TW200827478A - Raw material for forming thin film and method for producing thin film - Google Patents

Abstract

To provide a raw material suitable for producing a thin film containing zinc, and to provide a method for producing the thin film through a chemical vapor deposition technique using the same. The raw material for forming the thin film is formed of a solution in which bis(pentane-2, 4-dionate) zinc nonhydrate of 0.1 to 1 mol dissolves in an organic solvent containing no hydroxy group of 1,000 ml, as an essential component. The method for producing the thin film comprises the steps of: introducing a vapor containing the bis(pentane-2, 4-dionate) zinc nonhydrate, which has been obtained by vaporizing the raw material for forming the thin film, onto a substrate; and decomposing and/or chemically reacting the vapor to form the thin film containing zinc atoms on the substrate.

Description

[Technical Field] The present invention relates to a raw material for forming a film containing zinc, and more particularly, the present invention relates to a raw material for forming a film composed of the following solution, and use thereof A method for producing a film of the raw material, wherein the bis(sebacate) zinc anhydrate complex is dissolved as an essential component in 1000 ml of an organic solvent. [Prior Art]

Since the film containing zinc has various characteristics such as optical characteristics, electrical characteristics, and catalytic activity, it can be used as a component of an electronic component or an optical component. Examples of the method for producing the film include a flame deposition method, a forging method, an ion plating method, a coating pyrolysis method, a sol (Metai 〇rganic Depositi〇n'organometallic decomposition) method, and a chemical vapor deposition method. The method has good composition controllability, surface coverage, and is suitable for mass production of 'hybrid integme' and other advantages, so 'chemical vapor deposition by ALD (Atomic Layer De-, Atomic Layer Deposition) method (below) Sometimes referred to as cv D) the best manufacturing process in the legal system. The diacid process has a hydrate and a non-hydrate (anhydrate). From the viewpoint of self-crystallinity and reproducibility, in the CVD process, the industry has multiple self-stability and safety, and β_ as a precursor. Diketone complexes were studied. For example, in Patent Documents i to 3, there is no CVD in which a solid precursor which is easily volatilized, that is, bis(pentane-s, 2,4-dicarboxylate) zinc is used. It is disclosed in Patent Document 3 that bis (e.g., the film is preferably produced in the form of 1 hydrate 122675.doc 200827478 is 'two:= the solvent is (10) w alkane pentane, cyclohexane, Cycloheptane, cyclooxygen, and βJ 壬 壬 ' as an alcohol, exemplified by methanol, ethanol, 70 precursors, such as hydrazine and butyl, as bis (pentane-2,4-diacid) zinc, but for The diacid (10) liquid is not specifically described. In addition to the non-special (=, 4_2 (戍 pit from diacid) zinc diethylene glycol monomethyl bond solution as a raw material, Patent Document 5 discloses a liquid of #25t Double (β•二于根) zinc is double (Xinyuan·2,4-diacid) and bis(2,2·dimethyl 'dioxane-3,5-diacid) zinc. (Essence of 2,4 · diacid), the refining point of anhydrate is 13 (circle rc, the melting point of hydrate is! The high melting point solid is grasped; in the process of gasification engineering such as CVD There is a problem in the supply of the raw material gas such as the problem that the amount of volatilization is insufficient when volatilization occurs with sublimation, and the change in the amount of volatilization. The use of solutions such as solution CVD and M〇D method is used. There is a problem in that a solution in which a solid phase does not exist in a solution raw material cannot be obtained at a concentration suitable for use. An aliphatic flue solvent does not provide sufficient solubility, and an alcohol solvent is due to bis(pentane-2, There is a problem that the precursor is deteriorated by the reaction of 4_diacid) zinc with the hydroxyl group of the alcohol. The bis (β-diacid) cause of the liquid disclosed in Patent Document 5 also has sufficient solubility, so the above can be avoided. The problem is that the volatility of the precursor itself does not necessarily avoid the problem of the above deterioration. [Patent Document 1] Japanese Patent Publication No. Hei 6-64738 (especially [Request Item 9]) 122675.doc 200827478 [Patent Document 2 Japanese Laid-Open Patent Publication No. 2003-236376 (especially [Embodiment]) [Patent Document 3] Japanese Patent Laid-Open No. 2003-3 1846 (especially paragraphs [0015], [0016]) [Patent Literature 4] Japanese Patent Laid-Open Publication No. 2005-298874 (especially [Request Item 1], paragraph [0012]) [Patent Document 5] Japanese Patent Laid-Open No. 2005-350423 (especially [Request Item 1] to [Request Item 6]) [Non-Patent Document 1] NREL/SR-520-3179 December 2001 (especially [Survey of the Invention] [Problems to be Solved by the Invention] An object of the present invention is to provide a raw material which is preferably used for producing a film containing zinc, and a film which is produced by using the chemical vapor deposition method using the raw material. [Technical means for solving the problem] After careful discussion, the present inventors came to the conclusion that a solution of bis(pentane-2,4-dione)zinc anhydrate having a specific organic solvent as a solvent has It has a high concentration and exhibits good stability, so that it can reach the cost of the invention. That is, the present invention provides a raw material for film formation comprising a solution of bis(pentane·2,4-diate) zinc anhydrate 0.1 to 1 mol as an essential component. It is obtained by dissolving in 1000 ml of an organic solvent which does not have a hydroxyl group. Further, the present invention provides a method for producing a film to achieve the above-mentioned object 122675.doc 200827478, which is obtained by forming a film of the above-mentioned film with bis(pentene-2,4-diacid) and obtaining the containing double (The pentium 24 U mouth of the ^ introduced into the substrate 'will be, · one acid base) zinc anhydrate decomposition of the base of the chemical reaction, and formed on the base boat containing zinc atoms:; solution and / or advance [invention效果 4 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜 膜In the gasification process, the raw material produced by the raw material for film formation of the present invention is used as an electronic component or an optical component. [Embodiment] The raw material for film formation of the invention will be Bis(pentazone-2,4-diacid) zinc no-mouth as a film precursor, and the bis(pentane-2,4-diacidate) = hydrated material essential component is dissolved in the organic solvent without (4) Served in the middle. It is characterized by 'zinc precursor charging By dissolving, it is possible to give a film manufacturing process with good productivity' and, because of its good volatility, it is particularly effective as a raw material for a process that is accompanied by gasification of eVD, etc. ^, a bis (pentane) which can be obtained from the market a 2,4-diacid)zinc hydrate or a mixture of a hydrate and an anhydrate, and a hydrate is known for a hydrate. The presence or absence of the combined water can be determined according to the absorption of the combined water in the IR analysis. Trying to put the bis(pentazone-2,4-diacidate) zinc into various organic solvents and dissolve it, it will produce a suspension and dissolved residue. The suspension and dissolved residue are difficult to completely remove, so it cannot be self-contained. The hydrate bis (pentane _ 122675.doc 200827478 '4 鱿 root) zinc obtains a solution having a sufficient concentration of the solid phase in the absence of the solid phase. Further, as an essential component of the present invention, bis(pentane-2,4-di) The method of manufacturing the squid is not particularly limited, and a well-known general method can be used. For example, in a non-aqueous environment in which water has been removed, zinc halide (IU 匕 zinc zinc chloride, zinc bromide, iodine) is used. Chemical, zinc sulfate, zinc nitrate, etc. The method of reacting with pentanedione in the presence of salt hydrazine; in the water system %& in the 'inorganic zinc salt and pentane 2,4_: sodium sulphate, pentane 2,4-diacid -2,4-acid clock, etc. method for reacting a metal complex; in a non-aqueous environment, a method of reacting a dimethoxy group, a diethoxy group, etc. with a '4 ketone A method for directly producing an anhydrate without reacting a guanamine such as bis(ethylamino)zinc or bis(propylamino)zinc with a pentane bromide 2,4·dione in a non-aqueous environment And removing water by using water as a solvent and reacting the inorganic zinc or inorganic dance hydrate with the brothel n in the presence of ruthenium oxidation (4), and removing the di-dipentane 2,4:diacid) zinc A method of combining water with hydrates. As a method of removing the chemical, a method of using a dehydrating agent, a method of removing water by heating and dust reduction, and a method of removing the combined water from a square hydrate in which the two methods are combined or more are used to obtain an anhydrate. In the case of a package: = and the stable solution is a raw material for film formation, and as an impurity, (, alkane 2,4 · diacidate) zinc hydrate, preferably 1 mol% or less, more preferably It is 0.3% or less below. (4) In the case where the solid precursor is dissolved, the solid precursor phase and the solid precursor phase must have sufficient solubility. If the solubility is low, sufficient film formation speed and dissolution tolerance can not be obtained, and the concentration of the organic component and the dilution of some organic agents are likely to cause solid precipitation and cause the film formation speed to elapse. Change, deterioration of membranous quality.

Therefore, the raw material for film formation of the present invention uses an organic solvent having no hydroxyl group as the above solvent, and dissolves (pentane-2,4-diacid) zinc anhydrate in 1 〇〇〇ml of the organic solvent. 〇. hi Moer, it is better to 〇. 2~1 Mo Er. When bis(pentane-2,4-diate) zinc anhydrate is less than 0.1 mol: ', sufficient productivity cannot be obtained, and when it is larger than !mol, the solubility limit becomes smaller from the upper limit of solubility. There is a possibility that the organic solvent having no reserve at the above-mentioned concentration used for the raw material for forming a film of the present invention is produced, and examples thereof include a ketone compound, an ether compound, an anthracene compound, and an aromatic compound. The organic solvent may be used alone or in combination of two or more. Examples of the ketone compound include acetone, methyl ethyl ketone, methyl butyl ketone, and methyl butyl ketone. Ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, methyl cyclohexanone and the like. Examples of the ether compound include tetrahydrofuran, tetrahydrofuran, morpholine, ethyl alcohol dimethyl ether, i ethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and dibutyl. Ether, diethyl ether, dioxane, and the like. J乍 is the above ester compound, and examples thereof include methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetonate, second butyl acetate, and third acetic acid. Ester, amyl acetate, isoamyl acetate 122675.doc -11- 200827478 ester, acetic acid third pentyl, phenyl acetate, methyl propionate, ethyl propionate, isopropyl sulfonate propionate, butyl phthalate Isobutyl propionate, second butyl propionate, second butyl vinegar, amyl propionate, isoamyl propionate, third amyl propionate, phenyl vinegar propionate, lactic acid, lactic acid Ethyl ester, methyl methoxypropionate, methyl acetoacetate, ethyl methoxypropionate, ethyl ethoxy propionate, ethylene glycol monomethyl acetate, bismuth ethylene glycol Ethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl sulphate acetic acid, ethylene glycol single second Ether acetate, ethylene glycol monoisobutyl acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propanol monoethyl ether acetate, propylene glycol monopropyl ether acetate ester Propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol single second butyl acetate, propylene glycol monoisobutyl ether acetate, propylene glycol monobutyl ether acetate g曰, butanediol monomethyl Ether acetate, butanediol monoethyl ether acetate, butanol monopropyl ether acetate, butanediol monoisopropyl ether acetate, butanediol monobutyl ether acetate, butanediol single Dibutyl ether acetate, butanediol monoisobutyl ether acetate, butanediol mono-tert-butyl acetate, methyl acetate, ethyl acetate, ethyl sulphate, butyrate Oxygen butyrate ethyl vinegar, γ-endo vinegar, internal sputum, etc. Examples of the aromatic compound include benzene, toluene, ethylbenzene, xylene, mesitylene, diethylbenzene, cumene, isobutylbenzene, isopropyl benzene, tetrahydronaphthalene, and benzene. ether. Examples of the hydrocarbon compound having a cyano group include 1-cyanopropyl, 1-cyanobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, cyanopropane, and hydrazine. Dicyanobutane, 1,6-dicyanohexane, hydrazine, 4-dicyano 122675.doc -12- 200827478 cyclohexane, 1,4-dicyanobenzene, etc. as the above-mentioned not dissolved Sex and "solvent, self-contained to a preferred concentration range or if the surface is considered" better ether compound, vinegar two-component h-fragrance compound. Also, better machine solvent in the atmosphere r The order of the Buddha is (four) thief. Eight has the thin boat of the present invention, containing double (the raw material of the sulphur 24, according to the composition of the film produced can also be etched, the monoacid) zinc anhydrate The film precursor is set according to the desired film composition.

For example, it is stored as LV T ^ , the underarm method: manufacturing a film containing a plurality of symplectic films by CVD: in the case of a multi-component film precursor in a manner independent of each component: deuteration: a method of supply (hereinafter referred to as Single-source method), and a method in which a plurality of knives are mixed with a desired composition to obtain a mixed raw material, a raw material is vaporized and supplied (hereinafter referred to as a composite source method); The raw material for forming a film of the present invention is a mixed solution of a zinc anhydrate and another film precursor. The film precursor other than the zinc anhydrate used in the above case is not particularly limited. A well-known precursor which is well known in the raw materials for CVD can be used. Examples of the precursor, the above-mentioned precursors include one or more organic complex compounds such as an alcohol compound and/or a diol compound and/or a β-- and/or a cyclopentadiene compound or an organic amine compound. A compound with a metal, an alkyl metal compound, an aryl metal compound, or the like. Moreover, the metal species as the precursor may be niobium, titanium, zirconium, hafnium, vanadium, niobium, niobium, manganese, 122675.doc -13- 200827478 iron, nail, cobalt, ruthenium, rhodium, nickel, palladium, platinum, copper, Silver, gold, gallium, indium, antimony, tin, lead, antimony, bismuth, antimony, antimony, bismuth, antimony, bismuth, convergent, 钣, Peng, 铕, this, 轼, 镝, 鈥, 铒, recorded, mirror. Examples of the alcohol compound used as the organic ligand include methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, isobutanol, tert-butanol, pentanol, isoamyl alcohol, and Alkyl alcohols such as triamyl alcohol; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2·(2-methoxyethoxy)ethanol, 2-methoxymethyl Ethanol, 2-methoxycarbonylethanol, decyloxy-1,1-dimethylethanol, 2-isopropyloxydimethylethanol, 2·butoxy-1,1-dimethyl Ethanol, 2-(2. methoxyethoxydipin, ^dimethylethanol, 2-propoxydiethylethanol, second butoxydiethylethanol, methoxy-u-di An ether alcohol such as methyl propanol; a dialkylamine alcohol to which a nicotinyl metal compound of the present invention is administered. Examples of the ethylene glycol compound used as the above organic ligand include 1,2_ethylene glycol and L2- Propylene glycol, 1,3-propanediol, 2,4-hexanediol, 2,2-methyl1,3-propanol, 2,2-diethyl-1,3-propanediol, iota, 3-butanediol Butanol, 2,2, diethyl-1,3-butanediol, 2-ethyl-2-butylene, 'propanol, 2,4-pentanediol , 2-methyl-hydrazine, 3-propanediol, 2-methyl-2,4·pentanol, 2,4-hexanediol, 2,4-dimethyl-2,4·pentanediol. Examples of the β-diketone compound used in the above organic ligand include acetyl blood acetone, hexanone-2,4-dione, 5-methylhexan-2,4-dione, and gypsum-2,4. , with methyl heptane-3,5·dione, 5-methylheptane-2,4-dione, 6-methylheptane 2,4-mono-, 2,2-dimethylheptane- 3,5·dione, 2,6-dimethylheptane_3,5-dioxa, 2,2,6-trimethylheptane-3,5-dione, 2,2,6, 6-四甲122675.doc -14- 200827478 hexeptane-3,5-dione, octane-2,4-dione, 2,2,6-trimethyloctane-3,5·dione 2,6-Dimethyloctane-3,5-dione, 2,9-dimethyldecane-4,6-dione, 2-methyl-6-ethyldecane, 5-di Ketone, 2,2-dimethyl-6-ethyloxime-3,5-dione, etc., substituted 0-diketones; 1,1,1-trimorphic pentane-2,4-dione 1,1,1-Trifluoro-5,5-dimercaptohexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione , 1,3-diperfluorohexylpropane-1,3-dione and other fluorocarbon substituted alkyl 0-diketones; 1,1,5,5-tetramethyl-1-methoxyhexanone- 2,4-two , 2,2,6,6-tetramethyl-1-methoxyheptane-3,5-dione, 2,2,6,6-tetramethyl-1-(2-methoxyethoxy The β-diketone is substituted with an ether such as heptane-3,5-dione. Examples of the cyclopentadiene compound used as the above organic ligand include cyclopentadiene, methylcyclopentadiene, and B. Cyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, second butylcyclopentadiene, isobutylcyclopentadiene, tert-butyl ring Examples of the organic amine compound used as an organic ligand for pentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, etc., may be exemplified by methylamine, ethylamine, propylamine, isopropylamine. , butylamine, second butylamine, tert-butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethylmethylamine, C Methylamine, isopropylmethylamine, and the alkyl group as the alkyl metal compound may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a second butyl group, a third butyl group or a different group. Butyl, pentyl, third pentyl, isopentyl, etc., as the aryl group of the aryl metal, phenyl, A Phenyl, dimethylphenyl, ethylphenyl and the like. The raw material for forming a film of the present invention does not have impurities such as a hetero atom metal component other than the precursor component of the film forming material, and impurities such as ruthenium chloride, and the organic component of the impurity. The impurity metal element component is preferably 100 ppb or less, more preferably 1 Å ppb or less per element. It is preferably 1 ppm or less in the total amount, more preferably 1 GG ppb or less. The impurity element component is preferably loo ppm or less, more preferably 1 〇 ppm or less, and further preferably 疋 1 ppm or less. The impurity organic component is preferably 5 〇〇 ppm or less or 50 ppm or less in the total amount, more preferably 1 〇 or less. In addition, when it is used as a CVD raw material, it will cause the use of double (eating)

2,4-diacid) hydrated (10) granules are produced in the raw materials or granules are produced when using coffee, so it is preferred to remove all the moisture as much as possible in advance. The water content is preferably 1 GG ppm or less, more preferably 1 G ppm or less, and still more preferably 1 ppm or less. Further, the raw material for forming a film of the present invention is used to reduce or prevent contamination of the particles of the film to be produced, and in the process of particle measurement by using a particle detector in a liquid-scattering liquid liquid, it is preferably more than 0.3 (d). The number of particles is 1〇0 or less, and more preferably, the number of particles in the liquid phase (10) is larger than 〇.2 _ is 1 G00 or less, and more preferably, the particles in the liquid phase i(4) are larger than 〇·2 μιη. The number is less than one. The thin manufacturing method of the present invention is to vaporize the original film for forming a daily film and other precursors used as needed, and to obtain a vapor obtained by vaporization and a reactive gas used as needed. It is introduced onto the substrate and then the precursor is decomposed and/or chemically reacted on the substrate, and the film is deposited and deposited on the substrate by CVD to obtain a film of Yang Ming. The raw material supply and supply method, the deposition method, the production conditions, the production equipment, and the like are not particularly limited. The general conditions known in the art, and the method of 122675.doc -16-200827478 can be used. Examples of the reactive gas used in accordance with the above-mentioned needs include oxygen, odor, oxygen, -®, emulsification, sputum, sputum, sulphur, peroxy hydrazine, formic acid, acetic acid, Examples of the anhydrous product such as anhydrous acetic acid include chlorine, and examples of the production of vaporized compounds include organic amine compounds such as monoalkylamine, dialkylamine and =amineamine, #, ammonia, etc., as a sulfide. List hydrogen sulfide.

Further, examples of the deposition method include thermal CVD in which a raw material gas or a material gas and a reactive gas are reacted only by heat to form a thin film, and plasma CVD using heat and plasma, and CVD using heat and light. The photo-cracking CVD of heat, light, and t-pulp is used to divide the CVD stacking reaction into a basic process and perform ALD (Atomic Layer Deposition) at a molecular level. Further, examples of the production conditions include a reaction temperature (substrate temperature), a reaction pressure, a deposition rate, and the like. With respect to the reaction temperature, it is preferred that the above-mentioned compound of the present invention has a sufficient reaction temperature of 16 〇〇c or more, more preferably 25 0 C 800 C. Further, it is preferred that the reaction pressure is atmospheric pressure ~ 1 〇 Pa, more preferably atmospheric pressure ~ 5 〇〇 pa. The combination of the deposition method and the reaction pressure is arbitrary, and examples thereof include reduced pressure thermal CVD, reduced pressure plasma CVD, reduced pressure photo CVD, reduced pressure photo-paste cvd, atmospheric pressure thermal CVD, atmospheric piezoelectric CVD, atmospheric pressure photo CVD, and atmospheric pressure photoelectric. Pulp cVD. The stacking speed can be controlled according to the supply conditions of the raw materials (gasification temperature, vaporization pressure), reaction temperature, and reaction pressure. The characteristics of the film obtained may be deteriorated when the stacking speed is large, and the productivity may occur when the stacking speed is small. Therefore, the stacking speed is preferably 05 to 5000 nm. /min, better is 1~1000 nm/min. Further, when ALD is used, in order to obtain a desired film thickness, control is performed in accordance with the number of cycles. Further, in the method for producing a film of the present invention, after the film is deposited, an annealing treatment may be performed in order to obtain better electrical characteristics, and when a step is required to be buried, a reflow step may be provided. In this case, the temperature is 500 to 1200 ° C, preferably 6 to 8 Torr. Hey. According to the film produced by the method for producing a film of the present invention using the raw material for forming a film of the present invention, a metal, an alloy, a sulfide, or an oxide can be selected by appropriately selecting a precursor of the other component, a reactive gas, and a production condition. A desired type of film such as ceramics, nitride ceramics, or glass. Examples of the type of the film to be produced include zinc, ZnSe, zinc oxide, zinc sulfide, a zinc-indium composite oxide, an oxidation word of an addition clock, a ferrite added, a lead-zinc composite oxide, and a lead-zinc. _铌 composite oxide, yttrium-zinc-yttrium composite oxide, ytterbium-rhodium-yttrium composite oxide, tin-zinc composite oxide, as b • for the use of such films, for example, for transparent conductors, illuminants , phosphors, photocatalysts, magnetic materials, electrical conductors, high dielectrics, ferroelectrics, piezoelectrics, microwave dielectrics, optical waveguides, optical amplifiers, optical switches, electromagnetic shielding, solar cells, etc. [Examples] Hereinafter, the present invention will be described in more detail based on production examples, evaluation examples, and examples. However, the present invention is not limited by the following examples and the like. [Production Example] Manufacture of bis(anthraquinone-2,4-diacid) zinc anhydrate. Commercially available bis(pentane-2,4-dicarboxylate) zinc (manufactured by Kanto Chemical Co., Ltd.) 122675.doc -18 · 200827478 The combined water was removed by sublimation purification using heating and depressurization, and bis(pentane-2,4-diacid) zinc anhydrous was obtained in a yield of 60% from 130 ° C, 30 Pa. Things. The obtained crystals were subjected to IR, ^-NMR, elemental analysis of carbon and hydrogen, and TG-DTA, and identified as bis(pentane-2,4-diacid) zinc anhydrate. • IR measurement 'IR diagram of bis(pentane-2,4-diacid) zinc anhydrate as shown in [Figure 1], the commercial product bis(pentane-2,4-diate) before removal of the combined water The IR image of zinc is shown in [Fig. 2] ^. In the IR diagram of the bis(pentane-2,4-diacid) zinc before the removal of the combined water, it can be confirmed that the absorption of the combined water reaches the apex of 3324 cnT1, but after the removal of the combined water, the bis(pentane-2,4) In the crystal of the -diacid)zinc anhydrate, it was confirmed that the absorption was not present. • b-NMR measurement (1 wt% heavy benzene solution) The peak value of the combined water of bis(pentane-2,4-diacid)zinc hydrate detected in the vicinity of 0.28 ppm was not detected. φ • The carbon content of the bis(pentane-2,4-diacid) anhydrate obtained by elemental analysis was 45.5% by mass (theoretical value: 45.56 mass%), and the hydrogen content was 5.3 mass•°/〇. (Theoretical value: 5.35 mass%), which is consistent with the theoretical value of the bis(pentane-2,4-diacid) zinc anhydrous product. Further, the commercially available bis(pentane-2,4-diacid)zinc has a carbon content of 42.4% by mass and a hydrogen content of 5.9% by mass. The theoretical value of the monohydrate is 42.65% by mass of carbon and 5.73 mass% of hydrogen, so that it is in conformity with the result of the above 111 measurement, and the commercially available product can be identified as a monohydrate. • TG-DTA (Ar 100 ml/min, 10 〇C/min, the amount of sample, ······························································ The obtained bis(ephthene-2,4-diacidate) zinc anhydrate exhibits a weight reduction by volatilization of the stage, and when the commercial product reaches 1 〇 (rc, the weight is reduced due to the detachment of the combined water, And the weight loss of the two stages of the weight reduction by volatilization. [Evaluation Example 1] Evaluation of Volatilization 'The bis(pentane-2,4-diacid) zinc anhydrous φ substance obtained in the above production example, Bis(octane-2,4-diacid) zinc, bis(2,2-dimethylethyldecane-3,5-diate), at Ar 100 ml/min, l〇°C/min The TG measurement was carried out under the temperature rising condition, and the temperature at which the mass was reduced by 50% was measured. Under the above conditions, the temperature at which the mass obtained by TG measurement was reduced by 5% was bis(pentanol-2,4-diacidate). Zinc anhydrate (measured using sample 9.495 mg) is 202 C 'bis(octane-2,4-diacid) (using sample 1〇·561 postal measurement) to 245 C, double (2, 2) -dimethyl -6-ethylnonane_3,5-diacid) zinc (measured using the sample 9.282 11^) was 263. (: H) [Evaluation Example 2] Evaluation of solubility The double obtained in the above production example ( Pentane 2,4-diacid) zinc anhydrate and bis(pentane-2,4-diacid) zinc before removal of compound water, in an organic solvent having no hydroxyl group, ie having isobutyl ketone, tetrahydrogen The solubility in decyl, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, butyl acetate, and toluene, and an organic solvent having a hydroxyl group, i.e., diethylene glycol monomethyl ether, was evaluated. It is carried out in the following method: 'In the organic solvent i 〇 (10) ml, the mixed content is (M, 0.2, 0.3, 〇.5, 〇·7, 1 〇 Mo Er double (decane_2, 4·2 Acidate) Zinc anhydrate and bis(pentane-2, each diacid) before removal of compound water 122675.doc -20- 200827478 Zinc 'closed static 24 A & 〇Lu... Test to confirm the usefulness of solid phase The solid phase is transparent to the other..., and it is not shown in the cold liquid 1000 nu organic solution. In addition, the insufficient broadening is dissolved! As shown in Table 1, the Moer is expressed as > ≪. Shu square 'work by dissolving [Table 1]

According to Table i, it was confirmed that the bis(ephthene-2,4-diacid)zinc anhydrate had sufficient solubility for each solvent, did not contain a solid phase, and was given a solution having a sufficient concentration. On the other hand, it was confirmed that a commercial product containing hydrates was bis (pentan 2,4·:acid), and a fine powder was also present in the molar solution. Further, after collecting the dissolved residue and measuring IR, it was identified as bis(pentane-2,4-diacid) zinc monohydrate. [Evaluation Example 3] The solution of the maximum concentration in various organic solvents in the bis(pentane-2,4-diacid) zinc anhydrate solution prepared in the above Evaluation Example 2, in Ar 100 ml/rnin, The tg_DTA measurement was carried out under the temperature rising condition of 10 ° C / min. The bis(pentane-2,4-acidate) zinc anhydrate is mixed with a relative organic solvent having a base group, that is, diethylene glycol monomethyl ether 1000..., to obtain a composition' The results of this composition are shown in Figure 3. It can be confirmed from Fig. 3 that there is a 7.22% residue at 271.8 °C. When using a solution of organic 122675.doc -21 - 200827478 / mixture without a hydroxyl group, it is impossible to confirm the volatilization indicating the presence of the reaction product of only the m τ of the reaction product of the antimony 4 & The weight loss caused by the volatilization of the organic solvent and bis(penta-2,4-diate). From the above, it was confirmed that the f: group from the acetonitrile reacted with the bis(ephthene-2,4-diacid)zinc anhydrate and gave a nonvolatile reaction product. ^

According to the above evaluation examples 1 to 3, it was confirmed that a composition of a bis(pentane-2,4-diacid)zinc anhydrate and an organic solvent having no hydroxyl group, in particular, an organic solvent-based ether solvent or a vinegar solvent The composition of the aromatic solvent can be supplied to a sufficiently concentrated and stable solution, and can be preferably used as a raw material for CVD. [Example] Production of Oxidation Film The bismuth (pentane-2,4-diacid) obtained by the above production example was dissolved on a ruthenium wafer by using a CVD apparatus shown in Fig. 4 under the following conditions. A zinc oxide film was produced by using this solution as a raw material for forming a thin crucible in 1000 ml of tetrahydrofuran. The film thickness and composition of the film after manufacture were identified using a fluorescent twist line. (Manufacturing conditions) Gasification chamber temperature··140°C, raw material flow rate···5 sccm, oxygen flow rate: 500 seem, reaction pressure: 1〇〇〇pa, reaction time·· 2〇 minutes, substrate temperature: 450 °C, carrier gas: argon gas 500 seem (result) film thickness: 240 nm, composition: zinc oxide [schematic description] Figure 1 shows the IR of bis(pentane-2,4·diate) zinc anhydrate Figure. Fig. 2 shows an IR chart of a commercially available bis(pentane-2,4-dicarboxylate) zinc. 122675.doc -22- 200827478 Fig. 3 shows the results of TG-DTA measurement of a composition of bis(pentane-2,4-diacid) zinc anhydrate and a solvent having an organic solvent of dihydroxyethylene glycol monomethyl ether. Fig. 4 is a schematic view showing an example of a CVD apparatus used in the method for producing a film of the present invention in the examples.

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Claims (1)

200827478 X. Applying for a patent garden: A raw material for forming a thin film comprising the following solution: bis (pentane-2,4-diacid) zinc anhydrate, 〇·丨~〗, as an essential component, dissolved in an organic solvent having no hydroxyl group 1所得m丨 obtained. The raw material for film formation according to Item 1, wherein the organic solvent not having the above hydroxyl group is selected from an ether compound, an ester compound, or an aromatic compound. 3. The raw material for film formation according to claim 1 or 2, wherein the organic solvent having no hydroxyl group has a boiling point of 6 〇 18 (at a pressure of atmospheric pressure) (rc. 4) a method for producing a film, the method The vapor containing bis(pentane-2, dodecanoate) anhydrate obtained after gasification of the raw material for forming a film of any one of claims 3 to 3 is introduced onto the substrate, and the double is contained: The alkane 2'4-diacid)zinc anhydrate is decomposed by steam and/or chemically reacted to form a film containing a radical. 122675.doc