TWI465401B - "dope or undoped zinc oxide thin film manufacturing method and a method for producing the zinc oxide thin film using the same - Google Patents

Description

Doped or undoped zinc oxide film manufacturing composition and method for producing zinc oxide film using same

The first aspect of the present invention relates to a composition for producing a zinc oxide thin film which is prepared by using an organic zinc compound as a raw material, which is non-flammable and easy to handle, and a method for producing a zinc oxide thin film using the same. In particular, the present invention relates to a composition for producing a zinc oxide thin film which can form a transparent zinc oxide thin film having high transmittance for visible light by heating at a temperature of about atmospheric pressure and at a temperature of 300 ° C or lower. And a method for producing a zinc oxide film using the composition.

Further, a second aspect of the present invention relates to a composition for producing a zinc oxide thin film doped with a Group 3A element which is prepared by using an organozinc compound as a raw material, is non-flammable, and is easy to handle, and is doped with the same. A method for producing a zinc oxide film of a Group 3A element. In particular, the present invention relates to an oxidation of a group of 3A-doped transparent zinc oxide thin films having high transmittance for visible light by heating at a temperature of about atmospheric pressure and at a temperature of 300 ° C or lower. A composition for producing a zinc thin film and a method for producing a zinc oxide thin film doped with a 3A group element using the composition.

Further, the third aspect of the present invention relates to an oxidation capable of producing an average transmittance of 80% or more for visible light and having a low volume resistivity which can be used for an antistatic film, an ultraviolet cut film, a transparent electrode film, or the like. A composition for producing a zinc oxide film of a zinc thin film. The composition for producing a zinc oxide thin film of the present invention is prepared by using an organic zinc compound as a raw material, has no ignitability and is easy to handle, and further has a volume resistivity of less than 8 when used as a spin coating or dip coating raw material. zinc oxide thin film properties × 10 ^-2 Ω‧cm, the spray pyrolysis when used as the coating material, may provide a volume resistivity of zinc oxide thin film less than 1 × 10 ^-3 Ω‧cm of characteristics.

The fourth aspect of the present invention relates to a zinc oxide film having a low transmittance of 80% or more for visible light and having a low volume resistivity which can be used for an antistatic film, an ultraviolet cut film, a transparent electrode film, or the like. The method further relates 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, when spin coating or dip coating, a zinc oxide film having a volume resistivity of less than 8 × 10 ^-2 Ω ‧ cm can be obtained, and when spray pyrolysis is used, A zinc oxide film having a volume resistivity of less than 1 × 10 ^-3 Ω ‧ cm can be obtained.

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 zinc oxide thin film doped with a Group 3A element, and a method for producing a zinc oxide thin film doped with a Group 3A element.

A transparent zinc oxide film doped with a 3A element or an undoped film having high transmittance for visible light can be used for a photocatalyst film, an ultraviolet cut film, an infrared reflective film, a CIGS (Copper Indium Gallium Selenide) solar cell. The buffer layer, the electrode film of the dye-sensitized solar cell, the antistatic film, the compound semiconductor light-emitting element, the thin film transistor, and the like have a wide range of uses.

As a method of manufacturing a doped or undoped transparent zinc oxide film, it is known There are various methods (Non-Patent Document 1), and as a representative method for using an organic zinc compound as a raw material, there are a chemical vapor deposition (CVD) method (Non-Patent Document 2), and a spray pyrolysis method (non-patent) Patent Document 3), a spin coating method (Patent Document 1), and a dip coating method (Non-Patent Document 4).

However, in the chemical vapor deposition (CVD) method, there are the following problems, etc., it is necessary to use a large-sized vacuum container, and the film formation speed is very slow, so that the manufacturing cost is increased, and, since, zinc oxide can be formed according to the size of the vacuum container. The size of the film is limited and it is impossible to form a large one.

Compared with the above chemical vapor deposition (CVD) method, the above coating method has the advantages that the productivity is high and the manufacturing cost is low because the apparatus is simple and the film formation speed is high. Moreover, since it is not necessary to use a vacuum container and is not restricted by the vacuum container, a large zinc oxide film can be produced.

In the above spray pyrolysis method, solvent drying is carried out while spraying, and then the substrate temperature is heated to 360 ° C or higher to obtain a zinc oxide thin film coating film.

In the spin coating method or the dip coating method, the solvent is dried after spin coating or dip coating, and then the substrate temperature is heated to 400 ° C or higher to obtain a zinc oxide thin film coating film.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 7-182939

[Non-patent literature]

[Non-Patent Document 1] Japan Society for the Promotion of Science, Transparent Oxide Photoelectron Materials 166 Committee Editing, Transparent Conductive Film Technology Revision 2 (2006), p165~173

[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

A doped or undoped transparent zinc oxide film uses a plastic substrate as a substrate. Therefore, the heating applied when the transparent zinc oxide film is formed must be carried out below the heat resistant temperature of the plastic substrate. However, in the spray pyrolysis method described in Non-Patent Document 3, the spin coating method described in Patent Document 1, and the dip coating method described in Non-Patent Document 4, transparent oxidation cannot be obtained by heating at a temperature lower than the heat resistance temperature of the plastic substrate. Zinc film. In consideration of the heat resistant temperature of the plastic substrate and the cost required for heating, etc., the heating required for film formation is desirably 300 ° C or less.

According to the study by the inventors of the present invention, an aqueous solution of zinc acetate used in the spray pyrolysis method described in Non-Patent Document 3 and an organic zinc compound and an organic solvent used in the spin coating method described in Patent Document 1 are used. In the solution or the solution containing the organic zinc compound and the organic solvent used in the dip coating method described in Non-Patent Document 4, the film is formed at 300 ° C or lower, and a transparent zinc oxide film cannot be obtained, and only an opaque zinc oxide film is obtained. . Patent Document 1 also discloses a method of using a diethyl zinc hexane solution. The use of this solution attempted to form a film below 300 ° C, but a transparent zinc oxide film could not be obtained.

Further, diethylzinc is a compound which is flammable in the atmosphere and must be paid attention to during storage and use. Therefore, in practical use, it is difficult to use it in a spray pyrolysis method, a spin coating method, or the like which is usually carried out in an environment where water is not diluted without diluting diethylzinc. In the state in which diethylzinc is dissolved in an organic solvent, the risk of ignitability and the like can be reduced. However, as described in Patent Document 1, a zinc oxide film of diethylzinc dissolved in an alcohol-based organic solvent is used while reacting. In the film formation, it is necessary to perform heating at a high temperature of 400 ° C or higher.

An object of the present invention is to provide a composition for producing a zinc oxide thin film which is prepared by using an organic zinc compound as a raw material, but which is flammable and easy to handle, and can be doped with heating at 300 ° C or lower even if heating is required. A 3A element or an undoped transparent zinc oxide film. Further, an object of the present invention is to provide a method in which, in consideration of the heat-resistant temperature of a plastic substrate and the cost required for heating, the composition is not required to be heated at the time of film formation, or may be heated at 300 ° C or lower even if heated. A transparent zinc oxide film doped with a Group 3A element or undoped is obtained.

A first aspect of the present invention relates to a composition for producing a zinc oxide thin film, comprising: adding water to a solution S1 or a solution S2, at least partially hydrolyzing the following organic zinc compound; and the solution S1 is The organozinc compound represented by the above formula (1) is dissolved in an electron-donating organic solvent; the solution S2 is an organozinc compound represented by the following formula (1), and the following formula (2) Or at least one of the Group 3A element compounds represented by the following formula (3) is dissolved in an electron-donating organic solvent: R ¹ -Zn-R ¹ (1) (wherein R ¹ is carbon a straight or branched alkyl group of 1 to 7) M _c X _d ‧aH ₂ O (2) (wherein M is a Group 3A element, X is a halogen atom, nitric acid or sulfuric acid, and X is a halogen atom or nitric acid When c is 1, and d is 3, when X is sulfuric acid, c is 2, d is 3, and a is an integer of 0 to 9) (wherein M is a Group 3A 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; a carboxylic acid group or an acetoacetone group, and further L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and n 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 zinc oxide thin film and a method for producing a zinc oxide thin film using the composition. The first aspect 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 organozinc compound is 0.6 to 0.9, and at least partially hydrolyzing the organozinc compound. A composition of the product. The composition of the first aspect is described in the following 1-1 to 1-7, and the manufacturing method of the first aspect is as described in the following 1-8 to 1-9.

[1-1]

A composition for producing a zinc oxide thin film comprising a product produced by dissolving an organozinc compound represented by the following formula (1) in an electron donating organic solvent, Water is added in a manner that the molar ratio of the organozinc compound is in the range of 0.6 to 0.9, and the above organozinc compound is at least partially hydrolyzed: R ¹ -Zn-R ¹ (1) (wherein R ¹ is a carbon number of 1) ~7 linear or branched alkyl).

[1-2]

The composition of [1-1], which comprises a solution obtained by dissolving the above-mentioned product separated from the above organic solvent in an organic solvent for forming a film different from the above-mentioned electron-donating organic solvent.

[1-3]

A composition according to [1-2], wherein the concentration of the above product is in the range of 3 to 12% by mass.

[1-4]

The composition according to any one of [1-1] to [1-3] wherein the above organozinc compound R ¹ is a compound having an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms.

[1-5]

The composition of any one of [1-1] to [1-4] wherein the above organozinc compound is diethylzinc.

[1-6]

The composition according to any one of [1-1] to [1-5] wherein the electron donating organic solvent is tetrahydrofuran.

[1-7]

The composition of any one of [1-2] to [1-6], wherein the organic solvent for forming the film is 1,4-two alkyl.

[1-8]

A method for producing a zinc oxide 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 a temperature of 300 ° C or lower Heating is performed to form a zinc oxide film.

[1-9]

The 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 a zinc oxide thin film doped with a Group 3A element, and a method for producing a zinc oxide thin film using the composition. The second aspect is a composition comprising the above-mentioned solution S2 and the addition ratio of the group 3A element compound in the solution S2 is in the range of 0.005 to 0.3 with respect to the molar ratio of the above organozinc compound, and The organozinc compound is at least partially hydrolyzed. The composition of the second aspect is described in the following 2-1 to 2-12, and the manufacturing method of the second aspect is as described in the following 2-13 to 2-14.

[2-1]

A composition for doping a zinc oxide thin film, which comprises an organozinc compound represented by the following formula (1) and a group 3A represented by the following formula (2) or the following formula (3); a product obtained by at least one of an elemental compound dissolved in an electron-donating organic solvent and having at least partially hydrolyzed the above-mentioned organozinc compound, and the above-mentioned Group 3A element compound is relative to the above-mentioned organozinc compound The ratio of the ear ratio is 0.005 to 0.3: R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) M _c X _d ‧aH ₂ O (2 (wherein M is a Group 3A element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, d is 3, and when X is sulfuric acid, c is 2, and d is 3 , a is an integer from 0 to 9) (wherein M is a Group 3A 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; a carboxylic acid group or an acetoacetone group, and further L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9).

[2-2]

The composition of [2-1], wherein the above product comprises a hydrolyzate of the above-mentioned Group 3A element compound.

[2-3]

The composition of [2-1] or [2-2], wherein the molar amount of the above-mentioned water added is in the range of 0.4 to 0.9 with respect to the total amount of the above organozinc compound and the 3A group element compound.

[2-4]

A composition for doping a zinc oxide thin film, comprising a product obtained by dissolving an organozinc compound represented by the formula (1) in a solution obtained by dissolving an organic zinc compound in an electron-donating organic solvent; After at least partially hydrolyzing the above-mentioned organozinc compound, the compound of the group 3A or the compound of the group 3A represented by the formula (3) is added in a ratio of 0.005 to 0.3 with respect to the molar ratio of the organozinc compound. At least one species: R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) M _c X _d ‧aH ₂ O (2) (wherein M is a Group 3A element, X is a halogen atom, nitric acid or sulfuric acid. When X is a halogen atom or nitric acid, c is 1, and d is 3. When X is sulfuric acid, c is 2, d is 3, and a is 0~ 9 integer) (wherein M is a Group 3A 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; a carboxylic acid group or an acetoacetone group, and further L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9).

[2-5]

A composition according to [2-4], wherein the above product is substantially free of a hydrolyzate of the above-mentioned Group 3A element compound.

[2-6]

The composition of [2-4] or [2-5], wherein the amount of water added is in a range of from 0.4 to 0.9 with respect to the molar ratio of the above organozinc compound.

[2-7]

The composition of any one of the above-mentioned composition, wherein the content of the organozinc compound represented by the formula (1) in the above composition is 0.5% by mass or less.

[2-8]

The composition according to any one of [2-1] to [2-7], which comprises dissolving the above product in an organic solvent for forming a film different from the above-mentioned electron-donating organic solvent A solution from the middle.

[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.

[2-10]

The composition according to any one of [2-1] to [2-9] wherein the above organozinc compound R ¹ is a compound having an alkyl group having 1, 2, 3, 4, 5 or 6 carbon atoms.

[2-11]

The composition of any one of [2-1] to [2-10] wherein the above organozinc compound is diethylzinc.

[2-12]

The composition of any one of [2-1] to [2-11] wherein the above-mentioned electron-donating organic solvent is 1,4-two alkyl.

[2-13]

A method for producing a doped zinc oxide film, comprising: applying a composition according to any one of [2-1] to [2-12] on a surface of a substrate, and then applying the obtained coating film to 300 ° C or lower Heating at a temperature to form a zinc oxide thin film doped with a Group 3A element.

[2-14]

The method according to [2-13], wherein the doped zinc oxide film has an average transmittance of 80% or more for visible light.

The third aspect is a composition for producing a zinc oxide thin film doped with a Group 3A element. The third aspect is a composition comprising the following product, which uses an electron-donating organic solvent having a boiling point of 110 ° C or higher, or a boiling point of 110 ° C. The above-mentioned organic solvent containing an electron-donating organic solvent as a main component is obtained as an electron-donating organic solvent, and at least partially hydrolyzed the organozinc compound. The composition of the third aspect is as described in the following 3-1 to 3-10.

[3-1]

A composition comprising a product obtained by dissolving an organozinc compound represented by the following formula (1) in an electron-donating organic solvent having a boiling point of 110 ° C or higher, or having a boiling point of 110 ° C. In the solution having a concentration of 4 to 12% by mass in the above-mentioned organic solvent as a main component, the organic solvent is added in a range of 0.4 to 0.8 with respect to the molar ratio of the organic zinc compound. Further, at least the above organozinc compound is partially hydrolyzed: R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms).

[3-2]

A composition according to the composition [3-1], wherein the organic 3A represented by the following formula (3) is added in such a manner that the molar ratio of the organozinc compound is 0.005 to 0.1. Obtained by a group of elemental compounds: (wherein M is a Group 3A 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; A carboxylic acid or an acetoacetone group, and L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9).

[3-3]

A composition comprising a product obtained by the following general formula (1), R ¹ -Zn-R ¹ (1) (wherein R ¹ is a carbon number) 1 to 7 linear or branched alkyl groups)

An organic 3A group compound represented by the following formula (2) or (3) in a molar ratio of 0.005 to 0.09 with respect to the above organozinc compound (wherein M is a Group 3A 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; , carboxylic acid, or acetoacetone, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9) M _c X _d ‧aH ₂ O (2) (wherein, M Is a group 3A 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, when X is sulfuric acid, c is 2, d is 3, a is 0-9 The integer).

The total concentration of the organic zinc compound and the organic Group 3A element compound is determined by being dissolved in an electron-donating organic solvent having a boiling point of 110 ° C or higher or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component. In the solution in the range of 4 to 12% by mass, water is added so as to have a molar ratio of 0.4 to 0.8 with respect to the organic zinc compound, and at least the organic zinc compound is partially hydrolyzed.

[3-4]

The composition according to any one of [3-1] to [3-3] wherein the electron-donating organic solvent has a boiling point of 230 ° C or lower.

[3-5]

The composition of any one of [3-1] to [3-4] wherein the above organozinc compound is diethylzinc.

[3-6]

The composition according to any one of [3-2] to [3-5] wherein the organic Group 3A element compound of the above formula (2) is trimethylindium.

[3-7]

The composition of any one of [3-2] to [3-5], wherein the organic 3A group compound of the above formula (2) is aluminum triacetate, gallium triacetate, triacetonitrile indium.

[3-8]

The composition according to any one of [3-2] to [3-5] wherein the above organic Group 3A element compound is aluminum chloride, 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]

The composition according to any one of [3-1] to [3-8] wherein the mixed organic solvent is a mixed solvent of 1,2-diethoxyethane and tetrahydrofuran.

The second aspect of the present invention is a method for producing a zinc oxide thin film according to a fourth aspect of the present invention. A zinc oxide film of the second aspect (fourth aspect) of the present invention In the production method, the composition of the third aspect of the first aspect of the present invention is used. The manufacturing method of the second aspect (fourth aspect) of the present invention is as described in the following 4-1 to 4-10.

[4-1]

A method for producing a zinc oxide film having an average transmittance of 80% or more for visible light and a volume resistivity of less than 8 × 10 ^-2 Ω ‧ cm, the manufacturing method comprising performing at least one of the following operations: The composition A, B or C is applied to the surface of the substrate under an inert gas atmosphere, and then the obtained coating film is heated; Composition A: the composition contains the product obtained in the following manner, that is, The organozinc compound represented by the formula (1) is dissolved in an electron-donating organic solvent having a boiling point of 110 ° C or higher, or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or higher as a main component. In the solution having a concentration in the range of % by mass, water is added so as to have a molar ratio of 0.4 to 0.8 with respect to the above-mentioned organozinc compound, and at least partially hydrolyzed, R ¹ -Zn-R ¹ ( 1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms); and composition B: the composition is in the above composition A to be compared with the molar ratio of the above organozinc compound Add the following general formula (3) in a ratio of 0.005 to 0.1 Obtained as an organic 3A group compound as shown, (wherein M is a Group 3A 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; a carboxylic acid or an acetoacetone group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9; and composition C: the composition comprises a product obtained in the following manner, That is, an organozinc compound represented by the following formula (1) and R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms)

An organic 3A group compound represented by the following formula (2) or (3) in a molar ratio of 0.005 to 0.09 with respect to the above organozinc compound (wherein M is a Group 3A 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; , carboxylic acid, or acetoacetone, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9) M _c X _d ‧aH ₂ O (2) (wherein, M Is a group 3A 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, when X is sulfuric acid, c is 2, d is 3, a is 0-9 The integer).

The total concentration of the organic zinc compound and the organic Group 3A element compound is determined by being dissolved in an electron-donating organic solvent having a boiling point of 110 ° C or higher or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component. In the solution in the range of 4 to 12% by mass, water is added so as to have a molar ratio of 0.4 to 0.8 with respect to the organic zinc compound, and at least the organic zinc compound is partially hydrolyzed.

[4-2]

A method for producing a zinc oxide thin film according to [4-1], wherein the inert gas atmosphere contains water vapor.

[4-3]

The manufacturing method of [4-2], wherein the inert gas atmosphere containing water vapor has a relative humidity of 2 to 15%.

[4-4]

A method for producing a zinc oxide film having an average transmittance of 80% or more for visible light and a volume resistivity of less than 1 × 10 ^-3 Ω ‧ cm, the method comprising: preparing composition A, B or C Sprayed on the surface of the heated substrate in an inert gas atmosphere containing water vapor; Composition A: The composition comprises a product obtained in the following manner, that is, an organozinc compound represented by the following formula (1) a solution prepared by dissolving in an electron donating organic solvent having a boiling point of 110 ° C or higher or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component in a concentration of 4 to 12% by mass; Water is added in such a manner that the molar ratio of the above organozinc compound is in the range of 0.4 to 0.8, and at least the above organozinc compound is partially hydrolyzed, R ¹ -Zn-R ¹ (1) (wherein R ¹ is a carbon number) a straight or branched alkyl group of 1 to 7); composition B: the composition is added to the above composition A, and the following ratio is added to the ratio of the molar ratio of the above organozinc compound to 0.005 to 0.1. Obtained as an organic 3A group compound represented by the formula (3) , (wherein M is a Group 3A 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; a carboxylic acid or an acetoacetone group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9; and composition C: the composition comprises a product obtained in the following manner, That is, an organozinc compound represented by the following formula (1) and R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms)

An organic 3A group compound represented by the following formula (2) or (3) in a molar ratio of 0.005 to 0.09 with respect to the above organozinc compound (wherein M is a Group 3A 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; , carboxylic acid, or acetoacetone, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9) M _c X _d ‧aH ₂ O (2) (wherein, M Is a group 3A 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, when X is sulfuric acid, c is 2, d is 3, a is 0-9 The integer).

The total concentration of the organic zinc compound and the organic Group 3A element compound is determined by being dissolved in an electron-donating organic solvent having a boiling point of 110 ° C or higher or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component. In the solution in the range of 4 to 12% by mass, water is added so as to have a molar ratio of 0.4 to 0.8 with respect to the organic zinc compound, and at least the organic zinc compound is partially hydrolyzed.

[4-5]

A method for producing a zinc oxide thin film according to [4-4], wherein an inert gas atmosphere containing water vapor is formed by supplying water vapor to the vicinity of the surface of the substrate under atmospheric pressure or under pressure.

[4-6]

A method for producing a zinc oxide thin film according to [4-4], wherein a heating temperature of the surface of the substrate is 400 ° C or lower.

[4-7]

A method for producing a zinc oxide thin film according to [4-5] or [4-6], wherein the supply of the water vapor is in a range of 0.1 to 5 in terms of a molar ratio of water to zinc in the supplied composition. The way to do it.

[4-8]

The method for producing a zinc oxide thin film according to any one of [4-1] to [4-7] wherein the electron-donating organic solvent has a boiling point of 230 ° C or lower.

[4-9]

The composition of any one of [4-1] to [4-8] wherein the above organozinc compound is diethylzinc.

[4-10]

The method for producing a zinc oxide thin film according to any one of [4-1] to [4-9] wherein the organic Group 3A element compound of the above formula (2) is trimethylindium.

[4-11]

The method for producing a zinc oxide thin film according to any one of [4-1] to [4-9] wherein the organic 3A group element compound of the above formula (2) is aluminum triacetate, gallium triacetate, Indium triacetate.

[4-12]

The method for producing a zinc oxide thin film according to any one of [4-1] to [4-9] wherein the organic Group 3A element compound is aluminum chloride, gallium chloride or indium chloride.

[4-13]

The method for producing a zinc oxide thin film according to any one of [4-1] to [4-12] wherein the electron-donating organic solvent is 1,2-diethoxyethane.

[4-14]

a method for producing a zinc oxide thin film according to any one of [4-1] to [4-12], wherein The above mixed organic solvent is a mixed solvent of 1,2-diethoxyethane and tetrahydrofuran.

[4-15]

An antistatic film comprising a zinc oxide film produced by the production method according to any one of [4-1] to [4-14].

[4-16]

An ultraviolet cut film comprising a zinc oxide film produced by the production method according to any one of [4-1] to [4-14].

[4-17]

A transparent electrode film comprising a zinc oxide film produced by the production method according to any one of [4-1] to [4-14].

The third aspect of the present invention is a method for producing a zinc oxide thin film-forming composition according to a fifth aspect of the present invention and a zinc oxide thin film doped with a 3A-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 the zinc oxide thin film doped with the 3A group element are as described in the following 5-1 to 5-11.

[5-1]

A composition for forming a zinc oxide thin film, comprising an organic zinc compound represented by the following formula (1) and an organic 3A group represented by the following formula (20) in an organic solvent having electron donating properties; An elemental compound, wherein the molar ratio of the above organic Group 3A element compound to the above organozinc compound is in the range of 0.001 to 0.3; R ¹ -Zn-R ¹ (1) (wherein R ¹ is a carbon number of 1 to 7) Linear or branched alkyl) (wherein M is a Group 3A element, and R ²⁰ , R ³⁰ and R ^{40 are} independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms).

[5-2]

A composition according to [5-1], wherein the above Group 3A element is B, Al, Ga or In.

[5-3]

The composition of [5-1] or [5-2] wherein, in the above organozinc compound, R ¹ is an ethyl group, and among the above organic group 3A element compounds, M is aluminum, and R ²⁰ , R ³⁰ and R ⁴⁰ are both It is an ethyl group.

[5-4]

The composition of [5-1] or [5-2] wherein, in the above organozinc compound, R ¹ is an ethyl group, and among the above organic group 3A element compounds, M is gallium, and R ²⁰ , R ³⁰ and R ⁴⁰ are both Is a methyl group.

[5-5]

The composition of [5-1] or [5-2] wherein, in the above organozinc compound, R ¹ is an ethyl group, and in the above organic group 3A element compound, M is indium, and R ²⁰ , R ³⁰ and R ⁴⁰ are both Is a methyl group.

[5-6]

The composition according to any one of [5] to [5-5] wherein the total concentration of the organic zinc compound and the organic 3A compound is 15% by mass or less.

[5-7]

The composition according to any one of [5] to [5-6] wherein the organic solvent is Diisopropyl ether.

[5-8]

A method for producing a zinc oxide film doped with a 3A group element, characterized in that under atmospheric pressure or pressure, in the presence of water, and at a substrate temperature of 300 ° C or lower, such as [1] to [7] The composition of any one of the compositions is sprayed on the surface of the substrate to form a zinc oxide film doped with a Group 3A element.

[5-9]

[5-8] The method according to [5-8], wherein the spraying of the composition is performed by spraying the composition from the spray nozzle so that the droplet size is in the range of 1 to 30 μm, and the distance between the spray nozzle and the substrate is within 50 cm. get on.

[5-10]

The manufacturing method of [5-8] or [5-9], wherein the ambient temperature at which the spraying is performed is 40 ° C or lower.

[5-11]

The production method according to any one of [5-8] to [5-10] wherein the zinc oxide film has an average transmittance of 80% or more for visible light and a surface resistance of 1 × 10 ⁵ Ω/□ or less.

The composition for producing a zinc oxide thin film according to the first aspect of the present invention is ignitable and easy to handle, and when the composition for producing a zinc oxide thin film of the present invention is used, the film can be formed at a temperature of 300 ° C or lower. A transparent zinc oxide film is produced.

The composition for producing a zinc oxide thin film doped with a Group 3A element according to the second aspect of the present invention is ignitable and easy to handle, and if the doping of the present invention is used A composition for producing a zinc oxide thin film having a Group 3A element can produce a transparent zinc oxide film doped with a Group 3A element even when formed at a temperature of 300 ° C or lower.

When the composition for producing a zinc oxide thin film according to the third aspect of the present invention is used, in the spin coating method or the dip coating method, an average transmittance of 80% or more for visible light can be produced and the volume resistivity is less than 8×. A zinc oxide film with a characteristic of 10 ^-2 Ω‧cm. Moreover, when the composition for producing a zinc oxide thin film of the present invention is used, in the spray pyrolysis method, an average transmittance of 80% or more for visible light can be produced and the volume resistivity is less than 1 × 10 ^-3 Ω ‧ cm A zinc oxide film of the characteristics.

According to the fourth aspect of the present invention, in the method for producing a zinc oxide thin film, in the spin coating method or the dip coating method, an average transmittance of 80% or more for visible light can be produced and the volume resistivity is less than 8 × 10 ^-2 Ω. ‧ cm characteristics of zinc oxide film. Further, according to the method for producing a zinc oxide thin film of the present invention, in the spray pyrolysis method, oxidation having an average transmittance of 80% or more for visible light and having a volume resistivity of less than 1 × 10 ^-3 Ω · cm can be produced. Zinc film. Further, since the produced zinc oxide thin film has excellent transparency and conductivity as described above, it can be applied to an antistatic film, an ultraviolet cut film, a transparent electrode film, and the like.

The inventors of the present invention have attempted to form a film using the following method: Patent Document 1 discloses a spin coating method using a solution containing a Group 3A element compound and an organozinc compound, and Non-Patent Document 2 uses an organic zinc compound and an organic compound. A dip coating method of a solvent solution and a spray pyrolysis method using a solution containing a 3A element compound and zinc acetate described in Non-Patent Documents 3 and 4. However, when a spin coating method or a dip coating method is used, only a zinc oxide film having a volume resistivity of 1 × 10 ^-1 Ω ‧ cm or more can be obtained, and in the spray pyrolysis method, only a volume resistivity of 1 × 10 can be obtained. ^A zinc oxide film of ^-3 Ω ‧ cm or more, and a zinc oxide film having a lower electric resistance cannot be obtained.

Further, in the spray pyrolysis method, when the heating temperature of the substrate at the time of film formation is 400 ° C or lower, only a zinc oxide film having a volume resistivity of 1 × 10 ^-2 Ω ‧ cm or more can be obtained, and resistance cannot be obtained. Its lower zinc oxide film.

Further, the inventors of the present invention attempted to form a film by a spin coating method using a composition obtained by partially hydrolyzing diethyl zinc or a composition obtained by partially hydrolyzing a group 3A element compound and diethyl zinc. A zinc oxide film (second aspect) having an average transmittance of 80% or more for visible light is obtained. The zinc oxide film obtained in the second embodiment has a volume resistivity of 1 × 10 ^-1 Ω · ‧ cm or more, and is obtained by coating at a boiling point higher than the second aspect in order to obtain a zinc oxide film having a lower electric resistance. a composition containing a partial hydrolyzate prepared by partially hydrolyzing an organozinc compound such as diethyl zinc in an organic solvent of an organic solvent to obtain an average transmittance of 80% or more for visible light, and an antistatic film A low-volume resistivity zinc oxide film of equal degree.

According to a fifth aspect of the present invention, there is provided a composition for forming a doped zinc oxide thin film which can be obtained by doping a zinc oxide thin film doped with a 3A group element, wherein the zinc oxide thin film doped with a 3A element has visible light The average transmittance is 80% or more, and the surface resistance is 1 × 10 ⁵ Ω/□ or less. Further, according to the present invention, there is provided a method of producing a doped group of a group 3A having the above transparency and low electrical resistance without heating, or heating at 300 ° C or lower, even when heated. Zinc oxide film.

[The composition for producing a zinc oxide film (first aspect)]

The composition for producing a zinc oxide thin film of the present invention contains a zinc oxide thin film production composition containing a product (hereinafter sometimes referred to as a partially hydrolyzed product) produced by the following formula (1). The organozinc compound is dissolved in an electron-donating organic solvent solution S1, and water is added in such a manner that the molar ratio of the organozinc compound is in the range of 0.6 to 0.9, and the above-mentioned organozinc compound is at least partially hydrolyzed: R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms).

For the organozinc compound represented by the formula (1), for example, Shisen Mianyang, Takeda Shingen, Tsuruta Hiroshi 964 (166), 1967, Japanese Patent Laid-Open No. Sho 38-26099, Japanese Patent Laid-Open No. 38-6646, etc. It is described as a polymerization catalyst which is used as propylene oxide. When used as a polymerization catalyst for propylene oxide, water is added to the above-mentioned organic zinc composition so that the molar ratio of the organozinc compound is 1.0 or more to form a partially hydrolyzed product.

However, in the above-mentioned literature, the reaction product containing a partial hydrolyzate obtained by adding water in such a manner that the molar ratio of the organozinc compound is in the range of 0.6 to 0.9 is heated at a temperature of 300 ° C or lower. A transparent zinc oxide film can also be formed, neither as described nor suggested. As a result of research by the inventors and the like, it is clear that as long as the molar ratio of water to the organic zinc compound is in the range of 0.6 to 0.9, the obtained partial hydrolyzate is reversed. A transparent zinc oxide film can also be formed by heating the product at a temperature below 300 °C. By setting the molar ratio to 0.6 or more, the organozinc composition can be obtained in a high yield of 90% or more based on the zinc contained in the raw material, and the unreacted raw material, that is, the organozinc compound of the general formula (1) can be suppressed. The amount of residuals. Further, by setting the molar ratio to 0.9 or less, it is possible to suppress the generation of a gel during the reaction.

The electron-donating organic solvent may be any one having solubility in the organozinc compound represented by the formula (1) and water, and examples thereof include diethyl ether, di-n-propyl ether, diisopropyl ether, and dibutyl ether. Tetrahydrofuran, two An ether solvent such as an alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or triethylene glycol dimethyl ether; an amine solvent such as trimethylamine, triethylamine or triphenylamine. As the solvent having electron donating property, tetrahydrofuran is preferred.

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

The composition of the present invention comprises a partial hydrolyzate produced by adding a water of the above molar ratio to a solution of the compound represented by the formula (1) and an electron-donating organic solvent, and at least the above compound Partial hydrolysis. The concentration of the compound represented by the formula (1) in the solution of the compound of the formula (1) and the electron-donating organic solvent is appropriately determined in consideration of solubility in a solvent, etc., for example, suitably 2 to 50 mass. The range of %.

The addition of water may be carried out without mixing water with other solvents, or by mixing water with other solvents. The addition of water also depends on the scale of the reaction, for example, it can take between 60 seconds and 10 hours. From the viewpoint of a good yield of the product, it is preferred to add it by dropwise addition of water to the organozinc compound of the above formula (1) as a raw material. The addition of water may be carried out without stirring the mixture of the compound represented by the formula (1) and the electron-donating organic solvent (in a state of being left standing), or while stirring. The temperature at the time of addition can be selected from any temperature between -90 and 150 °C. From the viewpoint of the reactivity of water with an organic zinc compound, it is preferably -15 to 5 °C.

After the addition of water, in order to carry out the reaction of water with the compound represented by the formula (1), for example, it is allowed to stand for 1 minute to 48 hours without stirring (in a state of standing) or stirred. Regarding the reaction temperature, the reaction can be carried out at any temperature between -90 and 150 °C. From the viewpoint of obtaining a partial hydrolyzate in a high yield, it is preferably from 5 to 80 °C. There is no limit to the reaction pressure. Regarding the progress of the reaction of water with the compound represented by the formula (1), the reaction mixture may be sampled as needed, and the sample may be analyzed by NMR (nuclear magnetic resonance) or IR (infrared spectroscopy) or the like, or Monitoring is performed by sampling the generated gas.

The organic solvent, the organozinc compound of the above formula (1) as a raw material, and water may be introduced according to all conventional methods, or may be introduced as a mixture with a solvent. The reaction step may be any one of a batch operation type, a semi-batch operation type, and a continuous operation type, and is not particularly limited, and is preferably a batch operation type.

By the above reaction, the organozinc compound of the above formula (1) is at least partially hydrolyzed by water to obtain a product containing a partial hydrolyzate. When the organozinc compound of the formula (1) is diethylzinc, the analysis of the product obtained by the reaction with water has been carried out since the beginning, but the results are different depending on the report, and the product is not clearly determined. The composition. Further, the composition of the product may also vary depending on the molar ratio of water added, the reaction time, and the like. It is presumed that in the present invention, the main component of the product is a mixture of one to several kinds of compounds different in m in the compound represented by the following formula (2): R ¹ -Zn-[O-Zn] _m -R ¹ (2 (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20).

After completion of the 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. 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 preferably recovered.

The composition recovered by separating the electron-donating organic solvent by the above method may be dissolved in an organic solvent for forming a film different from the electron-donating organic solvent used in the reaction to prepare a coating solution. Further, the reaction mixture may be directly or appropriately adjusted in concentration without separating the electron-donating organic solvent to prepare a coating solution.

The organic solvent for forming a film different from the electron-donating organic solvent used in the reaction is, for example, preferably a solvent having a boiling point of 85 ° C or higher. The reason for this is that since the boiling point is relatively high, the volatility is low, and workability in which the solvent is evaporated during the coating operation and the coating film becomes dry can be prevented from deteriorating.

Examples of the organic solvent for forming a film include an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane or petroleum ether, and an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene or xylene. Diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, two An ether solvent such as an alkane or tetrahydrofuran; an amine solvent such as trimethylamine, triethylamine or triphenylamine. Further, these may be used alone or in combination of two or more. When considering the solubility of the reaction product of the partially hydrolyzed product of the organozinc compound contained in the above reaction product, and the volatility of the organic solvent itself, the organic solvent for film formation is preferably 1,4-two. Alkane, methyl monoethylene glycol dimethyl ether, ethyl monoethylene glycol dimethyl ether, methyl diethylene glycol dimethyl ether.

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. When the concentration is higher, the film can be produced with a smaller number of coating times. Considering the solubility of the reaction product containing a part of the hydrolyzate of the organozinc compound and the ease of formation of the transparent zinc oxide film, 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 a zinc oxide thin 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 at a temperature of 300 ° C or lower to form a zinc oxide thin film.

The application to the surface of the substrate can be carried out by a conventional method such as a dip coating method, a spin coating method, a spray pyrolysis method, an inkjet method, or a screen printing method. The spray pyrolysis method is a method in which the substrate is heated while being coated, so that the solvent can be dried at the same time as the coating, and depending on the conditions, there is also no need to apply the coating. The heating of the drying solvent. Further, depending on the conditions, in addition to drying, at least a part of the hydrolyzate of the organozinc compound is reacted with zinc oxide. Therefore, there is also a case where it is easier to carry out the subsequent step of forming a zinc oxide thin film 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 50 to 250 °C.

The composition may be applied to the surface of the substrate in an inert gas atmosphere such as nitrogen, in an air environment, in an air environment having a relatively high relative humidity of a large amount of water vapor, in an oxidizing gas atmosphere such as oxygen, or in a reducing gas atmosphere such as hydrogen, or It is carried out under any atmosphere or the like in such a mixed gas atmosphere under atmospheric pressure or under pressure. The product contained in the composition of the present invention reacts slowly with water in the environment to be slowly decomposed, and therefore is preferably carried out 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 preferably simpler in terms of equipment at atmospheric pressure, and thus is preferable.

After coating the coating liquid on the surface of the substrate, the substrate is set to a specific temperature as needed, and 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, in the range of 20 to 200 ° C, and may be appropriately set depending on the type of the organic solvent to be coexisted. The heating temperature for forming zinc oxide after drying the solvent is, for example, in the range of 20 to 300 ° C, preferably in the range of 50 to 250 ° C, more preferably in the range of 100 to 200 ° C. It is also possible to make the solvent drying temperature the same as the heating temperature for forming zinc oxide, while performing solvent drying and zinc oxide formation.

If necessary, it is also possible to use hydrogen gas in an oxidizing gas atmosphere such as oxygen. The above heating is carried out in a plasma atmosphere such as hydrogen, argon or oxygen under a reducing gas atmosphere to promote the formation of zinc oxide or to improve crystallinity. The film thickness of the zinc oxide film is not particularly limited, and is practically preferably in the range of 0.05 to 2 μm. According to the production method of the present invention, a film having a film thickness in the above range can be suitably produced by repeating the above coating (drying) heating one time or more.

The zinc oxide thin 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 has an average transmittance of 85% or more for visible light. The "average transmittance to visible light" is defined and measured as follows. The average transmittance for visible light refers to the average of the transmittance of light in the range of 380 to 780 nm, which can be measured by an ultraviolet-visible spectrophotometer. Furthermore, the average transmittance for visible light can also be expressed by the transmittance of visible light of 550 nm. Since the transmittance to visible light changes (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 80% or more. The heating conditions (temperature and time) at the time of spraying or after coating are set.

In the first aspect of the present invention, 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 polyester (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), poly (meth) acrylate (for example, polymethyl methacrylate). Ester (PMMA), polycarbonate (PC), polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, cyclic polyolefin (COP), ethylene-vinyl acetate copolymer, Polyurethane, triacetate, celecin. Among these, PET, PEN, PC, PMMA are preferred. Transparent substrate film Depending on the type of polymer, there may be no stretch film or a stretch film. For example, a polyester film such as a PET film is usually a biaxially stretched film, and a PC film, a triacetate film, a cellophane film or the like is usually a non-stretched film.

[Composition for producing a zinc oxide thin film doped with a 3A element (second aspect)]

The composition for producing a zinc oxide thin film doped with a Group 3A element of the present invention comprises: (i) an organozinc compound represented by the following formula (1), and the following formula (2) or (3); At least one of the group 3A element compounds shown in the solution is dissolved in the solution S2 in an electron-donating organic solvent, and water is added to at least partially hydrolyze the organic zinc compound (hereinafter sometimes referred to as a partial hydrolyzate). 1); or (ii) after dissolving the organozinc compound represented by the above formula (1) in an electron-donating organic solvent, adding water to at least partially hydrolyze the organozinc compound, and adding the above-mentioned a product obtained by at least one of the Group 3A element compounds represented by the formula (2) or (3) (hereinafter sometimes referred to as a partial hydrolyzate 2): R ¹ -Zn-R ¹ (1) (wherein, R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) M _c X _d ‧ aH ₂ O (2) (wherein M is a Group 3A element, X is a halogen atom, nitric acid or sulfuric acid, and X is a halogen In the case of an atom or nitric acid, c is 1, and d is 3. When X is sulfuric acid, c is 2, d is 3, and a is an integer of 0 to 9) (wherein M is a Group 3A 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 any one of nitrogen, oxygen, and phosphorus, and b is an integer of 0 to 9).

In the case of the partial hydrolyzate 1, since water is added to the mixed solution of the organozinc compound and the group 3A element compound, the above product usually contains the hydrolyzate of the above-mentioned group 3A element compound. The hydrolyzate of the Group 3A element compound may be a partial hydrolyzate depending on the amount of addition of water or the like. Further, in the case of the partial hydrolyzate 2, a compound of a 3A group element is added after adding water to the organozinc compound, and therefore, depending on the amount of addition of water, etc., after the added water is consumed by hydrolysis of the organozinc compound, In the case where a Group 3A element compound is added, the above product is usually free of the hydrolyzate of the above Group 3A element compound. The Group 3A element compound also has a possibility of being contained in a state of a raw material without being hydrolyzed, or an organic group (coordination) which is a compound of a Group 3A element is exchanged with an organic group of a partial hydrolyzate of the organozinc compound ( With the seat exchange).

In the case of the partial hydrolyzate 1, the amount of water added is in the range of 0.4 to 0.9 with respect to the total molar ratio of the organozinc compound and the group 3A element compound. Further, in the case of the partial hydrolyzate 2, the amount of water added is in the range of 0.4 to 0.9 with respect to the molar ratio of the organozinc compound.

It is preferred to limit the water to the total amount of the organozinc compound and the organic Group 3A element compound or the molar ratio of the organic zinc compound to 0.4 to 0.9. By setting the molar ratio to 0.4 or more, an organozinc composition containing a product obtained by partially hydrolyzing an organozinc compound can be obtained in a high yield of 90% or more based on the zinc contained in the raw material. Also, in partial hydrolyzate 1 In the case of the case, the compound of the Group 3A element is also partially hydrolyzed. When the molar ratio is 0.4 or more, in the case of the partial hydrolyzate 1, the residual amount of the unreacted raw material, that is, the organic zinc compound and the 3A element compound can be suppressed, and in the case of the partial hydrolyzate 2, the organic substance can be suppressed. The residual amount of the zinc compound results in a safely operable organozinc composition. Further, by setting the molar ratio to 0.9 or less, gelation in the hydrolysis reaction can be suppressed. If a gel is produced in the hydrolysis reaction, there is a case where the viscosity of the solution rises and the subsequent operation becomes difficult. The addition of water to the molar is preferably in the range of 0.6 to 0.8, more preferably in the range of 0.6 to 0.75.

The electron-donating organic solvent may be any one of the organozinc compound represented by the formula (1), the group 3A element compound represented by the formula (2) or (3), and water, and examples thereof include, for example, : diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, two An ether solvent such as an alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or triethylene glycol dimethyl ether; an amine solvent such as trimethylamine, triethylamine or triphenylamine. As the solvent having electron donating property, tetrahydrofuran and diene are preferred. alkyl.

The organozinc compound represented by the above formula (1) is the same as those described in the first aspect of the invention.

Specific examples of the metal represented by M in the group 3A element compound represented by the above formula (2) include B, Al, Ga, and In. Further, specific examples of the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, sulfuric acid, and phosphoric acid. Specific examples of the Group 3A 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 3A element compound represented by the above formula (3) include B, Al, Ga, and In. Further, R ² , R ³ and R ^{4 are} preferably hydrogen. Further, R ² , R ³ and R ^{4 are} also preferably an alkyl group, and specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a second group. Butyl, tert-butyl, pentyl, isopentyl, neopentyl, third pentyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. It is also preferred that at least one of R ² , R ³ and R ⁴ is hydrogen and the balance is an alkyl group. Examples of the ligand represented by L include trimethylamine, triethylamine, triphenylamine, and pyridine. Porphyrin, N,N-dimethylaniline, N,N-diethylaniline, triphenylphosphine, dimethylsulfide, diethyl ether, tetrahydrofuran. Specific examples of the Group 3A element compound represented by the formula (3) include diborane, borane-tetrahydrofuran complex, borane-trimethylamine complex, and borane-triethylamine complex. , triethylborane, tributylborane, aluminum hydride-trimethylamine complex, aluminum hydride-triethylamine complex, trimethylaluminum, dimethylaluminum hydride, triisobutylene Aluminum, diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, triethylindium. 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 organozinc compound represented by the above formula (1) and the compound of the group 3A represented by the above formula (2) or (3) are added to give the above formula (2) or (3) The molar ratio of the 3A element compound to the organozinc compound is 0.005 to 0.3. When the amount of the Group 3A element compound added is too large, the film properties tend to be deteriorated as an impurity. Therefore, the ratio of 0.005 to 0.1 is preferable. Among them, partial hydrolyzate 1 In the case of the above, a partial hydrolyzate is obtained by adding water to a solution containing the organozinc compound and the group 3A element compound in the above molar ratio. Further, in the case of the partial hydrolyzate 2, water is added to the solution containing the organozinc compound to obtain a partial hydrolyzate, and the 3A element compound is added in the above molar ratio.

a compound obtained by dissolving the compound represented by the above formula (1) and the group 3A element compound represented by the above formula (2) or (3) in the above-mentioned electron-donating organic solvent, the above formula (1) The concentration of the compound in the total amount of the compound of the above formula (2) or (3) is appropriately determined in consideration of the solubility in the solvent, and the like, and is, for example, suitably in the range of 0.1 to 50% by mass. .

When the organozinc compound of the above formula (1) is at least partially hydrolyzed, and the compound of the above formula (2) or (3) is added, the compound represented by the above formula (1) is dissolved in the above. In the solution of the electron-donating organic solvent, the concentration of the compound represented by the above formula (1) is appropriately determined in consideration of the solubility in the solvent, and the like, and is, for example, suitably in the range of 0.1 to 50% by mass.

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

After the addition of water, in order to carry out a reaction between water and a compound represented by the formula (1) and a compound represented by the formula (2) or (3) or a compound represented by the formula (1), for example, Leave it for 1 minute to 48 hours without stirring (in a state of standing) or stir. Regarding the reaction temperature, the reaction can be carried out at any temperature between -90 and 150 °C. From the viewpoint of obtaining a partial hydrolyzate in a high yield, it is preferably from 5 to 80 °C. There is no limit to the reaction pressure. It can usually be carried out under normal pressure (atmospheric pressure). Regarding the progress of the reaction of water with the compound of the formula (1), the reaction mixture may be sampled as needed, analyzed by NMR or IR, or by sampling the gas produced. .

The organic solvent, the organozinc compound of the above formula (1) as a raw material, and water may be introduced into the reaction vessel according to all conventional methods, or may be introduced as a mixture with a solvent. The reaction step may be any one of a batch operation type, a semi-batch operation type, and a continuous operation type, and is not particularly limited, and is preferably a batch operation type.

By the above reaction, the organozinc compound of the above formula (1) and the compound of the group 3A of the above formula (2) or (3) or the organozinc compound of the above formula (1) are at least partially hydrolyzed by water. And a product containing a partial hydrolyzate is obtained. When the organozinc compound of the formula (1) is diethylzinc, the analysis of the product obtained by the reaction with water has been carried out since the beginning, but the results are different depending on the report, and the product is not clearly determined. The composition. Further, the composition of the product may also vary depending on the molar ratio of water added, the reaction time, and the like. In the present invention, the partial hydrolyzate 1 is a compound in which the main component of the product is a combination of a structural unit represented by the following general formulae (4) and (5) and a structural unit represented by the following general formula (6). Or a mixture of compounds of different m: (R ₁ -Zn)- (4)

-[O-Zn] _m - (5) (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20) (wherein M is the same as M in the formula (2) or (3), and Q is the same as any of X, R ² , R ³ and R ^{4 in} the formula (2) or (3), and m is An integer from 2 to 20).

Regarding 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 having different m.

R ¹ -Zn-[O-Zn] _p -R ¹ (8) (wherein R ^{1 is the} same as R ¹ in the formula (1), and p is an integer of 2 to 20).

In the case where the above-mentioned Group 3A element compound does not coexist at the time of hydrolysis of the above-mentioned organozinc compound, after the completion of the reaction, the compound of Group 3A of the above formula (2) or (3) is added, whereby a composition is produced. The amount of the above-mentioned Group 3A element compound to be added is 0.005 to 0.3 with respect to the amount of the above-mentioned organic zinc compound. In view of the fact that the addition effect of the compound of the group 3A element can be surely obtained, and when the amount of addition is increased, the film properties tend to be deteriorated as an impurity, and therefore it is particularly preferably 0.005 to 0.1.

After completion of the hydrolysis reaction, part or all of the above products may be recovered and purified by a usual method such as filtration, concentration, extraction, column chromatography or the like. Further, when a compound of a 3A group element is added after completion of the hydrolysis reaction, part or all of the above product may be recovered and purified by filtration. Organic zincation of the general formula (1) remaining as a raw material in the reaction product In the case of the compound, it can also 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 organozinc compound represented by the formula (1). The content is 0.5% by mass or less. When the composition of the present invention is used as a coating liquid, it is preferred that the organic zinc compound represented by the formula (1) remaining unreacted is contained in the viewpoint of forming a uniform film.

The composition recovered by separating the electron-donating organic solvent by the above method may be dissolved in an organic solvent for forming a film different from the electron-donating organic solvent used in the reaction to prepare a coating solution. Further, the reaction mixture may be directly or appropriately adjusted in concentration without separating the electron-donating organic solvent to prepare a coating solution.

The organic solvent for forming a film different from the electron-donating organic solvent used in the reaction is, for example, preferably a solvent having a boiling point of 85 ° C or higher. The reason for this is that since the boiling point is relatively high, the volatility is low, and workability in which the solvent is evaporated during the coating operation and the coating film becomes dry can be prevented from deteriorating.

Examples of the organic solvent for forming a film include an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, octane or petroleum ether, and an aromatic hydrocarbon solvent such as benzene, toluene, ethylbenzene or xylene. Diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, two An ether solvent such as an alkane or tetrahydrofuran; an amine solvent such as trimethylamine, triethylamine or triphenylamine. Further, these may be used alone or in combination of two or more. When considering the solubility of the reaction product of the partially hydrolyzed product of the organozinc compound contained in the above reaction product, and the volatility of the organic solvent itself, the organic solvent for film formation is preferably 1,4-two. Alkane, methyl monoethylene glycol dimethyl ether, ethyl monoethylene glycol dimethyl ether, methyl diethylene glycol dimethyl ether.

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. When the concentration is higher, the film can be produced with a smaller number of coating times. When considering the solubility of the reaction product containing a partial hydrolyzate of the organozinc compound and the ease of formation of the transparent zinc oxide film, it is preferably 3 to 12 quality%.

[Method for Producing Zinc Oxide Thin Film (Second Aspect)]

The present invention relates to a method of producing a zinc oxide thin 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 at a temperature of 300 ° C or lower to form a zinc oxide thin film.

The application to the surface of the substrate can be carried out by a conventional method such as a dip coating method, a spin coating method, a spray pyrolysis method, an inkjet method, or a screen printing method. The spray pyrolysis method is a method in which the substrate can be coated while heating the substrate. Therefore, the solvent can be dried at the same time as the coating, and depending on the conditions, there is a case where heating for drying the solvent is not required after coating. Further, depending on the conditions, in addition to drying, at least a part of the hydrolyzate of the organozinc compound is reacted with zinc oxide. Therefore, there is also a case where it is easier to carry out the subsequent step of forming a zinc oxide thin film 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 50 to 250 °C.

The coating of the composition on the surface of the substrate can be carried out under an inert gas atmosphere such as nitrogen. In an air environment, in an air environment with a relatively high relative humidity of a large amount of water vapor, in an oxidizing gas atmosphere such as oxygen, in a reducing gas atmosphere such as hydrogen, or in such a mixed gas environment, at atmospheric pressure Or under pressure. The product contained in the composition of the present invention reacts slowly with water in the environment to be slowly decomposed, and therefore is preferably carried out 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 preferably simpler in terms of equipment at atmospheric pressure, and thus is preferable.

After coating the coating liquid on the surface of the substrate, the substrate is set to a specific temperature as needed, and 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, in the range of 20 to 200 ° C, and may be appropriately set depending on the type of the organic solvent to be coexisted. The heating temperature for forming zinc oxide after drying the solvent is, for example, in the range of 20 to 300 ° C, preferably in the range of 50 to 250 ° C, more preferably in the range of 100 to 200 ° C. It is also possible to make the solvent drying temperature the same as the heating temperature for forming zinc oxide, while performing solvent drying and zinc oxide formation.

If necessary, the above heating may be carried out in a plasma atmosphere such as oxygen or a reducing gas atmosphere such as hydrogen or a plasma atmosphere such as hydrogen, argon or oxygen to promote zinc oxide formation or to improve crystallinity. The film thickness of the zinc oxide film is not particularly limited, and is practically preferably in the range of 0.05 to 2 μm. According to the production method of the present invention, a film having a film thickness in the above range can be suitably produced by repeating the above coating (drying) heating one time or more.

The zinc oxide film formed by the manufacturing method of the present invention is preferably a pair The visible light has an average transmittance of 80% or more, and more preferably has an average transmittance of 85% or more for visible light. The "average transmittance to visible light" is defined and measured as follows. The average transmittance for visible light refers to the average of the transmittance of light in the range of 380 to 780 nm, which can be measured by an ultraviolet-visible spectrophotometer. Furthermore, the average transmittance for visible light can also be expressed by the transmittance of visible light of 550 nm. Since the transmittance to visible light changes (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 80% or more. The heating conditions (temperature and time) at the time of spraying or after coating are set.

Further, since the zinc oxide thin film formed by the production method of the present invention is doped with a Group 3A element, the possibility of obtaining a low-resistance film is further increased by further investigating the film formation method.

The system usable as the substrate in the second aspect of the present invention is the same as the substrate exemplified in the first aspect of the present invention.

[The composition for producing a zinc oxide film (the third aspect)]

The composition for producing a zinc oxide thin film according to the third aspect of the present invention comprises the following three aspects: (i) a solution obtained by dissolving the organozinc compound represented by the above formula (1) in an electron-donating organic solvent. In S1, a product obtained by at least partially hydrolyzing the above-mentioned organozinc compound (hereinafter sometimes referred to as a partial hydrolyzate 1); (ii) dissolving the organozinc compound represented by the above formula (1) in a supply A product obtained by adding at least one of the compound of the Group 3A compound represented by the above formula (2) or (3) to the solution S1 in which the water is added to the solution S1, and the organic zinc compound is at least partially hydrolyzed. (hereinafter sometimes referred to as partial hydrolyzate 2); (iii) an organozinc compound represented by the following formula (1) and a compound of a group 3A compound represented by the following formula (2) or (3); At least one of the solution S2 dissolved in the electron-donating organic solvent, and at least partially hydrolyzed by adding the above-mentioned organic zinc compound (hereinafter sometimes referred to as partial hydrolyzate 3); R ¹ -Zn -R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) (wherein M is a Group 3A 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; a carboxylic acid group or an acetoacetone group, and further L is a coordinating organic compound containing any one of nitrogen, oxygen, and phosphorus, and b is an integer of 0 to 9) M _c X _d ‧aH ₂ O (2) ( Wherein M is a Group 3A element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, d is 3, and when X is sulfuric acid, c is 2, and d is 3, a It is an integer from 0 to 9.)

In the above-mentioned electron-donating organic solvent, an electron-donating organic solvent having a boiling point of 110 ° C or higher or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or higher as a main component is used. The present inventors have found that by using such a solvent, a zinc oxide thin film having an average transmittance of 80% or more and having a volume resistivity of less than 8 × 10 ^-2 Ω ‧ cm can be formed.

In the examples of Patent Document 2, tetrahydrofuran (boiling point 66 ° C) is used as the organic solvent for partial hydrolysis, and in the example of Patent Document 3, 1,4-two is used. Alkane (boiling point 101.1 ° C) as an organic solvent for partial hydrolysis, in any case, a transparent zinc oxide film can be obtained, but zinc oxide having a low resistivity of volume resistivity of less than 8 × 10 ^-2 Ω ‧ cm cannot be obtained film. Use tetrahydrofuran or 1,4-two The reason for the alkane is that when these solvents are used, it is easy to suppress the formation of a gel at the time of hydrolysis, and it is advantageous for the formation of a partial hydrolyzate. However, as a result of the repeated test, it was found that even if an electron-donating organic solvent having a boiling point of 110 ° C or more is used, a gel is not formed upon hydrolysis, and a partial hydrolyzate can be produced.

In the above-mentioned electron-donating organic solvent, an electron-donating organic solvent having a boiling point of 110 ° C or higher is preferred in view of workability in the subsequent coating step, particularly drying property. The electron-donating organic solvent may have solubility in the organozinc compound represented by the formula (1) and water, in addition to the boiling point, and examples thereof include di-n-butyl ether (boiling point: 142.4 ° C). ), dihexyl ether (boiling point 226.2 ° C), anisole (boiling point 153.8 ° C), phenyl ether (boiling point 172 ° C), butyl phenyl ether (boiling point 210.3 ° C), pentyl ether (boiling point 214 ° C), methoxy toluene (boiling point 171.8 ° C), benzyl ether (boiling point 189 ° C), diphenyl ether (boiling point 258.3 ° C), veratrole (boiling point 206.7 ° C), three Ethylene glycol dimethyl ether such as alkane (boiling point 114.5 ° C) and 1,2-diethoxyethane (boiling point 121 ° C), 1,2-dibutoxyethane (boiling point 203.3 ° C), again, double (2-methoxyethyl)ether (boiling point 162 ° C), bis(2-ethoxyethyl)ether (boiling point 188.4 ° C), bis(2-butoxyethyl) ether (boiling point 254.6 ° C), etc. Diethylene glycol dimethyl ether, further 1,2-bis(2-methoxyethoxy)ethane (boiling point 216 ° C), bis[2-(2-methoxyethoxyethyl)]ether (ether 275 ° C) and other ether solvents such as triethylene glycol dimethyl ether, tri-n-propylamine (boiling point 150 ~ 156 ° C), tri-n-pentylamine (boiling point 130 ° C), N, N-dimethylaniline An amine solvent such as (boiling point: 193 ° C), N,N-diethylaniline (boiling point: 217 ° C), or pyridine (boiling point: 115.3 ° C). As an electron-donating organic solvent, from the viewpoints of gel inhibition at the time of preparation of the composition and volatility of the solvent itself, 1,2-diethyl as a kind of ethylene glycol dimethyl ether is preferred. Oxyethane (boiling point 121 ° C). The upper limit of the boiling point of the electron-donating organic solvent is not particularly limited, and is preferably 230 ° C or less from the viewpoint of relatively short drying time when the composition is applied and the solvent is removed to form a coating film.

The mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component may be one which is soluble in the organic zinc compound represented by the formula (1) and water in a mixed state, and may be, for example, List: octane (boiling point 125.7 ° C) and tetrahydrofuran (boiling point 66 ° C), octane and 1,4-two Alkane, decane (boiling point 150.8 ° C) and tetrahydrofuran, decane and 1,4-two Alkanes, decanes (boiling point 174.1 ° C) and tetrahydrofuran, decane and 1,4-two Alkanes, undecane and tetrahydrofuran, undecane and 1,4-two Alkane, dodecane (boiling point 216.3 ° C) and tetrahydrofuran, dodecane and 1,4-two Alkane, toluene (boiling point 110.6 ° C) and tetrahydrofuran, toluene and 1,4-two Alkane, xylene (boiling point 138~145 ° C) and tetrahydrofuran, xylene and 1,4-two Alkane, ethylbenzene (boiling point 136.2 ° C) and tetrahydrofuran, ethylbenzene and 1,4-two Alkane, butylbenzene (boiling point 169~183 °C) and tetrahydrofuran, butylbenzene and 1,4-two Alkane, pentylbenzene (boiling point 205.4 ° C) and tetrahydrofuran, pentylbenzene and 1,4-two Alkane, mesitylene (boiling point 164.7 ° C) and tetrahydrofuran, mesitylene and 1,4-two Alkane, diethylbenzene (boiling point 181~184 °C) and tetrahydrofuran, diethylbenzene and 1,4-two Alkane, etc. When the volume resistivity of the formed zinc oxide thin film is considered, it is preferred that the subcomponent is tetrahydrofuran. Further, in consideration of workability at the time of film formation, tetrahydrofuran or 1,4-di, which is an accessory component, is preferred. The weight ratio of the alkane to the main component is 0.05 to 0.45.

When the compound represented by the above formula (1) is dissolved in the above-mentioned electron donating organic solvent or a mixed organic solvent containing the electron donating organic solvent, the concentration of the compound represented by the above formula (1) is higher. Good is in the range of 4 to 12% by mass. When the concentration of the compound represented by the above formula (1) is less than 4% by mass and more than 12% by mass, it is difficult to form an electron-donating organic solvent having a boiling point of 110 ° C or higher. The tendency of a zinc oxide film that requires transparency and conductivity. The concentration of the compound represented by the formula (1) in the solution obtained by dissolving in the above organic solvent is preferably in the range of 6 to 10% by mass.

In the case of the partial hydrolyzate 1, 2, the molar ratio of the above-mentioned organic zinc compound is set to a range of 0.4 to 0.8, and in the case of the partial hydrolyzate 3, it is relatively The molar ratio of the total amount of the above organozinc compound and the Group 3A element compound is in the range of 0.4 to 0.8. By adding the amount of water to the range, in the case of the spin coating method or the dip coating method, the obtained reaction product containing a partial hydrolyzate can be formed to have a volume resistivity of less than 8 × 10 ^-2 Ω · cm The zinc oxide film having a characteristic can form a zinc oxide film having a volume resistivity of less than 1 × 10 ^-3 Ω ‧ cm in the case of a spray pyrolysis method.

Further, by setting the molar ratio to 0.4 or more, an organozinc composition containing a product obtained by partially hydrolyzing an organozinc compound can be obtained in a high yield of 90% or more based on the zinc contained in the raw material. Further, in the case of the partial hydrolyzate 3, the compound of the Group 3A element is also partially hydrolyzed. When the molar ratio is 0.4 or more, in the case of the partial hydrolyzate 1, 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. The residual amount of the compound with the Group 3A element results in a safely operable organozinc composition. Further, by setting the molar ratio to 0.8 or less, gelation in the hydrolysis reaction can be suppressed. If a gel is produced 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 molar is preferably in the range of 0.6 to 0.8, more preferably in the range of 0.6 to 0.75.

In the case of the partial hydrolyzate 2, since the compound of the 3A group element is added after adding water to the organozinc compound, it is added after the water to be added is consumed by the hydrolysis of the organozinc compound depending on the amount of water added and the like. In the case of a Group 3A element compound, the above product usually does not contain a hydrolyzate of the above Group 3A element compound. The Group 3A element compound also has a possibility of being contained in a state of a raw material without being hydrolyzed, or an organic group (coordination) which is a compound of a Group 3A element is exchanged with an organic group of a partial hydrolyzate of the organozinc compound ( With the seat exchange). In the case of the partial hydrolyzate 3, since water is added to the mixed solution of the organozinc compound and the group 3A element compound, the above product usually contains the above-mentioned group 3A element compound. Hydrolyzate. The hydrolyzate of the Group 3A element compound may be a partial hydrolyzate depending on the amount of addition of water or the like.

The addition of water may be carried out only in water without mixing water with another solvent, or may be carried out by using a mixed solvent obtained by mixing water with another solvent. From the viewpoint of suppressing the local hydrolysis, it is preferred to use a mixed solvent, and the content of water in the mixed solvent can be, for example, in the range of 1 to 50% by mass, preferably 2 to 20% by mass. The solvent which can be used in the mixed solvent with water can be, for example, the above-mentioned electron-donating organic solvent. Further, the electron-donating organic solvent may be an organic solvent having a boiling point of 110 ° C or higher, or an organic solvent having a boiling point of not higher than 110 ° C. However, from the viewpoint of being inert to diethyl zinc and having high solubility in water, an organic solvent having a boiling point of less than 110 ° C is preferred.

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

After the addition of water, in order to carry out a reaction between water and a compound represented by the formula (1) and a compound represented by the formula (2) or (3) or a compound represented by the formula (1), for example, Leave it for 1 minute to 48 hours without stirring (in a state of standing) or stir. Regarding the reaction temperature, it can be any between -90 and 150 °C. Reaction at temperature. From the viewpoint of obtaining a partial hydrolyzate in a high yield, it is preferably in the range of 5 to 80 °C. There is no limit to the reaction pressure. It can usually be carried out under normal pressure (atmospheric pressure). Regarding the progress of the reaction of water with the compound of the formula (1), the reaction mixture may be sampled as needed, analyzed by NMR or IR, or by sampling the gas produced. .

The organozinc compound represented by the above formula (1) is the same as those described in the first aspect of the invention.

The Group 3A element compound represented by the above formula (2) and the Group 3A element compound represented by the above formula (3) are the same as those described in the second aspect of the invention. In the third aspect of the invention, the group 3A element compound represented by the formula (2) is a group 3A element compound represented by the formula (3) in the second aspect of the invention, and the third aspect of the invention The Group 3A element compound represented by the formula (3) is a Group 3A element compound represented by the formula (2) in the second aspect of the present invention.

In the case of the partial hydrolyzates 2 and 3 of the composition of the present invention, it is preferable to add the above-described general formula (1) from the viewpoint of obtaining a zinc oxide thin film in which the addition effect of the 3A group element is moderately exhibited. An organozinc compound, and a compound of a Group 3A compound represented by the above formula (2) or (3), such that the compound of the Group 3A compound represented by the above formula (2) or (3) is relative to the organic zinc compound The ratio is 0.005 to 0.09. Here, in the case of the partial hydrolyzate 2, water is added to the solution containing the organozinc compound to obtain a partial hydrolyzate, and the 3A element compound is added in the above molar ratio. Further, in the case of the partial hydrolyzate 3, the organic zinc compound and the 3A are contained in the above molar ratio. Water is added to the solution of the group element compound to obtain a partial hydrolyzate.

The organic solvent, the organozinc compound of the above formula (1) as a raw material, and a mixed solvent of water or water can be introduced into the reaction vessel according to all conventional methods. The reaction step may be any one of a batch operation type, a semi-batch operation type, and a continuous operation type, and is not particularly limited, and is preferably a batch operation type.

By the above reaction, the organozinc compound of the above formula (1) and the compound of the group 3A of the above formula (2) or (3) or the organozinc compound of the above formula (1) are partially hydrolyzed by water. A product containing a partial hydrolyzate is obtained. When the organozinc compound of the formula (1) is diethylzinc, the analysis of the product obtained by the reaction with water has been carried out since the beginning, but the results are different depending on the report, and the product is not clearly determined. The composition. Further, the composition of the product may also vary depending on the molar ratio of water added, the reaction time, and the like.

Regarding the partial hydrolyzates 1, 2, it is presumed that it is a compound represented by the following formula (4) or a mixture of a plurality of compounds different in m: R ¹ -Zn-[O-Zn] _p -R ¹ (4) (wherein R ^{1 is the} same as R ¹ in the formula (1), and p is an integer of 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 mixture of compounds or compounds of different m: (R ₁ -Zn)- (5)

-[O-Zn] _m - (6) (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20) (wherein M is the same as M in the formula (2) or (3), and Q is the same as any of X, R ² , R ³ and R ^{4 in} the formula (2) or (3), and m is An integer from 2 to 20).

In the case of the partial hydrolyzate 2 in which the above-mentioned Group 3A element compound does not coexist when the organozinc compound is hydrolyzed, the compound 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 3A element compound to be added is suitably from 0.005 to 0.09 with respect to the amount of the organic zinc compound to be added as described above.

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 compound of a 3A group element is added after completion of the hydrolysis reaction, part or all of the above product may be recovered 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 preferably recovered. The reaction product obtained by recovering the remaining raw materials by these methods is preferably any one of the partial hydrolyzates 1 to 3, and the organozinc compound represented by the general formula (1) is not contained, for example, it is preferred to pass The content of the organozinc compound represented by the formula (1) is 0.5% by mass or less. When the composition of the present invention is used as a coating liquid, it is preferred that the organic zinc compound represented by the formula (1) remaining unreacted is contained in the viewpoint of forming a uniform film.

The solution prepared by the above method can be directly used as a coating solution for forming a zinc oxide thin film. Or it can be simplified by appropriate dilution or concentration. From the viewpoint of the production step, it is preferred that the solution prepared by the above method is a concentration which can be directly used as a coating solution for forming a zinc oxide thin film.

[Manufacturing method of zinc oxide film]

A method for producing a zinc oxide thin film using the composition for forming a zinc oxide thin film according to the third aspect of the present invention will be described below in the method for producing a zinc oxide thin film according to a fourth aspect of the present invention.

[Method for Producing Zinc Oxide Thin Film (Fourth Aspect)]

The composition for producing a zinc oxide thin film used in the production method of the fourth aspect of the present invention comprises the following three aspects and compositions A to C. The composition A is the same as the composition (i) for producing a zinc oxide thin film of the third aspect, and the composition B is the same as the composition (ii) for producing a zinc oxide thin film of the third aspect, and the composition C and the third aspect are the same. The composition (iii) for producing a zinc oxide film is the same.

(Composition A) is a product (hereinafter sometimes referred to as partial hydrolyzate 1) which is obtained by dissolving the organozinc compound represented by the above formula (1) in an electron-donating organic solvent. It is obtained by adding water to at least partially hydrolyze the above-mentioned organozinc compound; (composition B) is a product (hereinafter sometimes referred to as partial hydrolyzate 2) which is based on the organic zinc represented by the above formula (1) The compound is dissolved in a solution containing an electron-donating organic solvent, and at least one of the compound of the Group 3A compound represented by the above formula (2) or (3) is added after at least one of the above-mentioned organozinc compounds is at least partially hydrolyzed by adding water. (Compound 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 3A element compounds shown in the solution dissolved in an electron-donating organic solvent, and at least partially hydrolyzed with the above-mentioned organozinc compound by adding water: R ¹ -Zn-R ¹ ( 1) (wherein, R ¹ is C 1-7 straight-chain or branched-chain alkyl group _{of) M c X d ‧aH 2 O} (2) ( in the formula, M being 3A Element, X is a halogen atom, nitric acid or sulfuric acid, when in X is a halogen atom or a nitrate, c is 1, d is 3, when the X is sulfuric acid, c is 2, d is 3, a is an integer of 0 to 9 of) (wherein M is a Group 3A 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; Further, the carboxylic acid group or the acetoacetone group, and further, L is a coordinating organic compound containing any one of nitrogen, oxygen, and phosphorus, and b is an integer of 0 to 9).

[Production method]

The fourth aspect of the present invention relates to a method for producing a zinc oxide thin film. This production method is a method in which the composition for forming a zinc oxide thin film is applied onto the surface of a substrate, and then the obtained coating film is heated to obtain a zinc oxide thin film. For example, when coating is carried out 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 × 10 ^-2 Ω ‧ cm can be obtained. For example, when it is applied by a spray pyrolysis method, a zinc oxide thin film having an average transmittance of 80% or more for visible light and having a volume resistivity of less than 1 × 10 ^-3 Ω ‧ cm can be formed.

Coating on the surface of the substrate can be carried out by dip coating, spin coating, spray thermal decomposition Conventional methods such as a method, an inkjet method, and a screen printing method are used.

The composition may be applied to the surface of the substrate in an inert gas atmosphere such as nitrogen, in an air environment, in an air environment having a relatively high relative humidity of a large amount of water vapor, in an oxidizing gas atmosphere such as oxygen, or in a reducing gas atmosphere such as hydrogen, or It is carried out under any atmosphere or the like in such a mixed gas atmosphere under atmospheric pressure or under pressure.

In the spin coating method or the dip coating method, it may be formed in an inert gas atmosphere, or may be carried out in an environment where the relative humidity of the inert gas and the water vapor is 2 to 15%.

The spray pyrolysis method is a method in which the substrate can be coated while heating the substrate. Therefore, the solvent can be dried at the same time as the coating, and depending on the conditions, there is no need to heat the solvent. Further, depending on the conditions, in addition to drying, at least a part of the hydrolyzate of the organozinc compound is reacted with zinc oxide. Therefore, there is also a case where it is easier to carry out the subsequent step of forming a zinc oxide thin film by heating at a specific temperature. The heating temperature of the substrate may be, for example, in the range of 50 to 550 °C.

Fig. 17 shows a spray film forming apparatus which can be used in the spray pyrolysis method of the present invention. In the figure, 1 denotes a spray bottle filled with a coating liquid, 2 denotes a substrate holder, 3 denotes a spray nozzle, 4 denotes a compressor, 5 denotes a substrate, and 6 denotes a water vapor introduction pipe. Regarding the spraying, the substrate is placed on the substrate holder 2, and is heated to a specific temperature by using a heater as needed, and then the compressed inert gas and the coating are simultaneously supplied from the spray nozzle 3 disposed above the substrate in a specific environment. The cloth liquid is sprayed by atomizing the coating liquid, whereby a zinc oxide film can be formed on the substrate. The zinc oxide film is sprayed without It is formed by additional heating or the like.

From the viewpoint of producing a zinc oxide thin film having good film characteristics in the case of spraying a coating liquid, it is preferred that the coating liquid is ejected from the spray nozzle so that the droplet size is in the range of 1 to 15 μm, and The distance between the spray nozzle and the substrate was set to be within 50 cm.

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

It is preferable to make the distance between the spray nozzle and the substrate within 50 cm from the viewpoint that the solvent is partially evaporated from the time of the spray nozzle until the substrate reaches the substrate to reduce the droplet size. 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.

In the spray pyrolysis method, from the viewpoint of forming a zinc oxide thin film having a lower volume resistivity, it is preferred to introduce water vapor from the water vapor introduction pipe 6 in an inert gas atmosphere to promote decomposition of the composition. For example, the introduction amount of water vapor is preferably 0.1 to 5 with respect to the molar ratio of zinc in the above-mentioned composition, and it is more preferable from the viewpoint of obtaining a zinc oxide film having a lower volume resistivity. 0.3~2. When the amount of introduction of water vapor is in the range of 0.3 to 2 in terms of the above molar ratio, a zinc oxide thin film having more excellent film properties of a volume resistivity of less than 1 × 10 ^-3 Ω ‧ cm can be formed.

The method of introducing the water vapor can be introduced into the zinc oxide film production container according to all conventional methods. Preferably, the water vapor is reacted with the composition in the vicinity of the heated substrate, and for example, an inert gas containing water vapor produced by bubbling water with an inert gas by a tube is introduced into the addition. Near the hot substrate.

After coating the coating liquid on the surface of the substrate, the substrate is set to a specific temperature as needed, and 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, in the range of 20 to 200 ° C, and may be appropriately set depending on the type of the organic solvent to be coexisted. The heating temperature for forming zinc oxide after drying the solvent is, for example, in the range of 50 to 550 ° C, preferably in the range of 50 to 500 ° C. It is also possible to make the solvent drying temperature the same as the heating temperature for forming zinc oxide, while performing solvent drying and zinc oxide formation.

If necessary, the above heating may be carried out in a plasma atmosphere such as oxygen or a reducing gas atmosphere such as hydrogen or a plasma atmosphere such as hydrogen, argon or oxygen to promote zinc oxide formation or to improve crystallinity. The film thickness of the zinc oxide film is not particularly limited, and is practically preferably in the range of 0.05 to 2 μm. According to the production method of the present invention, in the case of the spray pyrolysis method, the film having the film thickness in the above range can be suitably produced by repeating the above coating (drying) heating one time or more.

The zinc oxide film formed by the production method of the present invention varies depending on the coating method and subsequent drying conditions or heating conditions, and preferably has a volume resistivity of less than 8 × 10 ^-2 Ω ‧ cm More preferably, it has a volume resistivity of less than 1 × 10 ^-3 Ω ‧ cm. The volume resistivity is a resistance per unit volume which can be obtained by multiplying the surface resistance by the film thickness. The surface resistance is measured, for example, by a four-probe method, and the film thickness is measured by, for example, SEM (scanning electron microscope), a stylus type film thickness gauge, or the like. 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 consider the volume resistivity of the film to be 8 × 10 ^-2 Ω. The heating conditions (temperature and time) at the time of spraying or after coating are set in cm.

The zinc oxide thin 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 has an average transmittance of 85% or more for visible light. The "average transmittance to visible light" is defined and measured as follows. The average transmittance for visible light refers to the average of the transmittance of light in the range of 380 to 780 nm, which can be measured by an ultraviolet-visible spectrophotometer. Furthermore, the average transmittance for visible light can also be expressed by the transmittance of visible light of 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. The substrate can be, for example, an alkali glass, an alkali-free glass, or a transparent substrate film, and the transparent substrate film can be a plastic film. However, it is not intended to be limited to such exemplified materials.

[Use of zinc oxide film]

The zinc oxide thin film produced by the above method can be used as an antistatic film, an ultraviolet cut film, a transparent conductive film, or the like because of its excellent transparency and conductivity. The antistatic film can be used, for example, in fields such as solid electric field capacitors, chemically amplified resists, and window materials such as window glass. UV cut film can be, for example It is used in the fields of image filters such as front filters, drive recorders, drive instruments such as high-pressure discharge lamps, cover glass for watches and clocks, and building materials such as window glass. Further, the transparent conductive film can be used, for example, for FPD (flat panel display), resistive touch panel and capacitive touch panel, thin film solar cell and compound (CdTe, CIS) thin film solar cell, and dye-sensitized sun. Batteries, organic thin film solar cells, etc. However, it is not intended to be limited to such fields.

Although repeated, the zinc oxide film produced by the above method is highly transparent, transparent, and has a volume resistivity of less than 8×10 ⁻² Ω·cm, which can be used for FPD (flat panel display). Electrode, resistive film touch panel and electrode of capacitive touch panel, thin film, solar cell and compound (CdTe, CIS (copper indium selenide)) thin film solar cell, dye-sensitized solar cell, organic thin film sun The upper electrode of the battery, the ultraviolet cut film, the antistatic film, the infrared reflective film, etc., have a wide range of uses.

[Zinc oxide film forming composition (the fifth aspect)]

The composition for forming a doped zinc oxide thin film according to a fifth aspect of the present invention is characterized by comprising an organic zinc compound represented by the following formula (1) and a general formula (hereinafter) in an organic solvent having electron donating properties. 20) The organic Group 3A element compound shown, wherein the molar ratio of the above organic Group 3A element compound to the above organozinc compound is in the range of 0.001 to 0.3: R ¹ -Zn-R ¹ (1) (wherein R ¹ a linear or branched alkyl group having a carbon number of 1 to 7) (wherein M is a Group 3A element, and R ²⁰ , R ³⁰ and R ^{40 are} independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms).

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

Examples of the Group 3A element represented by M in the organic Group 3A element compound represented by the formula (20) include B, Al, Ga, In, and Tl. Further, specific examples of the alkyl group represented by R ²⁰ , R ³⁰ and R ⁴⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a second butyl group, and the like. Tributyl, pentyl, isopentyl, neopentyl, third pentyl, hexyl, isohexyl, second hexyl, third hexyl, 2-hexyl, and heptyl. The compound represented by the formula (20) preferably has M of B, Al, Ga or In, and R ²⁰ , R ³⁰ and R ^{40 are} independently hydrogen or have a carbon number of 1, 2, 3 or 4, a compound of 5 or 6. Particularly preferred compounds of the formula (20) are borane, aluminum hydride triethylamine, triethylaluminum, trimethylgallium, triethylgallium, trimethylindium, triethylindium. From the viewpoint of being inexpensive and easily available, the above organic Group 3A element compound is particularly preferably: triethylaluminum wherein M is aluminum and R ²⁰ , R ³⁰ and R ⁴⁰ are both ethyl; M is gallium, and R ²⁰ , R ³⁰ and R ⁴⁰ are each a trimethylgallium group of a methyl group; M is a trimethylindium of indium and each of R ²⁰ , R ³⁰ and R ⁴⁰ is a methyl group.

The organic Group 3A element compound represented by the formula (20) is represented by the formula (1) The molar amount of the organic zinc compound is preferably 0.001 to 0.3, more preferably 0.01 to 0.1.

Examples of the solvent having an electron donating property include an amine solvent such as trimethylamine, triethylamine or triphenylamine, diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether and tetrahydrofuran. ,two An ether solvent such as an alkane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or triethylene glycol dimethyl ether. As the solvent having electron donating property, diisopropyl ether is particularly preferable.

In the present invention, from the viewpoint of producing a transparent zinc oxide thin film, the total concentration of the organic zinc compound and the organic 3A compound is preferably 15% by mass or less. The total concentration of the above organozinc compound and the organic 3A compound is preferably from 1 to 10% by mass, more preferably from 3 to 10% by mass. The total concentration of the above-mentioned organozinc compound and the organic 3A compound has an influence on the danger in the production of a zinc oxide film such as fire. By setting it as the above range, it is possible to safely and efficiently produce a zinc oxide film having good transparency without special care. The concentration of the organic Group 3A element compound of the above composition is appropriately determined in consideration of the molar ratio of the organic Group 3A element compound to the above-mentioned organic zinc compound.

The composition of the present invention can be produced by dissolving the organozinc compound of the above formula (1) and the organic 3A 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 even if the mixture with the solvent is dissolved in each other. The compound of the above formula (1) and the compound of the above formula (2) can be dissolved in any order.

[Manufacturing method of zinc oxide film doped with Group 3A element (Fifth aspect)]

The method for producing a zinc oxide film doped with a Group 3A element of the present invention is characterized in that the composition of the present invention is sprayed under the conditions of atmospheric pressure or pressure, in the presence of water, and at a substrate temperature of 300 ° C or lower. On the surface of the substrate, a zinc oxide film doped with a Group 3A element is formed.

The manufacturing method of the present invention uses a spray coating method.

The spraying on the surface of the substrate is carried out under atmospheric pressure or under pressure in the presence of water, which is an oxygen source of a zinc oxide film. In the case of pressurization, for example, the pressure is in the range of 101.3 to 202.6 kPa. However, it is not intended to be limited thereto. Further, the spraying in the method of the present invention can also be carried out under reduced pressure, but it is not advantageous to carry out under reduced pressure, and it is also simpler and more preferable to carry out the apparatus at atmospheric pressure.

The "environment of water" in the spraying of the surface of the substrate may be, for example, an aqueous air environment having a relative humidity of 20 to 90%. It can also be carried out in a mixed gas atmosphere in which nitrogen and water are mixed, instead of being carried out in an air atmosphere. In terms of the smooth formation of the zinc oxide film, 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 300 ° C or lower. More specifically, it is preferred to set the ambient temperature for spraying to 40 ° C or lower and the substrate temperature to 300 ° C or lower. In view of the fact that the formation of the zinc oxide film is relatively stable, the ambient temperature for spraying is preferably in the range of 10 to 30 ° C, and the substrate temperature is preferably in the range of 10 to 200 ° C, more preferably in the range of 20 to 100 ° C. .

Fig. 23 is a view showing a spray film forming apparatus which can be used in the present invention. In the figure, 1 denotes a spray bottle filled with a coating composition, 2 denotes a substrate holder, and 3 It means a spray nozzle, 4 is a compressor, and 5 is a board|substrate. Regarding the spraying, the substrate is placed on the substrate holder 2, and if necessary, it is heated to a specific temperature of 300 ° C or lower by using a heater, and then placed in the atmosphere (at atmospheric pressure, in air), and the spray nozzle is disposed above the substrate. (3) The compressed inert gas and the coating composition are simultaneously supplied, and the coating composition is atomized and sprayed, whereby a zinc oxide thin film can be formed on the substrate. The zinc oxide thin film doped with the Group 3A element is formed by spraying without additional heating or the like.

In the case of spraying a coating composition, it is preferred that the coating composition is ejected from the spray nozzle so that the droplet size is in the range of 1 to 30 μm from the viewpoint of producing a zinc oxide film having good transparency. And the distance between the spray nozzle and the substrate was set to be within 50 cm. Further, from the viewpoint of the influence of heat on the substrate and the energy cost, it is preferred that the ambient temperature at which the coating is performed is 40 ° C or lower, and the temperature of the substrate is 300 ° C or lower.

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

It is preferable to make the distance between the spray nozzle and the substrate within 50 cm from the viewpoint that the solvent is partially evaporated from the time of the spray nozzle until the substrate reaches the substrate to reduce the droplet size. 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.

Further, even if the substrate and the ambient temperature are not heated, the compressed inert gas and the coating composition are simultaneously supplied from the spray nozzle 3 disposed above the substrate, and the coating composition is atomized and sprayed. According to the conditions (droplet size, composition of the composition (concentration), distance between the spray nozzle and the substrate Then, a zinc oxide film doped with a 3A element having high transparency is formed on the substrate.

The zinc oxide thin film doped with a Group 3A element formed by the production method of the present invention is one in which zinc oxide is contained in the form of an oxide in the form of an oxide. The oxide of the Group 3A element is solid-dissolved in the zinc oxide, or the Group 3A element oxide is separately mixed with the zinc oxide, or both of them coexist.

The film thickness of the zinc oxide thin film doped with the Group 3A element formed by the production method of the present invention is not particularly limited. For example, it can be appropriately adjusted within the range of 100 to 2000 nm. The film thickness of the zinc oxide film can be appropriately adjusted by adjusting the concentration of the coating composition for spraying and the spraying time. Further, the spraying operation may be performed in two or more times as needed.

The zinc oxide film doped with the Group 3A element formed by the production method of the present invention preferably has an average transmittance of 80% or more for visible light, and more preferably has an average transmittance of 85% or more for visible light. In addition, the "average transmittance to visible light" is defined and measured as follows. The average transmittance for visible light refers to the average of the transmittance of light in the range of 380 to 780 nm, which can be measured by an ultraviolet-visible spectrophotometer.

Further, the zinc oxide film doped with the Group 3A element formed by the production method of the present invention preferably has a surface resistance of 1 × 10 ⁵ Ω/□ or less. More preferably, the surface resistance is 5 × 10 ⁴ Ω / □ or less, and particularly preferably, the surface resistance is 1 × 10 ⁴ Ω / □ or less.

For example, the 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: Such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), poly (meth) acrylate (such as polymethyl methacrylate (PMMA)), polycarbonate (PC ), polystyrene, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyethylene, cyclic polyolefin (COP), ethylene-vinyl acetate copolymer, polyurethane, triacetate Sai Fan. Among these, PET, PC, and PMMA are preferred. The transparent base film may be a stretchless film or a stretched film depending on the kind of the polymer. For example, a polyester film such as a PET film is usually a biaxially stretched film, and a PC film, a triacetate film, a cellophane film or the like is usually a non-stretched film.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited to the examples. The preparation of all the products containing the partial hydrolyzate derived from the organozinc compound and the film formation using the same are carried out under a nitrogen atmosphere, and the solvent is all dehydrated and degassed. Examples 1-1 to 1-4 are examples of the first aspect, Examples 2-1 to 2-8 are the second embodiment, and Examples 3-1 to 3-17 are the third and fourth embodiments. In the embodiment of the embodiment, Examples 4-1 to 4-6 are examples of the fifth aspect.

Method for measuring surface resistance value

The surface resistance was measured by using the Loresta-GP manufactured by Mitsubishi Chemical in accordance with the probe method of JIS K 7194.

[Example 1-1]

41.66 g of diethyl zinc was added to 165.0 g of tetrahydrofuran. After thorough stirring, it was cooled to -10 °C. A tetrahydrofuran solution containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.6. then, After reacting at room temperature (22 ° C) for 18 hours, the solvent and unreacted diethyl zinc were vacuum distilled off to obtain 33.02 g of a product containing a partial hydrolyzate. The spectrum of Figure 1 was obtained by NMR (THF-d8, ppm). The zinc content was 57.8% as measured by ICP (Inductively Coupled Plasma). The yield of the zinc base was 91%.

The product containing the partial hydrolyzate obtained in the above manner is dissolved in the 1,4-dimer in an amount of only 15% by concentration. After the alkane, a trace amount of the insoluble matter remaining is filtered, whereby a product-containing coating liquid containing a partial hydrolyzate is obtained. The viscosity of the coating liquid was measured by a 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 Corning 1737 glass substrate of 18 mm square. Then, the solvent was dried by heating the substrate at 120 ° C for 4 minutes while forming zinc oxide. The above operation was repeated once more. The film formed had a film thickness of 0.25 μm, and was confirmed to be zinc oxide by XRD (X-ray diffraction) as shown in Fig. 3 . Further, the visible light transmittance at 550 nm was 83%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 1-2]

After the application, the substrate was heated at 120 ° C for 2 minutes to dry the solvent, and further heated at 200 ° C for 2 minutes, and the same procedure as in Example 1-1 was carried out. The film formed had a film thickness of 0.21 μm. The visible light transmittance at 550 nm is 80%, and a transparent zinc oxide film having a transmittance of 80% or more can be obtained.

[Example 1-3]

41.66 g of diethyl zinc was added to 165.0 g of tetrahydrofuran. After thorough stirring, it was cooled to -10 °C. A tetrahydrofuran solution containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.8. Then, after reacting at room temperature for 18 hours, the solvent, unreacted diethyl zinc was distilled off in vacuo to obtain a product containing a partial hydrolyzate. The spectrum of Figure 2 was obtained by NMR (THF-d8, ppm). The zinc content was measured by ICP to be 57.3%. The yield of the zinc base is 90%.

The product containing the partial hydrolyzate obtained in the above manner was dissolved in the 1,4-dimer in an amount of only 12% by concentration. After the alkane, a trace amount of the insoluble matter remaining is filtered, whereby a product-containing coating liquid containing a partial hydrolyzate is obtained. The viscosity of the coating liquid was measured by a Ubum viscometer and found to be 1.17 mPa·s.

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 120 ° C for 4 minutes while forming zinc oxide. The above operation was repeated once more. The film formed had a film thickness of 0.27 μm, and was confirmed to be zinc oxide by XRD as shown in Fig. 5 . Further, the visible light transmittance at 550 nm was 81%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 1-4]

After the application, the substrate was heated at 120 ° C for 2 minutes to dry the solvent, and further heated at 200 ° C for 2 minutes, and the same procedure as in Example 1-3 was carried out. The film formed had a film thickness of 0.23 μm, and was confirmed to be zinc oxide by XRD as shown in Fig. 6 . Also, visible light transmission at 550 nm The rate was 95%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Reference Example 1-1]

41.66 g of diethyl zinc was added to 165.0 g of tetrahydrofuran. After thorough stirring, it was cooled to -10 °C. A tetrahydrofuran solution containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethylzinc was 1.05. Then, the reaction was carried out at room temperature for 18 hours, and as a result, a large amount of gel was produced, and the resulting gel was insoluble in any organic solvent, so that a coating liquid could not be prepared.

[Comparative Example 1-1]

To the 48.24 g of 2-methoxyethanol, 8.50 g of zinc acetate dihydrate and 2.39 g of ethanolamine as an auxiliary agent were added, and the mixture was sufficiently stirred to obtain a coating liquid.

A film was obtained in the same manner as in Example 1-1 except that the coating liquid obtained in the above manner was used. The visible light transmittance at 550 nm was 27%, 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.

[Comparative Example 1-2]

After the application, the substrate was heated at 120 ° C for 2 minutes to dry the solvent, and further heated at 200 ° C for 2 minutes, except that the same operation as in Comparative Example 1-1 was carried out. The visible light transmittance at 550 nm was 31%, 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 2-1]

1,4-two To the 30.0 g of the alkane, 1.91 g of diethyl zinc was added. After thorough stirring, it was cooled to 12 °C. Will contain 1,4-two of 5.0% water The alkane solution was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.6. Thereafter, the temperature was raised to room temperature (22 ° C) and reacted at room temperature for 18 hours, and then triethylaluminum was added so as to be 0.02 in terms of molar ratio with respect to the charged diethyl zinc. The solution obtained in the above manner was filtered with a membrane filter, whereby 32.1 g of a partially hydrolyzate solution (concentration: 5.6% by mass) containing aluminum was obtained. The spectrum of Fig. 8 was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying.

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 120 ° C for 4 minutes while forming zinc oxide. The above operation was repeated twice more. The film formed had a film thickness of 0.15 μm, and was confirmed to be zinc oxide by XRD as shown in Fig. 9 . Further, the visible light transmittance at 550 nm was 87%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 2-2]

31.5 g of a partial hydrolyzate solution (concentration: 5.5% by mass) containing gallium was obtained in the same manner as in Example 2-1 except that triethylaluminum was changed to trimethylgallium. The spectrum of Fig. 10 was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying.

A product-containing coating liquid containing a partial hydrolyzate obtained in the above manner was applied in the same manner as in Example 2-1. The film formed had a film thickness of 0.14 μm, and was confirmed to be zinc oxide by XRD as shown in Fig. 11 . Moreover, the visible light transmittance at 550 nm is 84%, and transparency with a transmittance of 80% or more can be obtained. Zinc oxide film.

[Example 2-3]

32.3 g of a partial hydrolyzate solution (concentration: 5.5% by mass) containing indium was obtained in the same manner as in Example 2-1 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.

A product-containing coating liquid containing a partial hydrolyzate obtained as described above was applied in the same manner as in Example 2-1, except that the substrate heating temperature was changed to 150 °C. The film thickness of the formed film was 0.14 μm, and as shown in Fig. 13, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 89%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Comparative Example 2-1]

1.23 g of zinc acetate dihydrate and 0.34 g of ethanolamine as an auxiliary agent were added to 24.12 g of 2-methoxyethanol, and aluminum triethylacetonate was added in a molar ratio of 0.02 to zinc acetate dihydrate. The mixture was thoroughly stirred to obtain a coating liquid containing aluminum.

A film was obtained in the same manner as in Example 2-1 except that the coating liquid obtained in the above manner was used in the air. The visible light transmittance at 550 nm is 75%, and only an opaque film having a transmittance of 80% or less can be obtained. Further, the film was not uniform, and a peak derived from zinc oxide (not shown) was not confirmed by XRD.

[Comparative Example 2-2]

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

The coating liquid obtained in the above manner was subjected to the same operation as in Comparative Example 1 to obtain a film. Further, the visible light transmittance at 550 nm was 66%, 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.

[Comparative Example 2-3]

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

The coating liquid obtained in the above manner was subjected to the same operation as in Comparative Example 1 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]

To 20.0 g of bis(2-methoxyethyl)ether, 2.62 g of diethyl zinc was added. After thorough stirring, it was cooled to -12 °C. A tetrahydrofuran solution containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.6. Then, the temperature was raised to room temperature (22 ° C) and allowed to react at room temperature for 18 hours. The solution obtained in the above manner was filtered with a membrane filter, whereby a partial hydrolyzate solution (concentration: 7.8% by mass) of 33.1 g was obtained. The spectrum of Fig. 14 was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying.

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 120 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. Formed The film thickness of the film was 0.36 μm, which was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 93%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 2-5]

In the partial hydrolyzate solution of diethylzinc prepared in Example 2-4, trioctyl aluminum was added in a molar ratio of 0.01 to the charged diethyl zinc, thereby obtaining A partial hydrolyzate solution containing indium was 33.2 g.

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 120 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. The film formed had a film thickness of 0.33 μm and was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 93%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 2-6]

In the partial hydrolyzate solution of diethylzinc prepared in Example 2-4, trimethylgallium was added in a molar ratio of 0.03 with respect to the charged diethylzinc, thereby obtaining A partial hydrolyzate solution containing indium was 33.0 g.

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 120 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. Formed The film thickness of the film was 0.35 μm, which was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 94%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 2-7]

In the partial hydrolyzate solution of diethylzinc prepared in Example 2-4, trimethylindium was added in a molar ratio of 0.03 with respect to the charged diethyl zinc, thereby obtaining A partial hydrolyzate solution containing indium was 32.8 g.

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 120 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. The film formed had a film thickness of 0.32 μm and was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 94%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 2-8]

1.97 g of diethyl zinc was added to 30.0 g of 1,2-diethoxyethane. After thorough stirring, it was cooled to -12 °C. A tetrahydrofuran solution containing 5.0% of water was intermittently introduced by using the apparatus shown in Fig. 15, whereby the molar ratio of water to diethylzinc was 0.8. Then, the temperature was raised to room temperature (22 ° C) and allowed to react at room temperature for 18 hours. The solution obtained in the above manner was filtered with a membrane filter, whereby a partial hydrolyzate solution (concentration: 7.8% by mass) of 33.1 g was obtained. The spectrum of Fig. 16 was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying.

[Example 3-1]

3.39 g of diethyl zinc (corresponding to 8.7% by mass) was added to 39.9 g of 1,2-diethoxyethane (boiling point: 121 ° C). After thorough stirring, it was cooled to -12 °C. Will contain 1,4-two of 5.0% water The alkane (boiling point 101.1 ° C) solution was added dropwise in such a manner that the molar ratio of water to diethyl zinc was 0.6 (total amount added: 6.02 g). Then, the mixture was heated to room temperature (24 ° C) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, whereby a partial hydrolyzate solution (concentration: 6.5% by mass) of 48.1 g was obtained. The spectrum of Fig. 15 was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. The formed film had a surface resistance of 1300 Ω/□, a film thickness of 0.35 μm, and a volume resistivity of 4.6×10 ^-2 Ω·cm. Further, it was confirmed to be zinc oxide by XRD (see Fig. 16). Further, the visible light transmittance at 550 nm was 90%, 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, trimethylindium was added in a molar ratio of 0.03 with respect to the charged diethylzinc, whereby 488.1 g of a partially hydrolyzate solution containing indium 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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. The formed film had a surface resistance of 587 Ω/□, a film thickness of 0.37 μm, and a volume resistivity of 2.2×10 ^-2 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 91%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 3-3]

The product-containing coating liquid containing a partial hydrolyzate obtained as in Example 3-2 was applied by spin coating on the surface of a Cornish 1737 glass substrate of 18 mm square. Then, the solvent was dried by heating the substrate at 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 30 times. The formed film had a surface resistance of 55 Ω/□, a film thickness of 1.71 μm, and a volume resistivity of 9.4×10 ^-3 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 85%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 3-4]

17.45 g (corresponding to 8.7% by mass) of diethyl zinc was added to 200.3 g of 1,2-diethoxyethane (boiling point: 121 ° C). After thorough stirring, it was cooled to -12 °C. A tetrahydrofuran (boiling point 66 ° C) solution containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethyl zinc was 0.6 (total amount added: 30.1 g). Then, the mixture was heated to room temperature (24 ° C) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, whereby a partial hydrolyzate solution (concentration: 6.4% by mass) of 245.2 g was obtained. In the partial hydrolyzate solution, trimethylindium is added in such a manner that the molar ratio is 0.01 with respect to the charged diethyl zinc. Thus, 245.3 g of a partial hydrolyzate solution containing indium was obtained.

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. After the glass substrate was heated to 400 ° C in a nitrogen atmosphere, the water vapor introduction tube 6 was introduced into the vicinity of the substrate by introducing nitrogen gas which foamed at 24 ° C in water at 24 ° C to introduce water. Then, the coating liquid was sprayed at 4 ml/min for 16 minutes from the spray nozzle. 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 30 cm. The formed film had a surface resistance of 15 Ω/□, a film thickness of 0.49 μm, and a volume resistivity of 7.4×10 ^-4 Ω·cm. Further, it was confirmed to be zinc oxide by XRD (see Fig. 17). Further, the visible light transmittance at 550 nm was 83%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 3-5]

It was confirmed that the zinc oxide thin films obtained in Examples 3-1 to 3-4 have an antistatic function and can be used as an antistatic film. Further, it was confirmed that the zinc oxide thin films obtained in Examples 3-1 to 3-4 have an ultraviolet cut-off function and can be used as an ultraviolet cut film.

[Examples 3-6]

It was confirmed that the zinc oxide thin film obtained in Example 3-4 was formed into a transparent electrode, and it was confirmed that it can be used as a transparent conductive film.

[Reference Example 3-1]

To 40.0 g of 1,2-diethoxyethane, 1.26 g of diethyl zinc (corresponding to 3.15 mass%) was added. After thorough stirring, it was cooled to -12 °C. Will contain 1,4-two of 5.0% water The alkane solution was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.6 (total amount added: 2.06 g). Then, the mixture was heated to room temperature (24 ° C) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, whereby a partial hydrolyzate solution (concentration: 2.7% by mass) of 43.1 g 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 500 ° C for 4 minutes. The above operation was repeated 5 times. However, the formed film had a surface resistance of more than 10 ⁷ Ω/□ (outside the measurement range) and a visible light transmittance of 5% at 16 nm, and only an opaque and high-resistance film having a transmittance of 80% or less was obtained.

[Reference Example 3-2]

To 39.9 g of 1,2-diethoxyethane, 6.53 g (corresponding to 16.4% by mass) of diethyl zinc was added. After thorough stirring, it was cooled to -12 °C. Will contain 1,4-two of 5.0% water The alkane solution was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.6 (total amount added: 9.83 g). Then, the mixture was heated to room temperature (24 ° C) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, whereby a partial hydrolyzate solution (concentration: 12.5% by mass) of 83.5 g 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 500 ° C for 4 minutes. The above operation was repeated 5 times. However, the surface resistance of the formed film was more than 10 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.

[Reference Example 3-3]

To 39.9 g of tetrahydrofuran (boiling point 66 ° C), 3.50 g of diethyl zinc (corresponding to 8.7% by mass) was added. After thorough stirring, it was cooled to -12 °C. A tetrahydrofuran solution containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethylzinc was 0.6 (total amount added: 6.01 g). Then, the mixture was heated to room temperature (24 ° C) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, whereby a partial hydrolyzate solution (concentration: 6.6% by mass) of 43.9 g 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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated twice more. The formed film had a surface resistance of 2.2 × 10 ⁵ Ω/□ and a visible light transmittance of 5% at 550 nm, and only an opaque film was obtained. As shown in Fig. 18, in addition to zinc oxide, XRD was confirmed to form zinc.

[Reference Example 3-4]

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 at 4 ml/min from the spray nozzle for 16 minutes without introducing steam. The formed film had a surface resistance of 3590 Ω/□, a film thickness of 0.31 μm, and a visible light transmittance of 5% at 550 nm, and only an opaque and high-resistance film was obtained.

[Reference Example 3-5]

1,4-two To 500.0 g of an alkane (boiling point: 101.1 ° C), 43.5 g of diethyl zinc (corresponding to 8.0% by mass) was added. After thorough stirring, it was cooled to -12 °C. Will contain 1,4-two of 5.0% water The alkane (boiling point 101.1 ° C) solution was added dropwise in such a manner that the molar ratio of water to diethyl zinc was 0.6 (total amount added: 77.4 g). Then, the mixture was heated to room temperature (24 ° C) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, whereby 616.8 g of a partial hydrolyzate solution (concentration: 6.5% by mass) was obtained. In the partial hydrolyzate solution, trimethylindium was added in an amount of 0.01 with respect to the charged diethyl zinc, whereby 617.2 g of a partially hydrolyzate solution containing indium 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 500 ° C for 4 minutes. The above operation was repeated twice more. However, the formed film had a surface resistance of 1.9 × 10 ⁵ Ω/□, a film thickness of 0.37 μm, and a volume resistivity of 4.8 × 10 ^-1 Ω ‧ cm. The visible light transmittance at 550 nm is 95%, and only a film having a high resistance can be obtained.

[Reference Example 3-6]

A product-containing coating liquid containing a partial hydrolyzate as obtained in Reference Example 5 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 500 ° C for 4 minutes. The above operation was repeated 5 times. However, the formed film had a surface resistance of 9.3 × 10 ⁴ Ω/□, a film thickness of 0.35 μm, and a volume resistivity of 3.2 × 10 ^-1 Ω ‧ cm. The visible light transmittance at 550 nm is 67%, and only a film having high resistance and opacity can be obtained.

[Examples 3-7]

3.39 g of diethyl zinc (corresponding to 8.7% by mass) was added to 39.9 g of 1,2-diethoxyethane (boiling point: 121 ° C). After thorough stirring, it was cooled to -12 °C. A solution of tetrahydrofuran (boiling point 66.0 ° C) containing 5.0% of water was added dropwise in such a manner that the molar ratio of water to diethyl zinc was 0.6 (total amount added: 6.11 g). Then, the mixture was heated to room temperature (24 ° C) and allowed to react at room temperature for 18 hours, and filtered through a membrane filter, whereby a partial hydrolyzate solution (concentration: 6.5% by mass) of 48.6 g was obtained. The spectrum of Fig. 22 was obtained by measuring NMR (THF-d8, ppm) after removal of a solvent or the like by vacuum drying.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. The formed film had a surface resistance of 1050 Ω/□, a film thickness of 0.35 μm, and a volume resistivity of 3.7×10 ^-2 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 89%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-8]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, trimethylgallium was added in a molar ratio of 0.03 with respect to the charged diethylzinc, whereby 48.7 g of a partially hydrolyzate solution containing indium 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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 5 times. The formed film had a surface resistance of 420 Ω/□, a film thickness of 0.37 μm, and a volume resistivity of 1.6 × 10 ^-2 Ω ‧ cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-9]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, trioctyl aluminum was added in a molar ratio of 0.01 to the charged diethyl zinc, thereby obtaining A solution containing a portion of the hydrolyzate of aluminum was 48.7 g.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 44 Ω/□, a film thickness of 1.91 μm, and a volume resistivity of 8.4×10 ^-3 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 84%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-10]

In the partial hydrolyzate solution of diethylzinc prepared in Examples 3-7, 0.5 M aluminum hydride ‧ three B was added in a molar ratio of 0.01 to the charged diethyl zinc The base amine complex was dissolved in a toluene solution, whereby 48.4 g of a partial hydrolyzate solution 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 solvent was dried by heating the substrate at 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 57 Ω/□, a film thickness of 1.86 μm, and a volume resistivity of 1.1 × 10 ^-2 Ω ‧ cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 84%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-11]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, trimethylgallium was added in a molar ratio of 0.03 with respect to the charged diethylzinc, thereby obtaining A partial hydrolyzate solution containing gallium was 48.5 g.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 62 Ω/□, a film thickness of 1.74 μm, and a volume resistivity of 1.1 × 10 ^-2 Ω ‧ cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 91%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-12]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, triethylgallium was added in a molar ratio of 0.03 with respect to the charged diethylzinc, thereby obtaining Partially hydrolyzed solution containing gallium 48.2g.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 40 Ω/□, a film thickness of 1.66 μm, and a volume resistivity of 6.6×10 ^-3 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-13]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, gallium chloride was added in a molar ratio of 0.03 with respect to the charged diethyl zinc, thereby obtaining a content. A portion of the hydrolyzate solution of gallium was 48.6 g.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 38 Ω/□, a film thickness of 1.66 μm, and a volume resistivity of 6.6 × 10 ^-3 Ω ‧ cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 90%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-14]

Partially hydrolyzed solution of diethylzinc prepared in Examples 3-7 In addition, indium chloride was added so as to be 0.03 in terms of a molar ratio with respect to the charged diethyl zinc, thereby obtaining 48.3 g of a partial hydrolyzate solution containing gallium.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 35 Ω/□, a film thickness of 1.76 μm, and a volume resistivity of 6.6×10 ^-3 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-15]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, gallium acetylacetonate was added in a molar ratio of 0.03 with respect to the charged diethyl zinc, thereby obtaining A partial hydrolyzate solution containing gallium was 48.4 g.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 41 Ω/□, a film thickness of 1.63 μm, and a volume resistivity of 6.7×10 ^-3 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 91%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-16]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, indium acetoacetate was added in a molar ratio of 0.03 with respect to the charged diethyl zinc, thereby obtaining A partial hydrolyzate solution containing gallium was 48.2 g.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 42 Ω/□, a film thickness of 1.61 μm, and a volume resistivity of 6.8×10 ^-3 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 94%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Examples 3-17]

In the partial hydrolyzate solution of diethylzinc prepared in Example 3-7, indium acetate was added in a molar ratio of 0.03 with respect to the charged diethyl zinc, thereby obtaining gallium-containing A portion of the hydrolyzate solution was 48.5 g.

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 500 ° C for 4 minutes while forming zinc oxide. The above operation was repeated 29 times. The formed film had a surface resistance of 38 Ω/□, a film thickness of 1.60 μm, and a volume resistivity of 6.1×10 ^-3 Ω·cm. Further, it was confirmed to be zinc oxide by XRD. Further, the visible light transmittance at 550 nm was 92%, and a transparent zinc oxide film having a transmittance of 80% or more was obtained.

[Example 4-1]

The preparation of the coating composition was carried out under a nitrogen atmosphere, and the solvent was all dehydrated and degassed. 10.54 g of diethyl zinc was added to 200.1 g of diisopropyl ether, and 1.0 mol% (0.11 g) of triethylaluminum was added to diethyl zinc. After sufficiently stirring, it was filtered to obtain a coating composition.

The coating composition obtained as described above was filled in a spray bottle in the spray film forming apparatus of Fig. 23. The slide substrate is placed on the substrate holder. After heating the glass substrate to 100 ° C, the coating composition was sprayed at 3 ml/min for 10 minutes from the spray nozzle under atmospheric pressure at 25 ° C in the presence of water at 60% relative humidity. 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 40 cm. 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 is 84%, and the surface resistance is 4.2 × 10 ⁴ Ω/□, and a low-resistance having a transmittance of 80% or more and a surface resistance of 1 × 10 ⁵ Ω/□ or less can be obtained. Zinc oxide 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 210 nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown in Fig. 25 . Further, the average transmittance of visible light was 86%, and the surface resistance was 4.3 × 10 ⁴ Ω/□, and a transparent, low-resistance zinc oxide thin 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 150 nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown in Fig. 26 . Further, the average transmittance of visible light was 83%, and the surface resistance was 6.7 × 10 ³ Ω/□, and a transparent, low-resistance zinc oxide thin film having a transmittance of 80% or more was obtained.

[Example 4-4]

The same procedure as in Example 1 was carried out except that the glass substrate was heated to 200 °C. The film thickness of the film formed on the substrate was determined by SEM measurement and was about 300 nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown in Fig. 27 . Further, the average transmittance of visible light was 82%, and the surface resistance was 1.7 × 10 ⁴ Ω/□, and a transparent, low-resistance zinc oxide thin film having a transmittance of 80% or more was obtained.

[Example 4-5]

The same procedure as in Example 2 was carried out except that the glass substrate was heated to 200 °C. The film thickness of the film formed on the substrate was determined by SEM measurement and was about 250 nm. The film formed on the substrate was confirmed to be zinc oxide by XRD as shown in Fig. 28 . Further, the average transmittance of visible light was 86%, and the surface resistance was 8.0 × 10 ³ Ω/□, and a transparent, low-resistance zinc oxide thin film having a transmittance of 80% or more was obtained.

[Examples 4-6]

The same procedure as in Example 3 was carried out except that the glass substrate was heated to 200 °C. 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 . Further, the average transmittance of visible light was 89%, and the surface resistance was 3.6 × 10 ³ Ω/□, and a transparent, low-resistance zinc oxide thin film having a transmittance of 80% or more was obtained.

The following Comparative Examples 1 to 3 were carried out based on the technique of Article 17 (Document No. 199) of Table 168 of Non-Patent Document 1. However, the results obtained are not the characteristics described in the tables of the above documents, but are very poor values as shown in the following comparative examples.

[Comparative Example 4-1]

10.54 g of zinc acetate dihydrate was added to 200.3 g of a mixed solvent of ethanol and water in a volume ratio of 3:1, and 1.0 mol% (0.09 g) of aluminum chloride hexahydrate was added with respect to zinc acetate dihydrate. The mixture was thoroughly stirred and filtered to obtain a coating composition.

The coating composition obtained as described above was filled in a spray bottle in the spray film forming apparatus of Fig. 23. The slide substrate is placed on the substrate holder. After heating the glass substrate to 200 ° C, the coating composition was sprayed at 3 ml/min for 10 minutes from the nozzle. A peak derived from zinc oxide (not shown) was not confirmed by XRD. Further, the average transmittance of visible light was 10%, and the surface resistance was more than 1.0 × 10 ⁷ Ω/□ (outside the measurement range), and only an opaque and high-resistance film was obtained.

[Comparative Example 4-2]

All were carried out in the same manner as in Comparative Example 1, except that aluminum chloride hexahydrate was changed to gallium chloride. A peak derived from zinc oxide (not shown) was not confirmed by XRD. Further, the average transmittance of visible light was 9%, and the surface resistance was more than 1.0 × 10 ⁷ Ω/□ (outside the measurement range), and only an opaque and high-resistance film was obtained.

[Comparative Example 4-3]

All were carried out in the same manner as in Comparative Example 1, except that the aluminum chloride hexahydrate was changed to indium chloride tetrahydrate. A peak derived from zinc oxide (not shown) was not confirmed by XRD. Further, the average transmittance of visible light was 12%, and the surface resistance was more than 1.0 × 10 ⁷ Ω/□ (outside the measurement range), and only an opaque and high-resistance film was obtained.

[Industrial availability]

The invention can be used in the manufacture of doped and undoped zinc oxide films.

1‧‧‧ spray bottle

2‧‧‧Substrate holder (with heater)

3‧‧‧ spray nozzle

4‧‧‧Compressor

5‧‧‧ Alkali-free glass substrate

6‧‧‧Water vapor introduction tube

1 is an NMR spectrum of the organozinc composition obtained in Example 1-1; FIG. 2 is an NMR spectrum of the organozinc composition obtained in Example 1-2; and FIG. 3 is an oxidation obtained in Example 1-3. XRD spectrum of the zinc film; FIG. 4 is an XRD spectrum of the zinc oxide film obtained in Example 1-4; FIG. 5 is an XRD spectrum of the zinc oxide film obtained in Example 1-5; FIG. 6 is Example 1-6 XRD spectrum of the zinc oxide film obtained in FIG. 7; FIG. 7 is an NMR spectrum of diethylzinc (see FIG.); FIG. 8 is an NMR spectrum after vacuum drying of the composition obtained in Example 2-1; XRD spectrum of the aluminum-doped zinc oxide film obtained in Example 2-1; Figure 10 is an NMR spectrum after vacuum drying of the composition obtained in Example 2-2; Figure 11 is an XRD spectrum of the gallium-doped zinc oxide film obtained in Example 2-2; Figure 12 is Example 2-3 The NMR spectrum of the composition obtained after vacuum drying; FIG. 13 is an XRD spectrum of the indium-doped zinc oxide film obtained in Example 2-3; and FIG. 14 is a vacuum drying of the composition obtained in Example 2-4. NMR spectrum; FIG. 15 is an explanatory diagram of the apparatus used in Examples 2-8; FIG. 16 is an NMR spectrum after vacuum drying of the composition obtained in Example 2-8; and FIG. 17 shows a spray film formation. Figure 18 is a NMR spectrum after vacuum drying of the composition obtained in Example 3-1; Figure 19 is an XRD spectrum of the zinc oxide film obtained in Example 3-1; Figure 20 is Example 3 XRD spectrum of the zinc oxide film obtained in 4; FIG. 21 is an XRD spectrum of the zinc oxide film obtained in Reference Example 3-3; and FIG. 22 is a NMR spectrum after vacuum drying of the composition obtained in Example 3-7; Figure 23 is a view showing a spray film forming apparatus; Figure 24 is an XRD spectrum of the zinc oxide film obtained in Example 4-1; Figure 25 is a view of Example 4-2. The XRD spectrum of the zinc oxide thin film; Figure 26 is an XRD spectrum of the zinc oxide thin film obtained in Example 4-3; Figure 27 is an XRD spectrum of the zinc oxide thin film obtained in Example 4-4; and Figure 28 is a zinc oxide thin film obtained in Example 4-5. XRD spectrum; and Figure 29 is an XRD spectrum of the zinc oxide film obtained in Examples 4-6.

Claims (55)

A composition for producing a zinc oxide thin film, comprising: a product obtained by partially adding water to a solution S1 or a solution S2 and at least partially hydrolyzing the following organozinc compound; and the solution S1 is represented by the following formula (1) The organozinc compound (however, the concentration of the compound represented by the formula (1) in the solution S1 is 50% by mass or less) is dissolved in an electron-donating organic solvent; the solution S2 is a compound of the following formula ( 1) an organozinc compound as shown, and a 3A element compound represented by the following formula (2) or the following formula (3) (however, in the above solution S2, the group 3A element compound corresponds to the above organozinc At least one of the compounds having a molar ratio of 0.3 or less is dissolved in an electron-donating organic solvent; the electron-donating organic solvent is an ether solvent or an amine solvent; and the above-mentioned Group 3A element is B or Al. , Ga or In; the main component of the above product is of the formula R ¹ -Zn-[O-Zn] _m -R ¹ (wherein R ^{1 is the} same as R ¹ in the formula (1), m is 2-20 a mixture of 1 to several kinds of compounds having different m in the compound shown by the formula or a structural unit represented by the following general formulas (4) and (5) and the following general formula (6) a compound in which the structural units are combined, or a mixture of a plurality of compounds different in m: R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched chain having 1 to 7 carbon atoms; Alkyl)M _c X _d ‧aH ₂ O (2) (wherein M is a Group 3A element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, and d is 3, When X is sulfuric acid, c is 2, d is 3, and a is an integer of 0-9. (wherein M is a Group 3A 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; a carboxylic acid group or an acetoacetone group, and further L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, n is an integer from 0 to 9) (R ₁ -Zn)-(4) -[O-Zn _m - (5) (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20) (wherein M is the same as M in the formula (2) or (3), and Q is the same as any of X, R ² , R ³ and R ^{4 in} the formula (2) or (3), and m is An integer from 2 to 20). The composition of claim 1, which comprises partially hydrolyzing the above-mentioned organozinc compound obtained by adding water to the solution S1 in a range of from 0.6 to 0.9 with respect to the molar ratio of the organozinc compound, thereby suppressing gel production. The product. The composition of claim 2, which comprises a solution obtained by dissolving the product separated from the organic solvent in an organic solvent for forming a film different from the electron-donating organic solvent, but the organic solvent for forming the film is An aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent, an ether solvent or an amine solvent. The composition of claim 3, wherein the concentration of the above product is in the range of 3 to 12% by mass. The composition of claim 2, wherein the electron donating organic solvent is tetrahydrofuran. The composition of claim 3, wherein the organic solvent for forming the film is 1,4-two alkyl. The composition of claim 1, wherein the product obtained from the above S2 solution comprises a hydrolyzate of the above-mentioned Group 3A element compound. The composition of claim 7, wherein the molar amount of the above-mentioned water added is in the range of 0.4 to 0.9 with respect to the total amount of the organozinc compound and the group 3A element compound. A composition for doping a zinc oxide thin film, which comprises the composition of claim 1 obtained by adding water to the solution S1, and has a molar ratio of 0.005 to 0.3 with respect to the above organozinc compound. a product obtained by adding at least one compound of the group 3A element represented by the formula (2) or the formula (3) in a ratio of a ratio, and the main component of the above product is a formula R ¹ -Zn-[O-Zn a mixture of 1 to several compounds of _m -R ¹ (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20) a compound obtained by combining a structural unit represented by the general formulae (4) and (5) with a structural unit represented by the following general formula (6) or a mixture of a plurality of compounds different from m; the above-mentioned Group 3A element is B, Al, Ga or In, M _c X _d ‧ aH ₂ O (2) (wherein M is a Group 3A element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, d 3, when X is sulfuric acid, c is 2, d is 3, and a is an integer of 0-9) (wherein M is a Group 3A 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; a carboxylic acid group or an acetoacetone group, and further L is a coordinating organic compound containing nitrogen, oxygen or phosphorus, n is an integer from 0 to 9) (R ₁ -Zn)-(4) -[O-Zn _m - (5) (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20) (wherein M is the same as M in the formula (2) or (3), and Q is the same as any of X, R ² , R ³ and R ^{4 in} the formula (2) or (3), and m is An integer from 2 to 20). The composition of claim 9, wherein the product is substantially free of a hydrolyzate of the above-described Group 3A element compound. The composition of claim 9, wherein the amount of water added to the solution S1 is in the range of 0.4 to 0.9 with respect to the molar ratio of the organozinc compound. The composition of claim 1, wherein the content of the organozinc compound represented by the formula (1) in the above composition is 0.5% by mass or less. The composition of claim 1, which comprises a solution obtained by dissolving the above product in an organic solvent for forming a film different from the electron-donating organic solvent, but the organic solvent for forming a film is an aliphatic hydrocarbon solvent or aromatic A hydrocarbon solvent, an ether solvent or an amine solvent. The composition of claim 1, wherein the concentration of the above product is in the range of 1 to 30% by mass. The composition for producing a zinc oxide thin film according to claim 1, wherein the electron-donating organic solvent is an electron-donating organic solvent having a boiling point of 110 ° C or higher. a solution or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or higher as a main component, and the solution S1 is dissolved in the solvent to dissolve the organozinc compound represented by the formula (1) in an amount of 4 to 12% by mass. A solution having a concentration in the range; the amount of water added is in the range of 0.4 to 0.8 in terms of a molar ratio with respect to the above organozinc compound. A composition according to the composition of claim 15 which is added with an organic 3A group element represented by the following formula (3) in such a manner that the molar ratio of the above organozinc compound is 0.005 to 0.1. Obtained by the compound: (wherein M is a Group 3A 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; A carboxylic acid or an acetoacetone group, and L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 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 higher as a main component; The solution S2 is a solution in which the concentration of the organic zinc compound and the organic Group 3A element compound is 4 to 12% by mass in total, and the amount of water added is in the range of 0.4 to 0.8 in terms of the molar ratio with respect to the above organozinc compound. The composition of claim 15 wherein the electron donating organic solvent is boiling The point is below 230 °C. The composition of claim 1, wherein the organozinc compound R ¹ is a compound having an alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The composition of claim 1 wherein the organozinc compound is diethylzinc. The composition of claim 1, wherein the electron donating organic solvent is 1,4-two alkyl. The composition of claim 16, wherein the organic Group 3A element compound of the above formula (2) is trimethylindium. The composition of claim 16, wherein the organic Group 3A element compound of the above formula (2) is aluminum triacetate, gallium triacetate, and indium triacetate. The composition of claim 16, wherein the organic Group 3A element compound is aluminum chloride, gallium chloride or indium chloride. The composition of claim 16, wherein the electron donating organic solvent is 1,2-diethoxyethane. The composition of claim 15, wherein the mixed organic solvent is a mixed solvent of 1,2-diethoxyethane and tetrahydrofuran. A method for producing a zinc oxide film, comprising: applying a composition according to claim 1 to a surface of a substrate, and then heating the obtained coating film at a temperature of 300 ° C or lower to form a zinc oxide film or doping A zinc oxide film of a Group 3A element. The method of claim 27, wherein the zinc oxide film has an average transmittance of 80% or more for visible light. A method for producing a zinc oxide film having an average transmittance of 80% or more for visible light and a volume resistivity of less than 8 × 10 ^-2 Ω ‧ cm, the manufacturing method comprising performing at least one of the following operations: The composition A, B or C is applied to the surface of the substrate under an inert gas atmosphere, and then the resulting coating film is heated; Composition A: The composition comprises a product obtained in the following manner: (1) The organic zinc compound is dissolved in an electron-donating organic solvent having a boiling point of 110 ° C or higher, or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component, and is 4 to 12% by mass. In the solution having the concentration in the range, water is added so as to be in the range of 0.4 to 0.8 with respect to the molar ratio of the organozinc compound, and at least the organic zinc compound is partially hydrolyzed, R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms); Composition B: the composition is in the above composition A, and the molar ratio to the above organozinc compound is 0.005. Add the following formula (3) in a ratio of ~0.1 Obtained from an organic 3A group compound, (wherein M is a Group 3A 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; a carboxylic acid or an acetoacetone group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9); Composition C: The composition comprises a product obtained as follows: With respect to the above-mentioned organozinc compound represented by the following formula (1), R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) An organic 3A element compound represented by the following formula (2) or (3) in which the molar ratio of the organozinc compound is 0.005 to 0.09 (wherein M is a Group 3A 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; , carboxylic acid, or acetoacetone, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9) M _c X _d ‧aH ₂ O (2) (wherein, M Is a group 3A 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, when X is sulfuric acid, c is 2, d is 3, a is 0-9 The above-mentioned organozinc compound and an organic 3A group element compound are dissolved in an electron-donating organic solvent having a boiling point of 110 ° C or higher or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component. In the solution having a total concentration of 4 to 12% by mass, water is added so as to have a molar ratio of 0.4 to 0.8 with respect to the organic zinc compound, and at least the organic zinc compound is partially hydrolyzed, and the electron supply is performed. organic solvent is an ether solvent or an amine-based solvent; and the 3A group elements as B, Al, Ga or In; the main component of the above product based formula R _{^{1 -Zn- [O-Zn] m}} -R 1 ( formula , R ¹ is the same as the formula R (1) in the ^1, m is an integer of 2 to 20) shown in FIG. 1 or a mixture of several compounds of the following general formula of m different compounds of formula (4) and (5 a compound in which the structural unit shown is combined with a structural unit represented by the following formula (6) or a mixture of a plurality of compounds different from m (R ₁ -Zn)-(4) -[O-Zn] _m - (5) (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20) (wherein M is the same as M in the formula (2) or (3), and Q is the same as any of X, R ² , R ³ and R ^{4 in} the formula (2) or (3), and m is An integer from 2 to 20). A method of producing a zinc oxide film according to claim 29, wherein the inert gas atmosphere contains water vapor. The manufacturing method of claim 30, wherein the inert gas atmosphere containing water vapor has a relative humidity of 2 to 15%. A method for producing a zinc oxide film having an average transmittance of 80% or more for visible light and a volume resistivity of less than 1 × 10 ^-3 Ω ‧ cm, the method comprising: preparing composition A, B or C Spraying on the surface of the heated substrate in an inert gas atmosphere containing water vapor; Composition A: The composition comprises a product obtained by dissolving an organozinc compound represented by the following formula (1) a solution having a boiling point of 110 ° C or more, an electron-donating organic solvent, or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component, in a concentration of 4 to 12% by mass, relative to The organic zinc compound is added with water in such a manner that the molar ratio is in the range of 0.4 to 0.8, and at least the organic zinc compound is partially hydrolyzed, and R ¹ -Zn-R ¹ (1) (wherein R ¹ is a carbon number of 1~) a straight or branched alkyl group of 7); composition B: the composition is added to the above composition A, and the following formula is added in such a manner that the molar ratio of the above organozinc compound is 0.005 to 0.1. (3) obtained as an organic 3A group compound, (wherein M is a Group 3A 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; a carboxylic acid or an acetoacetone group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9); Composition C: The composition comprises a product obtained as follows: With respect to the above-mentioned organozinc compound represented by the following formula (1), R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) An organic 3A element compound represented by the following formula (2) or (3) in which the molar ratio of the organozinc compound is 0.005 to 0.09 (wherein M is a Group 3A 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; , carboxylic acid, or acetoacetone, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, n is an integer from 0 to 9) M _c X _d ‧aH ₂ O (2) (wherein, M Is a group 3A 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, when X is sulfuric acid, c is 2, d is 3, a is 0-9 The above-mentioned organozinc compound and an organic 3A group element compound are dissolved in an electron-donating organic solvent having a boiling point of 110 ° C or higher or a mixed organic solvent containing an electron-donating organic solvent having a boiling point of 110 ° C or more as a main component. In the solution having a total concentration of 4 to 12% by mass, water is added so as to have a molar ratio of 0.4 to 0.8 with respect to the organic zinc compound, and at least the organic zinc compound is partially hydrolyzed, and the electron supply is performed. organic solvent is an ether solvent or an amine-based solvent; and the 3A group elements as B, Al, Ga or In; the main component of the above product based formula R _{^{1 -Zn- [O-Zn] m}} -R 1 ( formula , R ¹ is the same as the formula R (1) in the ^1, m is an integer of 2 to 20) shown in FIG. 1 or a mixture of several compounds of the following general formula of m different compounds of formula (4) and (5 a compound in which the structural unit shown is combined with a structural unit represented by the following formula (6) or a mixture of a plurality of compounds different from m (R ₁ -Zn)-(4) -[O-Zn] _m - (5) (wherein R ^{1 is the} same as R ¹ in the formula (1), and m is an integer of 2 to 20) (wherein M is the same as M in the formula (2) or (3), and Q is the same as any of X, R ² , R ³ and R ^{4 in} the formula (2) or (3), and m is An integer from 2 to 20). The method for producing a zinc oxide thin film according to claim 32, wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor to the vicinity of the surface of the substrate under atmospheric pressure or under pressure. The method for producing a zinc oxide thin film according to claim 32, wherein the heating temperature of the surface of the substrate is 400 ° C or lower. The method for producing a zinc oxide thin film according to claim 33 or 34, wherein the supply of the water vapor is carried out so that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5. The method for producing a zinc oxide thin film according to claim 29, wherein the electron-donating organic solvent has a boiling point of 230 ° C or lower. The method for producing a zinc oxide thin film according to claim 29, wherein the organozinc compound is diethylzinc. The method for producing a zinc oxide thin film according to claim 29, wherein the organic Group 3A element compound of the above formula (2) is trimethylindium. The method for producing a zinc oxide thin film according to claim 30, wherein the organic Group 3A element compound of the above formula (2) is aluminum triacetate, gallium triacetate, and indium triacetate. The method for producing a zinc oxide thin film according to claim 29, wherein the organic Group 3A element compound is aluminum chloride, gallium chloride or indium chloride. The method for producing a zinc oxide thin film according to claim 29, wherein the electron-donating organic solvent is 1,2-diethoxyethane. The method for producing a zinc oxide thin film according to claim 29, wherein the mixed organic solvent is a mixed solvent of 1,2-diethoxyethane and tetrahydrofuran. An antistatic film comprising a zinc oxide film produced using the manufacturing method of claim 29. An ultraviolet cut film comprising a zinc oxide film produced using the manufacturing method of claim 29. A transparent electrode film comprising a zinc oxide film produced using the manufacturing method of claim 29. A composition for forming a zinc oxide thin film, comprising an organic zinc compound represented by the following formula (1) and an organic 3A group represented by the following formula (20) in an organic solvent having electron donating properties; An elemental compound, wherein a molar ratio of the above organic Group 3A element compound to the above organozinc compound is in the range of 0.001 to 0.3, and the above Group 3A element is B, Al, Ga or In; R ¹ -Zn-R ¹ (1) (wherein R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms) (wherein M is a Group 3A element, and R ²⁰ , R ³⁰ and R ^{40 are} independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms). The composition of claim 46, wherein, in the above organozinc compound, R ¹ is an ethyl group, and in the above organic group 3A element compound, M is aluminum, and R ²⁰ , R ³⁰ and R ⁴⁰ are each an ethyl group. The composition of claim 46, wherein, in the above organozinc compound, R ¹ is an ethyl group, and in the above organic group 3A element compound, M is gallium, and R ²⁰ , R ³⁰ and R ⁴⁰ are each a methyl group. The composition of claim 46, wherein, in the above organozinc compound, R ¹ is an ethyl group, and in the above organic group 3A element compound, M is indium, and R ²⁰ , R ³⁰ and R ⁴⁰ are each a methyl group. The composition of claim 46, wherein the total concentration of the organic zinc compound and the organic 3A compound is 15% by mass or less. The composition of claim 49, wherein the organic solvent is diisopropyl ether. A method for producing a zinc oxide film doped with a Group 3A element, characterized in that the composition of claim 49 is obtained under atmospheric pressure or under pressure, in the presence of water, and at a substrate temperature of 300 ° C or lower. Sprayed on the surface of the substrate to form a zinc oxide film doped with a Group 3A element. The method of claim 52, wherein the spraying of the composition is performed by spraying the composition from the spray nozzle so that the droplet size is in the range of 1 to 30 μm, and the distance between the spray nozzle and the substrate is 50 cm or less. The manufacturing method of claim 52, wherein the ambient temperature at which the spraying is performed is 40 ° C or lower. The method of claim 52, wherein the zinc oxide film has an average transmittance of 80% or more for visible light and a surface resistance of 1 × 10 ⁵ Ω/□ or less.