KR20140140654A - Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film - Google Patents
Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film Download PDFInfo
- Publication number
- KR20140140654A KR20140140654A KR1020147032942A KR20147032942A KR20140140654A KR 20140140654 A KR20140140654 A KR 20140140654A KR 1020147032942 A KR1020147032942 A KR 1020147032942A KR 20147032942 A KR20147032942 A KR 20147032942A KR 20140140654 A KR20140140654 A KR 20140140654A
- Authority
- KR
- South Korea
- Prior art keywords
- group
- compound
- composition
- water
- thin film
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02565—Oxide semiconducting materials not being Group 12/16 materials, e.g. ternary compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02612—Formation types
- H01L21/02617—Deposition types
- H01L21/02623—Liquid deposition
- H01L21/02628—Liquid deposition using solutions
Abstract
The present invention provides a composition capable of forming a composite oxide thin film applicable to an oxide semiconductive film or the like by spray pyrolysis or the like, and a method of forming a composite oxide thin film by using the composition. The present invention relates to a composition for preparing a composite oxide containing at least one element selected from the group consisting of a Group 4A element and a Group 4B element, at least one element selected from the group consisting of a zinc element and a Group 3B element . At least one compound selected from the group consisting of a compound including a zinc element and a compound including a group 3B element, a partial hydrolyzate of the compound with water or a compound containing the compound and the partial hydrolyzate, and a compound including a group 4A element and At least one compound selected from the group consisting of compounds including a Group 4B element, a partial hydrolyzate of the compound with water or the compound and the partial hydrolyzate. The present invention relates to a composite oxide thin film having an average transmittance of 80% or more with respect to visible light, including the step of coating the composition on the surface of a substrate in an inert gas atmosphere and then heating the obtained coating film at least once, And a method for producing the same.
Description
This application claims priority to Japanese Patent Application No. 2012-100168, filed April 25, 2012, and Japanese Patent Application No. 2012-100174, filed April 25, 2012, all of which are incorporated herein by reference in their entirety Is used.
The present invention relates to a composite oxide thin film having an average transmittance of 80% or more with respect to visible light and applicable to an oxide semiconductor film such as ZTO or ATO used for a switching element (thin film transistor) of a liquid crystal display, a thin film electroluminescence display, To a composition for preparing a composite oxide thin film. The present invention also relates to a method for producing a composite oxide thin film applicable to the oxide semiconductor film and the like, and a composite oxide thin film produced using the method.
The composition for preparing a composite oxide thin film of the present invention is prepared as a raw material from a compound containing at least two or more elements from an organozinc compound, a Group 4A element compound, a Group 3B element compound and a Group 4B element compound, and has no ignitability, In addition, when it is used as a raw material for coating a spin coat, a raw material for applying a dip coating, or a raw material for spray pyrolysis coating, a composite oxide thin film having an average transmittance of 80% or more with respect to visible light can be provided. Further, according to the method for producing a composite oxide thin film of the present invention, a compound containing at least two or more elements from an organozinc compound, a Group 4A element compound, a Group 3B element compound and a Group 4B element compound is prepared as a raw material, It is possible to provide a composite oxide thin film having an average transmittance of 80% or more with respect to visible light when it is used as a raw material, a dip coating application raw material or spray pyrolysis coating raw material.
An oxide semiconductor film made of an oxide (IGZO) of In, Ga, and Zn, for example, is known as an oxide semiconductor film made of a metal composite oxide, which is one of complex oxides, and has an electron mobility higher than that of an amorphous Si film Has recently attracted attention. Since these oxide semiconductor films have higher electron mobility than amorphous Si films and high visible light transmittance, they are expected to be applied to switching devices (thin film transistors) such as liquid crystal display devices and thin film electroluminescence display devices It is getting attention.
On the other hand, oxides of Zn and Sn (ZTO), oxides of Al and Sn (ATO), and oxides of ATO of ZO and 3B group elements such as Ga, In and Al, ZO and Hf, Such as Zn, Ga, and In, and a 4A group element such as Zr, Hf, etc., are interesting in the thin film properties of the thin film, and they are being studied in electronic devices and the like as in IGZO.
As a film forming method of the amorphous oxide film, a method of forming a thin film by treating a sintered object of IGZO in vacuum, such as a PVD method and a sputtering method, is generally known. It is known that a sputtering target of IGZO is used to form an amorphous oxide film (
On the other hand, in the formation of an oxide thin film, film formation by a coating method is known. This coating method is advantageous in that it is possible to make a large oxide thin film because the apparatus is simple and the film forming speed is fast and thus the productivity is high and the manufacturing cost is low and there is no need to use the vacuum vessel and there is no restriction by the vacuum vessel There is an advantage.
As a coating method for forming a general oxide thin film, spin coating (Patent Document 2), dip coating (non-patent document 3), spray pyrolysis (
As a material for forming the oxide thin film for the application method, a material for forming a zinc oxide thin film for the purpose of using a transparent conductive film or the like is known. Specifically, a zinc oxide thin film is formed by reacting diethyl zinc , A composition obtained by partially hydrolyzing diethyl zinc, and the like.
On the other hand, in the film formation by application of oxide of Zn and Sn (ZTO), oxide of Al and Sn (ATO), chloride, nitrate, acetylacetonato compound, alkoxide etc. of Zn and Sn (Non-Patent Document 6).
The inventors attempted to form a film by spin coating, dip coating and spray pyrolysis using the materials described in the
The present invention relates to a process for producing a 3B group element compound or a 3B group element compound such as a partial hydrolyzate of an organic zinc compound such as diethylzinc or diethylzinc, an alkylaluminum such as triethylaluminum or a partial hydrolyzate of an organic aluminum such as an alkylaluminum, In which a thin film of an oxide such as ZTO or ATO can be formed by using a water-based partial hydrolyzate as a base.
As a result of intensive investigations to achieve the above object, the present inventors have found that a partial hydrolyzate of an organic zinc compound such as diethylzinc or diethylzinc, an alkylaluminum such as triethylaluminum or a partial hydrolyzate of an organic aluminum such as an alkylaluminum Or a 4B group element such as Zr or Hf based on the partial hydrolyzate of the 3B group element compound or the 3B group element compound such as Sn as a base, And an oxide thin film such as ZTO or ATO having an average transmittance of 80% or more with respect to visible light can be easily obtained, thereby completing the present invention.
The present invention for solving the above problems is as follows.
(1-1)
And at least one element selected from the group consisting of a Group 4A element and a Group 4B element, wherein the composition is at least one element selected from the group consisting of zinc,
At least one compound selected from the group consisting of a compound containing a zinc element and a compound including a group 3B element, a partial hydrolyzate of the compound with water or a compound containing the compound and the partial hydrolyzate, At least one compound selected from the group consisting of compounds including Group 4B elements, a partial hydrolyzate of the compound with water, or the composition and the partial hydrolyzate.
(1-2)
The composition according to 1-1, wherein the zinc element-containing compound is an organic zinc compound represented by the following general formula (1).
R 1 -Zn-R 1 (One)
(Wherein R < 1 > is a linear or branched alkyl group having 1 to 7 carbon atoms)
(1-3)
The partial hydrolyzate of the organic zinc compound with water is obtained by mixing the organic zinc compound represented by the general formula (1) and water so that the molar ratio is in the range of 0.05 to 0.8, and at least partially hydrolyzing the
(1-4)
The composition according to any one of
Wherein M is a Group 3B element and R 2 , R 3 and R 4 are independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms and L is a saturated or unsaturated hydrocarbon group containing nitrogen, Organic compound, and n is an integer of 0 to 9.)
(1-5)
The partial hydrolyzate of the 3B group element compound by water is obtained by mixing the 3B group element compound represented by the general formula (2) and water so that the molar ratio is in the range of 0.05 to 0.8, and at least the 3B group element compound is partially The composition according to any one of < RTI ID = 0.0 > 1-4 < / RTI >
(1-6)
Wherein the compound including the 4A group element and the compound including the 4B group element are the 4A group element compound represented by the following formula (3) or (4) and the 4B group element compound represented by the following formula Composition.
(Wherein M is a Group 4A element or a Group 4B element and R 5 , R 6 , R 7 and R 8 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkyl group having 1 to 7 carbon atoms, An acyloxy group, an acetylacetonato group or an amide group, L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
M c X d揃 aH 2 O (4)
Wherein X is a halogen atom, nitric acid or sulfuric acid, X is a halogen atom or nitric acid, c is 1, d is 3, and X is sulfuric acid, c Is 2, d is 3, and a is an integer of 0 to 9.)
(1-7)
The partial hydrolyzate of the 4A group element compound and the 4B group element compound by water is prepared by mixing the compound represented by the general formula (3) or (4) and water so that the molar ratio is in the range of 0.05 to 0.8, Wherein the product is obtained by partial hydrolysis of a Group IV element compound and a Group 4B element compound.
(1-8)
A partial hydrolyzate of at least one compound selected from the group consisting of the compound including the 4A group element and the compound including the 4B group element, and a compound including the zinc element and a compound including the group 3B element The water partial hydrolyzate of at least one kind of compound selected from the group consisting of at least one compound selected from the group consisting of the compound including the 4A group element and the compound including the 4B group element and the compound including the zinc element and the group 3B group Is added to at least one kind of compound selected from the group consisting of a compound containing an element and a compound which is obtained by partially hydrolyzing the compound in such a manner that the molar ratio of water to the total amount of the compounds is in the range of 0.05 to 0.8, The composition according to any one of
(1-9)
A composition according to any one of
(1-10)
Wherein the organic solvent comprises at least one of an electron donating solvent, a hydrocarbon solvent, and a mixture thereof.
(1-11)
Wherein the organic solvent has a boiling point of < RTI ID = 0.0 > 230 C. < / RTI >
(1-12)
The electron donor solvent is selected from the group consisting of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, dioxane, and hydrocarbon solvents such as hexane, heptane, octane, toluene, xylene, and cyclohexane A composition as described in 1-10, wherein the composition comprises at least one species.
(1-13)
The composition according to any one of
(1-14)
Wherein the Group 3B element compound of the general formula (2) is selected from the group consisting of trimethyl indium, triethyl indium, trimethyl gallium, triethyl gallium, trimethyl aluminum, triethyl aluminum, trioctyl aluminum, trimethyl borane, The composition according to any one of
(1-15)
The composition according to any one of claims 1-11, wherein the Group 3B element is Al, Ga and In.
(1-16)
The composition according to any one of
(1-17)
The composition according to any one of
(2-1)
At least one compound selected from the group consisting of a compound including a zinc element and a compound including a group 3B element, a partial hydrolyzate of the compound with water or a compound containing the compound and the partial hydrolyzate, and a compound including a group 4A element and At least one compound selected from the group consisting of compounds including a Group 4B element, a partial hydrolyzate of the compound with water or a compound containing the compound and the partial hydrolyzate selected from the group consisting of a zinc element and a group 3B element And at least one element selected from the group consisting of 4A group elements and 4B group elements is applied to the surface of the substrate in an inert gas atmosphere and then the resulting coating film is heated Including at least one operation to be performed on the visible light The method of producing a composite oxide thin film having at least 80% the average transmittance.
(2-2)
The production method according to 2-1, wherein the zinc element-containing compound is an organic zinc compound represented by the following general formula (1).
R 1 -Zn-R 1 (1)
(Wherein R < 1 > is a linear or branched alkyl group having 1 to 7 carbon atoms)
(2-3)
The partial hydrolyzate of the organic zinc compound with water is obtained by mixing the organic zinc compound represented by the general formula (1) and water so that the molar ratio is in the range of 0.05 to 0.8, and at least partially hydrolyzing the organic zinc compound The production method according to 2-2, which is a obtained product.
(2-4)
The production method according to any one of 2-1 to 3-1, wherein the compound containing the Group 3B element is a Group 3B element compound represented by the following general formula (2).
Wherein M is a Group 3B element and R 2 , R 3 and R 4 are independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms and L is a saturated or unsaturated hydrocarbon group containing nitrogen, Organic compound, and n is an integer of 0 to 9.)
(2-5)
The partial hydrolyzate of the 3B group element compound by water is obtained by mixing the 3B group element compound represented by the general formula (2) and water so that the molar ratio is in the range of 0.05 to 0.8, and at least the 3B group element compound is partially Wherein the product is obtained by hydrolysis.
(2-6)
The compound including the 4A group element and the compound including the 4B group element may be any one of the 4A group element compound represented by the following formula (3) or (4) and the 4B group element compound described in any one of 2-1-5 Gt;
(Wherein M is a Group 4A element or a Group 4B element and R 5 , R 6 , R 7 and R 8 are independently hydrogen, a straight or branched alkyl group having 1 to 7 carbon atoms, a straight or branched alkyl group having 1 to 7 carbon atoms, An acyloxy group, an acetylacetonato group or an amide group, L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
M c X d揃 aH 2 O (4)
Wherein X is a halogen atom, nitric acid or sulfuric acid, X is a halogen atom or nitric acid, c is 1, d is 3, and X is sulfuric acid, c Is 2, d is 3, and a is an integer of 0 to 9.)
(2-7)
The partial hydrolyzate of the 4A group element compound and the 4B group element compound by water is prepared by mixing the compound represented by the general formula (3) or (4) and water so that the molar ratio is in the range of 0.05 to 0.8, Group-element compound and a Group 4B element compound.
(2-8)
A partial hydrolyzate of at least one compound selected from the group consisting of the compound including the 4A group element and the compound including the 4B group element, and a compound including the zinc element and a compound including the group 3B element The water partial hydrolyzate of at least one kind of compound selected from the group consisting of at least one compound selected from the group consisting of the compound including the 4A group element and the compound including the 4B group element and the compound including the zinc element and the group 3B group Wherein the molar ratio of water to the total amount of the compounds is in the range of 0.05 to 0.8, and the product obtained by partial hydrolysis of the compound is added to at least one kind of compound selected from the group consisting of 2 The production method according to any one of
(2-9)
[8] The method according to any one of [1] to [8], wherein the composition further comprises an organic solvent.
(2-10)
Wherein the organic solvent comprises at least one of an electron donating solvent, a hydrocarbon solvent, and a mixture thereof.
(2-11)
Wherein the organic solvent has a boiling point of 230 DEG C or less.
(2-12)
The electron donor solvent is selected from the group consisting of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, dioxane, and hydrocarbon solvents such as hexane, heptane, octane, toluene, xylene and cyclohexane The method according to any one of < RTI ID = 0.0 > 2- < / RTI >
(2-13)
The production method according to any one of
(2-14)
The Group 3B element compound of the general formula (2) is at least one selected from the group consisting of trimethyl indium, triethyl indium, trimethyl gallium, ethyl gallium, trimethyl aluminum, triethyl aluminum, trioctyl aluminum, trimethyl borane, The production method according to any one of
(2-15)
The production method according to any one of 2-1 to 14, wherein the Group 3B element is Al, Ga and In.
(2-16)
The production method according to any one of 1 to 15, wherein the 4A group element is Ti, Zr and Hf.
(2-17)
Wherein the Group 4B element is Si, Ge, and Sn.
(2-18)
The production method according to any one of 2-1 to 17, wherein the inert gas atmosphere contains water vapor.
(2-19)
Wherein the inert gas atmosphere containing water vapor has a relative humidity of 2 to 15%.
(2-20)
A method for producing a composite oxide thin film having an average transmittance of 80% or more with respect to visible light, including spraying a composition for a composite oxide described in 2-1) on a heated substrate surface in an inert gas atmosphere containing water vapor.
(2-21)
The method for producing a composite oxide thin film according to 2-20, wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure.
(2-22)
Wherein the heating temperature of the substrate surface is 400 占 폚 or less.
(2-23)
Wherein the supply amount of the water vapor is such that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5. The method for producing a composite oxide thin film according to 2-21 or 22,
(2-24)
An oxide semiconductor film comprising a composite oxide thin film produced by the manufacturing method according to any one of
By using the composition for preparing a composite oxide thin film of the present invention, a useful composite oxide thin film such as an oxide semiconductor film such as ZTO or ATO can be easily formed by forming a coating film such as a spin coating method, a dip coating method, a spray pyrolysis method or the like And a composite oxide thin film having an average transmittance of 80% or more with respect to visible light can be produced.
1 is a view showing a spray film forming apparatus.
[Composition for preparing composite oxide thin film]
The composition for preparing a composite oxide thin film according to the present invention is a composite oxide composition containing at least one element selected from the group consisting of a zinc element and a 3B group element and at least one element selected from the group consisting of a 4A group element and a 4B group element Oxides. The composition comprises at least one compound selected from the group consisting of a compound including a zinc element and a compound including a group 3B element, a partial hydrolyzate of the compound with water or the compound and the partial hydrolyzate, and a group 4A element And a compound including a group 4B element, a partial hydrolyzate of the compound with water, or the compound and the partial hydrolyzate.
(1) Compounds containing zinc element
Examples of the compound containing a zinc element include an organic zinc compound represented by the following general formula (1).
R 1 -Zn-R 1 (1)
(Wherein R < 1 > is a linear or branched alkyl group having 1 to 7 carbon atoms)
Specific examples of the alkyl group represented by R 1 in the organic zinc compound represented by the general formula (1) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- Hexyl group, tert-hexyl group, 2-hexyl group, and heptyl group can be given as examples of the alkyl group having 1 to 20 carbon atoms. In the compound represented by the general formula (1), R 1 is preferably a compound having 1, 2, 3, 4, 5, or 6 carbon atoms. The compound represented by the general formula (1) is particularly preferably diethyl zinc, in which R 1 is 2 carbon atoms.
(2) Compounds containing Group 3B elements
Examples of the compound containing a Group 3B element include a Group 3B element compound represented by the following Formula (2).
(Wherein M is a Group 3B element and R 2 , R 3 and R 4 are independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms)
Specific examples of the metal represented by M in the 3B group element compound represented by the general formula (2) include B, Al, Ga and In. R 2 , R 3 and R 4 are preferably hydrogen or an alkyl group. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, Hexyl group, tert-hexyl group, 2-hexyl group, and heptyl group can be given as examples of the alkyl group having 1 to 20 carbon atoms. The ligand represented by L may be one or more selected from the group consisting of trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, N, N-diethylaniline, triphenylphosphine, dimethylsulfate, Hydrofluorene. Particularly, in the compound represented by the general formula (2), R 2 , R 3 and R 4 are preferably compounds having 1, 2, 3, 4, 5 or 6 carbon atoms and trimethylaluminum, triisobutylaluminum , Diisobutyl aluminum hydride, trimethyl gallium, triethyl gallium, trimethyl indium, trimethyl indium, triethyl indium, trimethyl borane, triethyl borane, and coordination compounds by these ligands.
(3) a compound including a group 4A element and a compound including a group 4B element
Examples of the compound including the 4A group element and the group 4B element include the 4A group element compound and the 4B group element compound represented by the following general formula (3) or (4).
(Wherein M is a Group 4A element or a Group 4B element and R 5 , R 6 , R 7 and R 8 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkyl group having 1 to 7 carbon atoms, An acyloxy group, an acetylacetonato group or an amide group, L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
M c X d揃 aH 2 O (4)
Wherein X is a halogen atom, nitric acid or sulfuric acid, X is a halogen atom or nitric acid, c is 1, d is 3, and X is sulfuric acid, c is 2, d is 3, and a is an integer of 0 to 9.)
Specific examples of the metal represented by M in the 4A group element compound represented by the general formula (3) include Ti, Zr, and Hf. These alkyl compounds are generally unstable and R 5 , R 6 , R 7 and R 8 in the formulas are ligands containing oxygen or nitrogen elements such as alkoxy groups, acyloxy groups, acetoxy groups, acetylacetonato groups and amide groups . For example, specific examples of these ligands include generally known alkoxy groups, acetoxy groups, acyloxy groups, acetylacetonato groups, and amide groups. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, and a tert-butoxy group. Examples of the amide group include an acyloxy group such as an acetoxy group, and an amide group such as acetylacetonato group, trimethylamide, triethylamide, isopropylamide and tert-butylamide.
Specific examples of the element represented by M in the 4B group element compound represented by the general formula (3) include, for example, Si, Ge and Sn. Specific examples of these compounds include generally known alkyl groups, alkoxy groups, acyloxy groups, acetylacetonato groups and amide groups. Specific examples of the alkyl group of R 5 , R 6 , R 7 and R 8 include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, Pentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, 2-hexyl group and heptyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxide group, and a tert-butoxy group. Examples of the amide group include an acyloxy group such as an acetoxy group, and an amide group such as acetylacetonato group, trimethylamide, triethylamide, isopropylamide and tert-butylamide. The 4B group element compound represented by the general formula (3) is preferably at least one selected from the group consisting of ethyltin, butyltin, methoxysilicon, ethoxysilicon, isopropoxysilicon, tert-butoxysilicon, methoxygermanium, ethoxygermanium, But are not limited to, germanium, germanium, germanium, germanium, germanium, germanium, germanium, germanium, germanium, germanium, Isopropyl amide germanium, dimethyl amide tin and diisopropyl amide tin.
The ligands represented by L in the 4A and 4B group element compounds represented by the general formula (3) can be exemplified by trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, N, N - diethylaniline, triphenylphosphine, dimethylsulfone, diethyl ether, and tetrahydrofuran. For example, the 4A group element compound represented by the general formula (3) is, for example, methoxy titanium, ethoxy titanium, isopropoxy titanium, butoxy titanium, methoxy zirconium, ethoxy zirconium, isopropoxy But are not limited to, zirconium, butoxy zirconium, methoxy hafnium, isopropoxy hafnium, butoxy hafnium, titanium nitrate, zirconium acetate, hafnium acetate, acetylacetonato titanium, acetylacetonato zirconium, acetylacetonato hafnium, Titanium, diisopropylamide titanium, ditertiary butyl titanium, dimethyl amide zirconium, diethyl amide zirconium, diisopropyl amide zirconium, ditert-butyl amide zirconium, dimethyl amide hafnium, diethyl amide hafnium, diisopropyl amide Hafnium, ditert-butylamide hafnium, and coordination compounds thereof.
Specific examples of the metal represented by M in the 4A group element compound represented by the general formula (4) include Ti, Zr and Hf. Specific examples of the counterpart forming the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. For example, the 4A group element compound represented by the general formula (4) is, for example, titanium fluoride, zirconium fluoride, hafnium fluoride, titanium chloride, zirconium chloride, hafnium chloride, titanium nitrate, zirconium nitrate, hafnium nitrate, Zirconium sulfate, hafnium sulfate, and hydrates thereof.
Specific examples of the metal represented by M in the 4B group element compound represented by the general formula (4) include Si, Ge and Sn. Specific examples of the counterpart forming the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. For example, the 4B group element compound represented by the general formula (4) is, for example, silicon fluoride, germanium fluoride, tin fluoride, silicon chloride, germanium chloride, tin chloride, tin bromide, germanium nitrate, tin nitrate, Tin and their hydrates.
The composition for preparing a composite oxide thin film of the present invention described above specifically includes the following embodiments.
(i) an organic zinc compound represented by the general formula (1), a partial hydrolyzate of an organic zinc compound represented by the general formula (1) with water, or an organic zinc compound represented by the general formula (1) The 4A group element compound and / or the 4B group element compound represented by the above-mentioned general formula (3) or (4), the above-mentioned general formula (3) Or a product obtained by partially hydrolyzing a 4A group element compound and / or a 4B group element compound represented by the general formula (3) or (4), or a product obtained by partial hydrolysis of a 4A group element compound represented by the general formula (3) 4B group element compound and a product obtained by partial hydrolysis of the compound.
(ii) the 3B group element compound represented by the general formula (2), the partial hydrolyzate of the 3B group element compound represented by the general formula (2) with water, or the 3B group element represented by the general formula (2) The 4A group element compound and / or the 4B group element compound represented by the above general formula (3) or (4) is added to the partial hydrolyzate of the elemental compound and the 3B group element compound represented by the general formula (2) The product obtained by partially hydrolyzing the 4A group element compound and / or the 4B group element compound represented by the above general formula (3) or (4), or the product obtained by partial hydrolysis of the 4A group element represented by the above general formula (3) A compound and / or a Group 4B element compound and a product obtained by partial hydrolysis of the compound.
In the following
(I) a composition comprising an organic zinc compound represented by the general formula (1) and a 3B group element compound represented by the general formula (2) (hereinafter, also referred to as composition 1)
(Ii) a composition containing an organic zinc compound represented by the general formula (1) and a partial hydrolyzate of a 3B group element compound represented by the general formula (2) by water (hereinafter, also referred to as composition 2)
(Iii) an organic zinc compound represented by the general formula (1), a 3B group element compound represented by the general formula (2) and a partial hydrolyzate of a 3B group element compound represented by the general formula (2) (Hereinafter, also referred to as composition 3)
(Iv) a composition containing the partial hydrolyzate of water and the Group 3B element compound of the organic zinc compound represented by the general formula (1) (hereinafter also referred to as Composition 4)
(V) a composition containing a partial hydrolyzate of a water-based partial hydrolyzate of an organozinc compound represented by the general formula (1) and a partial hydrolyzate of a Group 3B element compound by a water.
(Vi) a partial hydrolyzate of an organic zinc compound represented by the general formula (1) with water, a 3B group element compound represented by the general formula (2) and a 3B group element compound represented by the general formula (2) (Hereinafter also referred to as composition 6) containing a partial hydrolyzate of water,
(Iii) A composition containing an organic zinc compound represented by the general formula (1), a partial hydrolyzate of the organic zinc compound with water and a 3B group element compound represented by the general formula (2) )
(Iii) an organic zinc compound represented by the general formula (1), a partial hydrolyzate of the organic zinc compound with water, and a partial hydrolyzate of the 3B group element compound represented by the general formula (2) (Hereinafter also referred to as composition 8)
(Iii) The water-solubilized partial hydrolyzate of the organic zinc compound represented by the general formula (1) and the organic zinc compound with the water of the 3B group element compound and the 3B group element compound represented by the general formula (2) A composition containing a partial hydrolyzate (hereinafter also referred to as composition 9)
In the composition of the present invention, as the zinc compound, for example, a zinc compound represented by the following general formula (5) or (6) may be added as a compound other than the general formula (1).
R 9 -M-R 10 (L) n (5)
Wherein M is a zinc element and R 9 and R 10 are independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms (excluding R 9 and R 10 are all alkyl groups) An acyloxy group, an acetylacetonato group or an amide group, L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
M c X d揃 aH 2 O (6)
Wherein X is a halogen atom, nitric acid or sulfuric acid, X is a halogen atom or nitric acid, c is 1, d is 2, X is sulfuric acid, c is 1, d is 1, and a is an integer of 0 to 9.)
Specific examples of the zinc compound represented by the above general formula (5) that can be added as a compound other than the general formula (1) include a commonly known alkyl group (R 9 , R 10 (Excluding all of the alkyl groups), an alkoxy group, an acyloxy group, an acetylacetonato group and an amide group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxide group, and a tert-butoxy group. Examples of the amide group include an acyloxy group such as an acetoxy group, and an amide group such as acetylacetonato group, trimethylamide, triethylamide, isopropylamide and tert-butylamide.
The ligand represented by L in the above general formula (5) is at least one selected from the group consisting of trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, N, N-diethylaniline, Dimethyl sulfoxide, diethyl ether, and tetrahydrofuran. For example, the zinc compound represented by the general formula (5) is preferably at least one selected from the group consisting of dimethoxy zinc, diethoxy zinc, diisopropoxyzinc, tert-butoxyzinc, zinc acetate, acetylacetonato zinc, bisdimethylamidozinc, Bisdiisopropylamide zinc and the like, and coordination compounds thereof.
Specific examples of the counterpart of the salt represented by X in the zinc compound represented by the general formula (6) include fluorine, chlorine, bromine, iodine, nitric acid and sulfuric acid. For example, examples of the zinc compound represented by the general formula (6) include zinc fluoride, zinc chloride, zinc nitrate, zinc carbonate, zinc sulfate, and hydrates thereof.
In the present invention, as the compound other than the compound represented by the formula (2), the compound of the group 3B element represented by the following formula (7) or (8) may be added as the compound of the group 3B element.
Wherein M is a Group 3B element and R 11 , R 12 and R 13 are independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms (all of R 11 , R 12 and R 13 excluding an alkyl group) An acyloxy group, an acetylacetonato group or an amide group; L is a chelating organic compound containing nitrogen, oxygen or phosphorus; and n is an integer of 0 to 9 It is an integer.)
M c X d揃 aH 2 O (8)
(Wherein M is a Group 3B element, X is a halogen atom, nitric acid or sulfuric acid, and when X is a halogen atom or nitric acid, c is 1, d is 3, 3, and a is an integer of 0 to 9.)
Specific examples of the metal represented by M in the Group 3B element compound represented by the general formula (7) include B, Al, Ga and In. R 11 , R 12 , and R 13 each represent a hydrogen atom or an alkyl group (all of R 11 , R 12 , and R 13 except for the alkyl group), and specific examples of the alkyl group include methyl, ethyl, A tert-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a hexyl group, A 2-hexyl group, and a heptyl group. It is also preferable that at least one of R 2 , R 3 and R 4 is hydrogen and the remainder is an alkyl group. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxide group, and a tert-butoxy group. Examples of the amide group include an acyloxy group such as an acetoxy group, and amide groups such as acetylacetonato group, trimethylamide, triethylamide and isopropylamide.
The ligand represented by L in the general formula (7) is preferably at least one selected from the group consisting of trimethylamine, triethylamine, triphenylamine, pyridine, morpholine, N, N-dimethylaniline, Dimethyl sulfoxide, diethyl ether, and tetrahydrofuran. The 3B group element compound represented by the general formula (7) is preferably selected from the group consisting of diborane, borane tetrahydrofuran complex, borane trimethylamine complex, borane triethylamine complex, triethylborane, tributylborane, Triethylamine, tri-n-butylamine, tri-n-butylamine, tri-n-butylamine, Ethoxyborane, triisopropoxy indium, triisopropoxy gallium, triisopropoxy aluminum, tri-tert-butoxy indium, and tri-tert-butoxy gallium. From the viewpoint that the price is low and the availability is easy, it is preferable that triethyl aluminum, triisobutyl aluminum, trimethyl gallium, trimethyl indium, trimethoxyborane, triethoxyborane, triisopropoxy indium, triisopropoxy gallium, Particularly preferred are aluminum trioxide, tri-tert-butoxy indium, and tri-tert-butoxy gallium.
Specific examples of the metal represented by M in the 3B group element in the 3B group element compound and the 3B group element compound represented by the general formula (8) include, for example, B, Al, Ga and In . Specific examples of the counterpart forming the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. Examples of the Group 3B element compound represented by the general formula (8) include boron fluoride, boron chloride, aluminum chloride, aluminum chloride hexahydrate, aluminum nitrate nonahydrate, gallium chloride, gallium nitrate hydrate, indium chloride, Hydrate, indium tetrahydrate, and the like.
The compounds represented by the general formulas (1) and (2) can be obtained by reacting a compound represented by the general formula (3) in which R 5 , R 6 , R 7 and R 7 are a straight chain or branched alkyl group having 1 to 7 carbon atoms, A substituent other than the alkyl group among the alkyl compound of the compound or the 4B group element compound and the zinc compound represented by the formula (5) or (6), the 3B group compound represented by the formula (7) In the solution of the composition by a substituent exchange reaction with the compound having the substituent. The composition of the present invention also includes a composition containing a compound produced by such a substituent exchange reaction.
The present invention also includes the above composition further containing an organic solvent.
More specific examples of the composition of the present invention include the following. However, the present invention is not intended to be limited thereto.
(A) A 4A group element compound represented by the general formula (3) and / or a 4B group element and / or a 4B group element represented by the general formula (4) are added to a solution in which an organic zinc compound represented by the general formula (1) A composition comprising a compound (hereinafter also referred to as Mixture 1).
(B) a 4A group element compound represented by the general formula (3) and / or a 4B group element represented by the general formula (4) and / or a 4B group element represented by the general formula (4) are added to a solution of the 3B group element compound represented by the general formula (2) A composition comprising an elemental compound-containing product (hereinafter also referred to as Mixture 2).
(C) water is added to a solution obtained by dissolving the organic zinc compound represented by the general formula (1) in an organic solvent, and after the organic zinc compound is at least partially hydrolyzed, the solution containing at least one 3B group element, A mixture of a mixture of a compound of the group 3B element represented by the above general formula (2) and / or the general formula (7) and a mixture of a mixture of a mixture of a mixture of a mixture of a mixture of a mixture of a mixture of a 4A group element compound represented by the above formula (3) and / (Hereinafter, also referred to as partial hydrolyzate 1).
(D) water is added to a solution obtained by dissolving the 3B group element compound represented by the above general formula (1) in an organic solvent, and after at least partially hydrolyzing the 3B group element compound, And / or a product containing a Group 4A element compound and / or a Group 4B element compound represented by the general formula (4) (hereinafter, also referred to as partial hydrolyzate 2).
(E) To a solution obtained by dissolving a mixture of an organic zinc compound represented by the general formula (1) and a Group 3B element compound represented by the following general formula (2) containing at least one 3B group element in an organic solvent, (Hereinafter, also referred to as a partial hydrolyzate 3) obtained by at least partially hydrolyzing at least the organic zinc compound and a 4A group represented by the general formula (3) and / or the general formula (4) And a product comprising an elemental compound and / or a Group 4B element compound.
(F) an organo-zinc compound represented by the general formula (1) and at least one Group 3B element, a Group 3B element compound represented by the following general formula (2) To a solution obtained by dissolving a mixture of a 4A group element compound and / or a 4B group element compound represented by the formula (4) in an organic solvent, and at least partially hydrolyzing the organic zinc compound (Hereinafter, also referred to as partial hydrolyzate 4).
In the present invention, an organic solvent may be used to dissolve the above-mentioned metal-containing compound. The organic solvent dissolves each of the compounds of zinc, the Group 3B element, the Group 4A element and the Group 4B element, or the partial hydrolyzate of the above-described zinc compounds, and is not particularly limited as long as there is no problem in use. An electron-donating organic solvent such as ether or a hydrocarbon compound such as hexane or toluene is preferably used. These organic solvents may be used alone or as a mixture with other solvents. By dissolving the composition of the present invention by dissolving the composition of the present invention using such a solvent, an oxide thin film such as ZTO or ATO having an average transmittance of 80% or more with respect to visible light can be easily obtained.
Examples of the electron-donating organic solvent include ether compounds, amine compounds, and the like, and may be those having solubility in water and raw material compounds such as an organic zinc compound represented by the general formula (1). Examples of the preferable electron donor organic solvent include those having a boiling point of 230 ° C or lower. Examples thereof include di-n-butyl ether (boiling point 142.4 ° C), dihexyl ether (boiling point 226.2 ° C) Methoxy toluene (boiling point 171.8 占 폚), benzyl ethyl ether (boiling point 189 占 폚), diphenyl ether (boiling point 173 占 폚), phenethyl ether Ether (boiling point 258.3 占 폚), veratrol (boiling point 206.7 占 폚), trioxane (boiling point 114.5 占 폚), 1,2-diethoxyethane (boiling point 121 占 폚), 1,2-dibutoxyethane Bis (2-methoxyethyl) ether (boiling point: 162 占 폚), bis (2-ethoxyethyl) ether (boiling point: 188.4 占 폚), bis (Boiling point 216 ° C) and bis [2- (2-methoxyethoxyethyl)] ether (boiling point 275 ° C) N, N-dimethylaniline (boiling point: 193 ° C), N, N-dimethylaniline (boiling point: And amine-based solvents such as diethylaniline (boiling point: 217 ° C) and pyridine (boiling point: 115.3 ° C). As the electron donative organic solvent, 1,2-diethoxyethane (boiling point 121 캜), which is a kind of glyme, is preferable from the viewpoints of both suppression of gel at the time of preparation of the composition and volatility of the solvent itself. The upper limit of the boiling point of the electron-donating organic solvent is not particularly limited, but it is preferably 230 캜 or lower from the viewpoint of relatively short drying time when the solvent is removed after coating the obtained composition to form a coating film.
Further, in the present invention, a hydrocarbon compound can be used as a solvent. The hydrocarbon compound is preferably a straight chain, branched hydrocarbon compound or cyclic hydrocarbon compound having 5 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, aromatic hydrocarbon compound having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, For example.
Specific examples of these hydrocarbon compounds include pentane, n-hexane, heptane, isohexane, methylpentane, octane, 2,2,4-trimethylpentane (isooctane), n-nonane, , Aliphatic hydrocarbons such as eicosane, methylheptane, 2,2-dimethylhexane and 2-methyloctane, alicyclic hydrocarbons such as cyclopentane, cyclohexanemethylcyclohexane and ethylcyclohexane, aliphatic hydrocarbons such as benzene, toluene, xylene, cumene, Aromatic hydrocarbons such as trimethylbenzene, hydrocarbon spirits such as mineral spirit, solvent naphtha, kerosene and petroleum ether.
The upper limit of the boiling point of an organic solvent or a hydrocarbon compound different from that of the electron-donating organic solvent is not particularly limited, but it is preferable that the drying time when the solvent is removed after coating the obtained composition to become a coating film is relatively short , It is preferably 230 deg. C or less like the electron-donating compound. From the viewpoint of improving the stability of the metal-containing compound, it is preferable that the electron-donating compound is contained in the composition of the present invention.
(1) to (4) or the like in a solution obtained by dissolving the compound represented by the general formula (1) in the electron-donating organic solvent or the mixed organic solvent containing the electron-donating organic solvent The concentration of the raw material compound is preferably in the range of 4 to 12 mass%. The concentration of the starting compound represented by the general formulas (1) to (4) in the solution dissolved in the organic solvent is preferably in the range of 6 to 10 mass%.
A composition obtained by dissolving an electric compound or a partial hydrolyzate in an organic solvent may be a composition in which the composition dissolves or reacts as it is, as described above. Alternatively, after the product is obtained by partial hydrolysis reaction or the like, an electron donating organic solvent or a hydrocarbon compound Or the like can be arbitrarily added to the composition of the present invention to adjust the composition of the composition.
The amount of water to be added in the preparation of the partial hydrolyzate is, for example, in the case of
The reaction product containing the partial hydrolyzate obtained by adding the water in this range can form a transparent and conductive zinc oxide thin film by spin coating, dip coating and spray pyrolysis. Even when the partial hydrolysis of the Group 3B elemental compound is carried out singly, the molar ratio of water to the Group 3B elemental compound is preferably in the range of 0.05 to 0.8.
For example, when the molar ratio of water is 0.4 or more, partial hydrolysis of an organozinc compound is achieved by partially hydrolyzing the organozinc compound at a high yield of 90% or more based on the zinc contained in the raw material . In the
By controlling the addition amount of the water, the physical properties such as viscosity and boiling point of the composition can be controlled. For example, in the case of a coating which is difficult to carry out a reaction such as a spin coat method, it is possible to facilitate formation of an oxide film by increasing the addition amount of water. The composition of the present invention obtained by using a compound which does not undergo hydrolysis in the spraying method or the like or by using a partially hydrolyzed product in which the addition of water is reduced enables easy formation of a film at a low temperature.
In the
The addition of water may be carried out with water alone without mixing water with another solvent, or with a mixed solvent obtained by mixing water with another solvent. From the viewpoint of suppressing progress of local hydrolysis, it is preferable to use a mixed solvent. The content of water in the mixed solvent may be, for example, 1 to 50 mass%, preferably 2 to 20 mass% to be. The solvent which can be used for the mixed solvent with water can be, for example, the above electron-donating organic solvent. The electron-donating organic solvent may be an organic solvent having a boiling point of 110 ° C or higher, or an organic solvent having a boiling point of lower than 110 ° C. However, it is preferable that the organic solvent has a boiling point of less than 110 캜 from the viewpoint of being inert to diethylzinc and having high water solubility.
The addition of water varies depending on the scale of the reaction, but it can be carried out for a period of time ranging from 60 seconds to 10 hours, for example. From the viewpoint of a good yield of the product, it is preferable to add the organic zinc compound of the formula (1) as a raw material by dropwise adding water or a mixed solvent with water. The addition of water can be carried out with stirring the solution of the compound represented by the general formula (1) and the electron-donating organic solvent without stirring (in a stationary state) or with stirring. The temperature at the time of addition can be selected from any temperature between -90 and 150 캜. -15 to 30 캜 is preferable in view of the reactivity of water and the organic zinc compound.
The hydrolysis of the Group 3B element compound of the general formula (2) is slightly more intense than the reaction of the organozinc compound of the general formula (1), but the hydrolysis can be carried out in the same manner as the reaction of the organozinc compound of the general formula (1) And the reaction conditions can be controlled in the same manner by appropriately selecting the above-described reaction conditions. The 4A group element compound or the 4B group element compound represented by the general formula (3) and the general formula (4), the zinc compound represented by the general formula (5) and the general formula (6), the 3B group represented by the general formula (7) The same is true for the hydrolysis of group-element compounds.
After the addition of water, in order to accelerate the reaction between water and the compound represented by the general formula (1) and the compound represented by the general formulas (2) to (4) or the water and the compound represented by the general formula (1) For example, for 1 minute to 48 hours, without stirring (in a stationary state) or stirring. The reaction temperature can be reacted at any temperature between -90 and 150 캜. The reaction temperature is preferably in the range of 5 to 80 캜 from the viewpoint of obtaining the partial hydrolyzate in high yield. The reaction pressure is not limited. Normally, it can be carried out at normal pressure (atmospheric pressure). The progress of the reaction between water and the compound represented by the general formula (1) can be monitored, if necessary, by sampling the reaction mixture and analyzing the sample by NMR or IR or sampling the generated gas.
The organic solvent, the organic zinc compound of the general formula (1), the Group 3B element compound of the general formula (2), the 4A group element compound or the 4B group element compound of the general formula (3) and the general formula (4) The zinc compound of the general formula (5) and the general formula (6), the Group 3B element compound of the general formula (7) and the general formula (8) and the mixed solvent of water and water can be added to the reaction vessel Can be introduced. These reaction processes may be any one of a batch operation type, a half batch operation type and a continuous operation type, and there is no particular limitation, but a batch operation type is preferable.
By the above reaction, the organozinc compound of the general formula (1), the Group 3B element compound of the general formula (2) and the mixture thereof are partially hydrolyzed by water and a product containing the partial hydrolyzate is obtained . When the organic zinc compound of the general formula (1) is diethylzinc, the analysis of the product obtained by the reaction with water has been done for some time, but the results are different according to reports and the product composition is clearly specified no. Further, the composition of the product may vary depending on the addition mole ratio of water, the reaction time, and the like.
For example, in the
R 1 -Zn- [O-Zn] p -R 1 (9)
(Wherein, R 1 is the same as R 1 in the formula (1), p is an integer of 2-20.) In the partial hydrolyzate. 2, or to the compound represented by the general formula (10), Or a mixture of a plurality of kinds of compounds having different p values.
(Wherein M is the same as M in the general formula (2), Q is the same as any one of R 2 , R 3 and R 4 in the general formula (2), and M is an integer of 2 to 20 to be.)
In the present invention, as the main component of the product, for example, for the
(R < 1 > -Zn) - (11)
- [O-Zn] m - (12)
(Wherein, R 1 is the same as R 1 in the formula (1), M is an integer of 2-20.)
Zn-4A, Zn-4B, Zn-4A-4B, and 3B-4B in a composition for preparing a composite oxide thin film containing a zinc element (Zn), a group 3B element (3B), a group 4A element (4A), and a group 4B element 4A, 4B, 4B, 4B, 4B, 4B, 4B, 4B, 4B, The molar ratio of each compound of the general formulas (1) to (8) used in the present invention is arbitrarily adjusted so that the ratio of the composition of each element of Zn to 4B becomes the composition of the oxide containing the composite oxide of each element combination of the present invention It is possible to do. The molar ratio can be adjusted so as to obtain the general composition of the complex oxide reported, the oxygen-deficient compound and the like, and the composition ratios of the other components are not limited to the constant ratios. It is possible to dispense.
For example, the composition for the purpose of film formation of ZTO or ATO contains Sn as a Group 4B element in zinc or aluminum. It is possible to arbitrarily adjust the molar ratio of Zn, Sn, Al and Sn so that the ratio of this composition becomes the composition of the desired ZTO or oxide containing ATO. This molar ratio can be adjusted so as to obtain the general composition of ZTO or ATO and oxygen deficient compounds reported, and the composition ratio of the other components is not limited to the constant ratio, Can be prepared.
Examples of the composite oxide containing the zinc element (Zn), the 3B group element (3B), the 4A group element (4A) and the 4B group element (4B) obtained by using the composition of the present invention include the following oxides and oxides containing them .
Examples of Zn-4A:
Zn x Ti y O t , Zn x Zr y O t , Zn x Hf y O t , Zn x Ti y Zr y O t , Zn x Zr y Hf y Ot, Zn x Hf y Ti y O t Etc,
Examples of Zn-4B:
Zn x Sn y O t , Zn x Ge y O t , Zn x Si y O t , Zn x Sn y Si y O t , Zn x Ge y Sn y O t , Zn x Si y Ge y O t ,
Examples of Zn-4A-4B:
Zn x Sn y Zr y O t , Zn x Ge y Zr y O t , Zn x Si y Zr y O t , Zn x Sn y Zr y Hf y O t , Zn x Sn y Zr y Si y O t , Zn x Sn y Hf y O t , Zn x Sn y Ti y O t , Zn x Sn y Ge y Zr y Hf y O t ,
Examples of 3B-4A:
Al x Ti y O t , Al x Zr y O t , Al x Hf y O t , Al x Ti y Zr y O t , Al x Zr y Hf y O t , Al x Hf y Ti y O t , In x Ti y O t, In x Zr y O t, In x Hf y O t, In x Ti y Zr y O t, In x Zr y Hf y O t, In x Hf y Ti y O t, GaxTi y O t , GaxZr y O t, GaxHf y O t, Ga x Ti y Zr y O t, Ga x Zr y Hf y O t, Ga x Hf y Ti y O t, In x Al x Ti y O t, In x Al x Zr y O t, In x Al x Hf y O t, In x Al x Ti y Zr y O t, Ga x Al x Ti y Zr y O t, In x Al x Zr y Hf y O t, In x Hf x Ti y O yt Al, Ga x Al x In y Hf x Ti y O t Etc,
Examples of 3B-4B:
Al x Sn y O t , Al x Ge y O t , Al x Si y O t , Al x Sn y Si y O t , Al x Ge y Sn y O t , Al x Si y Ge y O t , Ga x Sn y O t, GaxGe y O t, Ga x Si y O t, Ga x Sn y Si y O t, Ga x Ge y Sn y O t, GaxSi y Ge y O t, In x Sn y O t, In x Ge y O t, In x Si y O t, In x Sn y Si y O t, In x Ge y Sn y O t, In x SiyGe y O t, In x Al x Sn y O t, In x Al x GeyO t , In x A x Si x O t , In x Al x Sn y Ge y O t , GaxAl x Sn y Ge y O t , In x Al x Ge y Si y O t , In x A x Si s y O t , Ga x In x Al x S y y G y O t ,
Examples of 3B-4A-4B:
Al x Sn y Zr y O t , Al x Ge y Zr y O t , Al x Si y Zr y O t , A x lSn y Zr y Hf y Ot, Al x Sn y Zr y Si y O t , Al x Sn y Hf y O t , Al x Sn y Ti y Ot, Al x Sn y Ge y Zr y Hf y O t , Ga x Sn y Zr y Ot, Ga x Ge y Zr y Ot, Ga x Si y Zr y O t, Ga x Sn y Zr y Hf y O t, GaxSn y Zr y Si y O t, GaxSn y Hf y O t, GaxSn y Ti y Ot, GaxSn y Ge y Zr y Hf y O t, In x Sn y Zr y O t , In x GeyZrOt, In x Si y Zr y O t And so on, In x Sn y Zr y Hf y Ot, In x Sn y Zr y Si y O t, x In y O SnyHf t, x SnyTiyOt In, Zn x In y Ge y Zr y Hf y O t , In x Al x Zn x Sn y Zr y Ot, In x Gax GeyZryO t , In x Gax Sn y Zr y Hf y O t , Al x Gax Sn y Zr y S y O t , In x Including Gax Sn y Hf y O t, In x Al x SnyTiyO t, Al x Gax Sn y Ge y Zr y Hf y O t,
Examples of Zn-3B-4A:
Zn x Al x Ti y O t , Zn x Al x Zr y O t , Zn x Al x Hf y O t , Zn x Al x Ti y Zr y O t , Zn x Al x Zr y Hf y O t , Zn x Al x Hf y Ti y O t, Zn x Ga x TiyO t, Zn x Ga x Zr y O t, Zn x Ga x Hf y O t, Zn x Ga x Ti y Zr y O t , Zn x Ga x Zr y Hf y O t , Zn x Ga x Hf y Ti y O t , Zn x In x Ti y O t , Zn x In x Zr y Ot, Zn x In x Hf y O t , Zn x In x Ti y Zr y O t , Zn x In x Zr y Hf y O t , Zn x In x Hf y Ti y O t , Zn x In x Al x Ti y O t , Zn x In x Al x Zr y O t , Zn x In x Al x Hf y O t , Zn x In x Al x Ti y Zr y O t , Zn x In x Al x Zr y Hf y O t , Zn x In x Al x Hf y Ti y O t , Zn x In x Gax Ti y O t , Zn x Ga x Al x Zr y O t , Zn x In x Ga x Hf y O t , Zn x Ga x Al x Ti y Zr y O t , Zn x Ga x In x Al x Zr y Hf y O t , Zn x In x Ga ax Hf y Ti y O t ,
Examples of Zn-3B-4B:
Zn x Al x Sn y O t , Zn x Al x Si y O t , Zn x Al x Ge y O t , Zn x Al x Sn y Ge y O t , Zn x Al x Sn y Si y O t , Zn x Al x Si y Ge y O t , Zn x Ga x Sn y O t , Zn x Ga x Ge y O t , Zn x Ga x Si y O t , Zn x Ga x Sn y Ge y O t , Zn x Ga x Si y Ge y O t , Zn x Ga x Sn y Si y O t , Zn x In x Sn y O t , Zn x In x Ge y O t , Zn x In x Si y O t , Zn x In x Sn y Ge y O t , Zn x In x Ge y Si y O t , Zn x In x Si y Sn y O t , Zn x Al x Sn y O t , Zn x Al x Ge y O t , Zn x Al x Si y O t , Zn x Al x Sn y Si y O t , Zn x Al x Ge y Sn y O t , Zn x Al x SiyGe y O t , Zn x In x Al x Sn y O t , Zn x In x Sn x Ge y O t, Zn x In x AlxSn y O t, Zn x In x Al x Sn y Ge y O t, Zn x In x Al x Sn y Sn y O t, Zn x In x Al x Sn y Si y O t , Zn x In x Ga x Sn y O t , Zn x Ga x Al x Ge y O t , Zn x In x Ga x SiyO t , Zn x Ga x Al x Sn y Ge y , Zn x Ga x In x Al x Sn y Ge y O t , Zn x In x Ga x Sn y Si y O t Etc
Examples of Zn-3B-4A-4B:
Zn x Al x Zr y Sn y O t , Zn x In x Zr y Sn y O t , Zn x Ga x Zr y Sn y O t , Zn x Ga x Al x Ti y Zr y Sn y O t , Zn x Ga x In x Al x Zr y Hf y Sn y O t , Zn x In x Ga x Hf y Ti y Sn y O t , Zn x In x Ga x Hf y Ti y Ge y O t Etc.
The elements of 3B, 4A and 4B may be contained in one or two or more. Here, x, y, z, s, and t, which are the ratios of the respective elements, are not particularly limited in the range in which oxides can be obtained and can be arbitrary numbers depending on the desired complex oxides, but are usually set in the range of 0.1 to 5, The molar ratio of each compound of the above general formulas (1) to (8) may be adjusted so as to obtain a composition. In this composite oxide, it is possible to prepare such an oxygen-deficient compound and the like, and other composition ratios are not limited to the integer ratios but can be prepared by adjusting the addition amount of each element.
By using the composition of the present invention, it is possible to form an oxide thin film of Zn, Sn oxide (ZTO), Al, Sn oxide (ATO), or the like. Examples of the elements other than Zn, 3B, 4A and 4B of the present invention include alkaline metals such as Group 1A elements, alkaline earth metals such as Group 2A elements, rare earths such as lanthanoids and arctinoids, and Group 3A, 5A, 6A and 7A A composite oxide containing elements of Zn to 4B and elements other than these elements may be formed by coexisting a metal compound capable of forming an oxide such as a noble metal, a transition metal, a 5B group element, .
Particularly, the composition of the present invention is a zinc-containing compound prepared as described above, which is obtained by partial hydrolysis of an organic zinc compound represented by the following general formula (1) and an organic zinc compound such as diethyl zinc and water Products can be used. This addition is a hydrolysis of the composition in which the alkyl group R < 1 > bonded to the product obtained by partial hydrolysis of the organozinc compound and the organozinc compound with water Is confirmed by the classification, determination of hydrocarbon R 1 H to produce mainly from (wherein, R 1 is straight or branched alkyl group having a carbon number of 1 to 7). For example, in the case of diethylzinc, the main component of the gas produced by hydrolysis is ethane.
Further, the alkyl group R 1 (wherein R 1 is a straight-chain or branched alkyl group having 1 to 7 carbon atoms) bonded to the product obtained by partial hydrolysis of the organozinc compound and the organic zinc compound with water is a 3B In the exchange reaction with R 2 , R 3 and R 4 (R 2 , R 3 and R 4 independently represent a hydrogen or a straight-chain or branched alkyl group having 1 to 7 carbon atoms) represented by the general formula (2) May also be generated.
The solution prepared by the above method can be used as it is as a coating solution for forming a composite oxide thin film. Alternatively, it may be appropriately diluted or concentrated. However, from the viewpoint that the production process can be simplified, it is preferable that the solution prepared by the above-described method is a concentration that can be used as a coating solution for forming the oxide complex oxide.
[Production method of composite oxide thin film]
A method for producing the composite oxide thin film of the present invention will be described. The method for producing a composite oxide thin film of the present invention is a method for producing a composite oxide thin film using the composite oxide thin film forming composition of the present invention. In this manufacturing method, the composition for forming a composite oxide thin film of the present invention is applied to the surface of a substrate, and then the obtained coating film is heated to obtain a composite oxide thin film.
Application to the surface of the substrate can be carried out by conventional means such as dip coating method, spin coating method, spray pyrolysis method, ink jet method, and screen printing method. When the application is carried out by, for example, a spin coating method, a dip coating method or a spray pyrolysis method, a composite oxide thin film having an average transmittance of 80% or more with respect to visible light can be formed. In other words, from the viewpoint of forming a composite oxide thin film having an average transmittance of 80% or more with respect to visible light, the coating method is preferably carried out by, for example, a spin coating method, a dip coating method, or a spray pyrolysis method.
The application of the composition to the substrate surface can be carried out under an atmosphere of inert gas such as nitrogen or the like in an air atmosphere containing a large amount of water vapor and a high relative humidity in an atmosphere of an oxidizing gas such as oxygen, Or in a mixed gas atmosphere thereof, under atmospheric pressure or under pressure.
The application of the composition to the surface of the substrate is preferably carried out in an inert gas atmosphere such as nitrogen. The pressure in the coating film forming atmosphere can be carried out under atmospheric pressure or under pressure, or under reduced pressure. In this inert gas atmosphere, a small amount of oxygen or moisture may be used as an oxygen source necessary for formation of the oxide, and a gas component containing oxygen such as oxygen or moisture may be added in an amount that does not affect the film quality of the inert gas thin film Even if it is included.
The spin coating method and the dip coating method may be carried out under an inert gas atmosphere or by mixing an inert gas and water vapor in an atmosphere having a relative humidity of 2 to 15%.
The spray pyrolysis method is a method which can be carried out while heating the substrate. Therefore, the solvent can be dried in parallel with the application, and in some cases, heating for solvent drying is unnecessary. Depending on the conditions, the reaction of the composition of the present invention to the composite oxide may be at least partially proceeded in addition to the drying. For this reason, the composite oxide thin film can be formed more easily by heating to a predetermined temperature, which is a subsequent step. The heating temperature of the substrate may be, for example, in the range of 50 to 550 占 폚.
Fig. 1 shows a spray-coating apparatus usable by spray pyrolysis. In the figure,
Spraying of the coating liquid is carried out by spraying the coating liquid so that the size of the liquid droplet is in the range of 1 to 15 mu m from the spray nozzle while the distance between the spray nozzle and the substrate is within 50 cm, Is preferable from the viewpoint of production of a composite oxide thin film.
Considering the adhesion to the substrate and the ease of evaporation of the solvent, it is preferable that the size of all liquid droplets ejected from the spray nozzle is in the range of 1 to 30 mu m. The size of the droplet is more preferably in the range of 3 to 20 mu m.
It is preferable that the distance between the spray nozzle and the substrate is within 50 cm, considering that the solvent evaporates slightly from the spray nozzle until reaching the substrate and the size of the droplet decreases. The distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint that the formation of the composite oxide thin film can be favorable.
In the spray pyrolysis method, it is preferable from the viewpoint of forming a composite oxide thin film that satisfactory film characteristics are obtained by introducing water vapor from the water
The method of introducing water vapor can be introduced into a composite oxide thin film production apparatus according to all common methods. The water vapor and the composition are preferably reacted in the vicinity of the heated substrate, and for example, an inert gas containing water vapor produced by bubbling water with an inert gas is introduced into the tube near the heated substrate.
After coating the surface of the substrate with the coating solution, the substrate is heated to a predetermined temperature as required, the solvent is dried and then heated to a predetermined temperature to form a composite oxide thin film.
The temperature at which the solvent is dried may be, for example, in the range of 20 to 200 占 폚, and may be set in a timely manner depending on the kind of coexisting organic solvent. The heating temperature for forming the complex oxide after solvent drying is, for example, in the range of 50 to 550 占 폚, preferably in the range of 50 to 500 占 폚. It is also possible to perform the solvent drying and the complex oxide formation at the same time by setting the solvent drying temperature to the same heating temperature for forming the complex oxide thereafter.
If necessary, the heating is carried out in a plasma atmosphere of hydrogen, argon, oxygen or the like in a reducing gas atmosphere such as hydrogen under an oxidizing gas atmosphere such as oxygen to promote the formation of zinc oxide, It is also possible to improve. The thickness of the composite oxide thin film is not particularly limited, but it is preferably in the range of 0.05 to 2 탆 in practical use. According to the above manufacturing method, in the case other than the spray pyrolysis method, the coating (drying) heating is repeated one or more times, so that a thin film having the film thickness within the above range can be suitably manufactured.
The composite oxide thin film formed by the above production method varies depending on the application method and subsequent drying conditions and heating conditions. The volume resistivity is a resistance per unit volume, which can be obtained by multiplying the surface resistance by the film thickness. The surface resistance is measured by, for example, the 4-probe method, and the film thickness is measured by, for example, SEM measurement, a stylus type step film thickness meter or the like. Since the volume resistivity changes (increases) by the degree of formation of the composite oxide upon application of the spray or after coating, the volume resistivity is preferably controlled so that the volume resistivity of the thin film becomes a desired resistance value, Time) is preferably set.
The composite oxide thin film formed by the above production method preferably has an average transmittance of 80% or more with respect to visible light, more preferably an average transmittance of 85% or more with respect to visible light. The " average transmittance to visible light " is defined and measured as follows. The average transmittance to visible light is the average of the transmittance of light in the range of 380 to 780 nm and is measured by an ultraviolet visible spectrophotometer. The average transmittance to visible light can also be expressed by showing the transmittance of visible light at 550 nm. Since the transmittance to visible light is changed (increased) by the degree of formation of zinc oxide upon application of the spray or after coating, the transmittance of the thin film to visible light is preferably 80% or more, It is desirable to set the heating conditions (temperature and time).
The substrate used may be, for example, an alkali glass, an alkali-free glass, or a transparent substrate film, and the transparent substrate film may be a plastic film. However, the present invention is not intended to be limited to these examples.
[Use of composite oxide thin film]
The composite oxide thin film produced by the above method has excellent transparency and mobility, and thus can be used as an antistatic film, an ultraviolet ray cut film, a transparent conductive film, and the like. The antistatic film can be used, for example, in fields such as solid electric field capacitors, chemically amplified resistors, construction materials such as glass windows, and the like. The ultraviolet cut film can be used, for example, in fields such as a front filter of an image display apparatus, an imaging apparatus such as a drive recorder, a lighting apparatus such as a high-pressure discharge lamp, a cover glass for a clock, Further, the transparent conductive film may be formed of a material such as an FPD, a resistive film touch panel, a capacitive touch panel, a thin film silicon solar cell, a compound (CdTe, CIS) thin film solar cell, It is available in the field.
Particularly, the composite oxide such as ZTO or ATO is an oxide semiconductor film made of them and is characterized in that it has higher mobility than an amorphous Si film together with an oxide semiconductor film made of oxide (IGZO) of In, Ga and Zn, (Thin film transistor) such as an electroluminescent display device and the like. Such a field effect transistor such as a thin film transistor (TFT) is widely used as a unit electronic element, a high frequency signal amplifying element, a liquid crystal driving element, and the like of a semiconductor memory integrated circuit, and is an electronic device which is most practically used at present. However, it is not intended to be limited to these fields.
(Example)
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The preparation of the product including partial hydrolyzate from all the organic zinc compounds and the film formation using the same were carried out under a controlled nitrogen gas atmosphere and all of the solvents were dehydrated and deaerated.
[Example 1]
2.0 g of a 1,2-diethoxyethane solution in which 6.6 g of a 1,2-diethoxyethane solution having 0.66 g of tetra-tert-butoxy tin dissolved therein and 0.2 g of diethyl zinc dissolved therein was mixed at room temperature to obtain ZTO ≪ / RTI > The molar ratio of each element of this composition is Zn: Sn = 1: 1. This composition is intended to form a film of ZnSnO x (x is an arbitrary number different depending on film formation conditions) as ZTO in the abundance ratio.
[Example 2]
5.3 g of 1,2-diethoxyethane solution in which 0.53 g of tetra-tert-butoxy tin was dissolved and 1.2 g of 1,2-diethoxyethane solution of the product obtained by hydrolyzing diethyl zinc and water with O / Zn = 0.6 (molar ratio) (Zn = 4.24 wt%) were mixed at room temperature to prepare a composition such that ZTO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn =. This composition is intended to form a film of ZnSnO x (x is an arbitrary number different depending on film formation conditions) as ZTO in the abundance ratio.
[Example 3]
7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxy tin was dissolved and 2.0 g of a 1,2-diethoxyethane solution in which 0.2 g of triethyl aluminum was dissolved were mixed at room temperature to obtain ATO ≪ / RTI > The molar ratio of each element of the present composition is Al: Sn = 1: 1. This composition, in the approximate abundance ratio, contains AlSnO x (x is an arbitrary number depending on the film forming conditions).
[Example 4]
6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxy tin was dissolved, 0.092 g of a 1,2-diethoxyethane solution in which 0.0092 g of triethyl aluminum was dissolved, and 0.2 g of 1,2- And 2.0 g of a diethoxyethane solution were mixed at room temperature to prepare a composition such that ZTAO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: Al = 1: 1: 0.1. This composition is intended to form a film of Zn 10 Sn 10 AlO x (x is an arbitrary number different depending on film formation conditions) as ZTAO in the abundance ratio.
[Example 5]
6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxy tin was dissolved, 0.25 g of a 1,2-diethoxyethane solution in which 0.025 g of triethyl gallium was dissolved, and 0.2 g of 1,2- And 2.0 g of a diethoxyethane solution were mixed at room temperature to prepare a composition such that ZTGO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: Ga = 1: 1: 0.1. This composition has, from a general ratio of ratios, Zn 10 Sn 10 GaO x (x is an arbitrary number depending on the film forming conditions).
[Example 6]
6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxy tin was dissolved, 0.26 g of a 1,2-diethoxyethane solution in which 0.026 g of trimethyl indium was dissolved, and 1,2- Was mixed at room temperature to prepare a composition such that ZTIO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: In = 1: 1: 0.1. This composition contains Zn 10 Sn 10 InO x (x is an arbitrary number depending on the film forming conditions).
[Example 7]
6.6 g of a 1,2-diethoxyethane solution in which 0.66 g of tetra-tert-butoxy tin was dissolved, 0.62 g of a 1,2-diethoxyethane solution in which 0.062 g of tetra-tert-butoxyzirconium was dissolved, And 2.0 g of a 2-diethoxyethane solution were mixed at room temperature to prepare a composition such that ZTZrO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: Zr = 1: 1: 0.1. This composition is intended to form a film of Zn 10 Sn 10 ZrO x (x is an arbitrary number depending on film formation conditions) as ZTZrO in the abundance ratio.
[Example 8]
Diethoxyethane solution in which 0.53 g of tetra-tert-butoxy tin was dissolved, 0.15 g of 1,2-diethoxyethane solution in which 0.0074 g of triethyl aluminum was dissolved, and 0.15 g of diethyl zinc and water in O / Zn = 0.6 2.0 g of a 1,2-diethoxyethane solution (Zn = 4.24% by weight) of the product obtained by hydrolyzing the resulting product at a molar ratio (molar ratio) was mixed at room temperature to prepare a composition such that ZTAO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: Al = 1: 1: 0.1. This composition is intended to form a film of Zn 10 Sn 10 AlO x (x is an arbitrary number different depending on film formation conditions) as ZTAO in the abundance ratio.
[Example 9]
Diethoxyethane solution in which 0.53 g of tetra-tert-butoxy tin was dissolved, 0.20 g of 1,2-diethoxyethane solution in which 0.020 g of triethyl gallium was dissolved, and 0.20 g of diethyl zinc and water in O / Zn = 0.6 2.0 g of a 1,2-diethoxyethane solution (Zn = 4.24 wt%) of the product obtained by hydrolysis at a molar ratio (molar ratio) was mixed at room temperature to prepare a composition such that ZTGO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: Al = 1: 1: 0.1. This composition is intended to form a film of Zn 10 Sn 10 GaO x (where x is an arbitrary number depending on film formation conditions) as ZTGO in the abundance ratio.
[Example 10]
Diethoxyethane solution in which 0.53 g of tetra-tert-butoxy tin was dissolved, 0.62 g of a 1,2-diethoxyethane solution in which 0.062 g of trimethyl indium was dissolved, and 0.62 g of diethyl zinc and water in an O / Zn ratio of 0.6 2.0 g of a 1,2-diethoxyethane solution (Zn = 4.24 wt%) of the product obtained by hydrolyzing the obtained mixture at room temperature to prepare ZTIO as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: In = 1: 1: 0.1. This composition is intended to form a film of Zn 10 Sn 10 InO x (x is an arbitrary number different depending on the film forming conditions) as ZTIO in the abundance ratio.
[Example 11]
Dioxyethane solution in which 0.53 g of tetra-tert-butoxy tin was dissolved, 0.50 g of a 1,2-diethoxyethane solution in which 0.050 g of tetra-tert-butoxyzirconium was dissolved, 2.0 g of a 1,2-diethoxyethane solution (Zn = 4.24 wt%) of the product obtained by hydrolysis with Zn = 0.6 (molar ratio) was mixed at room temperature to prepare a composition such that ZTZrO was obtained as a composite oxide. The molar ratio of each element of the composition is Zn: Sn: Zr = 1: 1: 0.1. This composition is intended to form a film of Zn10Sn10ZrOx (x is an arbitrary number depending on film formation conditions) as ZTZrO in the abundance ratio.
[Example 12]
7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxy tin was dissolved, 0.27 g of a 1,2-diethoxyethane solution in which 0.022 g of diethyl zinc was dissolved, and 0.2 g of 1,2- And 2.0 g of a diethoxyethane solution were mixed at room temperature to prepare a composition such that ATZO was obtained as a composite oxide. The molar ratio of each element of the composition is Al: Sn: Zn = 1: 1: 0.1. This composition is intended to form a film of Al 10 Sn 10 ZnO x (x is an arbitrary number depending on film formation conditions) as ATZO in the abundance ratio.
[Example 13]
7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxy tin was dissolved, 0.27 g of a 1,2-diethoxyethane solution in which 0.027 g of triethyl gallium was dissolved, and 0.2 g of 1,2- And 2.0 g of a diethoxyethane solution were mixed at room temperature to prepare a composition such that ATGO was obtained as a composite oxide. The molar ratio of each element of the composition is Al: Sn: Ga = 1: 1: 0.1. This composition contains, in the approximate abundance ratio, Al 10 Sn 10 GaO x (x is an arbitrary number depending on the film forming conditions).
[Example 14]
7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxy tin was dissolved, 0.28 g of a 1,2-diethoxyethane solution in which 0.028 g of trimethyl indium was dissolved, and 1,2- Ethoxyethane solution were mixed at room temperature to prepare a composition such that ATIO was obtained as a composite oxide. The molar ratio of each element of the composition is Al: Sn: In = 1: 1: 0.1. This composition is intended to form a film of Al 10 Sn 10 InO x (x is an arbitrary number different depending on film formation conditions) as ATIO in the abundance ratio.
[Example 15]
7.2 g of a 1,2-diethoxyethane solution in which 0.72 g of tetra-tert-butoxy tin was dissolved, 0.67 g of a 1,2-diethoxyethane solution in which 0.067 g of tetra-tert-butoxyzirconium was dissolved and 1 And 2.0 g of a 2-diethoxyethane solution were mixed at room temperature to prepare a composition such that ATZrO was obtained as a composite oxide. The molar ratio of each element of the composition is Al: Sn: Zr = 1: 1: 0.1. This composition is intended to form a film of Al 10 Sn 10 ZrO x (x is an arbitrary number depending on film formation conditions) as ATZrO in the abundance ratio.
[Example 16]
In Example 1 ZnSnO x (x is any number of different according to the film forming conditions) of forming a film as a coating solution for a transparent crystal clear solution portion of the intended film formation composition (0.2㎛ filtered through a PTFE made filter) obtained in Respectively. This product-containing coating solution was coated on the surface of a 18 mm square EAGL EXG (R) (manufactured by Corning) glass substrate at room temperature under a nitrogen atmosphere by a spin coat method.
Thereafter, the substrate was heated at 150 DEG C for 5 minutes to dry the solvent, and further heated at 200 DEG C for 5 minutes. The film formed was taken out into the air.
The obtained thin film was transparent, and the transmittance was 93% at 550 nm. The thin film was analyzed by FT-IR to confirm disappearance of peaks attributable to each vibration of CH, such as tert-butoxy group and ethyl group derived from the raw material. Further, the thin film was analyzed by XRD, and it was confirmed that there was no crystalline peak.
[Example 17]
The same operation as in Example 16 was repeated three times. The film formed was taken out into the air. The obtained thin film was transparent, and the transmittance was 89% at 550 nm. The thin film was analyzed by FT-IR to confirm disappearance of peaks attributable to each vibration of CH, such as tert-butoxy group and ethyl group derived from the raw material.
[Example 18]
The same operation as in Example 16 was repeated five times. The film formed was taken out into the air. The obtained thin film was transparent, and the transmittance was 85% at 550 nm.
[Examples 19 to 32]
Coating film formation was performed once in the same manner as in Example 16 by using the composition obtained in Examples 2 to 15 as a coating liquid to form a composite oxide thin film. Each composition was used in a clear, clear and clean solution portion or by filtration with a 0.2 占 퐉 PTFE filter in the same manner as in Example 1. [ The film formed was taken out into the air. Table 1 shows the appearance and transmittance of the obtained thin film.
Film forming conditions: application: room temperature, solvent drying conditions: 150 占 폚 / 5 minutes, heating conditions: 200 占 폚 / 5 minutes
Sample appearance: A: Thin film with high transparency, B: Less transparency than A, but transparent thin film
[Examples 33 to 46]
Using the composition obtained in Examples 2 to 15 as a coating liquid, coating films were formed three times in the same manner as in Example 17 to form composite oxide thin films. The film formed was taken out into the air. Table 2 shows the appearance and transmittance of the obtained thin film.
Film forming conditions: application: room temperature, solvent drying conditions: 150 占 폚 / 5 minutes, heating conditions: 200 占 폚 / 5 minutes
Sample appearance: A: Thin film with high transparency, B: Less transparency than A, but transparent thin film
[Examples 47 to 60]
Using the composition obtained in Examples 2 to 15 as a coating liquid, coating films were formed five times in the same manner as in Example 18 to form composite oxide thin films. The film formed was taken out into the air. Table 3 shows the appearance and transmittance of the obtained thin film.
Film forming conditions: application: room temperature, solvent drying conditions: 150 占 폚 / 5 minutes, heating conditions: 200 占 폚 / 5 minutes
Sample appearance: A: Thin film with high transparency, B: Less transparency than A, but transparent thin film
[Examples 61 to 72]
The composite oxide thin films obtained in Examples 47 to 60 were subjected to film formation under the nitrogen atmosphere at 300 DEG C for 5 minutes, 400 DEG C for 5 minutes, and 500 DEG C for 5 minutes under conditions And then heat treatment was carried out in that order. The thin film after heating was taken out into the air. The transmittances of the obtained thin films are shown in Tables 4, 5 and 6.
[Example 95]
A transparent clear and clean solution portion of each product-containing coating solution obtained in Example 2 was used for forming a coating film. This product-containing coating solution was applied to the surface of a quartz glass substrate of 18 mm square at room temperature by a spin coat method under a nitrogen atmosphere. Thereafter, the substrate was heated at 150 DEG C for 5 minutes to dry the solvent. In this film formation, baking was also carried out simultaneously at the drying temperature and time of the solvent. This operation was repeated to repeat the application three times in total to form a thin film. The film formed was taken out into the air.
The obtained thin film was transparent, and the transmittance was 94% at 550 nm. The thin film was analyzed by FT-IR to confirm disappearance of peaks belonging to each vibration of CH, such as tert-butoxy group and ethyl group derived from the raw material.
[Examples 96 to 99]
Using the coating liquids obtained in Examples 8, 9, 10 and 11, the same film formation and physical property evaluation were carried out in Example 95. Table 7 shows the obtained thin film properties, conditions and physical properties.
Film forming conditions: application: room temperature, solvent drying condition: 150 占 폚 / 5 minutes,
Sample appearance: A: Thin film with high transparency, B: Less transparency than A, but transparent thin film
[Example 100]
The thin film obtained in Example 98 was subjected to heat treatment at 200 ° C., 400 ° C., 600 ° C., and 800 ° C. for 30 minutes before the heat treatment in an air atmosphere using a RTA (Rapid Thermal Annealing) And the change of the structure of the oxide at each temperature was confirmed by XRD. Before the heat treatment, in the above-mentioned heat treatment conditions, no peak of crystallinity was observed, and peaks that could be considered to be amorphous broad at 2? = 26 to 40 were identified. Further, by performing a heat treatment at 800 占 폚 for one hour, crystalline peaks corresponding to oxides of zinc and tin were confirmed in the vicinity of 2? = 26, 32, 34 and 52 degrees.
[Example 101]
The thin film obtained in Example 99 was subjected to a heat treatment for 30 minutes at 200 ° C, 400 ° C, 600 ° C and 800 ° C for 30 minutes before the heat treatment in an air atmosphere using an RTA (rapid thermal annealing) The change of the structure of the oxide to the temperature was confirmed by XRD. Before the heat treatment, in the above-mentioned heat treatment conditions, no peak of crystallinity was observed, and peaks that could be considered to be amorphous broad at 2? = 26 to 40 were identified. Crystalline peaks corresponding to oxides of zinc and tin were observed at around 2? = 26, 32, 34 and 52 in the heat treatment at 800 占 폚.
[Comparative Example 1]
In the same manner as in Example 1 except that bisacetylacetonato tin was used instead of tetra-tert-butoxy tin, zinc acetate was used instead of diethyl zinc, 2-methoxyethanol as a solvent and ethanolamine as a coagent were used, Was prepared.
The obtained coating liquid was subjected to film formation at 200 캜 in the same manner as in Example 18 to obtain a thin film. The visible light transmittance at 550 nm was 60%, and only a thin film with low transmittance could be obtained.
[Comparative Example 2]
In Example 3, instead of tin tetrachloride and triethyl aluminum, aluminum acetate was used instead of tetra-tert-butoxy tin, and a coating liquid having the same composition was prepared by using 2-methoxyethanol as the solvent and ethanolamine as the auxiliary .
The obtained coating liquid was subjected to film formation at 200 占 폚 in the same manner as in Example 18 to obtain a thin film. The visible light transmittance at 550 nm was 65%, and only a thin film with low transmittance could be obtained.
(Industrial availability)
INDUSTRIAL APPLICABILITY The present invention is useful in the field of manufacturing composite oxide thin films containing oxides of zinc, Group 3B element, Group 4A element and / or Group 4B element.
One;
3;
5; Alkali-
Claims (23)
At least one compound selected from the group consisting of a compound containing a zinc element and a compound including a group 3B element, a partial hydrolyzate of the compound with water or a compound containing the compound and the partial hydrolyzate, At least one compound selected from the group consisting of compounds including Group 4B elements, a partial hydrolyzate of the compound with water, or the composition and the partial hydrolyzate.
Wherein the zinc element-containing compound is an organic zinc compound represented by the following general formula (1).
R 1 -Zn-R 1 (One)
(Wherein R < 1 > is a linear or branched alkyl group having 1 to 7 carbon atoms)
The partial hydrolyzate of the organic zinc compound with water is obtained by mixing the organic zinc compound represented by the general formula (1) and water so that the molar ratio is in the range of 0.05 to 0.8, and at least partially hydrolyzing the organic zinc compound ≪ / RTI >
Wherein the compound including the Group 3B element is a Group 3B element compound represented by the following Formula (2).
Wherein M is a Group 3B element and R 2 , R 3 and R 4 are independently hydrogen or a linear or branched alkyl group having 1 to 7 carbon atoms and L is a saturated or unsaturated hydrocarbon group containing nitrogen, Organic compound, and n is an integer of 0 to 9.)
The partial hydrolyzate of the 3B group element compound by water is obtained by mixing the 3B group element compound represented by the general formula (2) and water so that the molar ratio is in the range of 0.05 to 0.8, and at least the 3B group element compound is partially Wherein the product is obtained by hydrolysis.
Wherein the compound including the 4A group element and the compound including the 4B group element are the 4A group element compound and the 4B group element compound represented by the following general formula (3) or (4).
(Wherein M is a Group 4A element or a Group 4B element and R 5 , R 6 , R 7 and R 8 are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, a linear or branched alkyl group having 1 to 7 carbon atoms, An acyloxy group, an acetylacetonato group or an amide group, L is a chelating organic compound containing nitrogen, oxygen or phosphorus, and n is an integer of 0 to 9.)
M c X d揃 aH 2 O (4)
Wherein X is a halogen atom, nitric acid or sulfuric acid, X is a halogen atom or nitric acid, c is 1, d is 3, and X is sulfuric acid, c Is 2, d is 3, and a is an integer of 0 to 9.)
The partial hydrolyzate of the 4A group element compound and the 4B group element compound by water is prepared by mixing the compound represented by the general formula (3) or (4) and water so that the molar ratio is in the range of 0.05 to 0.8, Wherein the product is obtained by partial hydrolysis of a Group IV element compound and a Group 4B element compound.
A partial hydrolyzate of at least one compound selected from the group consisting of the compound including the 4A group element and the compound including the 4B group element, and a compound including the zinc element and a compound including the group 3B element The water partial hydrolyzate of at least one kind of compound selected from the group consisting of at least one compound selected from the group consisting of the compound including the 4A group element and the compound including the 4B group element and the compound including the zinc element and the group 3B group Which is a product obtained by adding water to at least one kind of compound selected from the group consisting of compounds containing an element so that the molar ratio of water to the total amount of the compounds is in the range of 0.05 to 0.8 and partially hydrolyzing the compound .
Further comprising an organic solvent.
Wherein the organic solvent comprises at least one of an electron donor solvent, a hydrocarbon solvent, and a mixture thereof.
Wherein the organic solvent has a boiling point of 230 캜 or less.
The electron donor solvent is selected from the group consisting of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, dioxane, and hydrocarbon solvents such as hexane, heptane, octane, toluene, xylene, and cyclohexane ≪ / RTI >
Wherein the organozinc compound is diethylzinc.
The Group 3B element compound of the general formula (2) is selected from the group consisting of trimethyl indium, triethyl indium, trimethyl gallium, triethyl gallium, trimethyl aluminum, triethyl aluminum, trioctyl aluminum, trimethyl borane, A composition comprising at least one species.
The Group 3B element is Al, Ga, and In,
The Group 4A element is Ti, Zr and Hf,
Wherein said Group 4B elements are Si, Ge and Sn.
Wherein the inert gas atmosphere contains water vapor.
Wherein the inert gas atmosphere containing water vapor has a relative humidity ranging from 2 to 15%.
Wherein the inert gas atmosphere containing water vapor is formed by supplying water vapor near the surface of the substrate under atmospheric pressure or under pressure.
Wherein the heating temperature of the substrate surface is 400 占 폚 or less.
Wherein the supply amount of the water vapor is such that the molar ratio of water to zinc in the supplied composition is in the range of 0.1 to 5.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JPJP-P-2012-100168 | 2012-04-25 | ||
| JP2012100174 | 2012-04-25 | ||
| JP2012100168 | 2012-04-25 | ||
| JPJP-P-2012-100174 | 2012-04-25 | ||
| PCT/JP2013/061729 WO2013161735A1 (en) | 2012-04-25 | 2013-04-22 | Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20140140654A true KR20140140654A (en) | 2014-12-09 |
| KR101980413B1 KR101980413B1 (en) | 2019-05-20 |
Family
ID=49483052
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020147032942A KR101980413B1 (en) | 2012-04-25 | 2013-04-22 | Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP6322573B2 (en) |
| KR (1) | KR101980413B1 (en) |
| CN (1) | CN104254495B (en) |
| TW (1) | TWI583628B (en) |
| WO (1) | WO2013161735A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190113824A (en) * | 2017-02-02 | 2019-10-08 | 토소 화인켐 가부시키가이샤 | Dialkyl zinc and dialkyl zinc partial hydrolyzate containing solution, and method for producing a zinc oxide thin film using such a solution |
| KR20200105693A (en) * | 2018-02-28 | 2020-09-08 | 토소 화인켐 가부시키가이샤 | Composition for forming zinc oxide thin film and method for manufacturing zinc oxide thin film |
| WO2022169290A1 (en) * | 2021-02-04 | 2022-08-11 | 주식회사 유피케미칼 | Hafnium precursor compound, composition for forming hafnium-containing film, comprising same, and method for forming hafnium-containing film |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6672835B2 (en) * | 2016-01-27 | 2020-03-25 | 株式会社村田製作所 | Electronic component manufacturing method |
| JP6926433B2 (en) * | 2016-09-30 | 2021-08-25 | 三菱ケミカル株式会社 | Laminated film and its manufacturing method |
| JP2018137371A (en) * | 2017-02-22 | 2018-08-30 | 日本放送協会 | Coating semiconductor precursor solution, coating oxide semiconductor, thin film transistor and manufacturing method thereof |
| CN106927689A (en) * | 2017-04-17 | 2017-07-07 | 华南理工大学 | A kind of oxide semiconductor thin-film and its preparation technology |
| CN115244715A (en) * | 2020-10-09 | 2022-10-25 | 株式会社东芝 | Solar cell, multi-junction solar cell, solar cell module, and solar power generation system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07182939A (en) | 1993-12-22 | 1995-07-21 | Mitsubishi Materials Corp | Transparent conducting film forming composition and transparent conducting film forming method |
| JPH08171824A (en) * | 1994-03-27 | 1996-07-02 | Gunze Ltd | Manufacture of transparent conductive film |
| JP2005097092A (en) * | 2003-09-01 | 2005-04-14 | Showa Denko Kk | Process for producing fine metal oxide particle |
| JP2007073312A (en) | 2005-09-06 | 2007-03-22 | Canon Inc | Sputtering target, and method of forming thin film using the target |
| WO2010131621A1 (en) * | 2009-05-12 | 2010-11-18 | 国立大学法人 宮崎大学 | Composition for production of doped zinc oxide thin film, process for production of zinc oxide thin film, antistatic thin film, ultraviolet ray blocking thin film, and transparent electrode thin film |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62247834A (en) * | 1986-04-18 | 1987-10-28 | Sumitomo Chem Co Ltd | Production of flaked substance |
| DE3736686A1 (en) * | 1987-10-29 | 1989-05-11 | Fraunhofer Ges Forschung | METHOD FOR PRODUCING MONODISPER CERAMIC POWDERS |
| JP2600341B2 (en) * | 1987-11-17 | 1997-04-16 | 日本合成ゴム株式会社 | Method for producing particulate metal compound |
| CN1369572A (en) * | 2001-04-03 | 2002-09-18 | 中国科学院长春光学精密机械与物理研究所 | Electrically conducting transparent oxide film |
| TW200510250A (en) * | 2003-09-01 | 2005-03-16 | Showa Denko Kk | Method for producing microparticles of metal oxide |
| US7491575B2 (en) * | 2006-08-02 | 2009-02-17 | Xerox Corporation | Fabricating zinc oxide semiconductor using hydrolysis |
| KR101137571B1 (en) * | 2008-05-12 | 2012-04-19 | 코니카 미놀타 비지니스 테크놀로지즈 가부시키가이샤 | Dye-sensitized solar cell and method for manufacturing the same |
| EP2431330B1 (en) * | 2009-04-21 | 2019-02-27 | Tosoh Finechem Corporation | Composition for forming doped or non-doped zinc oxide thin film, and method for producing zinc oxide thin film using same |
| KR101861394B1 (en) * | 2010-10-20 | 2018-05-28 | 토소 화인켐 가부시키가이샤 | Composition for production of oxide thin films and method for producing oxide thin films by using said composition |
-
2013
- 2013-04-22 JP JP2014512541A patent/JP6322573B2/en active Active
- 2013-04-22 WO PCT/JP2013/061729 patent/WO2013161735A1/en active Application Filing
- 2013-04-22 CN CN201380021829.3A patent/CN104254495B/en active Active
- 2013-04-22 KR KR1020147032942A patent/KR101980413B1/en active IP Right Grant
- 2013-04-25 TW TW102114874A patent/TWI583628B/en active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07182939A (en) | 1993-12-22 | 1995-07-21 | Mitsubishi Materials Corp | Transparent conducting film forming composition and transparent conducting film forming method |
| JPH08171824A (en) * | 1994-03-27 | 1996-07-02 | Gunze Ltd | Manufacture of transparent conductive film |
| JP2005097092A (en) * | 2003-09-01 | 2005-04-14 | Showa Denko Kk | Process for producing fine metal oxide particle |
| JP2007073312A (en) | 2005-09-06 | 2007-03-22 | Canon Inc | Sputtering target, and method of forming thin film using the target |
| WO2010131621A1 (en) * | 2009-05-12 | 2010-11-18 | 国立大学法人 宮崎大学 | Composition for production of doped zinc oxide thin film, process for production of zinc oxide thin film, antistatic thin film, ultraviolet ray blocking thin film, and transparent electrode thin film |
Non-Patent Citations (6)
| Title |
|---|
| C.Seok－Jun,etal., J.Phys.D：Appl.Phys.,42(035106), 2009 |
| F.ParaguayD,etal.ThinSolidFilms., 16(366), 2000 |
| H.Q.Chiang, etal.Appl.Phys.Lett., 86(13503),2005 |
| L.Castaneda, etal.ThinSolidFilms., 212(503), 2006 |
| Ohya, etal.J.Mater.Sci., 4099(29), 1994 |
| 일본 학술 진흥회 투명 산화물 광전자 재료 제 166 위원회편, 투명 도전막의 기술 개정 2판(2006), p165∼173 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190113824A (en) * | 2017-02-02 | 2019-10-08 | 토소 화인켐 가부시키가이샤 | Dialkyl zinc and dialkyl zinc partial hydrolyzate containing solution, and method for producing a zinc oxide thin film using such a solution |
| KR20200105693A (en) * | 2018-02-28 | 2020-09-08 | 토소 화인켐 가부시키가이샤 | Composition for forming zinc oxide thin film and method for manufacturing zinc oxide thin film |
| WO2022169290A1 (en) * | 2021-02-04 | 2022-08-11 | 주식회사 유피케미칼 | Hafnium precursor compound, composition for forming hafnium-containing film, comprising same, and method for forming hafnium-containing film |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2013161735A1 (en) | 2015-12-24 |
| KR101980413B1 (en) | 2019-05-20 |
| JP6322573B2 (en) | 2018-05-09 |
| TWI583628B (en) | 2017-05-21 |
| TW201402470A (en) | 2014-01-16 |
| CN104254495A (en) | 2014-12-31 |
| CN104254495B (en) | 2017-03-29 |
| WO2013161735A1 (en) | 2013-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101980413B1 (en) | Composition for producing compound oxide thin film, method for producing thin film using composition, and compound oxide thin film | |
| KR101743308B1 (en) | Composition for forming doped or non-doped zinc oxide thin film, and method for producing zinc oxide thin film using same | |
| KR101861394B1 (en) | Composition for production of oxide thin films and method for producing oxide thin films by using said composition | |
| JP5822449B2 (en) | Composition for producing zinc oxide thin film and composition for producing doped zinc oxide thin film | |
| JP5674186B2 (en) | Zinc oxide thin film production method, and antistatic thin film, ultraviolet cut thin film, transparent electrode thin film produced by this method | |
| JP2009536144A (en) | Method for depositing a zinc oxide coating on a substrate | |
| WO2010131621A1 (en) | Composition for production of doped zinc oxide thin film, process for production of zinc oxide thin film, antistatic thin film, ultraviolet ray blocking thin film, and transparent electrode thin film | |
| KR102412785B1 (en) | Composition for producing zinc oxide thin film containing group 2 element and production method for same | |
| JP5688225B2 (en) | Composition for producing zinc oxide thin film | |
| JP5702258B2 (en) | Composition for producing complex oxide thin film | |
| JP5702259B2 (en) | Thin film production method using composite oxide thin film production composition | |
| JP2011046566A (en) | Composition for producing doped zinc oxide thin film, and method for producing doped zinc oxide thin film using the same | |
| JP5756273B2 (en) | Zinc oxide thin film production composition and zinc oxide thin film production method using doped zinc oxide thin film production composition, and antistatic thin film, UV cut thin film, transparent electrode thin film produced by this method | |
| JP5892641B2 (en) | Zinc oxide thin film production method, and antistatic thin film, ultraviolet cut thin film, transparent electrode thin film produced by this method | |
| JP5756272B2 (en) | Composition for producing zinc oxide thin film and composition for producing doped zinc oxide thin film | |
| TWI465401B (en) | "dope or undoped zinc oxide thin film manufacturing method and a method for producing the zinc oxide thin film using the same | |
| JP2013067609A (en) | Vinylenediamide complex, method for manufacturing the same, and methods for preparing titanium oxide film and silicon oxide film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant |