G5 to 2 is practically used. Root: The production method of the present invention can be suitably produced by heating the above coating (drying) repeatedly or more. A film having a film thickness of a range. The zinc oxide film formed by the production method of the present invention preferably has an average transmittance of 80% or more for visible light, and more preferably 85% or more for visible light. . The "average transmittance to visible light" is defined and measured as follows. The average transmittance of visible light in terms of visible light and the average transmittance of light in the range of 38 〇 to nm can be measured by ultraviolet light-sensing spectrophotometer. The average transmittance of #人的光光 can also be expressed by the transmittance of visible light of 55G. The transmittance of visible light varies according to the degree of zinc oxide generated by spraying or heating after coating. In addition, it is preferable to set the heating conditions (temperature and time) at the time of spraying or after coating in consideration of the transmittance of the film to visible light of 8 〇% or more in consideration of J47876.doc -44 - 201109279. Further, since the oxidized film formed by the production method of the present invention is doped with a Group 3B element, the possibility of obtaining a low-resistance film is further increased by further investigating the film formation method. The system which can be used as the substrate in the second aspect of the present invention is the same as the substrate exemplified in the first aspect of the invention. [The composition for the production of the oxidized film] The composition for producing a zinc oxide film according to the third aspect of the third aspect of the invention includes the following three aspects: (1) Dissolving the organic compound represented by the above formula (1) a product obtained by at least partially hydrolyzing the above organic compound in a solution S1 in which an electron-donating organic solvent is added (hereinafter sometimes referred to as a partial hydrolyzate U; (ii) in the above formula (1) The organic compound shown in the above is dissolved in a solution 81 containing an electron-donating organic solvent, and water is added to at least partially hydrolyze the organozinc compound, and then the group 3b element represented by the above formula (2) or (3) is added. a product obtained by at least seeding of the compound (hereinafter sometimes referred to as a partial hydrolyzate 2); (iii) an organic compound represented by the following formula (1), and a formula or (3) a product obtained by dissolving at least a kind of a compound of a Group 3B element in a solution S2 in which an electron-donating organic solvent is added, and at least partially hydrolyzing the above-mentioned organic zincified person (hereinafter sometimes referred to as partial hydrolysis) 3), Ο) W-Zn-R1 147876.d Oc •45- 201109279 (wherein R1 is a linear or branched alkyl group having a carbon number of 1 to 7) ¢2) CD b (wherein Μ is a group 3B element, and r2, R3, and R4 are independently hydrogen and carbon a straight or branched alkyl group having a number of 7 or a linear or branched alkoxy group having a carbon number of 1 to 7, a carboxylic acid group or an acetoacetone group, and further L is a nitrogen, oxygen or phosphorus. a complex organic compound, b is an integer from 〇 to 9)

McXd.aH20 (3) (wherein, Μ is a Group 3B element, X is a halogen atom, a sulphuric acid or a sulphuric acid, and when χ is a radiant element or a sulphuric acid, c is 1, d is 3, and X is sulfuric acid. When 4, d is 3, a is an integer of 〇~9). In the present invention, the electron-donating organic solvent is an electron-donating organic solvent having a boiling point of C 、 or a boiling point of U 〇. 〇: A mixed organic solvent containing the above-mentioned electron-donating organic solvent as a main component. The present inventors et al; see 'by using such a solvent, can be formed with a gift. The oxidized film having the above-mentioned rate and having a volume resistivity of less than 8 x 10-2 cm. In the embodiment of Patent Document 2, it is 祛田 ^

, only fertilizer 1 phantom system using tetrahydrofuran (boiling point 66t) as A 邛 is the organic solvent for hydrolysis, "', a „ J document 3 in the example using 14 4 alkane (boiling point lout) as a part, shape It is possible to obtain a transparent oxidized word 2: the organic solvent used has a rate of less than 8x10-2, and a zinc oxide film having a low resistivity of a volume resistance of 2 is not obtained.喃 or 1,4-二崎拉夕柿 | # Μ &amp; 4 0 Fu Jie ☆ ～~: When using these solvents, it is easy to inhibit the formation of gels during the hydrolysis.卩 水解 水解 水解 水解 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 147 χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ χ A partial hydrolyzate is formed. (4) The above-mentioned electron-donating organic _, if it is (4) in the subsequent coating step, < 刼 刼 、 、 刼 刼 刼 刼 刼 刼 ' 较好 较好 rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc rc The electronic organic solvent may be one which is soluble in the organic compound represented by the general formula (1) and water in addition to the feSUx, and the rabbit 7 is exemplified by di-n-butyl ether (boiling point 〇). 142_4. 〇, 二己W弗点226.2. 〇, benzene (5) boiling point 153 8. 〇, phenyl ether (boiling point 172. 〇, butyl benzene is the point 21 〇 3. 〇, 戍 谜 ( (boiling point 214 C), Methoxytoluene (Buddha (7)), benzyl ether (boiling point: 89 ° C), diphenyl ether (boiling point 8.3 ^, # 芦 ether (ve_〇 (4) boiling point 2 〇 6.7. 〇, No. 3 ( Buddhism point 1145. 〇, and u diethoxyethane (boiling point 121. 〇, 1 &gt; 2 - dibutoxy ethane (boiling point 2 〇 3 3 〇 〇 etc. ethylene glycol dimethyl ether, double (2 -Methoxyethyl)ether (boiling point 162. 〇), bis(2-ethoxy ethane) ether G (188.4 C), bis(2-butoxyethyl) slit (boiling point 254 6). 〇) etc. = B = alcohol _, into And 1 &gt; 2 bis (2 - methoxyethoxy) Ethylene (boiling point 216 C) bis [2- (2-methoxyethoxyethyl (10) (Buddha 275. 〇) and other three ethylene two An ether solvent such as an alcohol diterpene ether, tri-n-propylamine (boiling point) ~ n-pentylamine ('/Fo 130 ° C) 'N,N-dimethylaniline (Buddha 193 ° C), N, An amine-based solvent such as N-diethylaniline (Buddhist point 217. 〇...bipyridine (Buddha point H5.3 °C). As an electron-donating organic solvent, the gel inhibition of the composition and the solvent itself From the viewpoint of the two aspects of volatility, it is preferred that 1,2-diethoxy 147876.doc as a kind of ethylene glycol diterpene ether. 47- 201109279 base ethylene burning (Buddha 121. 〇. For The electronic organic solvent is particularly limited, and the coating composition is applied, and the drying time of the upper limit is relatively short. The coating film is formed under the coating film. Preferably, 23 (TC is used as a coating point). The organic solvent which is an electron-donating organic solvent of 11 〇c or more may be a compound which is soluble in the compound of the formula (1) and water in a mixed state, and as an example, (^r(5$rC ^ ^^66〇C } ^ ^ =壬灿弗点150.8.〇和四气。夫喃,壬烧和】,4-二^*坑G弗点174.1.〇和四氢咬,癸烧和α二^院和四Hydrogen cough, ten, W,: two: ten - with and with tetrahydrogen ^, twelve burning and μ ten - hospital (Buddha shouting) and four ammonia cough L benzene with, 4, No. Buddha points 138~145. 〇 and four gas gnaw, dimethyl stupid fish two:: two, benzene (full point 136.2. 〇 and tetrahydroanthracene, B stupid - &quot; Hyun, ethylbenzene «point (10) ~ ah) and tetrachlorine, Ding II =, butyl benzene (boiling point window (a) and four gas gnaw, pentylene and heart, - two, Pentylbenzene (boiling point (6). η;) and tetragas. Furu, homobenzene dike, mesitylene (boiling point and tetrachloromethane, diethylbenzene disc), two-ethyl bromide to form the oxidation The volume of the zinc film is divided into tetrahydrofuran. 7 It is better that the by-product is the workability of the four-to-film film as a by-component, and the wind is better or the 14-two sigma. The amount of the ruthenium phase material is from 0.05 to 0.45. The compound of the above formula (1) a) is dissolved in the above-mentioned electron donating organic 147876.doc -48-201109279 solvent or contains the above with respect to the weight of the main component. In the electron-donating organic solution, the above formula (the organic solvent-soluble, eight (!) compound compound ° / 〇 range. The original, / is preferably 4 ~; 12 concentration is not When the power supply of the compound represented by the above formula (〖) is more than 12% by mass, the boiling point is required to be transparent and guided. The electroactive 4 solvent also has a tendency to form a solvent having a solvent (2 pass = film). The concentration of the compound represented by the range (%) is preferably

With respect to the above-mentioned amount of water added, in the case where the partial hydrolyzate 2 is relative to the above-mentioned organic zinc compound, the ratio of the mouth-like heart-like bucket is set to 〇4 to the partial hydrolyzate 3, and the range of 0.8, and 3B The above-mentioned organozinc compound of the group element compound. By setting the addition of water to 〇·4~〇.8, the reaction product containing the partial hydrolyzate can be formed to have volume resistance in the case of spin coating or dip coating. A zinc oxide film having a rate of less than 8 Χΐ〇·2 Ω, which is a characteristic of the spray enthalpy decomposition method, can form an oxidized film having a characteristic of a volume resistivity of not f3 ω. Further, by setting the molar ratio to 〇.4 or more, an organic zinc composition containing a product obtained by partially hydrolyzing an organic compound can be obtained in a high yield of more than or equal to the zinc contained in the raw material. Further, in the case of the partial hydrolyzate 3, the compound of the 3 steroid element is also partially hydrolyzed. When the molar ratio is 0.4 or more, in the case of the partial hydrolyzate 丨, 2, the residual amount of the unreacted raw material, that is, the organozinc compound can be suppressed, and in the case of the partial hydrolyzate 3, the organozinc compound can be suppressed. Residual amount of compound with a Group 3B element, 147876.doc -49· 201109279 The result is a safely operable organozinc composition. Further, by setting the molar ratio to 0.8 at T, gelation in the hydrolysis reaction can be suppressed. If a gel is formed in the hydrolysis reaction, there is a case where the viscosity of the solution rises and the subsequent operation becomes difficult. From the above point of view, the addition of water to the water is preferably in the range of 0.6 to 0.8, more preferably in the range of 〇 6 to 〇 75. In the case of the hydrolyzate 2, since the compound of the 3B group element is added after adding water to the organozinc compound, it depends on the amount of water added, etc., and the added water is added after the hydrolysis of the organic zinc compound is consumed. In the case of an elemental compound, the above product usually does not contain a hydrolyzate of the above-mentioned group element compound. The 3B group element compound also has the possibility of being contained in the state of the raw material without being hydrolyzed, or having the compound of the group 3b element compound (coordination) and the partial hydrolyzate of the organozinc compound. (With seat exchange). In the case of the partial hydrolyzate 3, since the organic zinc compound is added to the compound, the hydrolyzate (4) is hydrolyzed by the above-mentioned group 3B element compound disintegrator compound, and the like. Partially hydrolyzed. Adding Xia Xing Guan to the ruler: Adding water, you can mix water with other solvents and use only mixed solvent obtained by mixing water with other solvents in the water::: suppressing the viewpoint of local hydrolysis In other words, it is preferred that the content of water in the mixed solvent is, for example, 50 to 50%, preferably 2 to 2% by mass. The solvent for the blood enamel may be, for example, an organic solvent that can be used in the above-mentioned electron donating dextran, and may be an organic solvent on the 11 〇 CU, or may be 147,876. Doc -50- 201109279 Organic solvent with a temperature of less than 110 °C. However, in view of the fact that the diethylation is inert and the solubility of water is high, it is preferred that the organic solvent is not as high as 110 °C. ❹

The addition of G water also depends on the scale of the reaction, for example, the time between (9) seconds and the time of the call. In view of the fact that the yield of the product is good, it is preferred to add it by dropwise adding water or a mixed solvent with water to the organic compound of the above formula (1) as a raw material. The addition of water may be carried out without adding the compound represented by the formula (1) to the solution (4) of the electron-donating organic (tetra) oxime (in the state of standing). The temperature at the time of addition can be selected at any temperature between 90 1 50 C. From the viewpoint of the reactivity of water and organic compound, it is preferably _15 to 30 &lt; t. After the addition of water, in order to carry out the reaction of water with a compound represented by the formula (1) and a compound of the formula (2) or (3), or a compound of the formula (1) with water, for example, without mixing ( In the state of standing, place it for 1 minute~ call or mix. Regarding the reaction temperature, it can be reacted at the tone temperature between the shoulder and the boot. From the viewpoint of obtaining a partial hydrolyzate in a high yield, it is preferably in the range of 5 to 80C. There is no limit to the reaction pressure. It can usually be carried out under normal pressure. Regarding the reaction of water with the compound of the formula (1), it is necessary to sample the reaction mixture, and monitor it by means of a nuclear or the like (10) or by sampling the generated gas. j The organozinc compound represented by the above formula (1) is the same as those described in the above-mentioned sample. The first phase of the month is a compound of the 3β group element represented by the above formula (2) and 147876.doc of the above formula (7). 51 · 201109279 The Group 3B element compound is the same. In the second aspect of the second aspect of the present invention, the second aspect of the invention is described in the character #1, +4 (3) a group element of the formula (7): a compound of the group 3 element represented by the formula (3) in the above-mentioned embodiment, and a formula of the formula (2) The addition effect of the 3 lanthanum element in the composition of the composition of the present invention is a modest performance of the scorpion element. It is more appropriate to add the above formula (1) to the viewpoint of the addition of the above formula (10) (10) machine zinc. a compound, and a compound of the above, such that the compound of the above formula (2) = 3B element is relative to The proportion of the zinc compound of the machine is 5 〇.09, wherein, in the case of the partial hydrolyzate 2, and the addition of water to the solution of the organic zinc compound, a portion is obtained and 3B is added with the above molar ratio. Further, a partial hydrolyzate is obtained by the addition of water containing the organic compound and the 3B halogen compound in the above molar ratio. The organic solvent, the organic compound of the above formula (1) as a raw material, And the mixed solvent of water or water can be introduced into the reaction vessel according to all the conventional methods. The reaction steps can be any of batch operation mode, semi-batch operation mode and continuous operation type, and there is no special It is a batch operation formula. In the above reaction, the organozinc compound of the above formula (1) and the 3BM complex of the formula (7) or (3), or the above compound are partially hydrolyzed by water to obtain a partial hydrolyzate. 147876.doc -52- 201109279. When the organozinc compound of the formula (1) is diethylzinc, the analysis of the product obtained from the reaction with water has been carried out since the early days. Order, but the results vary from report to report, and the composition of the product is not clearly defined. The composition of the product may also vary depending on the molar ratio of water added to the reaction time or the reaction time, etc. Regarding the partial hydrolyzate 1, 2, it is speculated A mixture of a compound represented by the following formula (4) or a plurality of compounds different in m: R^Zn-tO-Znlp-R1 (4) (wherein R1 is the same as R1 in the formula (1) , p is an integer from 2 to 20).

In the present invention, the partial hydrolyzate 3 is a combination of a structural unit represented by the following general formulae (5) and (6) and a structural unit represented by the following general formula (7). a compound or a mixture of a plurality of compounds different in m: (5) (6) 'm is an integer of 2 to 20) (Ri-Zn)--[〇-Zn]m- (wherein R1 and formula ( 1) The same Ri in the middle

(7) (wherein, Μ is the same as Μ in the formula (2) or (3), Q is the same as any of XR, R, in the formula (2) or (3), and the melon is 2 to 2 Integer). In the case of the partial hydrolyzate 2 in which the above-mentioned Group 3B element compound does not coexist when the organozinc compound is hydrolyzed, the composition of the Group 3B of the above formula (2) or (3) is added after the completion of the reaction, thereby producing a composition. . The amount of the above-mentioned Group 3B element compound to be added is as described above. Between 147876.doc -53 and 201109279, the amount of the organic zinc compound is appropriately 0.005 to 0.09. After the reaction beam is not decomposed, for example, by filtering, concentrating, extracting, and the like, a conventional square ox, and the 往# layering method, part or all of the above product may be recovered and purified. Further, in the case where a compound of a 3B group element is added after completion of the hydrolysis reaction, it is also possible to recover part or all of the above-mentioned product by over-twisting, and to reproduce the organic reversion of the general formula (1) as a raw material in the reaction product. It is preferred to carry out the recovery by the above method, and it is preferred to carry out the reaction product obtained by recovering the remaining raw materials by these methods, and the preferred product is 1 to 3, and the organic compound represented by the general formula (1) is not contained in any case. For the zinc port, for example, it is preferred that the content of the organic compound represented by the formula (1) is not more than 5% by volume. The composition of the present invention is preferably an organic zinc compound represented by the formula (1) which does not contain an unreacted oxime from the viewpoint of using a film which is uniform in the coating liquid. The solution prepared by the method can be directly used as a zinc oxide film to form a bovine: solution. Alternatively, it may be appropriately diluted or concentrated. From the viewpoint of simplification, it is preferred that the solution prepared by the above method is used as the concentration of the coating solution for forming a zinc oxide film. [Manufacturing method of the oxidized ruthenium film] The oxygen production method of the composition for forming a zinc oxide thin film according to the third aspect of the present invention is described in the following method for producing the oxidized sputum film according to the fourth aspect of the present invention. . [Manufacturing Method of the Zinc Oxide Film (Fourth Aspect)] The oxidized film produced in the fourth aspect of the production method includes "the following three aspects, the composition A to c' composition Α and the third 147876.doc 201109279 The composition (1) is the same as the composition for the production of the oxidized film, and the composition B is the same as the composition (ii) for the production of the oxidized film of the third aspect, and the composition c and the oxidized film of the third aspect. The composition for manufacture (iii) is the same. (Composition A) is a product (hereinafter sometimes referred to as a partial hydrolyzate) which is obtained by dissolving an organozinc compound represented by the above formula (1) in electron donating property. In the solution obtained from the organic solvent, water is added to at least partially hydrolyze the above-mentioned organozinc compound; (composition B) is the following product (hereinafter sometimes referred to as a partial hydrolyzate), which is based on the above formula ( 1) The organozinc compound shown is dissolved in a solution containing an electron-donating organic solvent, and after adding at least partial hydrolysis of the above-mentioned organozinc compound by adding water, the 3B group represented by the above formula (2) or (3) is added. Obtained from at least one of elemental compounds; (Composition C) is a product (hereinafter sometimes referred to as partial hydrolyzate 3) which is an organozinc compound represented by the following formula (1), and the following formula (2) or (3) At least one of the group 3B element compounds shown in the above is dissolved in a solution of an electron donating ◎ organic, gluten, and water is added to at least partially hydrolyze the above organic compound: R'-Zn-R1 (1) (Order, R1 is a linear or branched alkyl group having a carbon number of 1 to 7)

McXd.aH20 (7) (wherein, Μ is a 3B group of τ, Z is a dentate atom, a sulphuric acid or a sulphuric acid, and when χ is a dentate atom or a supplemental acid, 'c is a d is 3, and when it is sulfuric acid, 2, d is 3, a is an integer from 0 to 9) 147876.doc -55- 201109279 R2-M-R3 ί *(L) b (3) R4 (where M is a 3B group element, R2' R3 and R4 are independently a hydrogen or a straight or branched alkyl group of carbon number 7, a linear or branched alkoxy 'carboxylic acid group having a carbon number of 丨7, or an acetoacetone group, and further, A coordinating organic compound of any of hydrazine, oxygen, and phosphorus, and b is an integer of 〇~9). [Production Method] The fourth aspect of the present invention relates to a method for producing an oxidized film. This production method is a method in which the composition for forming a zinc oxide thin film is applied onto a surface of a substrate, and then the obtained coating film is heated to obtain a zinc oxide thin film. For example, when it is applied by a spin coating method or a dip coating method, a zinc oxide thin film having an average transmittance of 80% or more and having a volume resistivity of less than 8 χΐ〇 2 can be obtained. For example, when applied by spray pyrolysis, an oxidized film having an average transmittance of 80% or more for visible light and having a bulk resistivity of less than lxlG_3 仏 (10) can be formed. The application to the surface of the substrate can be carried out by a conventional method such as dip coating, spin coating, spray pyrolysis, ink jet or screen printing. The coating of the composition on the surface of the substrate can be carried out under an inert gas atmosphere such as nitrogen, a two-gas atmosphere, an air environment containing a relatively large amount of water vapor, a oxidizing gas atmosphere such as oxygen emulsion, and a reducing gas atmosphere such as hydrogen. It is carried out under any atmosphere, such as under a mixed gas atmosphere, under atmospheric pressure or under pressure. In the spin coating method or the dip coating method, it can be formed under an inert gas atmosphere, and the relative humidity by bringing the inert gas into contact with water vapor is 147876.doc * 56 - 201109279 2~15% Under the environment. The spray thermal π solution is a surface-heatable substrate-surface coating. Therefore, the solvent can be dried at the same time as the coating, depending on the conditions &amp; Further, the reaction of the partial hydrolyzate of the organozinc compound to the oxidation is carried out at least partially according to the strip * Τ dry W. Therefore, there is also a case where it is easier to form a zinc oxide film by heating at a specific temperature. The heating temperature of the λ plate may be, for example, in the range of 50 to 550. Soil Figure 17 shows the spray film formation shock that can be used in the spray pyrolysis method of the present invention. The figure shows a spray bottle filled with a coating liquid, and 2 denotes a substrate holding: Mo 3 indicates a spray nozzle, 4 indicates a compressor, 5 indicates a substrate, and 6 indicates a water emulsion introduction tube. Regarding spraying, the substrate is placed on the substrate to hold "t" as needed to heat it to a specific temperature, and (4) in a specific environment, the spray nozzle 3 disposed above the substrate is simultaneously supplied with a compressed '隋The gas and the coating liquid are atomized and sprayed, whereby a zinc oxide thin film can be formed on the substrate. The zinc oxide thin film is formed by spraying without additional heating or the like. From the viewpoint of producing a oxidized film having good film characteristics, it is preferred that the coating liquid is ejected from the spray nozzle in such a manner that the droplet size becomes 1 to 15 μΐη, and The distance between the spray nozzle and the substrate is set to be within 5 〇cm. The right is considered to be adhesion to the substrate, easiness of evaporation of the solvent, etc., and it is preferable that the liquid droplets ejected from the spray nozzle are all liquids. The droplet size is in the range of 1 to 3 Å. The droplet size is preferably in the range of 3 to 2 。. 147876.doc -57- 201109279 If the droplet size is reduced from the time of the spray nozzle to the arrival of the substrate, Better partial evaporation Within the range of (10), the distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint of good formation of re-oxidation to re-M. In the spray pyrolysis method, the formation is performed. ± The lower resistivity of the oxidized thinner is guided by the introduction of I milk from water vapor in an inert atmosphere to promote the decomposition of the composition. For example, the guidance of water-based gas = relative to the above-mentioned composition supplied The Moer's in the middle of the word is better::·1:5, the viewpoint of obtaining a thin film with a lower volume resistivity:: 'Better is. 3~2. If the amount of water vapor introduced is the above In the range of molar ratio ~2, an oxide film having a volume resistivity of less than lxl0-3 can be formed. For the introduction method of water vapor, an emulsified zinc film can be introduced according to all the methods (4). In the production container, it is preferred that the water vapor reacts with the composition in the vicinity of the heated substrate. For example, the vicinity of the substrate containing water vapor (4) which is formed by bubbling water with a tube is used. After coating the coating solution, 'set the substrate as needed At a specific temperature, the solvent is dried and then heated at a specific temperature to form a oxidized film. The temperature at which the solvent is dried can be, for example, in the range of 20 to 20 Torr, and can be timely according to the type of the organic solvent coexisting. The heating temperature for forming zinc oxide after the solvent is dried is, for example, 50 to 55 (the range of rc, preferably 50 to 50 (the range of TC. The solvent drying temperature may also be used to form oxygen 147876. Doc -58- 201109279 The heating temperature of the word is the same, and the temperature is 10%. The drying and oxidation of the sputum agent can be used as needed, and can also be pushed under the reducing gas environment:: oxygen = chemical environment, hydrogen Heat's to promote the formation of zinc oxide... The above-mentioned addition of the slurry core is not particularly limited, and it is practically similar. The film of the oxidized film can be obtained by applying the above-mentioned coating (drying) to a thin film having a film thickness in the range of 雾 。. The above-mentioned oxidized film formed by the method of the present invention is suitably manufactured according to the method of coating the resistivity of the coating, and it is more preferable to have a volume which is not damped and can be buried. Resistivity. The volume resistivity is obtained per unit volume of electricity ^ by multiplying the surface resistance by the film thickness. The surface resistance is measured by, for example, a four-probe method. The film thickness is measured, for example, by (scan- 二j cn5scope ′ scanning electron microscope), stylus-type profile, and drought. Since the volume resistivity changes (increases) depending on the degree of formation of zinc oxide due to heating at the time of spraying or after coating, it is preferable to set the volume resistivity of the film to 8×10 −2 n·cm and set the spraying time. Or heating conditions (temperature and time) after coating. The oxidized film formed by the production method of the present invention preferably has an average transmittance of 80% or more for visible light, and more preferably 85% or more for visible light. The "average transmittance to visible light" is defined and measured as follows. The average transmittance for visible light 147876.doc •59- 201109279 means that the average transmittance of light in the range of 380 to 780 nm can be determined by an ultraviolet-visible spectrophotometer. Furthermore, the average transmittance of visible light can also be expressed by the transmittance of visible light at 550 nm. Since the transmittance to visible light changes (increases) depending on the degree of formation of zinc oxide due to heating at the time of spraying or after application, it is preferable to make the transmittance of the film to visible light 80% or more. Set the heating conditions (temperature and time) at the time of spraying or after coating. The substrate which can be used as the substrate in the third aspect and the fourth aspect of the present invention is the same as the substrate exemplified in the first aspect of the present invention. For example, the substrate may be an alkali glass, a non-glass, or a transparent substrate film, and the transparent substrate film may be a plastic film. However, it is not intended to be limited to such exemplified materials. [Use of Oxidation Film] The zinc oxide film is made of the above method. The zinc oxide film can be used as an antistatic film, an ultraviolet cut film, a transparent conductive film or the like because of its transparency. The antistatic film can be used, for example, in the fields of solid electric field capacitors, chemical amplification systems, (four) window glass, and the like. Ultraviolet cut-off film, for example; used in front of image display device, such as calendering film, driving recorder (1), camera device such as Μ, high-pressure discharge lamp, lighting device for watch, cover glass for clock, window glass, etc. . Further, the transparent conductive film can be used, for example, for rD (flat panel display » 4c - aa \ and capacitive touch panel, U-type touch panel

Plate/special film solar cells and compounds (CdT CIS) are thin-film solar cells, dye-sensitized solar cells, and other fields. However, it is not intended to be limited to such fields. Although the film is too repetitive, the oxidized film produced by the above method has high transmittance, transparent Η and ancient glory, and has a volume resistivity of less than 8X10- visible 147876.doc •60-201109279 2 Q.cm. Sexuality, which can be used for the electrode of Qing (flat panel display), the electrode of resistive film type touch panel and the electrode of electro-optical and electro-optical touch panel, and the thin film of solar cell solar cell (4), (coded) Copper steel)) is a thin-film solar cell, and the dye is sensitized too much; the organic thin-film solar cell upper electrode 'UV cut-off film, anti-static, infrared reflective film, etc., has a wide range of uses. [The composition for forming an oxidized film (the fifth aspect)] Ο Ο The composition for forming a doped zinc oxide thin film according to the fifth aspect of the present invention is characterized in that it is contained in an organic solvent having electron donating properties. The organozinc compound represented by the formula (1) and the organic warfare element compound represented by the following formula (2), wherein the molar ratio of the organic group 3B element compound to the organozinc compound is 0.001 to 〇·3 Range: R^Zn-R1 (!) (wherein, R1 is a linear or branched alkyl group having a carbon number of 1 to 7) r20-TMm-rsq I (2 0) R40 (wherein, Μ is a 3B group The elements, r20, r30 and r40 are independently a linear or branched alkyl group of chlorine or carbon number. Specific examples of the hospital base represented by R1 in the organozinc 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, and a second one. Base, tert-butyl, pentyl, isopentyl, neopentyl, third amyl, hexyl, #hexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. The compound of the formula is preferably a compound wherein R1 has a carbon number of 1, 2, 3, 4, 5 or 6. The compound represented by the formula (1) is particularly preferable. I47876.doc -61- 201109279 It is preferred that R1 is diethylzinc of ethyl. Examples of the 3 steroid element represented by μ in the organic Group 3B element compound represented by the formula (20) include β, a, Ga, In, and Τ1. Further, specific examples of the alkyl group represented by R20, R30, and R40 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and a third butyl group. Base, pentyl, isopentyl, neopentyl, third amyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. The compound represented by the formula (2〇) is preferably]V [ is B, Al, Ga or In, and R2. And r3q, and r4〇 are independently hydrogen, or a compound having a carbon number of 丨, 2, 3, 4, 5, or 6. Particularly preferred compounds of the formula (20) are borane, aluminum triethyl hydride, dimethyl sulphate, and triethyl succinimide. Diethylaluminum, trimethylgallium, triethylgallium, and the above-mentioned organic 3B group elemental R3° and R40 are all ethyl groups. From the viewpoint of being inexpensive and easily available, the compound is particularly desirable: Aluminum, and r2〇, triethyl Ilu; lanthanum is gallium, gallium; lanthanum is indium, and R20, and R20, R30 and R40 are all methyl, trimethyl R and R40 are methyl indium. The compound of the formula 3 is preferably a G.GOi~〇.3, more preferably 0.01 to 〇·1 相对 as the organic molybdenum compound represented by the formula (1). An example of an electronic solvent, an amine solvent such as trimethylamine, diethylamine or triphenylamine, hydrazine, di-n-propyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, Two _ diglycidyl dimethyl ether, two ethyl - Zhiyijia shout, triethylene glycol dimethyl ether and other laboratory solvents. Particularly preferred as the solvent for electron supply is diisopropyl ether. In the present invention, from the viewpoint of producing a transparent oxidized film, the total concentration of the above organozinc compound and the organic group 38 compound is preferably 15% by mass or less as compared with 147876.doc-62·201109279. The total concentration of the above organozinc compound and the organic 3B group compound is preferably from 1 to 10% by mass, more preferably from 3 to 1% by mass. The total concentration of the above-mentioned organozinc compound and the organic group 3B compound affects the risk of the production of the zinc oxide film such as fire, and by setting it as the above range, it is possible to produce a good transparency of the oxidized film without special care. The concentration of the organic Group 3B element compound of the above composition is appropriately determined in consideration of the molar ratio of the organic Group 3b element compound to the above organozinc compound.

The composition of the present invention can be produced by dissolving the organic compound of the above formula (1) and the organic 3B compound of the above formula (2) in an organic solvent having electron donating properties. The compound of the above formula (1) and the compound of the above formula (2) can be dissolved by any conventional method, and can be produced by dissolving a mixture with a solvent. The compound of the above formula (1) and the compound of the above formula (7) can be dissolved in any order. [Manufacturing method of an oxidized film doped with a Group 3B element (The second method of producing a oxidized film doped with a working element of the present invention is characterized in that it is under atmospheric pressure or under pressure]

The composition of the present invention is sprayed onto the surface of the substrate to form a oxidized film doped with a 3 lanthanum element. . The manufacturing method of the present invention uses a spray coating method. Or under pressure, under the so-called pressure of zinc oxide film, for example, pressure. However, it is not intended to be limited thereto. The spraying on the surface of the substrate is carried out in the presence of an oxygen source of atmospheric pressure, i.e., water. The case of the range of 101.3 to 202.6 kPa 147876.doc •63- 201109279 Actual: The nozzle of the method of I: can also be implemented under reduced pressure, but the effect is reduced, and the pressure is applied at atmospheric pressure. It is simple and therefore better. Back|Season is the so-called "spraying on the surface of the substrate...the environment in which water exists", for example, an aqueous air environment having a relative humidity of 20 to 90%. It can also be used in a mixed gas atmosphere in which nitrogen and water are mixed to replace the air. From the standpoint that the formation of the zinc oxide film is relatively stable, the relative humidity is preferably in the range of 30 to 70%. Spraying on the surface of the substrate can be carried out at a substrate temperature of 3 Torr or less. More specifically, it is preferable that the ambient temperature at which the spraying is performed is (10) or less and the substrate temperature is set to 3 G (rc or less.) The ambient temperature at which the zinc oxide film is formed is relatively stable from the viewpoint of smooth formation of the zinc oxide film. Preferably, the range of 1 〇 to 3 〇 ° C, the substrate temperature is preferably 10 to 20 〇 t, more preferably 20 〜 1 〇〇. (: the range. 疋 Figure 23 shows the present invention A spray film forming apparatus used, in which i denotes a spray bottle filled with a coating composition, 2 denotes a substrate holder, 3 denotes a spray nozzle, 4 denotes a compressor, and 5 denotes a substrate. It is disposed on the substrate holder 2, and is heated to a specific temperature of 300 ° C or lower by using a heater as needed, and then simultaneously supplied to the spray nozzle 3 disposed above the substrate in the atmosphere (at atmospheric pressure, in air). The compressed inert gas and the coating composition are sprayed by atomizing the coating composition, whereby an oxide film can be formed on the substrate. The zinc oxide film doped with the 3B group element is sprayed. It does not require additional heating or the like. The coating of the composition of the cloth can be used to produce a good transparency of the oxidation. 147876.doc -64 - 201109279 From the viewpoint of the film, it is preferred to apply the coating composition from the spray nozzle to the droplet size. The range of μΐη is ejected, and the distance between the spray nozzle and the substrate is set to be within 50 em. Further, from the viewpoint of the influence of heat on the substrate and the energy cost, it is preferable to carry out the ambient temperature of the spray. It is 4 〇t or less, and the temperature of the substrate is 3 〇〇 or less. 'If the adhesion to the substrate, the easiness of evaporation of the solvent, etc. are taken into consideration, the droplet size ejected from the spray nozzle is preferably All droplet sizes are in the range of 1~3〇μΓΠ. The droplet size is better in the range of 3~2 〇. 0 If the solvent is partially evaporated from the spray material until it reaches the substrate, the droplet size is reduced. Etc., it is preferred that the distance between the spray nozzle and the substrate is within 5 〇m. From the viewpoint of forming a zinc oxide film well, the distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm. Furthermore, even if it is not on the substrate and the environment Heating is performed, and only the compressed inert gas and the coating composition are supplied from the spray nozzle 3 disposed above the substrate, and the coating composition is atomized and sprayed, or may be according to the strip # The size, the composition of the composition (concentration), the distance between the spray nozzle and the substrate, etc.) form a zinc oxide film doped with a group 3B element having high transparency on the substrate. #Doping formed by the manufacturing method of the present invention Oxidation of Group 3B elements. (4) Membrane is contained in zinc oxide in the form of oxides containing Group 3B elements. The oxides of Group 3B elements are solid-dissolved in zinc oxide, or the oxides of Group 3B elements are separated from zinc oxide. The film thickness of the oxidized film doped with the Group 3B element formed by the production method of the present invention is not particularly limited. For example, it can be adjusted within the range of (10)~2_ nm 147876.doc -65- 201109279. The coating group for the zinc oxide film is “#] The hunting can be adjusted by the adjustment of the spraying, and the spraying time can be appropriately adjusted. In addition, the knife is rubbed twice or more as needed to perform the spraying operation. The formed doping with the 3B group element is better oxidized. If the visible light has an average transmittance of _ or more, the ancient stomach "has an average transmittance of more than 85% for the visible light. Furthermore, the average transmittance of the light seen", It is defined as follows and then 疋. The average transmittance for visible light refers to the average of the transmittance of light of ～78〇(10), which can be measured by an ultraviolet-visible spectrophotometer. Further, the π-group element is formed by the production method of the present invention, and the surface resistance is preferably 1 ΧΗ) 5 Ω/□ or less. A better surface resistance is 5 χ 1 〇 4 Ω / port or less, and particularly preferably a surface resistance of 1 χ 1 〇 4 Ω / □ or less. For example, the substrate can be a transparent substrate film, and the transparent substrate film can be a plastic film. The polymer forming the plastic film can be exemplified by polyacetal (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)), poly (meth) acrylate (for example, polymethacrylic acid). Methyl ester (IIA)), polycarbonate (PC), polystyrene, polyvinyl alcohol, polyethylene ethylene, vinylidene chloride, polyethylene, cyclic polyolefin (c〇p), ethylene-vinyl acetate Copolymers, polyurethanes, triacetates, celecoxime. Among these, PET, PC, and PMMA are preferred. The transparent substrate film may be a non-stretched film or a stretched film depending on the kind of the polymer. For example, a polypropylene film such as a PET film is usually a biaxially stretched film, and a pc film, a triacetate film, and a 147876.doc-66 - 201109279 film are generally non-stretched films. [Examples], but the present invention

Hereinafter, the present invention will be more specifically described by way of examples without limitation to the examples. All sources are included in the white, and the solvent is all dehydrated and degassed. Embodiments 1 to 1-4 are examples of the i-th aspect, and examples 2_i to 2_8 are the second embodiment, and the examples 3-1 to 3-17 are the third and fourth embodiments. Example 4_ 〇1 to 4-6 are examples of the fifth aspect. Method for Measuring Surface Resistance Value The surface resistance was measured by using a Loresta-GP manufactured by Mitsubishi Chemical in accordance with the probe method of JIS K 7 194. [Example 1-1] To a solution of 165.0 g of tetrahydrofuran, diethyl group 41.66 g was added. After fully approving, cool to -10t. The tetrahydrofuran solution containing 5_0% of water was added dropwise in such a manner that the molar ratio of the aqueous phase to monoethylzinc was 0.6. Then, after reacting at room temperature (22 ° C) for 18 hours, the solvent and unreacted diethyl ether were distilled off in vacuo to obtain 33 〇 2 g of a product containing a partial hydrolyzate. The optical error of Fig. 1 was obtained by 'NMR (THF-d8, ppm) measurement. The zinc content was determined to be 57.8% as measured by ICP (Inductively Coupled Plasma). The yield of the radical is 91%. The product containing the partial hydrolyzate obtained as described above is dissolved in 1,4-dioxane only in an amount of 15% by weight, and a trace amount of the insoluble matter is filtered, thereby obtaining a portion containing the hydrolyzate. Product coating solution. The viscosity of the coating liquid was measured by a Ukbel 147876.doc • 67-201109279 viscometer (Ubbelohde viscometer) and found to be 1.07 mPa.s. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied by spin coating on the surface of a l8 mm square Corning i 737 glass substrate. Then, the above operation was repeated i times by forming the substrate K12 (heating the solvent under rc for 4 minutes while forming zinc oxide.) The formed film had a film thickness of 0.25 μm, as shown in FIG. It was confirmed to be zinc oxide by XRD (X-ray diffraction), and the visible light transmittance at 550 nm was 83%, and a transparent oxide film having a transmittance of 8 % by or more was obtained. -2] After coating, the substrate was heated in the same manner as in Example 1 except that the substrate was heated at 12 ° C for 2 minutes to dry the solvent and further heated at 200 ° C for 2 minutes. The film thickness of the film is 80% of visible light transmittance of 〇21 μηι ^ 55 〇nm, and a transparent zinc oxide film having a transmittance of 8 〇% or more is obtained. [Example 1-3] Two hexanhydrofuran 165.0 g was added. 4166 g of ethyl zinc. After thorough stirring, it was cooled to -HTC. The tetrachlorocarbamate solution containing 5.0% water was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.8. Then, in the room After reacting for 18 hours at a temperature, the solvent and unreacted diethyl zinc were vacuum distilled off to obtain a package. a product containing a partial hydrolyzate. By *NMR (THF_d8,

Ppm) was measured to obtain the spectrum of Figure 2. The content of the word was determined to be 57.3% by ICP measurement. The yield of the zinc base is 90%. 147876.doc -68- 201109279 The product containing the partial hydrolyzate obtained in the above manner is dissolved in ruthenium and 4-dioxane in an amount of only 12%, and a small amount of residual insoluble matter is filtered, thereby obtaining A product-containing coating liquid containing a partial hydrolyzate. The viscosity of the coating liquid was measured by a Ubum viscometer and found to be 117 mPa, s. Ο

The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied onto the surface of a Corning 1737 glass substrate of 18 mm square by spin coating. Then, the substrate was dried by heating the substrate at 12 rc for 4 minutes to form zinc oxide. The above operation was repeated one time. The film thickness of the formed film was 〇·27 μιη' as shown in FIG. In general, it is confirmed by XRD to be an oxidized word. Further, the visible light transmittance at 550 nm is 81%, and a transparent zinc oxide film having a transmittance of 80°/. or more is obtained. [Example 1-4] The film was formed in the same manner as in Example 1-3 except that the substrate was heated at 12 ° C for 2 minutes to dry the solvent and further heated at 2 GG ° C for 2 minutes. 23 pottery, as shown in Fig. 6, is a transparent zinc oxide film of 550 nm visible light transmission. It is confirmed to be zinc oxide by XRD. Further, the rate is 95%, and the transmittance is 80% or more [Reference Example 1-1] Adding 4166 g of diethyl ether to 165.0 g of tetrahydrofuran. After thorough stirring, 'cooling to · ΐ η: will contain tetrahydrogen in water. The solution of water is compared with the molar ratio of water to diethyl zinc. In the manner of ..., the reaction was carried out, and then, the reaction was carried out for 18 hours at a temperature, and a large amount of gel was produced. The resulting gel was insoluble in any organic solvent, so that a coating liquid could not be prepared. [Comparative Example 1-1] 147876.doc -69- 201109279 Zinc acetate dihydrate 8.50 g was added to 2-methoxyacetate 48.24 g. And 2.39 g of ethanolamine as an auxiliary agent, and the mixture was sufficiently stirred to obtain a coating liquid. A film was obtained by the same operation as in Example 1-1 except that the coating liquid obtained in the above manner was used. The visible light transmittance was 27%. Only an opaque film having a transmittance of 80% or less was obtained. Further, the film was not uniform, and a peak derived from an oxidation word (not shown) was not confirmed by XRD. [Comparative Example 1-2 After the application, the substrate was subjected to the same operation as in Comparative Example j except that the substrate was heated at 2 Torr for 2 minutes to dry the solvent, and further heated at 2001: for 2 minutes. The transmittance was 31%, and only an opaque film having a transmittance of 8% by mass or less was obtained. Further, the film was uneven, and a peak derived from zinc oxide (not shown) was not confirmed by XRD. [Example 2-1] Add 7 ^ Ω1 &gt; in 1,4-dioxane 30_0 g, st hard One ethyl zinc lanthanum 9 丨 g. After thorough mixing, cool to 12 ° C. Will contain 50% ± # τ ^ ^ 3 order). υ / 〇 water 丨, 4- di-halane solution relative to water In the case of diethyl ether, the molar ratio is obtained by taking two υ. ί&gt; and then adding it to the room temperature (22. After the reaction at room temperature for 18 hours, the relative amount is Ethylzinc was added to add triethylamine in a molar ratio of 0.G2. The membrane was filtered in the above manner, and the mixture was filtered through a membrane filter to obtain a partially hydrolyzed cerium containing aluminum. , six, six, and song ^ fresh / liquid ("Chen degree 5_6 mass%) 32.1 g. The spectrum of Fig. 8 was obtained by NMR (but HF_d8, measured by vacuum drying) by vacuum drying. '147876.doc -70. 201109279 The product containing the partial hydrolyzate obtained in the above manner was coated. The solution was applied to the surface of a Corning 1737 glass substrate of 18 mm square by spin coating, and then the substrate was heated at UO C for 4 minutes by Φ to dry the solvent, and an oxidation term was formed. The above operation was repeated twice. The film formed has a film thickness of 0.15 μm, as shown in Fig. 9, which is confirmed by the lion as zinc oxide, and a visible light transmittance of 87% at 550 nm, and a transparent zinc oxide having a transmittance of 80% or more is obtained. [Example 2-2] A solution containing a partially hydrolyzed solution (concentration: 5.5% by mass) 31.5 was obtained in the same manner as in Example 2 except that triethylaluminum was changed to trimethylgallium. g. The spectrum of Fig. 1A was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying. The coating portion obtained in the above manner was applied in the same manner as in Example 2-1. a product-containing coating liquid of a hydrolyzate. The thickness is 〇.i4 μιη, as shown in Fig. 11, it is confirmed by XRD as an oxidation word. In addition, the visible light transmittance of 55 〇 melon is 84%, and a transparent bismuth zinc oxide having a transmittance of 8 〇% or more can be obtained. [Example 2-3] A solution of a partial hydrolyzate containing indium (concentration: 55 mass/〇) was obtained in the same manner as in the Example except that triethylaluminum was changed to trimethylindium. The spectrum of Fig. 12 was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying. The coating was applied in the same manner as in Example 2-1 except that the substrate heating temperature was changed to 15 °C. The film was coated with a 147876.doc 201109279 product containing a partial hydrolyzate as described above. The formed film had a film thickness of 0丨4 μη1, which was confirmed to be zinc oxide by XRD as shown in FIG. Moreover, the visible light transmittance of wo nm is 89%', and a transparent zinc oxide film having a transmittance of 8〇% or more can be obtained. [Comparative Example 2-1] Zinc acetate dihydrate is added to 2_methoxyethanol 24.12 g. 123 g and 0.34 g of ethanolamine as an auxiliary, and thus relative to zinc acetate dihydrate Adding aluminum triacetate azide in a ratio of molar ratio of 0.02, and sufficiently mixing, thereby obtaining a coating liquid containing aluminum. In addition to using the coating liquid obtained in the above manner in air, the visible light transmittance of nm is performed. A film was obtained in the same manner as in Example 2-1, and the radiance of the film was 75%, and only an opaque film having a transmittance of 8 % by or less was obtained. Further, the film was uneven, and zinc oxide was not confirmed to be derived from zinc oxide by XRD. The peak (not shown). [Comparative Example 2-2] A coating liquid containing gallium was obtained in the same manner as in Comparative Example i except that aluminum triacetate was changed to gallium chloride. The same operation as in Comparative Example 1 was carried out on the coating liquid obtained in the above manner to obtain a film. Moreover, the visible light transmittance of 550 nm is 66%, only available

[Comparative Example 2-3] A coating liquid solution containing indium was obtained in the same manner as in Comparative Example 1 except that the aluminum triethyl sulfonate aluminum was changed to the indium sulfide fourth comparative example 1 except for the tetrahydrate. The resulting coating liquid was obtained by a ratio of 147876.doc -72 to 201109279 to obtain a film. Further, the visible light transmittance at 550 nm was 71%, and only an opaque film having a transmittance of 80% or less was obtained. Further, the film was not uniform, and a peak derived from zinc oxide (not shown) was not confirmed by XRD. [Example 2-4] 2.62 g of diethyl zinc was added to bis(2-methoxyethyl)ether 3 〇.〇 g. After fully mixing, 'cool down to -12. (: The tetrahydrofuran domain solution containing 5.0% water was added dropwise in such a manner that water was compared with the monoethyl molar ratio of hexamethylene. Then, the temperature was raised to room temperature (22. 〇 and at room temperature) The reaction was carried out for 18 hours, and the solution obtained by the method of ruthenium was filtered through a membrane filter to obtain a partial hydrolyzate solution (concentration: 7.8% by mass) of 33·1 g. The solvent was removed by vacuum drying. The spectrum of Fig. 14 was obtained by NMR (THF-d8, ppm).

The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied onto the surface of a Corning 1737 glass substrate of 18 mm square by spin coating. Then, by placing the substrate at 12 Torr. (: heating was carried out for 4 minutes to dry the solvent, and zinc oxide was formed at the same time. The above operation was repeated 5 times. The thickness of the formed film was 0·36 μηι, which was confirmed to be zinc oxide by XRD. Further, 550 nm The visible light transmittance was 93%, and a transparent oxidized film having a transmittance of _ or more was obtained. [Example 2-5] In the partial hydrolyzate solution of diethylzinc prepared in Example 2-4, Adding trioctylsole in the manner of the molar ratio of the ethylene added to the molar ratio of the mixture, thereby obtaining a partial hydrolyzate solution containing indium 33.2 g. 147876.doc -73- 201109279 will be as above The product-containing coating liquid containing a part of the hydrolyzate was coated on the surface of a Corning 1737 glass substrate of 18 mm square by a slave coating method, and then the solvent was dried by heating the substrate M12 (rc for 4 minutes). 'The oxidation operation was simultaneously formed. The above operation was repeated 5 times. The film thickness of the formed film was 〇.33 μιη', which was confirmed to be an oxidation word by XRD. Further, the visible light transmittance of 550 was 93%, and transmission was obtained. A transparent oxide film with a rate of 80% or more. Example 2-6] In the example 2 - 4, in the partial hydrolyzate solution of the t-diethyl group, the method of "10" in terms of molar ratio with respect to the diethyl of the person to be cast is &quot; "Mouth-methylgallium" thereby obtaining a solution of a partial hydrolyzate containing indium 33.0 g. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied by spin coating to 18 mm square. On the surface of Corning 1737 glass substrate. Then, zinc oxide was formed by drying the substrate under a downdraft for 4 minutes to form a zinc oxide. The above operation was repeated 5 times. The film thickness of the formed film was G.35 μ. „ι' was confirmed to be an oxidized word by XRD. Further, the visible light transmittance was 94%, and a transparent oxidized film having a transmittance of 峨 or more was obtained. [Example 2-7] In Example 2-4 In the prepared partial hydrolyzate solution of the diethyl group, trimethylindium was added in a molar manner in the form of an ethyl group, thereby obtaining a partial hydrolyzate containing indium = 32.8 g. Doc -74· 201109279 The product-containing coating liquid containing a partial hydrolyzate obtained in the above manner, It was applied by spin coating on the surface of a Corning 1737 glass substrate of 18 mm square. Then, the solvent was dried by heating the substrate at 12 (rc for 4 minutes), and an oxidation term was formed. The above operation was repeated 5 times. The thickness of the formed film was 0.32 μm, which was confirmed to be zinc oxide by XRD, and the visible light transmittance at 550 nm was 94%, and a transparent zinc oxide film having a transmittance of 8 % by or more was obtained. -8] ◎ Indole, 2_diethoxyethane 3〇.〇g was added with diethyl 1.97 g. After stirring well, cool to -12. (: A solution of 5.0% water in tetrahydrofuran was intermittently introduced using the apparatus shown in Fig. 15, whereby the molar ratio of water to diethylzinc was 0 to 8. The temperature was raised to room temperature (22). The mixture was reacted at room temperature for 18 hours, and the solution obtained as above was filtered through a membrane filter, thereby obtaining a partial hydrolyzate solution (concentration: 7.8 mass 〇/〇) 3 3 · 1 g. The spectrum of Fig. 16 was obtained by vacuum drying after d8 'ppm) after removing the solvent, etc. 〇 [Example 3-1] Adding diethyl 2 to 1,2-diethoxyethane (boiling point 12 rc) 39 9 § Base letter 3.49 g (corresponding to 8.7% by mass). After thorough stirring, cool to -^ art. Will contain 5.0% water of 1,4_di, alkane (boiling point 1〇1丨. (:) solution relative to water The addition was carried out by adding dropwise (the total amount: 6 〇 2 g) to the molar ratio of ethylene to 0.6. Then, the temperature was raised to room temperature (24 〇 and reacted at room temperature for 18 hours to obtain a membrane filter). Filtration was carried out to thereby obtain a partial hydrolyzate solution (concentration 6.5 mass ° / 〇) 48.1 g. The solvent was removed by vacuum drying. 147876.doc • 75- 201109279 NMR (THF-d8 'ppm) measurement to obtain the spectrum of Fig. 15. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was coated by spin coating. On the surface of Corning 1737 glass substrate of 18 mm square, the solvent was dried by heating the substrate at 500 ° for 4 minutes, and zinc oxide was formed at the same time. The above operation was repeated 5 times. The surface resistance was 1300 Ω/□, the film thickness was 〇35 μm, and the volume resistivity was 4.6 ΧΗ)·2 Q.em. Further, it was confirmed to be zinc oxide by XRD (refer to Fig. 16). Further, visible light transmission at 550 nm The rate was 9% by mass, and a transparent zinc oxide film having a transmittance of 80% or more was obtained. [Example 3-2] In the partial hydrolyzate solution of diethylzinc prepared in Example 3-1, Adding trimethylindium in the form of (4) in terms of molar ratio to the diethylzinc charged, thereby obtaining a partial hydrolyzate solution containing 488.1 g of the solution containing the partial hydrolyzate as described above. Coating solution containing product, coated by spin coating on 18 mm square Corning 1737 On the surface of the glass substrate, the solvent was then dried by heating the substrate for 4 minutes, and zinc oxide was formed at the same time. The above operation was repeated 5 times. The surface resistance of the formed film was 587 Ω/□, film. The thickness is 0.37 _, and the volume resistivity is 2.2 Χ 10-2 〜 cm. Further, it is confirmed to be an oxidized word by investigation. Further, the visible light transmittance of (10) is 91%, and transparent oxidation having a transmittance of 8 〇 % or more can be obtained. Zinc film. [Example 3-3] A product containing a partial hydrolyzate obtained as a pin of Example 3 was coated with a solution of 147876.doc -76-201109279, which was applied by spin coating to Corning i737 of 18th position. On the surface of the glass substrate, then the substrate was heated at 500 ° t for 4 minutes to dry the solvent while forming zinc oxide. The above operation was repeated 3G times. The surface resistance of the film is 55 Ω/□, the film thickness is i7i, and the volume resistivity is 9,4χ10·3 Ω. Further, it was confirmed to be zinc oxide by coffee. Further, the visible light transmittance at 550 nm is a transparent zinc oxide film having a transmittance higher than that. [Example 3-4]

Add 1 2 - diethoxyethane (boiling point 12 Γ〇 fan 3 § to add diethyl 5 g (equivalent to 8.7 f%). Stir well and cool to hunger. Will contain 5 ships of water The hydrogen bite (Buddha) solution was added dropwise in such a manner that the molar ratio of water to diethylzinc was 〇.6 (addition amount: 30·1 phantom, then warmed to room temperature (24t) and The reaction was filtered at room temperature with a thin J filter for one hour, thereby obtaining a partial hydrolyzate solution (concentration 6.4 mass.) 245.2 g. In the partial hydrolyzate solution, in relation to the input diethyl ether (four) The molar ratio is added to the form of Q1 to add a triff group, thereby obtaining 245.3 g of a partial hydrolyzate solution containing indium. The coating liquid obtained in the above manner is filled into the spray film forming apparatus of FIG. In the T-fog bottle, place the 18 mm square Corning 1737 glass substrate on the wide plate holder @. In a nitrogen atmosphere, heat the glass substrate to 40 (the second use of the water vapor introduction tube 6 after the TC) Water is introduced into the vicinity of the substrate at a rate of Μ L per minute into the substrate, thereby introducing water. Then, from the spray nozzle, the coating liquid is Spray at 4 ml/min for 16 minutes. The droplet size from the spray nozzle is in the range of 3~20 μπι, and the distance between the spray nozzle and the substrate is 147876.doc •77· 201109279 is set to 3〇(10). The surface resistance of the film is 15 Ω/□, the film thickness is 0.49, and the volume resistivity is 7.4χ1〇-4~coffee. It is confirmed by XRD (refer to Fig. 17) as zinc oxide qa Μ Μ Α δ·3 〇 / 550 nm visible light transmission vehicle is 83% 'a transmission film is available. Half a transparent oxidized thinning of 8 〇 / ° [Example 3-5] Gift 5 endures the application 3-1 ~ 3-4 Φ 々 々 々 々 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 臈 臈 臈 臈 臈 臈 臈 臈 臈 臈 氧化 臈 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化 氧化

The zinc telluride film deposited in 4 has an ultraviolet cut-off function, and the film can be cut off by an external line. I

[Examples 3 to 6] It was confirmed that the emulsified film of the sputum of the exemplified application of the exemplification of the exemplification of the exemplified method of the invention was formed as a transparent electrode, and it was confirmed that it could be used as a transparent conductive film. [Reference Example 3-1] To the 1,2-diethoxyethyl bromide 4〇 〇 g, diethyl ether was added]% g (corresponding to 3.15 mass%). After fully mixing, 'cooling to η:. The liquid solution containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethyl ether was 〇6 (addition amount: 2_〇6 g). Then, the temperature was raised to room temperature = 4 C), and the reaction was carried out at room temperature for 18 hours, and filtration was carried out by a membrane transition apparatus, whereby a partial hydrolyzate solution (concentration of 27% by mass) was obtained. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied onto the surface of a Corning 1737 glass substrate of 18 mm square by spin coating. Then, the solvent was dried by heating the substrate at 50 °C for 4 minutes. The above operation was repeated 5 times. However, the surface resistance of the formed film was 147876.doc -78·201109279, and the sheet resistance was more than 107 〇/□ ( Outside the measurement range, the visible light transmittance at 550 nm is 16% 'only an opaque and high-resistance film with a transmittance of 80% or less is obtained. [Reference Example 3-2] On 1,2-diethoxyethane Add 39 g of diethyl zinc to 39 9 g (equivalent to 16.4% by mass). After stirring well, cool to -12. (:. I. The mixture was added dropwise (total amount: 9.83 g) in such a manner that the molar ratio of diethyl ether was 0.6. Then, the temperature was raised to room temperature (24 C) and allowed to react at room temperature for 18 hours to obtain a membrane filter. Filtration was carried out, whereby a partial hydrolyzate solution (concentration: 125% by mass) of 83 5 g was obtained. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied by spin coating to 18 mm square. On the surface of Corning 1737 glass substrate, the solvent was then dried by heating the substrate at 50 trc for 4 minutes. The above operation was repeated 5 times. However, the surface resistance of the formed film was larger than 1 〇 7 Ω/□ (outside the measurement range), and the visible light transmittance at 550 nm was 88%, and only a film having high resistance was obtained. 〇 [Reference Example 3-3] Add 4g of 35〇g (phase - as at 8.7% by mass) to the gas-trapping (stagnation point 66. 〇39.9 g). After full scramble, cool to ·i2〇c. 5 〇% • The tetrahydrogen solution of water is added dropwise in such a manner that the molar ratio of water to diethyl ether is 0.6 (total amount··6.01 g). Then, the temperature is raised to room temperature (24 C). And reacting at a temperature for 18 hours to filter with a membrane filter, thereby obtaining a portion of the hydrolyzate solution (concentration: 6.6% by mass) of 43.9 g, which will contain a partial hydrolyzate such as F-V. The product-containing coating solution, 147876.doc -79- 201109279 was applied by spin coating on the surface of a Corning 1737 glass substrate of 18 mm square. Then the solvent was made by heating the substrate at 50 rc for 4 minutes. Drying and simultaneously forming an oxidation word. The above operation was repeated twice. The surface resistance of the formed film was 2.2 χ 105 Ω/α. 55〇 nm visible light transmittance of 4%, the opaque film is only obtained. As shown in FIG. 18, in addition to confirmation by XRD to zinc oxide, also confirmed the formation of zinc.

[Reference Example 3-4J The coating liquid obtained in the above manner was filled in the spray bottle in the spray film forming apparatus of Fig. 14. A 18 mm square Corning 1737 glass substrate was placed on the substrate holder. The glass substrate was heated to 400 C under a nitrogen atmosphere. Then, the coating liquid was sprayed from the spray nozzle at 4 d/rnin for 16 minutes without introducing water vapor. The surface resistance of the formed film was Μ% Ω / the thickness of the two films was 可见光.31 (four), 55 〇 (10), and only the opaque and high-resistance film was obtained.

[Reference Example 3 - 5 J In the y second material (stagnation point lGl.lt: ). () § Add diethyl 53.5 g (corresponding to 8.0% by mass). After fully mixing, cool to _ hunger. Will contain 5.0. /. Water K 吟 吟 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( The reaction was carried out at room temperature for 18 hours to carry out a transition with a membrane filter, thereby obtaining a partial hydrolyzate solution (concentration_% by mass) of 616.8 g. In the partial hydrolyzate solution, it was compared with the diethylzinc charged. The ear ratio meter is added to trimethyl indium in the manner of 〇. 6171, thereby obtaining a partial hydrolyzate solution containing indium 617 2 g. 147876.doc -80· 201109279 will be partially hydrolyzed as described above. The product-containing coating solution was applied by spin coating on the surface of a Corning 1737 glass substrate of 18 mm square. Then, the substrate was dried by heating the substrate at 50 rc for 4 minutes. However, the surface resistance of the formed film was Ω/□, the film thickness was 〇37 哗, and the visible light transmittance of the volume resistivity of 4.8×UT1 55 〇nm was %%, and only a film having high resistance was obtained. [Reference Example 3-6] A partial hydrolyzate containing the same as Reference Example 5 The product coating solution was applied onto the surface of a Cornish 1737 glass substrate of 18 mm square by spin coating. Then, the solvent was dried by heating the substrate at 5 ° C for 4 minutes. 5 times. However, the formed film had a surface resistance of 9·3 χΐ〇Ω/□, a film thickness of 0.35 μηι, and a volume resistivity of 3-2ΧΚΤ1 Ωπηι. The visible light transmittance of 55〇nm was 67%, which was only available. A film having a south resistance and being opaque. [Example 3-7] 3.39 g (corresponding to 8.7% by mass) of diethyl zinc was added to 39 9 g of 1,2-diethoxyethane (boiling point i21t). Thereafter, it was cooled to -12. A solution containing 4,000% water in tetrahydrofuran (boiling point 66.0 ° C) was added dropwise in such a manner that the molar ratio of water to diethyl zinc became 〇_6 (addition amount: 611 g). Then, the temperature was raised to room temperature (24 t:) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, thereby obtaining a partial hydrolyzate solution (concentration: 6.5 mass %) of 48.0 g. The spectrum of Fig. 22 was obtained by measuring NMR (THF_d8, Ppm) after removing the solvent or the like by vacuum drying. 6.doc -81 - 201109279 The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied by spin coating on the surface of a Corning 1737 glass substrate of 18 mm square. Then, by using a substrate The film was dried by heating at 500 ° C for 4 minutes to form a zinc oxide. The above operation was repeated 5 times. The surface resistance of the formed film was 1050 Ω / □, the film thickness was 〇 35 , and the volume resistivity was 3.7Χ10-2 Q.cm. Further, it was confirmed to be an oxidized word by XRD. Further, the visible light transmittance at 550 nm was 89%, and a transparent zinc oxide film having a transmittance of (four)% or more was obtained. [Example 3-8] In the partial hydrolyzate solution of the diethyl group prepared in Example 3-7, three were added in a manner of (10) in terms of molar ratio with respect to the charged diethyl group. Methyl gallium was used to obtain a product-containing coating solution containing 48.7 g of a partial hydrolyzate solution of indium - one to one sputum, and was applied by spin coating on a Corning 1737 glass of 18 mm square. Then, by heating the substrate at 50 (rc), the oxidation resistance is formed at the same time. The surface resistance of the film which is repeated five times in the above operation is 420 Ω/ο, and the film thickness is Al6x (V2n, "^ The volumetric electric I® is 550 μm. Further, it is confirmed to be zinc oxide by XRD. In addition, the visible light transmittance of 550 rnn is transparent and transparent oxide film.

[Examples 3-9J The two kinds of bismuth prepared in Examples 3-7 were obtained as 〇〇ι in terms of molar ratio with respect to the person-B (four) and the hydrolyzate solution-ethyl group. 147876.doc -82· 201109279 By adding trioctyl aluminum, a solution of 48.7 g of a partial hydrolyzate containing aluminum was obtained. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied onto the surface of a Corning 1737 glass substrate of 18 mm square by spin coating. Then, the substrate was heated at 50 °C for 4 minutes to dry the solvent while forming zinc oxide. The above operation was repeated 29 times. The surface film formed had a surface resistance of 44 Ω/□ and a film thickness of 191 μm. The volume resistivity is 8.4 Χ10·3 n.cm. Further, it is confirmed to be an oxidized word by XRD. Further, the visible light transmittance of 〇550 nm is 84%, and a transparent zinc oxide film having a transmittance of 8 〇% or more can be obtained. [Examples 3 to 10] In the partial hydrolyzate solution of the diethyl group prepared in Example 3-7, the molar ratio was measured in terms of molar ratio with respect to the charged diethyl zinc. By adding 0.5 hydrazine of a hydrogenated succinyl-triethylamine complex toluene solution, thereby obtaining 48 4 g of a partial hydrolyzate solution containing aluminum. 〇 A product-containing coating liquid containing a partial hydrolyzate obtained in the above manner It was applied by spin coating to the surface of a Corning 1737 glass substrate of the 18th position. Then, the solvent was dried by heating the substrate at 5 Torr for 4 minutes, and zinc oxide was formed at the same time. The surface resistance of the formed film is 57 Ω/□, The thickness is 86 (four), and the volume resistivity is i.ixio-2 n.cm. Further, it is confirmed by XRD as an oxidation word. Further, the visible light transmittance at 550 nm is 84%, and transparent oxidation having a transmittance of (four) or more can be obtained. [Examples 3-11] 147876.doc -83- 201109279 In Example 3-7, 'triethyl gallium, 4 8 · 5 g was added relative to the input mode. Preparation of diethyl a part of the hydrolyzate solution of diethylzinc and a molar ratio of 0.03 to obtain a partial hydrolyzate solution containing gallium. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner, The spin coating method was applied to the surface of a Corning 1737 glass substrate of 18 mm square, and then the solvent was dried by heating the substrate at 500 t: for 4 minutes to form zinc oxide. The above operation was repeated (4). The surface resistance is 62 Ω/□, the film thickness is &quot;4 _, and the volume resistivity is l.lxio-2 〜 cm. Further, it is confirmed to be an oxidized word by XRD. Further, the visible light transmittance at 550 nm is 91%. A transparent oxide film having a transmittance of 80% or more can be obtained. [Examples 3-12]; It is known that triethyl gallium is added in a partial hydrolyzate solution of diethylzinc prepared in Examples 3-7 in such a manner that it is 〇· in terms of molar ratio with respect to the charged diethyl zinc. This obtained a partial hydrolysis of gallium containing 48.2 g. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied by red coating on the surface of a Cornish 1737 glass substrate of 18 mm square. The solvent was dried by heating the substrate at 500 t for 4 minutes while forming an oxidized word. The above operation was repeated 29 times. The formed film had a surface resistance of 40 Ω/□, a film thickness of (10) _, and a volume resistivity of 6.6×W 仏 (10). Furthermore, it was confirmed by the Qing as an oxidation word. Further, the visible light transmittance of 55 〇 rnn was 92%', and a transparent oxidized film having a transmittance of 147876.doc _ 84 · 201109279 was obtained. [Examples 3-13] In the partial hydrolyzate solution of the diethyl group prepared in Examples 3-7, 'in the form of 〇〇3 in terms of molar ratio with respect to the input diethyl zinc Adding gallium chloride, thereby obtaining a partial hydrolyzate solution containing gallium

# The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied by spin coating to the surface of a Corning 1737 glass raft on 18 _ square. Then, the substrate was dried by heating the solvent at 50 (TC for 4 minutes) to form an oxidation term. The above operation was repeated 29 times. The surface resistance of the formed film was 38 Ω/□, and the film thickness was i” The volume resistivity is "xW~m. Further," it is confirmed by oxidation as a oxidized word. Further, a visible light transmittance of 550 nm is 90%, and a transparent zinc oxide film having a transmittance of 8% or more can be obtained. 3-14]; in the partial hydrolyzate solution of diethylzinc prepared in Examples 3-7, chlorination is added in such a manner that it becomes 〇〇3 in terms of molar ratio with respect to the charged diethyl zinc. Indium, thereby obtaining a partial hydrolyzate solution containing gallium... It is applied by spin coating to a surface containing product containing a partial hydrolyzate, as described above, on the surface of a Corning 1737 glass substrate. Then, 'the substrate was heated at 5 Torr. Thickness is &quot;6 _, volume resistance 147876.doc -85- 201109279 rate is 6 6χ1 () 3 Q.em ° Further, as confirmed by XRD zinc oxide. Yet, 550 nm of the visible light transmittance was 92% or more of transmittance of the obtained transparent oxide film speech.

[Example 3-1 5J] The manner in which the hydrazine in the partial hydrolyzate solution of diethylzinc prepared in κ3 to 3-7 was oxime in terms of molar ratio with respect to the diethylzinc which was incorporated. Ethyl gallium acetonate was added, whereby 48.4 g of a partial hydrolyzate solution containing gallium was obtained. The product-containing coating liquid containing the partial hydrolyzate obtained in the above manner was applied by coating onto a surface of a Corning 1737 glass substrate of 18 mm square. Then, the substrate was heated at 5 Torr (rc for 4 minutes to dry the solvent while zinc oxide was formed. The above operation was repeated (four times). The surface film formed had a surface resistance of 41 Ω/□ and a film thickness of 1.63. _, volume resistivity is 6.7x10, .cm. Further, it is confirmed by XRD that zinc oxide... The visible light transmittance at 550 nm is 91%, and a transparent oxidized film having a transmittance of not more than coffee can be obtained. 16] In the partial hydrolyzate solution of the diethyl group prepared in Example 3-7, acetonitrile (tetra) indium was added in a manner of 0.03 in terms of molar ratio with respect to the charged diethyl zinc. This obtained 48.2 g of a partial hydrolyzate solution containing gallium. The swelling was applied to the surface of a Corning 1737 glass substrate of 18 mm square by a spin coating method in the above manner. The solvent 147876.doc -86 - 201109279 was dried by heating the substrate for 4 minutes, and zinc oxide was formed at the same time. Further, the film was repeated 29 times with .^ ^ ^ * 。. The surface resistance of the formed ruthenium film was 42 Ω/□, , 1 μΠ thick, volume resistivity 6.8&gt;&lt;1 〇_3仏(^. The hunting was confirmed by XRD as an oxidation word. In addition, the visible light transmittance at 550 nm was 94%, and the transparent zinc oxide film having a transmittance of 80% or more was obtained. [Example 3-1 7 In the partial hydrolyzate solution of the radicals prepared in Examples 3-7, it is measured in a molar ratio with respect to the -r ❹ ❹ Adding acetic acid steel in the manner of 〇.03, by the person who is a person who has obtained a partial hydrolyzate solution containing gallium, 48.5 g ° The spin coating method was applied to the surface of a Corning 1737 glass substrate of 18 mm square. Then, the solvent was dried by heating the substrate at 500 t for 4 minutes: zinc oxide was simultaneously formed. Further, the above operation was repeated. The surface resistance is 38 Ω/□, and the film thickness is! 6 The rate is further determined by XRD as zinc oxide. Further, the visible light transmittance at 550 nm is 92%, and the transmittance is above 嶋. Transparent oxidized film. [Example 4-1] Preparation of coating composition was carried out in a nitrogen atmosphere The solvent was all dehydrated and degassed. In diisopropyl hydrazine (addition of diethyl quinone 1 〇 54 g' to KM g and 1 添加 with respect to diethylzinc was 1% (〇 11 phantom diethyl IS. After filling (4), the coating composition was obtained by hydrating. The coating composition obtained as above was filled into the mouth of the nozzle of Fig. 23 147876.doc •87· 201109279 In the spray bottle in the membrane device, the slide substrate is placed on the substrate holder. After heating the glass substrate to 100 Torr, the coating group was applied from the spray nozzle under atmospheric pressure at 25 t: in the presence of water at a relative humidity of 60 Torr. The spray was sprayed at 3 ml/min for 1 minute. The droplet size ejected from the spray nozzle was in the range of 3 to 20 μm, and the distance between the spray nozzle and the substrate was set to 4 Torr. The film thickness of the film formed on the substrate was determined by SEM measurement and was about 240 nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown in Fig. 24 . Further, the average transmittance of visible light and the surface resistance are 4·2χ1〇4 Ω/□, and a low-resistance oxidation having a transmittance of 8〇% or more and a surface resistance of 1χ1〇5 Ω/□ or less can be obtained. Zinc film. [Example 4-2] All were carried out in the same manner as in Example 1 except that triethylaluminum was changed to trimethylgallium. The film thickness of the film formed on the substrate was determined by SEM measurement and was about 21 G _. The film formed on the substrate was confirmed to be an oxidized word by XRD as shown in Fig. 25. Further, the average transmittance of visible light was 86%, and the surface resistance was 4·3 χ 1 〇 4..., and a transparent, low-resistance oxidized film having a transmittance of 80% or more was obtained. [Example 4-3] All were carried out in the same manner as in Example 1 except that triethylaluminum was changed to trimethylindium. The film thickness of the film formed on the substrate was determined by SEM measurement and was about 15 Å nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown in Fig. 26 . Further, the average visible light transmittance was 83%, and the surface resistance was 6.7 x 10 〇 3 〇 / □, and a transparent, low-resistance zinc oxide film having a transmittance of 147876.doc -88 - 201109279 80% or more was obtained. [Example 4-4] The same procedure as in Example i was carried out except that the glass substrate was heated to war. The thickness of the film (4) formed on the substrate was determined by capsule measurement and was about 300 nm. The film formed on the 柘μ 兮 wind on the base plate is as shown in Fig. 27, and it is determined by XRD that it is zinc oxide. Further, it is possible to obtain a transparent, low-resistance oxidized film having a transmittance of 80% or more and an average surface transmittance of 82% and a surface resistance of ι.7 χ 1 〇 4 Ω / U i2 / port. Ο

[Example 4-5] The same procedure as in Example 2 was carried out except that the glass substrate was heated to 2 °C. The film thickness of the thin film formed on the substrate was determined by subtractive measurement and was about 250 nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown. Further, the average transmittance of visible light was 86%, and the surface resistance was 8.0 XH) 3 Ω/□, and a transparent 'and low-resistance zinc oxide thin film having a transmittance of 8 % or more was obtained. [Example 4-6] The same procedure as in Example 3 was carried out except that the glass substrate was heated to 200 t. The film thickness of the film formed on the substrate was determined by SEM measurement and was about 280 nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown in Fig. 29 . Moreover, the average transmittance of visible light is 890/. The surface resistance is 3·6 χ 3 Ω/□, and a transparent, low-resistance zinc oxide film having a transmittance of 8〇% or more can be obtained. The following Comparative Examples 1 to 3 were carried out based on the technique of Article 17 (Document No. 199) of the table on page i68 of Non-Patent Document 1. However, the result obtained is 147876.doc •89·201109279, but is a very poor value as shown by the following comparative examples. [Comparative Example 4-1J 卞 肢 肢 肢 肢 · 肢 肢 肢 肢 肢 肢 肢 肢 肢 肢 肢 : : : : 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 20 The chlorinated hexahydrate of 〇9g) was sufficiently discarded to obtain a coating composition. w Apply the above method to the spray bottle in the spray film making device of the Μ 丨 丨 丨 丨 丨 。 。 。. The slide substrate is placed on the substrate holder. The glass substrate is heated to (10). After the crucible, the coated electric object was sprayed at 3 mi/min for 1 G minutes from the nozzle. The peak derived from oxygen (4) was not confirmed by interest (not shown). Further, it can be seen that the average transmittance is 10%, and the surface resistance is larger than ι.〇χίο7, which is an opaque and high-resistance film. [Comparative Example 4-2] - Chlorination will be carried out! All of the hydrates were changed to gallium chloride, and all were carried out in the same manner as in comparison with m. Unrecognized by xrd

Wave crest (not shown). In addition, it can be seen that the average transmittance of the +TJ see nine is 9%, the surface resistance is greater than 1 · 0X 1 〇 7 Ω / □ (measured tendons k, V 疋 dry circumference), only opaque and high can be obtained A film of resistance. [Comparative Example 4-3] In addition to changing the gasification of Mingliushui people's love s &amp; masculine to gasified indium tetrahydrate, the whole op was carried out in the same manner as in Comparative Example 1 . The peak derived from the oxidation word (not shown) was not confirmed by XRD. ^ 147876.doc -90. 201109279 /〇The surface resistance is greater than 1, 〇χ1〇7 Ω/α (outside the measurement range), only opaque, high-resistance films are available. [Industrial Applicability] This month's month can be used in the field of manufacturing of doped and undoped zinc oxide thin films. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an NMR spectrum of an organozinc composition of the 女 女 Μ Μ 人 人 人 实施 实施 实施 实施 ; ; ; ; ; ; ; ; ; NMR NMR 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机 有机

Figure 3 is a spectrum of the zinc oxide film obtained in Example 3; Figure 4 is a spectrum of the zinc oxide film obtained in Example W. Figure 5 is a zinc oxide obtained in Example 1-5. XRD spectrum of the film FIG. 6 is an XRD spectrum of the zinc-zinc film obtained in Example 1 -6. FIG. 7 is an NMR spectrum of diethylzinc (see FIG.); FIG. 8 is obtained in Example 2-1. NMR spectrum after vacuum drying of s; Figure 9 is the spectrum obtained in Example 2-1; Figure 10 is the spectrum obtained in Example 2-2; Figure 11 is the result obtained in Example 2-2 The XRD pattern of the NMR-doped zinc oxide film after vacuum drying of the XRD light of the oxidized film of the oxidized film is the spectrum obtained in Example 2 - 3; Figure 13 is an example The spectrum obtained in 2-3; the XRD light of the NMR steel doped oxidation film after vacuum drying of the composition 147876.doc -91 - 201109279 Figure 14 is obtained in Example 2_4

NMR FIG. 15 is an explanatory diagram of the apparatus used in the drawing (10) to (2) in Example 2-8; FIG. 16 is the result obtained in Example 2-8.

NMR; and NMR of the s object after vacuum drying FIG. 17 is a view showing a spray film forming apparatus; FIG. 18 is an example obtained in the embodiment.

NMR FIG. 19 is the XRD spectrum of the emulsified zinc film obtained in Example 3-1; FIG. 2 is the value of Example 3 - 4 + &amp; The XRD spectrum of the zinc-vaporized film; FIG. 21 is the XRD spectrum of the emulsified zinc film of the room 参考 参考 参考 ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; ; 乳化 乳化 乳化 乳化 乳化

FIG. 23 is a view showing a spray film forming apparatus; FIG. 24 is an XRD of the emulsified film of the eve &amp; Figure 25 is the XRD spectrum of the zinc telluride film of the rod and the hearing piece in Example 4-2; Figure 2 is the zinc film rolled by the film &amp; T in Example 4-3 Figure 27 is an XRD spectrum of the emulsified zinc film obtained in Example 4-4; Figure 28 is an XRD spectrum of the emulsified zinc ruthenium film obtained in Example 4-5; and Figure 29 is The XRD spectrum of the zinc telluride film obtained in Example 4-6. [Main component symbol description] Spray bottle 2 3 〇

CJ substrate holder (with heater) Spray nozzle 147876.doc -92- 201109279 4 Compressor 5 No glass substrate 6 Water vapor introduction tube

147876.doc -93-

Claims (1)

201109279 VII 1. 、, the scope of application for patents: - for the production of zinc oxide film, add water to S2, at least the next, ten? It comprises the product obtained in the solution S1 or the solution. The compound of the organic zinc compound is at least partially hydrolyzed and the product is obtained. The above solution 81 is a substance, a solution, and an organic zinc represented by the following formula (1). The solution S2 is obtained by the following general formula (1), m, s々, phonological compound, and At least one of the steroid and the steroid compound represented by the above formula (2) or the following formula (3) is dissolved in an electron-donating organic solvent: R^Zn-R1 (1) (wherein Rl is a linear or branched alkyl group having a carbon number of 1 to 7) McXd.aH2〇(7) (wherein Μ is a 3B group of genus' χ is a dentate atom, citric acid or sulfuric acid, and is a dentate atom or stone. In the case of erythric acid, (4) and d are 3, when X is sulfuric acid, 'c is 2, d is 3, and a is an integer of 〇~9. r8-~m~r3 * (5) η (3) 〇 (where, The MWB group element, R2, R3, and R4 are independently hydrogen, a linear or branched alkyl group having a carbon number W, a linear or branched alkoxy group having a carbon number of 1 to 7, a decanoic acid group, or an acetoacetone group. Further, L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and η is 0~ 9 integer). 2. The composition of claim 1, wherein the solution 81 is added in such a manner that the molar ratio of the organozinc compound is in the range of 0.6 to 0.9. The composition of claim 2, which comprises a solution obtained by dissolving the above-mentioned product separated from the above organic solvent in a thin 貘 147876.doc 201109279 organic solvent which is different from the above-mentioned electron-donating organic solvent. 4. 12% by mass of the composition of claim 3 wherein the concentration of the above product is in the range of 3. 5. The composition solvent of any one of claims 2 to 4 is tetrahydrofuran. The composition of any one of claims 3 to 5 is an organic solvent of 1,4-second. Wherein the above-mentioned electron donating property has the composition of the above-mentioned film forming claim 1, which is used for the production of a doped oxidized film, wherein the above-mentioned solution is in the middle of the above-mentioned three-element compound relative to the above-mentioned organic compound compound. The ear ratio is a ratio of 0.005 to 0.3. 8. The composition of claim 7 wherein the product comprises a hydrolysate of the above compound of the group 3b. 9. The composition of claim 7 or 8, wherein the molar ratio of the water added to the total of the organic compound and the 3B element compound is in the range of 〇, 4 to 0.9. A composition for the production of a doped oxidized film, which comprises the composition according to any one of claims 1 to 5, which is obtained by adding water to the solution S 2 as described above. A product obtained by adding at least one compound of the group 3B element represented by the formula (2) or the formula (3) in such a manner that the molar ratio of the organozinc compound is 〇·〇〇5 to 0.3, McXd.aH20 (2) (In the formula, Μ is a 3 B group' X is a halogen atom, a sulphuric acid or a sulfuric acid. When χ is a halogen atom or nitric acid, C is 1, d is 3, and when X is sulfuric acid, C is 2, d is 3, a is an integer from 0 to 9) 147876.doc 201109279 R Xuan~~ϊ?容I *(L)a (8) R4 (where M is a 3B element 'R2, R3, R4 are independent a hydrogen or a linear or branched alkyl group having a carbon number of 1 to 7, a linear or branched alkoxy group having a carbon number of 1 to 7, a buffered acid group, or an ethyl acetonide group, and further L is a nitrogen, oxygen or phosphorus. The coordinating organic compound, η is an integer from 0 to 9). The composition of claim 9, wherein the product is substantially free of the hydrolyzate of the above-mentioned compound of the 3 steroid element. The composition of claim 9 or 10, wherein the amount of water added to the above solution (4) is in the range of 〇 4 to 〇 9 with respect to the molar ratio of the above organic compound. The content of the organozinc compound represented by the formula (1) in the above composition, wherein the content of the organozinc compound represented by the formula (1) is 0.5% by mass or less. 13. The composition according to any one of claims 7 to 12, which comprises a solution which is obtained by using the above-mentioned product 〇: = the above-mentioned electron-donating organic solvent to form a film-forming organic/encapitant. 14. The composition of any one of claims 7 to 13, which has a degree of from 1 to 30% by mass. . Concentration of the seat 15. According to the composition of claim 1, the power supply of the above is _ above = raw; 1 the organic solvent is more than the above, the μ point is i, the electronic organic solvent is used as the agent: the above solution si The amount of c dissolved in the above-mentioned solvent in the range of the general organic machine:::: TM is relative to the above-mentioned molar ratio of 147876.doc 201109279 0.4 to 0.8. 16. 17. 18. 19. 20. A composition according to the composition of claim 15 which is added in a ratio of 0.005 to 〇丨 with respect to the molar ratio of the above organozinc compound. Obtained as an organic Group 3B element compound represented by formula (2): Ra-M-R3 I ♦ (L) n (2) R4 (wherein Μ is a group 3B element' R2, r3, and R4 are independently hydrogen and carbon a straight or branched alkyl group, a linear or branched alkoxy group having a carbon number of 1 to 7, a carboxylic acid, or an acetoacetone group, and L is a coordinating organic group containing nitrogen, oxygen, or phosphorus. The compound, η is an integer from 0 to 9). The composition of claim 1, wherein the electron-donating organic solvent is an electron-donating organic solvent having a boiling point of 110 ° C or higher, or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component. The solution S2 is a solution in which the organic zinc compound and the organic 3B group element are dissolved in a total concentration of 4 to 12% by mass; the amount of water added is 〇4 in terms of the molar ratio with respect to the above organic compound. ~0.8 range. The composition of any one of Claims 15 to 17, wherein the above-mentioned electron-donating organic solvent is a composition having a boiling point of 23 or less. The compound of any one of claims 1 to 19, wherein the above-mentioned organic zinc &amp; The composition of any one of claims 1 to 14, wherein the electron-donating organic solvent is 1,4-second. 22. The combination of any one of claims 16 to 21 The composition of the organic group 3B element of the above formula (III) is a composition of any one of claims 16 to 21, wherein the organic group 3B element compound of the above formula (?) is triethyl醯Aluminum acetonide, triethyl hydrazine propyl gallium, gamma gallium, and urethane. 〇〇 24. The 70-mer compound of any one of claims 16 to 21 is aluminum chloride, gallium chloride, indium chloride 25· The composition of any one of claims 16 to 21, wherein the electron donating organic agent is 1,2-diethoxyethane. The composition of any one of 5 to 24, wherein the mixed organic solvent is a mixed solvent of 1,2-diethoxyethane and tetrahydrofuran. 27. A method for producing a zinc oxide film, comprising: The composition of the above-mentioned item is applied to the surface of the substrate, and then the obtained coating film is heated at a temperature of WC or lower to form an oxidized film or an oxidized film doped with a group 3B element. According to the manufacturing method of claim 27, the emulsified film of the basin has an average transmittance of 80% or more for visible light. 29. A method for producing a zinc oxide film, the flying zinc oxide film has a light transmittance of 80/ό or more. The average transmittance is 4 τ and the volume resistivity is less than 8 χΐ〇 2. The manufacturing method includes performing at least the following operations: applying the following compositions A and MC to the surface of the substrate under an inert gas atmosphere, and then The obtained coating film is heated; 147876.doc 201109279 Composition A: The following compound comprises a product obtained by dissolving an organic compound of the following formula at a boiling point of 11 (TC or higher) = organic solvent, or an electron-donating material having a point of (10) or more; a mixed organic solvent as a main component is formed in a solution of 4 to 12 mass% in a solution of the above-mentioned organozinc compound. Adding water in such a manner as to be in the range of 0.4 to 0.8, and at least partially hydrolyzing the above-mentioned compound, W-Zn-Ri (1) (wherein R is a linear or branched alkyl wide composition B of carbon number 7 The composition is added to the above-mentioned composition A, and the organic 3B group compound represented by the following formula (2) is added in such a manner that the molar ratio of the organic compound is 〇〇〇5 to 〇". And R3 ^4 · (U η (2) (wherein, Μ is a 3 steroid element, r2, r3, ^ are independently chlorine, a straight or branched alkyl group having a carbon number w, and a carbon number of 1 to 7 a linear or branched alkoxy group, a carboxylic acid, or a propyl group, L is a coordinating organic compound containing nitrogen, oxygen, or a dish, and η is an integer of 〇~9; Composition C: This combination The product contains the product obtained in the following manner: an organozinc compound represented by the following formula (1), W-Zn-R1 (1) 147876.doc 201109 279 (wherein R1 is a linear or branched alkyl group of carbon number 7), and the following formula (2) is a ratio of 莫5 to 〇〇9 of the above organic compound; (7) The organic steroidal compound R2~M*~ R3 R4 (L) (2) (wherein Μ is a group 3B element, R2, R3, and ruler 4 are independent of chlorine, carbon number 7 or a branched alkyl group, a linear or branched (tetra)oxy group 1 Ο Ο acid or an acetoacetone group, and L is a coordinating organic compound containing nitrogen, oxygen, or lin, and η is 0 to 9 Integer) McXd«aH20 (3) (In the formula, 'Μ is a 3B element' X is a crypto-atom, a sulphuric acid or a sulphuric acid, when X is a sulphate atom or a sour acid '..., 呜 3' In the case of sulfuric acid, c is 2, d is 3, and a is an integer of 〇~9.) It is dissolved in an electron-donating organic solvent having a boiling point of 11 〇t or more, or an electron-donating organic solvent having a boiling point of UOt or more as a main component. Mixing an organic solvent to form a solution having a total concentration of the above organozinc compound and an organic grouping compound in a range of 4 to 12% by mass, relative to the above-mentioned organic compound Water becomes 〇.4~0.8 scope of the embodiment, the speech of the organic compound at least partially hydrolyzed. A method for producing a zinc oxide film according to claim 29, wherein the inert gas contains water vapor per site. The method for producing the product of the invention, wherein the inert gas containing water vapor has a relative humidity of 2 to 15%. 32. A method for producing a chemical film, wherein the zinc oxide thin film has a flat transmittance of 80% or more and a small volumetric electric power rate (10) for a visible light device 147876.doc 201109279, and the manufacturing method comprises a composition of a composition of A1. , B or C in the gas; in the inert gas atmosphere of the steamed composition A: sprayed on the surface of the heated substrate; : combination t contains the product obtained as follows: (d) the following two formula: The compound is dissolved in a solution having a concentration of 4 to 12 or a mixture of a solvent having a boiling point of (10) or more, or a mixed organic solvent having a boiling point of (10) or more and an electron-donating organic solvent as a main component;斟 斟 L L + ' 軏 軏 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对 相对-Zn-R丨(1) (wherein R1 is a linear or branched alkyl group having a carbon number of i to 7); Composition B: The composition is in the above composition A in relation to the above-mentioned organic zinc The molar ratio of the compound becomes 0.005~〇 The ratio of the organic group 3B element compound represented by the following formula (2) is added in a ratio of R3 I * (L) η (2) R4 (wherein, VI) is a group 3B element, R2, R3, R4 a linear or branched alkyl group independently of hydrogen, having a carbon number of 1 to 7, a linear or branched alkoxy group having a carbon number of 1 to 7, a buffered acid, or an acetonitrile acetone group 'L containing nitrogen, oxygen, or a coordinating organic compound of phosphorus, η is an integer of 0 to 9); Composition C: 147876.doc 201109279 The composition contains a product obtained by: an organic zinc represented by the following general formula (1) a compound, R^Zn-R^l) (wherein R1 is a linear or branched alkyl group having 1 to 7 carbon atoms), and the molar ratio of the above organic compound is 〇〇〇5 to 〇〇9 In the proportion of the organic group 3B element compound I, * α) η (2) represented by the following formula (2) or (3) (wherein, Μ is a 3 steroid element, and R 2 , R 3 , and R 4 are independently hydrogen and carbon number 丨a straight or branched alkyl group, a linear or branched alkoxy group having a carbon number of 丨7, a carboxylic acid, or an acetamidine group, and L is a ligand containing nitrogen, oxygen, or arsenic. Organic compound, η is an integer from 0 to 9 McXd.aH20 (3) (wherein Μ is a Group 3B element, X is a halogen atom, citric acid or sulfuric acid, and when 〇Χ is a functional atom or nitric acid, c is l, d is 3, when hydrazine is sulfuric acid , 'c is 2, d is 3, and a is an integer of 0 to 9.) An organic solvent which is dissolved in a stagnation point of not more than or more, or a mixed organic compound containing an electron-donating organic solvent having a boiling point of uot or more as a main component The solvent is added to the solution in which the total concentration of the organic zinc compound and the organic trihetero compound is in the range of 4 to 12% by mass, and is added so as to be in the range of 〇4 to 〇8 with respect to the molar ratio of the organic zinc compound. Water, at least partially hydrolyzed the above organozinc compound. ^ 33. The method of producing a zinc oxide film according to claim 32, wherein the inert gas atmosphere containing water is formed by supplying water vapor at 147876.doc 201109279 to the vicinity of the surface of the substrate under atmospheric pressure or pressure. 34. The method of producing a zinc oxide film according to claim 32, wherein the substrate surface has a heating temperature of 400. The method of producing the oxidized film according to claim 33 or 34, wherein the supply of the water vapor is in a range of 0.1 to 5 with respect to the molar ratio of zinc in the supplied composition. 36. According to any one of claims 29 to 35, the method for producing an emulsified sputum film of the above-mentioned emulsified sputum film is 23 〇t or less. 37. The method for producing a oxidized film according to any one of claims 29 to 36, wherein the organozinc compound is diethyl. 38. The zinc film according to any one of claims 29 to 37. In the production method, the organic group 3B element compound of the above formula (2) is a trimethyl group. 39_ The method for producing an oxidized word film according to any one of claims 29 to 37, The organic 3B group of the above formula (2) is a compound of acetylated human inflammatory __ 凡 京 三 三 化合物 化合物 化合物 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 40 37中任—J制造 苜 好 好 之 之 之 薄膜 薄膜 , , , , , , , , The squadron of the squadron is vaporized aluminum, gallium chloride or chlorinated. 41. The method for producing a zinc oxide film according to any of claims 29 to 40, wherein the above-mentioned electron-donating organic solvent The method for producing a #1 zinc film according to any one of claims 29 to 40, wherein the mixed organic solvent is 1. A mixed solvent of 1,2-diethoxyethane and tetrahydrofuran. 43_ An antistatic film comprising I 3 manufactured by the method of manufacturing according to any one of claims 29 to 42 147876.doc -10·201109279 A zinc oxide film. 44. An ultraviolet cut film comprising a oxidized film produced by the method of any one of claims 29 to 42. 仏-type transparent electrode film comprising use as claimed in claims 29 to 42 A zinc oxide thin film produced by the method of any one of the inventions, wherein the composition for forming a zinc oxide thin film contains an organic word represented by the following general formula (1) in an organic solvent having electron donating properties. Compound Ο 以及 and the following formula ( 2)) the organic element compound shown, and the molar ratio of the above organic 3 lanthanum element compound to the above organic compound is in the range of 0.001 to 0.3; R^Zn-R^l) (wherein, R a linear or branched alkyl group having a carbon number of 1 to 7) (20) R20 - ^i - R30 4 0 R (wherein Μ is a Group 3B element, r2, r3g and independently hydrogen or a carbon number of 1 to 7) A linear or branched alkyl group;). The composition of claim 46, wherein the steroid element is b, VIII or In. The composition of claim 46 or 47, wherein, in the above organic compound, R1 is an ethyl group, and in the above organic group 3B element compound, M is aluminum, and r2〇, R30 and R4G are all ethyl groups. 49. The composition of claim 45 or 46, wherein, in the above organozinc compound, R is an ethyl group, and in the above organic group 3B element compound, μ is gallium, and r2〇, R30 and R40 are each a methyl group. 147876.doc -11 - 201109279 50. As requested in item 46 or 47 of 4a gossip L A. In the above organic compound, R is an ethyl group, and in the above organic compound, R3〇; in the Sd4〇^, a compound, the ruthenium is indium, and the r20 R and R40 are each a methyl group. K, wherein the above organic zincation is 15% by mass or less. Wherein the above-mentioned organic solvent is 51. The total concentration of the composition of any of the claims 46 to 50 and the organic 3B compound is 52. The composition of any one of claims 50 to 51 is two different. C. 53. A method for producing a zinc oxide film doped with a Group 3B element, which is to be subjected to a substrate temperature of 3 〇〇t or less under atmospheric pressure or under pressure in the presence of water. The composition of the item 52 is recorded on the surface of the substrate, and (4) is a film of the doped 3b and zinc. The method of claim 53, wherein the spraying of the composition ejects the composition from the spray nozzle in a range of droplet size to the range of the droplets and the distance between the spray nozzle and the substrate Set to within 5 〇cm. 55. The method of manufacturing of claim 53 or 54, wherein the ambient temperature at which the spraying is performed is 40 ° C or less. The manufacturing method according to any one of claims 53 to 55, wherein the zinc oxide film has an average transmittance of 80% or more for visible light and a surface resistance of Ιχίο5 Ω/□ or less. 147876.doc •12-