JP2012106916A - Composition for production of complex oxide thin film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new composition which is based on diethyl zinc or a partial hydrolyzate of an organic zinc compound such as diethyl zinc etc., and with which a complex oxide thin film applicable to an oxide semiconductor film etc. such as an IGZO can be deposited.SOLUTION: The composition for production of a complex oxide thin film contains an organic zinc compound represented by general formula (1) or a partial hydrolyzate of the organic zinc compound with water, and a compound of a group 3B element or a partial hydrolyzate of the compound of the group 3B element with water, wherein the molar ratio of the group 3B element to zinc is >0.1 and ≤5. R-Zn-R(1) (in formula, Ris a straight-chain or branched 1-7C alkyl group). The composition further optionally contains an organic solvent.

Description

  The present invention has an average transmittance of 80% or more with respect to visible light and is combined with an oxide semiconductor film of IGZO used for a switching element (thin film transistor) such as a liquid crystal display device and a thin film electroluminescence display device. The present invention relates to a composition for producing a complex oxide thin film capable of preparing a complex oxide thin film.

  The composition for producing a complex oxide thin film of the present invention is prepared using an organozinc compound and a group 3B element compound as raw materials, is not ignitable, and is easy to handle, and further includes spin coating and dip coating coating materials and spray pyrolysis. When used as a coating material, it has an average transmittance of 80% or more with respect to visible light and can provide a composite oxide thin film.

  As an oxide semiconductor film made of a metal composite oxide that is one of complex oxides, for example, an oxide semiconductor film made of an oxide of In, Ga, and Zn (IGZO) is known, which is more than an amorphous Si film. In recent years, it has attracted attention due to its high electron mobility. In addition, such an oxide semiconductor film has higher electron mobility and higher visible light transmittance than an amorphous Si film, so that a switching element (thin film transistor) such as a liquid crystal display device or a thin film electroluminescence display device is used. It is expected to be applied to and attracts attention.

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

  On the other hand, in the formation of an oxide thin film, film formation by a coating method is known. Since this coating method is simple and the film formation speed is high, the productivity is high and the manufacturing cost is low, and it is not necessary to use a vacuum vessel and there is no restriction by the vacuum vessel, so it is possible to create a large oxide thin film. There are advantages such as.

  Examples of a general coating method for forming an oxide thin film include a spin coating method (Patent Document 2), a dip coating method (Non Patent Literature 2), and a spray pyrolysis method (Non Patent Literatures 3 and 4).

  As an example of the material for forming the oxide thin film for the coating method, a material for forming a zinc oxide thin film intended for a transparent conductive film or the like is known. Specifically, zinc acetate, an alcohol-based organic solvent is used. Diethyl zinc dissolved while reacting with bismuth, a composition obtained by partially hydrolyzing diethyl zinc, and the like are used.

JP2007-73312A JP 7-182939 A Japanese Patent Application No. 2009-102544 (Japanese Patent Laid-Open No. 2010-254481) Japanese Patent Application No. 2009-197052 (Japanese Patent Laid-Open No. 2010-46566)

Japan Society for the Promotion of Science Transparent Oxide Optoelectronic Materials 166th Committee, Transparent Conductive Film Technology Revision 2 (2006), p165-173 Y. Ohya, et al. J. et al. Mater. Sci. , 4099 (29), 1994 F. Paraguay D, et al. Thin Solid Films. , 16 (366), 2000 L. Castaneda, et al. Thin Solid Films. , 212 (503), 2006

These patent documents relate to a zinc oxide thin film, and a 3B group element such as In or Ga is merely added in a small amount of about several weight% in order to provide conductivity.
The inventors adjusted the composition of the above-mentioned IGZO using materials of known patent documents and tried film formation by spin coating method, dip coating method, spray pyrolysis method, but obtaining a transparent thin film It was difficult.

  On the other hand, the present inventors tried to form a film by spin coating using a composition obtained by partially hydrolyzing diethylzinc or a solution obtained by partially hydrolyzing a group 3B element compound and diethylzinc. Thus, a zinc oxide thin film having an average transmittance of 80% or more was obtained, and patent applications were filed (Patent Documents 3 and 4).

  In the inventions of Patent Documents 3 and 4, in order to improve the conductivity of the zinc oxide thin film, a group 3B element such as In or Ga coexists in the composition, but the molar ratio of the group 3B element to zinc (composition) The ratio) is, for example, in the range of 0.005 to 0.1, and it is considered that further study is necessary for application to a material in which the molar ratio of the mixture of Group 3B elements to zinc, such as IGZO, exceeds 0.1. It was.

  Therefore, the present invention provides a new means capable of forming an oxide semiconductor film such as IGZO on a composition based on a partial hydrolyzate of an organic zinc compound such as diethyl zinc or diethyl zinc. With the goal.

  As a result of intensive studies to achieve the above object, the present inventors have found that a compound having a structure in which an alkyl group is bonded to zinc or a group 3B element, more specific examples include organozinc compounds such as diethyl zinc and diethyl In a composition containing a mixture of a product obtained by partial hydrolysis of an organic zinc compound such as zinc and water and a compound containing a group 3B element such as In and Ga, an organic zinc compound such as diethyl zinc and a diethyl zinc compound Even if the molar ratio of the group 3B element in the mixture of group 3B elements such as In and Ga to zinc in the product obtained by partial hydrolysis of the organic zinc compound and water exceeds 0.1, the coating is applied. Thus, the present invention was completed by finding that an oxide semiconductor film such as IGZO can be easily obtained with an average transmittance of 80% or more with respect to visible light.

The present invention for solving the above problems is as follows.
(Claim 1)
The organic zinc compound represented by the following general formula (1) or a partial hydrolyzate of the organic zinc compound with water and a partial hydrolyzate of the group 3B element compound or the group 3B element compound with water are converted into a group 3B element with respect to zinc. A composition for producing a complex oxide thin film, comprising a molar ratio in the range of more than 0.1 and 5 or less.
R ¹ —Zn—R ¹ (1)
(In the formula, R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms.)
(Claim 2)
The composition according to claim 1, further comprising an organic solvent.
(Claim 3)
The partial hydrolyzate of the organic zinc compound with water is prepared 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 the organic zinc compound is mixed. A product obtained by partially hydrolyzing a zinc compound, wherein the partial hydrolyzate of the group 3B element compound with water is a molar ratio of the group 3B element compound and water within a range of 0.05 to 0.8. The composition according to claim 1, wherein the composition is a product obtained by mixing at least partially hydrolyzing the Group 3B element compound.
(Claim 4)
The partial hydrolyzate of the organic zinc compound with water and the partial hydrolyzate of the group 3B element compound with water are the sum of the organic zinc compound and the group 3B element compound with water added to the organic zinc compound and the group 3B element compound. The product obtained by partially hydrolyzing the organozinc compound and the group 3B element compound by adding such that the molar ratio thereof is in the range of 0.05 to 0.8. The composition as described.
(Claim 5)
The composition according to any one of claims 1 to 4, wherein the 3B group element compound is a 3B group element compound represented by the following general formula (2) or (3).
(In the formula, M is a group 3B element, R ² , R ³ and R ⁴ are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, or a linear or branched group having 1 to 7 carbon atoms. An alkoxyl, carboxylic acid, or acetylacetonate group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)

_{M c X d · aH 2 O} (3)
(Wherein M is a group 3B element, X is a halogen atom, nitric acid or sulfuric acid, c is 1, when d is a halogen atom or nitric acid, d is 3, and when X is sulfuric acid, c is 2 D is 3, and a is an integer of 0 to 9.)
(Claim 6)
The composition according to claim 2, wherein the organic solvent contains at least one of an electron donating solvent, a hydrocarbon solvent, and a mixture thereof.
(Claim 7)
The composition according to claim 2, wherein the organic solvent has a boiling point of 230 ° C. or lower.
(Claim 8)
The electron donating solvent includes at least one of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, dioxane, and hexane, heptane, octane, toluene, xylene, and cyclohexane as a hydrocarbon solvent. Composition.
(Claim 9)
The composition according to claim 1, wherein the organic zinc compound is diethyl zinc.
(Claim 10)
The group 3B element compound of the general formula (2) is trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trisacetylacetonatoaluminum, trisacetylacetonatogallium, trisacetylacetonato At least one of indium, aluminum chloride, gallium chloride, indium chloride, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, tritert-butoxyindium, tritert-butoxygallium The composition in any one of Claims 5-9 containing.
(Claim 11)
The composition in any one of Claims 1-9 whose 3B group elements are Ga and In.

  By using the composition for producing a complex oxide thin film of the present invention, a useful complex oxide thin film such as an oxide semiconductor film such as IGZO can be applied by spin coating, dip coating, spray pyrolysis, etc. A complex oxide thin film which can be easily formed and has an average transmittance of 80% or more with respect to visible light can be produced.

It is a figure which shows a spray film forming apparatus.

[Composition for producing complex oxide thin film]
The composition for producing a complex oxide thin film of the present invention comprises an organic zinc compound represented by the following general formula (1) or a partial hydrolyzate of the organic zinc compound with water and a group 3B element compound or water of a group 3B element compound. The partial hydrolyzate according to the above is characterized in that the molar ratio of the group 3B element to zinc is in the range of more than 0.1 and 5 or less.
R ¹ —Zn—R ¹ (1)
(In the formula, R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms.)

The composition for producing a complex oxide thin film of the present invention includes the following aspects.
(I) A composition containing an organozinc compound represented by the general formula (1) and a group 3B element compound (hereinafter sometimes referred to as composition 1)
(Ii) A composition containing a partial hydrolyzate of the organic zinc compound represented by the general formula (1) and the group 3B element compound with water (hereinafter sometimes referred to as composition 2).
(Iii) A composition containing an organic zinc compound represented by the general formula (1), a group 3B element compound, and a partial hydrolyzate of the group 3B element compound with water (hereinafter sometimes referred to as composition 3).
(Iv) A composition containing a partial hydrolyzate of the organic zinc compound represented by the general formula (1) with water and a group 3B element compound (hereinafter sometimes referred to as composition 4).
(V) A composition containing a partial hydrolyzate of the organic zinc compound represented by the general formula (1) in water and a partial hydrolyzate of the group 3B element compound in water (hereinafter referred to as composition 5). is there)
(Vi) a composition containing a partial hydrolyzate of the organic zinc compound represented by the general formula (1) in water and a partial hydrolyzate of the group 3B element compound and the group 3B element compound in water (hereinafter referred to as composition) 6)
(Vii) A composition containing the organic zinc compound represented by the general formula (1), a partially hydrolyzed product of the organic zinc compound with water, and a group 3B element compound (hereinafter sometimes referred to as composition 7).
(Viii) A composition containing the 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 group 3B element compound with water (hereinafter referred to as composition) 8)
(Ix) A composition containing the 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 group 3B element compound and the group 3B element compound with water. (Hereafter, it may be called the composition 9)

  Furthermore, this invention includes the said composition further containing the organic solvent.

In the present invention, the group 3B element compound can be, for example, a group 3B element compound represented by the following general formula (2) or (3).
(In the formula, M is a group 3B element, R ² , R ³ and R ⁴ are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, or a linear or branched group having 1 to 7 carbon atoms. An alkoxyl, carboxylic acid, or acetylacetonate group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)

_{M c X d · aH 2 O} (3)
(Wherein M is a group 3B element, X is a halogen atom, nitric acid or sulfuric acid, c is 1, when d is a halogen atom or nitric acid, d is 3, and when X is sulfuric acid, c is 2 D is 3, and a is an integer of 0 to 9.)

The following can be mentioned as a more specific example of the composition of this invention. However, these are not intended to be limited.
(A) After adding water to a solution in which the organic zinc compound represented by the general formula (1) is dissolved in an organic solvent to at least partially hydrolyze the organic zinc compound, at least one 3B A product containing a group element and containing a mixture with the group 3B element compound represented by the general formula (2) and / or the general formula (3) (hereinafter sometimes referred to as a partial hydrolyzate 1) A composition comprising.

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

Specific examples of the alkyl group represented by R ¹ in the organozinc compound represented by the general formula (1) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, 2-hexyl group, and heptyl group. 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 has 2 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. Alternatively, R ² , R ³ , and R ⁴ are preferably alkyl groups, and specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. Tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, 2-hexyl group, and heptyl group. It is also preferable that at least one of R ² , R ³ , and R ⁴ is hydrogen and the rest is an alkyl group. Specific examples of the alkoxyl group include methoxy group, ethoxy group, isopropoxide group, tert-butoxy group and the like.

  Examples of the ligand represented by L include trimethylamine, triethylamine, triphenylamine, pyridine, monophorin, N, N-dimethylaniline, N, N-diethylaniline, triphenylphosphine, dimethylsulfur, diethyl ether, and tetrahydrofuran. be able to. The group 3B element compound represented by the general formula (3) includes, in particular, diborane, borane-tetrahydrofuran complex, borane-trimethylamine complex, borane-triethylamine complex, triethylborane, tributylborane, alane-trimethylamine complex, alane-triethylamine complex, Trimethylaluminum, dimethylamylnium hydride, triisobutylaluminum, diisobutylaluminum hydride, trimethylgallium, triethylgallium, trimethylindium, trimethylindium, triethylindium, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, tri Examples include isopropoxyaluminum, tritert-butoxyindium, and tritert-butoxygallium. Can. Triethylaluminum, triisobutylaluminum, trimethylgallium, trimethylindium, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, tritert. -Butoxyindium and tritert-butoxygallium are particularly preferred.

  Specific examples of the group 3B element in the group 3B element compound and the metal represented by M in the group 3B element compound represented by the general formula (3) include, for example, B, Al, Ga, and In. . Specific examples of the salt represented by X include fluorine, chlorine, bromine, iodine, nitric acid, and sulfuric acid. The group 3B element compound represented by the general formula (2) includes, in particular, boron fluoride, boron chloride, aluminum chloride, aluminum chloride hexahydrate, aluminum nitrate nonahydrate, gallium chloride, gallium nitrate hydrate, Examples thereof include indium chloride, indium chloride tetrahydrate, and indium nitrate pentahydrate.

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

  As examples of the electron-donating organic solvent, ether compounds, amine compounds, and the like can be used, and any organic solvent that has solubility in the organic zinc compound represented by the general formula (1) and water can be used. Examples of preferable electron donating organic solvents include those having a boiling point of 230 ° C. or lower, such as di-n-butyl ether (boiling point 142.4 ° C.), dihexyl ether (boiling point 226.2 ° C.), Anisole (boiling point 153.8 ° C.), phenetol (boiling point 172 ° C.), butyl phenyl ether (boiling point 210.3 ° C.), pentyl phenyl ether (boiling point 214 ° C.), methoxytoluene (boiling point 171.8 ° C.), benzyl ethyl ether ( Boiling point 189 ° C), diphenyl ether (boiling point 258.3 ° C), veratrol (boiling point 206.7 ° C), trioxane (boiling point 114.5 ° C) and 1,2-diethoxyethane (boiling point 121 ° C), 1,2- Glyme such as dibutoxyethane (boiling point 203.3 ° C.) and bis (2-methoxyether) ether (boiling point) Diglyme such as bis (2-ethoxy ether) ether (boiling point 188.4 ° C.), bis (2-butoxy ether) ether (boiling point 254.6 ° C.), and 1,2-bis (2-methoxyethoxy). ) Ethane solvent such as ethane (boiling point 216 ° C.), triglyme such as bis [2- (2-methoxyethoxyethyl)] ether (boiling point 275 ° C.), tri-n-propylamine (boiling point 150 to 156 ° C.), Amine solvents such as tri-n-pentylamine (boiling point 130 ° C.), N, N-dimethylaniline (boiling point 193 ° C.), N, N-diethylaniline (boiling point 217 ° C.), pyridine (boiling point 115.3 ° C.), etc. Can be mentioned. As the electron-donating organic solvent, 1,2-diethoxyethane (boiling point 121 ° C.), which is a kind of glyme, is preferable from the viewpoints of both suppression of gel during 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 is 230 ° C. or less from the viewpoint that the drying time is relatively short when the solvent is removed after application of the obtained composition to form a coating film. It is preferable that

  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, more preferably 6 to 12 carbon atoms. And aromatic hydrocarbon compounds and mixtures thereof.

  Specific examples of these hydrocarbon compounds include pentane, n-hexane, heptane, isohexane, methylpentane, octane, 2,2,4-trimethylpentane (isooctane), n-nonane, n-decane, n-hexadecane, Aliphatic hydrocarbons such as octadecane, eicosane, methylheptane, 2,2-dimethylhexane, 2-methyloctane; cycloaliphatic hydrocarbons such as cyclopentane, cyclohexanemethylcyclohexane, ethylcyclohexane, benzene, toluene, xylene, cumene, Aromatic hydrocarbons such as trimethylbenzene, hydrocarbon solvents such as mineral spirits, solvent naphtha, kerosene, petroleum ether, etc. can be raised.

The upper limit of the boiling point of the organic solvent and hydrocarbon compound different from the above electron-donating organic solvent is not particularly limited, but the drying time when the solvent is removed after application of the obtained composition to form a coating film From the viewpoint that is relatively short, the temperature is preferably 230 ° C. or lower as in the case of the electron donating compound. Further, from the viewpoint of improving the stability of the compound containing a metal, it is desirable that the electron donating compound is contained in the composition of the present invention.

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

  A composition in which the compound or the partial hydrolyzate is dissolved in an organic solvent is obtained by dissolving or reacting as described above to become a composition as it is, or after obtaining a product by, for example, a partial hydrolysis reaction, By arbitrarily adding an organic solvent such as a donating organic solvent or a hydrocarbon compound and adjusting the composition, the composition of the present invention can be obtained.

  The amount of water added in the preparation of the partial hydrolyzate is, for example, that in the partial hydrolyzate 1, the molar ratio to the organozinc compound is in the range of 0.05 to 0.8, and in the partial hydrolyzate 2, The molar ratio with respect to the total amount of the organozinc compound and the group 3B element compound is preferably in the range of 0.05 to 0.8. When the amount of water added is within this range, the reaction product containing the partial hydrolyzate obtained in spin coating, dip coating and spray pyrolysis forms a transparent and conductive zinc oxide thin film. be able to. Moreover, also when carrying out partial hydrolysis of the 3B group element compound independently, it is preferable to make the molar ratio of the water with respect to the 3B group element compound into the range of 0.05-0.8.

  For example, when the organic zinc compound is partially hydrolyzed by setting the molar ratio of water to 0.4 or more, the organic zinc compound is partially hydrolyzed with a high yield of 90% or more based on the zinc contained in the raw material. A partially hydrolyzed product can be obtained. In the partial hydrolyzate 2, an appropriate amount of the Group 3B element compound is also partially hydrolyzed. By making the molar ratio 0.4 or more, in the case of the partial hydrolyzate 1, the remaining amount of the organic zinc compound that is an unreacted raw material is used. In the case of the partial hydrolyzate 2, the organic zinc compound and the group 3B are used. The residual amount of elemental compounds can be suppressed. Moreover, generation | occurrence | production of the gel during a hydrolysis reaction can be suppressed by making molar ratio into 0.8 or less. When gel is generated during the hydrolysis reaction, the viscosity of the solution increases, and the subsequent operation may be difficult. From the above viewpoint, the upper limit of the molar ratio of water is preferably 0.8, more preferably 0.75.

  This control of the amount of water added enables control of physical properties such as viscosity and boiling point of the composition. For example, coating that is difficult to be accompanied by a reaction such as a spin coating method can be easily formed by increasing the amount of water added, and the spray method or the like does not hydrolyze or less water is added. With the composition of the present invention obtained by the above, film formation reflecting the reactivity of the organic zinc compound itself, such as film formation at a low temperature, can be performed.

  A mixture of the organozinc compound represented by the general formula (1) and at least one 3B group element, for example, the 3B group element compound represented by the general formula (2) and / or the general formula (3) In the product containing, for example, a composition is produced by adding the organozinc compound represented by the general formula (1) and the 3B group compound of the general formula (2) or (3) to an organic solvent or the like. can do. The addition amount of the group 3B element compound is suitably added in a ratio of more than 0.1 and 5 or less with respect to the charged amount of the organic zinc compound.

  In partial hydrolyzate 1, since water is added to the organozinc compound and the group 3B element compound is added, depending on the amount of water added, the added water was consumed for hydrolysis of the organozinc compound. When a group 3B element compound is added later, the product usually does not contain a hydrolyzate of the group 3B element compound. The group 3B element compound is not hydrolyzed and is contained as a raw material, or the organic group of the partial hydrolyzate of the organozinc compound and the organic group (ligand) of the group 3B element compound are exchanged ( Ligand exchange) may also occur. In the partial hydrolyzate 3, water is added to the mixed solution of the organozinc compound and the group 3B element compound, so that the product usually contains a hydrolyzate of the group 3B element compound. The hydrolyzate of the group 3B element compound may be a partial hydrolyzate depending on the amount of water added.

  The addition of water can be performed only with water without mixing water with another solvent, or can be performed with a mixed solvent obtained by mixing water with another solvent. From the viewpoint of suppressing the progress of local hydrolysis, it is preferable to use a mixed solvent, and the content of water in the mixed solvent can be, for example, in the range of 1 to 50% by mass, preferably It is 2-20 mass%. The solvent that can be used for the mixed solvent with water can be, for example, the above-described electron-donating organic solvent. Further, the electron-donating organic solvent may be an organic solvent having a boiling point of 110 ° C. or higher or an organic solvent having a boiling point of less than 110 ° C. However, an organic solvent having a boiling point of less than 110 ° C. is preferable from the viewpoint of being inert to diethyl zinc and requiring high water solubility.

  The addition of water can be performed, for example, over a time period of 60 seconds to 10 hours, depending on the scale of the reaction. From the viewpoint that the yield of the product is good, it is preferable to add water or a mixed solvent with water dropwise to the organic zinc compound of the general formula (1) as a raw material. The addition of water can be carried out without stirring (while standing) or stirring the solution of the compound represented by the general formula (1) and the electron donating organic solvent. The temperature at the time of addition can select arbitrary temperature between -90-150 degreeC. It is preferable that it is -15-30 degreeC from a viewpoint of the reactivity of water and an organic zinc compound.

  Reaction of water and the compound represented by general formula (1) and the compound represented by general formula (2) or (3), or water and the compound represented by general formula (1) after addition of water For example, leave for 1 minute to 48 hours without stirring (still standing) or stir. About reaction temperature, it can be made to react at arbitrary temperature between -90-150 degreeC. The reaction temperature is preferably in the range of 5 to 80 ° C. from the viewpoint of obtaining a partial hydrolyzate in high yield. The reaction pressure is not limited. Usually, 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) is monitored by sampling the reaction mixture, analyzing the sample by NMR or IR, or sampling the generated gas, if necessary. Can do.

  In the composition of the present invention, for example, the composition containing the partial hydrolysates 1 and 2, the general formula (2) or (3) for the organic zinc compound and the organic zinc compound represented by the general formula (1). When the molar ratio of the group 3B element compound represented by the formula is greater than 0.1 and less than 5 is added, an oxide semiconductor film such as IGZO in which the effect of adding the group 3B element is appropriately expressed is obtained. Appropriate from the viewpoint. From the same viewpoint, the upper limit of the amount of the 3B group element compound added is preferably 4.5, more preferably 4, still more preferably 2.5, still more preferably 2, particularly preferably 0.95. However, in the partial hydrolyzate 1, water is added to the solution containing the organozinc compound to obtain a partial hydrolyzate, and then the 3B group element compound is added at the above molar ratio. Moreover, in the partial hydrolyzate 2, water is added to the solution containing an organic zinc compound and a 3B group element compound by the said molar ratio, and a partial hydrolyzate is obtained.

  The organic solvent, the organic zinc compound of the general formula (1) as a raw material, and water or a mixed solvent with water can be introduced into the reaction vessel according to any conventional method. These reaction steps may be a batch operation method, a semi-batch operation method, or a continuous operation method, and are not particularly limited, but a batch operation method is desirable.

  By the above reaction, the organozinc compound of the general formula (1) and the group 3B element compound of the general formula (2) or (3), or the organozinc compound of the general formula (1) are partially separated by water. Hydrolysis yields a product containing a partial hydrolyzate. When the organozinc compound of the general formula (1) is diethyl zinc, the analysis of the product obtained by reaction with water has been conducted for a long time, but the results differ depending on the report, and the composition of the product is clearly It is not specified. Further, the composition of the product can be changed depending on the molar ratio of water, the reaction time, and the like.

For example, the partial hydrolysates 1 and 2 are presumed to be compounds represented by the following general formula (4) or a mixture of plural kinds of compounds having different p.
R ¹ —Zn— [O—Zn] _p —R ¹ (4)
(In the formula, ^{R 1} is the same as ^{R 1} in the general formula (1), p is an integer from 2 to 20.)

In the present invention, the main component of the product is, for example, a partial hydrolyzate 2 having a structural unit represented by the following general formulas (5) and (6) and a structure represented by the following general formula (7). It is presumed that the compound is a combination of units or a mixture of a plurality of types of compounds having different m.
(R ₁ -Zn)-(5)
— [O—Zn] _m − (6)
(In the formula, ^{R 1} is the same as ^{R 1} in the general formula (1), m is an integer from 2 to 20.)
(In the formula, M is the same as M in the general formula (2) or (3), and Q is the same as any of X, R ² , R ³ and R ^{4 in} the general formula (2) or (3). , M is an integer from 2 to 20.)

  In the case of the partial hydrolyzate 1 in which the 3B group element compound does not coexist at the time of hydrolysis of the organozinc compound, the 3B group element compound such as the general formula (2) or (3) is obtained after the reaction is completed. The composition can be produced by adding the group 3B compound. As described above, the addition amount of the group 3B element compound is suitably added in a ratio of more than 0.1 and 5 or less with respect to the charged amount of the organic zinc compound.

  By using the composition of the present invention, an oxide semiconductor film including an oxide of In, Ga, and Zn (IGZO) can be formed.

The composition intended for film formation of the IGZO contains zinc and Ga and In as essential elements in the composition as a group 3B element. That is, the composition of the present invention requires the use of Zn by using a product containing the organozinc compound of the general formula (1) and the partial hydrolyzate, and a group 3B compound such as the general formula (2). ) And / or (3) group 3B compounds include those that require the use of two components, In and Ga, as group 3B elements. The molar ratio of Zn, In, and Ga can be adjusted so that the composition ratio becomes a desired IGZO composition. This molar ratio is determined based on the general composition of IGZO in which InGaO ₃ (ZnO) _m (an integer from 1 to 20) such as InGaZnO ₄ , In ₂ Ga ₂ ZnO ₇ , InGaZn ₅ O _8, etc., and their oxygen deficiency are reported. Preparations can be made so as to obtain compounds and the like, and other composition ratios are not limited to integer ratios, and any composition can be prepared by adjusting the amount of each element added.

In particular, the composition of the present invention is a partially hydrolyzed organic zinc compound represented by the following general formula (1) and an organic zinc compound such as diethyl zinc and water as a compound containing zinc prepared as described above. Can be used. This addition is carried out by hydrolyzing the composition, and the alkyl group R ¹ (wherein R ¹ is the number of carbon atoms) bonded to the organic zinc compound and the product obtained by partial hydrolysis of the organic zinc compound and water. It is confirmed by identification and quantification of hydrocarbon R ¹ H mainly produced from 1-7 linear or branched alkyl groups. For example, in the case of diethyl zinc, the main component of the gas produced by hydrolysis is ethane.

In addition, the alkyl group R ¹ (wherein R ¹ is a linear or branched alkyl having 1 to 7 carbon atoms) bonded to the organic zinc compound and a product obtained by partial hydrolysis of the organic zinc compound and water. Group) is R ² , R ³ , R ⁴ (R ² , R ³ , R ⁴ are each independently hydrogen, a straight chain having 1 to 7 carbon atoms, as shown in the general formula (2) of the coexisting group 3B element compound Alternatively, it may be produced by an exchange reaction with a branched alkyl group.

  After completion of the hydrolysis reaction, a part or all of the product can be recovered and purified by a general method such as filtration, concentration, extraction, column chromatography and the like. Moreover, when adding a 3B group element compound after completion | finish of a hydrolysis reaction, a part or all of the said product can be collect | recovered and refine | purified by filtration. When the organic zinc compound of general formula (1) or the group 3B element compound of (2) or (3), which is a raw material, remains in the reaction product, it can be recovered by the above-mentioned method and recovered. Is preferred.

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

[Production method of composite oxide thin film]
A method for producing a complex oxide thin film using the composition for forming a complex oxide thin film of the present invention will be described. The composite oxide thin film-forming composition of the present invention is applied to the substrate surface, and then the obtained applied film is heated to obtain a composite oxide thin film. When coating is performed by, for example, spin coating, dip coating, or spray pyrolysis, a composite oxide thin film having an average transmittance of 80% or more with respect to visible light and having conductivity is formed. Can do.

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

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

  In the spin coating method and the dip coating method, they may be formed in an inert gas atmosphere, and further, may be performed in an atmosphere having a relative humidity of 2 to 15% by mixing an inert gas and water vapor. .

  The spray pyrolysis method is a method that can be performed while heating the substrate. Therefore, the solvent can be dried in parallel with the application, and heating for solvent drying may not be necessary depending on conditions. Furthermore, depending on the conditions, in addition to drying, the reaction of the composition of the present invention into the composite oxide may proceed at least partially. Therefore, there is a case where a complex oxide thin film can be formed more easily by heating at a predetermined temperature, which is a subsequent process. The heating temperature of a board | substrate can be the range of 50-550 degreeC, for example.

  FIG. 1 shows a spray film forming apparatus that can be used in the spray pyrolysis method. In the figure, 1 is a spray bottle filled with a coating solution, 2 is a substrate holder, 3 spray nozzles, 4 is a compressor, 5 is a substrate, and 6 is a water vapor introducing tube. In spray coating, a substrate is placed on the substrate holder 2 and heated to a predetermined temperature using a heater if necessary. Then, in a predetermined atmosphere, an inert gas compressed from a spray nozzle 3 disposed above the substrate A composite oxide thin film can be formed on a substrate by simultaneously supplying the coating liquid and atomizing and spraying the coating liquid. The composite oxide thin film is formed by spray coating without additional heating or the like.

  A good film can be formed by spraying the coating liquid by discharging the coating liquid from the spray nozzle so that the droplet size is in the range of 1 to 15 μm and keeping the distance between the spray nozzle and the substrate within 50 cm. This is preferable from the viewpoint that a complex oxide thin film having characteristics can be produced.

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

  Considering that the solvent evaporates somewhat before reaching the substrate from the spray nozzle and the size of the droplet is reduced, the distance between the spray nozzle and the substrate is preferably within 50 cm. The distance between the spray nozzle and the substrate is preferably in the range of 2 to 40 cm from the viewpoint that the composite oxide thin film can be satisfactorily formed.

  In the spray pyrolysis method, introduction of water vapor from the water vapor introduction tube 6 under an inert gas atmosphere to promote the decomposition of the composition from the viewpoint of forming a composite oxide thin film having a lower volume resistivity. preferable. For example, the amount of water vapor introduced is preferably 0.05 to 5 in terms of a molar ratio to the total amount of zinc and 3B group elements in the supplied composition, and a viewpoint of obtaining a highly transparent composite oxide thin film To 0.1-3.

  Water vapor can be introduced into the complex oxide thin film production apparatus according to any conventional method. It is preferable that the water vapor and the composition react near the heated substrate. For example, an inert gas containing water vapor produced by bubbling water with an inert gas is introduced into the vicinity of the heated substrate through a tube. Can be mentioned.

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

  The temperature at which the solvent is dried can be, for example, in the range of 20 to 200 ° C., and can be set as appropriate according to the type of the organic solvent that coexists. The heating temperature for forming the composite oxide after drying the solvent is, for example, in the range of 50 to 550 ° C, and preferably in the range of 50 to 500 ° C. It is also possible to perform the solvent drying and the complex oxide formation at the same time by setting the solvent drying temperature and the heating temperature for the subsequent complex oxide formation to be the same.

  If necessary, further promote the formation of zinc oxide by performing the above heating in an oxidizing gas atmosphere such as oxygen, a reducing gas atmosphere such as hydrogen, and a plasma atmosphere such as hydrogen, argon, oxygen, or the like, or It is also possible to improve crystallinity. Although there is no restriction | limiting in particular in the film thickness of a complex oxide thin film, It is preferable that it is the range of 0.05-2 micrometers practically. According to the said manufacturing method, in the case other than the spray pyrolysis method, the said application | coating (dry) heating can be suitably manufactured by repeating the said application | coating (drying) heating once or more.

  The complex oxide thin film formed by the above manufacturing method varies depending on the coating method and the subsequent drying and heating conditions. The volume resistivity is a resistance per unit volume, and is obtained by multiplying the surface resistance and the film thickness. The surface resistance is measured by, for example, a four-probe method, and the film thickness is measured by, for example, SEM measurement, a stylus type step thickness meter, or the like. The volume resistivity changes (increases) depending on the degree of formation of the composite oxide by spray application or by heating after application, so that the volume resistivity of the thin film becomes a desired resistance value. It is preferable to set the heating conditions (temperature and time) after application.

  The composite oxide thin film formed by the above production method preferably has an average transmittance of 80% or more with respect to visible light, and more preferably has an average transmittance of 85% or more with respect to visible light. . “Average transmittance for visible light” is defined and measured as follows. The average transmittance for visible light refers to the average of the transmittance of light in the range of 380 to 780 nm, and is measured by an ultraviolet-visible spectrophotometer. The average transmittance for visible light can also be expressed by presenting the visible light transmittance of 550 nm. Visible light transmittance changes (increases) depending on the degree of zinc oxide formation during spray coating or heating after coating, so that the transmittance of the thin film with respect to visible light is considered to be 80% or more during spray coating. Or it is preferable to set the heating conditions (temperature and time) after application.

  As the substrate, for example, alkali glass, non-alkali glass, or a transparent base film can be used, and the transparent base film can be a plastic film. However, it is not intended to be limited to these exemplary materials.

[Applications of complex oxide thin films]
Since the composite oxide thin film produced by the above method has excellent transparency and mobility, it can be used as an antistatic film, an ultraviolet cut film, a transparent conductive film and the like. The antistatic film can be used, for example, in fields such as solid electric field condensers, chemically amplified resists, and building materials such as window glass. The ultraviolet cut film can be used in fields such as a front filter of an image display device, an imaging device such as a drive recorder, a lighting device such as a high-pressure discharge lamp, a building material such as a watch cover glass and a window glass. Further, the transparent conductive film is, for example, FPD, resistive touch panel and capacitive touch panel, thin film silicon solar cell and compound (CdTe, CIS) thin film solar cell, dye-sensitized solar cell, organic thin film solar cell, etc. Can be used in the field of
In particular, an oxide semiconductor film made of an oxide of In, Ga, and Zn (IGZO) has a higher mobility than an amorphous Si film, and switching elements (thin film transistors) such as liquid crystal display devices and thin film electroluminescence display devices. It is possible to use in the field. Field effect transistors such as thin film transistors (TFTs) are widely used as unit electronic elements, high frequency signal amplifying elements, liquid crystal driving elements, etc. for semiconductor memory integrated circuits, and are currently the most widely used electronic devices. is there. However, it is not intended to be limited to these fields.

  EXAMPLES The present invention will be described in more detail with reference to examples below, but these examples do not limit the present invention. Preparation of a product containing a partial hydrolyzate from all organozinc compounds and film formation using the product were performed in a nitrogen gas atmosphere with controlled moisture, and all solvents were used after dehydration and deaeration.

[Example 1]
1.5388 g of 1,2-diethoxyethane solution in which 0.1879 g of indium triisopropoxide and 0.1579 g of gallium triisopropoxide are dissolved, and diethylzinc and water at O / Zn = 0.6 (molar ratio) 1.0986 g of 1,2-diethoxyethane solution (Zn = 3.85 wt%) of the product obtained by hydrolysis was mixed at room temperature, and further diluted with 6.2633 g of 1,2-diethoxyethane. The composition was prepared so that IGZO was obtained as a composite oxide. The molar ratio of each element of this composition is In: Ga: Zn = 1: 0.99: 1.01. This composition is intended to form a film of InGaZnO ₄ as IGZO from an approximate integer ratio.

[Example 2]
1.5713 g of 1,2-diethoxyethane solution in which 0.1807 g of indium triisopropoxide and 0.1612 g of gallium triisopropoxide are dissolved, and diethylzinc and water at O / Zn = 0.6 (molar ratio) 0.5205 g of a 1,2-diethoxyethane solution (Zn = 3.85 wt%) of the product obtained by hydrolysis was mixed at room temperature, and further diluted with 1,3,026 g of 1,2-diethoxyethane. The composition was prepared so that IGZO was obtained as a composite oxide. The molar ratio of each element of this composition is In: Ga: Zn = 2: 2.16: 1. This composition is intended for film formation of In ₂ Ga ₂ ZnO ₇ as IGZO from an approximate integer ratio.

[Example 3]
0.9093 g of a 1,2-diethoxyethane solution in which 0.1280 g of indium triisopropoxide and 0.0933 g of gallium triisopropoxide are dissolved, and diethylzinc and water at O / Zn = 0.6 (molar ratio) 3.5223 g of a 1,2-diethoxyethane solution (Zn = 3.85 wt%) of the product obtained by hydrolysis was mixed at room temperature, and further diluted with 3.6529 g of 1,2-diethoxyethane. The composition was prepared so that IGZO was obtained as a composite oxide.
The molar ratio of each element of this composition is In: Ga: Zn = 1: 0.86: 4.73.
This composition is intended to form a film of InGaZn ₅ O ₈ as IGZO from an approximate integer ratio.

[Example 4]
1.5659 g of 1,2-diethoxyethane solution in which 0.1741 g of indium triisopropoxide and 0.1607 g of gallium triisopropoxide are dissolved, and diethylzinc and water at O / Zn = 0.6 (molar ratio) 1.0816 g of a 1,2-diethoxyethane solution (Zn = 3.85 wt%) of the product obtained by hydrolysis was mixed at room temperature, and further diluted with 6.2927 g of toluene to obtain IGZO as a composite oxide. The composition was prepared as obtained. The molar ratio of each element of this composition is In: Ga: Zn = 1: 1.09: 1.07.
This composition is intended to form a film of InGaZnO ₄ as IGZO from an approximate integer ratio.

[Example 5]
1.5424 g of 1,2-diethoxyethane solution in which 0.1724 g of indium triisopropoxide and 0.1583 g of gallium triisopropoxide are dissolved, and diethylzinc and water at O / Zn = 0.6 (molar ratio) 0.5140 g of a 1,2-diethoxyethane solution (Zn = 3.85 wt%) of the product obtained by hydrolysis was mixed at room temperature, and further diluted with 6.2895 g of toluene to obtain IGZO as a composite oxide. The composition was prepared as obtained. The molar ratio of each element of this composition is In: Ga: Zn = 1.1.09: 0.51.
This composition is intended for film formation of In ₂ Ga ₂ ZnO ₇ as IGZO from an approximate integer ratio.

[Example 6]
0.9112 g of a 1,2-diethoxyethane solution in which 0.1185 g of indium triisopropoxide and 0.0935 g of gallium triisopropoxide are dissolved, and diethylzinc and water at O / Zn = 0.6 (molar ratio). A 1,2-diethoxyethane solution (Zn = 3.85 wt%) of 3.5092 g of the product obtained by hydrolysis was mixed at room temperature, and further diluted with 3.6729 g of toluene to obtain IGZO as a composite oxide. The composition was prepared as obtained. The molar ratio of each element of this composition is In: Ga: Zn = 1: 0.93: 5.09.
This composition is intended to form a film of InGaZn ₅ O ₈ as IGZO from an approximate integer ratio.

[Example 7]
1.9881 g of a 1,2-diethoxyethane solution in which 0.1746 g of indium triisopropoxide and 0.1511 g of gallium triisopropoxide are dissolved, and a 1,2-diethoxyethane solution of diethylzinc (Zn = 3.706 wt%) ) 1.2243 g was mixed at room temperature, and further diluted with 4.4200 g of toluene to prepare a composition so that IGZO was obtained as a composite oxide. The molar ratio of each element of this composition is In: Ga: Zn = 1: 1.02: 1.16.
This composition is intended to form a film of InGaZnO ₄ as IGZO from an approximate integer ratio.

[Example 8]
The product-containing coating solution obtained in Example 1 was filtered through a membrane filter and used for coating film formation. The solution obtained by filtration was a slightly yellowish, almost colorless clear solution. This product-containing coating solution was coated on the surface of an 18 mm square Corning 1737 glass substrate by spin coating. Thereafter, the substrate was heated at 300 ° C. for 5 minutes to dry the solvent and simultaneously form a composite oxide. The above operation was further repeated 5 times. The film thickness of the obtained thin film was 188 nm as analyzed by SEM, and the total transmittance was 96% at 550 nm. Further, the product-containing coating solution was coated on the surface of an 18 mm square Corning 1737 glass substrate by a dip method. Thereafter, the substrate was heated at 300 ° C. for 5 minutes to dry the solvent and simultaneously form a composite oxide. The above operation was further repeated 5 times. The transmittance of the obtained thin film was 94%.

[Example 9]
The solution obtained in Example 4 was coated and formed at 300 ° C. by the spin coating method in the same manner as in Example 8. The transmittance of the obtained thin film was 96% at 550 nm.

[Example 10]
The solution obtained in Example 6 was applied and formed at 300 ° C. by spin coating in the same manner as in Example 8. The transmittance of the obtained thin film was 81% at 550 nm.
When the obtained thin film was observed by SEM, the film thickness was 333 nm. Analysis by X-ray diffraction confirmed peaks considered to be broad amorphous at 2θ = 30 to 38 ° and 50 to 68 °.

[Example 11]
The solution obtained in Example 7 was applied and formed at 300 ° C. by spin coating in the same manner as in Example 8. The transmittance of the obtained thin film was 84% at 550 nm.
When the obtained thin film was observed by SEM, the film thickness was 207 nm. Analysis by X-ray diffraction confirmed peaks considered to be broad amorphous at 2θ = 30 to 38 ° and 50 to 68 °.

[Comparative Example 1]
In Example 1, indium acetylacetonate was used instead of indium triisopropoxide, gallium acetylacetonate was used instead of gallium triisopropoxide and zinc acetate was used instead of diethylzinc, 2-methoxyethanol as a solvent, auxiliary agent A coating solution having the same composition was prepared using ethanolamine.

The obtained coating solution was deposited at 300 ° C. in the same manner as in Example 8 to obtain a thin film. The visible light transmittance at 550 nm was 60%, and only an opaque thin film having a transmittance of 80% or less was obtained. Furthermore, the obtained film was turbid and non-uniform.

  INDUSTRIAL APPLICABILITY The present invention is useful in the field of manufacturing composite oxide thin films containing zinc oxide and Group 3B element oxides.

1 ... spray bottle,
2 ... Substrate holder (with heater),
3 ... spray nozzle,
4 ... Compressor,
5 ... alkali-free glass substrate,
6 ... Steam introduction tube

Claims (11)

The organic zinc compound represented by the following general formula (1) or a partial hydrolyzate of the organic zinc compound with water and a partial hydrolyzate of the group 3B element compound or the group 3B element compound with water are converted into a group 3B element with respect to zinc. A composition for producing a complex oxide thin film, comprising a molar ratio in the range of more than 0.1 and 5 or less.
R ¹ —Zn—R ¹ (1)
(In the formula, R ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms.) The composition according to claim 1, further comprising an organic solvent. The partial hydrolyzate of the organic zinc compound with water is prepared 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 the organic zinc compound. A product obtained by partially hydrolyzing a zinc compound, wherein the partial hydrolyzate of the group 3B element compound with water is a molar ratio of the group 3B element compound and water within a range of 0.05 to 0.8. The composition according to claim 1, wherein the composition is a product obtained by mixing at least partially hydrolyzing the Group 3B element compound. The partial hydrolyzate of the organic zinc compound with water and the partial hydrolyzate of the group 3B element compound with water are the sum of the organic zinc compound and the group 3B element compound with water added to the organic zinc compound and the group 3B element compound. The product obtained by partially hydrolyzing the organozinc compound and the group 3B element compound by adding such that the molar ratio thereof is in the range of 0.05 to 0.8. The composition as described. The composition according to any one of claims 1 to 4, wherein the 3B group element compound is a 3B group element compound represented by the following general formula (2) or (3).
(In the formula, M is a group 3B element, R ² , R ³ and R ⁴ are independently hydrogen, a linear or branched alkyl group having 1 to 7 carbon atoms, or a linear or branched group having 1 to 7 carbon atoms. An alkoxyl, carboxylic acid, or acetylacetonate group, L is a coordinating organic compound containing nitrogen, oxygen, or phosphorus, and n is an integer of 0 to 9.)
_{M c X d · aH 2 O} (3)
(Wherein M is a group 3B element, X is a halogen atom, nitric acid or sulfuric acid, c is 1, when d is a halogen atom or nitric acid, d is 3, and when X is sulfuric acid, c is 2 D is 3, and a is an integer of 0 to 9.) The composition according to claim 2, wherein the organic solvent contains at least one of an electron donating solvent, a hydrocarbon solvent, and a mixture thereof. The composition according to claim 2, wherein the organic solvent has a boiling point of 230 ° C. or lower. The electron donating solvent includes at least one of 1,2-diethoxyethane, tetrahydrofuran, diisopropyl ether, dioxane, and hexane, heptane, octane, toluene, xylene, and cyclohexane as a hydrocarbon solvent. Composition. The composition according to claim 1, wherein the organic zinc compound is diethyl zinc. The group 3B element compound of the general formula (2) is trimethylindium, triethylindium, trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trioctylaluminum, trisacetylacetonatoaluminum, trisacetylacetonatogallium, trisacetylacetonato At least one of indium, aluminum chloride, gallium chloride, indium chloride, trimethoxyborane, triethoxyborane, triisopropoxyindium, triisopropoxygallium, triisopropoxyaluminum, tritert-butoxyindium, tritert-butoxygallium The composition in any one of Claims 5-9 containing. The composition in any one of Claims 1-9 whose 3B group elements are Ga and In.