JP5063074B2 - Thin film forming raw material, thin film manufacturing method, and zinc compound - Google Patents

Description

  The present invention relates to a raw material for forming a thin film containing a zinc compound having a specific structure, a method for producing a thin film using the raw material, and a novel zinc compound used for the raw material for forming a thin film.

  A thin film containing zinc has various properties such as optical properties, electrical properties, and catalytic activity, and is used as a member of electronic components and optical components.

  Examples of the method for producing the above thin film include flame deposition, sputtering, ion plating, MOD such as coating pyrolysis and sol-gel, and chemical vapor deposition. It has many advantages such as being excellent in performance, suitable for mass production, and capable of hybrid integration. Therefore, chemical vapor deposition including ALD (Atomic Layer Deposition) (hereinafter simply referred to as CVD) Is the optimal manufacturing process.

  In the CVD method, many β-diketone complexes have been studied from the viewpoint of stability and safety as precursors for supplying zinc atoms to a thin film. For example, Patent Documents 1 and 2 disclose CVD using bis (pentane-2,4-dionato) zinc, and Non-Patent Document 1 discloses bis (2,2,6,6-tetramethylheptane). A method using -3,5-dione) zinc has been reported. In Patent Document 3, bis (octane-2,4-dionato) zinc and bis (2,2-dimethyl-6-ethyldecane-3,5-dionato), which are liquid bis (β-diketonato) zinc at 25 ° C. Zinc is disclosed.

  A property required for a compound (precursor) suitable for a raw material used in the CVD method is that a thin film is easily formed by a chemical reaction such as oxidation during the deposition of the thin film. Although the above β-diketone complex of zinc is a stable compound and is superior in terms of supply of the CVD process, the reactivity during the deposition of the thin film is not always satisfactory.

Non-Patent Documents 2 and 3 disclose the production of zinc oxide thin films by CVD using alkylzinc alkoxides. Specific compounds include MeZn (OPr ⁱ ), EtZn (OPr ⁱ ), MeZn ( OBu ^t) have been disclosed. These alkylzinc alkoxides are described as being more stable and easier to handle than dialkylzinc.
However, the alkylzinc alkoxide described here is a solid having a high melting point and is not sufficiently volatile, so that it is not always satisfactory as a raw material for forming a thin film, particularly as a raw material for CVD.

In Non-Patent Document 4, three molecules of RZnO · C ₂ H ₄ · NMe ₂ are associated (RZnO · C ₂ H ₄ · NMe ₂ ) ₃ (R = Me, Et), MeZnOCH ₂ · CH ₂ OMe. Tetramolecularly associated (MeZnOCH ₂ · CH ₂ OMe) ₄ is disclosed, but the use of this as a raw material for forming a thin film is not disclosed.

Japanese Patent Publication No. 6-64738 (particularly [Claim 9]) JP 2003-236376 A (particularly [Example]) Japanese Patent Laying-Open No. 2005-350423 (particularly [Claim 1] to [Claim 6]) Microelectron. Eng., 29 (1-4), 169-72 (1995) J.MATER.CHEM., 1994,4 (8), 1249-1253 Electrochemical Society Proceedings Volume 2003-08 1123-1130 J. Chem. Soc. (A), 1966, 1064-1069

  The problem to be solved by the present invention is to impart properties such as suitable reactivity and volatility to a precursor that supplies zinc to the thin film, and is particularly suitable for the production of a thin film by oxidation in a CVD method. It is to impart properties such as reactivity and volatility.

  As a result of repeated studies, the present inventors have found that a zinc compound having a specific structure can solve the above problems, and have reached the present invention.

  That is, this invention solves the said subject by providing the raw material for thin film formation containing the zinc compound represented by following General formula (1).

（式中、Ｒ¹は、炭素数１〜４のアルキル基を表し、Ｒ²及びＲ³は、各々独立して水素原子または炭素数１〜４のアルキル基を表し、Ｒ⁴は炭素数１〜４のアルキル基を表し、Ｒ⁵は、炭素数１〜４のアルキル基または−ＣＨ₂−ＣＨ₂−ＮＲ⁶Ｒ⁷を表し、Ｒ⁶及びＲ⁷は炭素数１〜４のアルキル基を表し、Ｘは、酸素原子または窒素原子を表し、ｍは、Ｘが酸素原子の場合は０であり、Ｘが窒素原子の場合は１である。）

(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to ⁴ carbon atoms, and R ⁴ represents 1 carbon atom. R 4 represents an alkyl group having 1 to 4 carbon atoms, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or —CH ₂ —CH ₂ —NR ⁶ R ⁷ , and R ⁶ and R ⁷ represent an alkyl group having 1 to 4 carbon atoms. X represents an oxygen atom or a nitrogen atom, and m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom.)

  The present invention also provides a method for producing a thin film in which a vapor containing a zinc compound obtained by vaporizing the thin film forming raw material is introduced into a substrate, and this is decomposed and / or chemically reacted to form a thin film on the substrate. Is to provide.

Further, in the above general formula (1), at least one of R ² and R ³ is to provide a novel zinc compound is an alkyl group having 1 to 4 carbon atoms.

According to the present invention, a thin film forming raw material having suitable properties such as reactivity and volatility can be provided as a CVD raw material.
Moreover, since the melting point and volatility of the zinc compound contained in the thin film forming raw material of the present invention differ depending on the structure, the thin film forming raw material that matches the thin film forming process can be selected.

The zinc compound represented by the general formula (1) used for the raw material for forming a thin film of the present invention exhibits a reactivity suitable as a precursor for a thin film, and is particularly suitable for forming a thin film by oxidation.
Of these compounds, those in which at least one of R ² and R ³ is an alkyl group having 1 to 4 carbon atoms are novel compounds. In addition, the zinc compound represented by the general formula (1) according to the present invention may have a stereoisomer, and X or NR ⁶ R ⁷ may be coordinated in the molecule to form a ring structure. In some cases, molecules associate to form an aggregate.
For example, as an association state of the zinc compound represented by the general formula (1) according to the present invention, for example, as an example in which two molecules are associated, the following general formula (1-1) or (1-2) is used. The structure represented by the following general formula (1-3) is mentioned as an example in which three molecules are associated.

（式中、Ｒ¹〜Ｒ⁵、Ｘ及びｍは、上記一般式（１）と同様である。）

(In formula, R < ¹ > -R < ⁵ >, X, and m are the same as that of the said General formula (1).)

  The zinc compound according to the present invention is not distinguished by these stereoisomers, coordination bodies, and aggregates, but includes any of them. In the following, it is shown representatively in the form without intramolecular coordination and association.

In the general formula (1), examples of the alkyl group having 1 to 4 carbon atoms represented by R ^{1 to} R ⁷ include methyl, ethyl, propyl, isopropyl, butyl, secondary butyl, tertiary butyl, and isobutyl. .

  Specific examples of the zinc compound represented by the general formula (1) according to the present invention include the following compound Nos. 1-No. 36.

Among these compounds, a zinc compound in which at least one of R ² and R ³ is an alkyl group having 1 to 4 carbon atoms in the above general formula (1) (in the above specific example, compound No. 7 to No. 15, No. 22 to No. 30, No. 32, No. 33, No. 35 and No. 36) are the novel zinc compounds of the present invention. Among these novel zinc compounds, in the above general formula (1), X is a nitrogen atom, R ⁴ is a methyl group or an ethyl group, and R ⁵ is a methyl group or —CH ₂ —CH ₂ —NR ⁶ R. is ^7, zinc compound R ⁶ and R ⁷ is a methyl group or an ethyl group (in the above specific example, No.22~No.26, No.28~No.30, No.32, No.33 , No. 35 and No. 36) are preferred.

  The zinc compound represented by the general formula (1) has different melting point and volatility depending on its structure. When used as a thin film forming raw material, the zinc compound has a melting point and volatility suitable for the thin film forming process. A compound may be selected and used.

  The zinc compounds represented by the general formula (1) have volatility that can be used for the CVD process, although there are differences in the degree. Preferable materials for CVD are those that easily volatilize, those that are solid but have a low melting point (120 ° C. or lower), or those that are liquid at room temperature. Further, when the zinc compound is hard to volatilize, is solid but has a low melting point (120 ° C. or less), is liquid at room temperature, or has high solubility in organic solvents, it is used as a raw material for MOD. Are also preferably used.

Among the zinc compounds represented by the general formula (1), those in which R ² and R ³ are hydrogen atoms, X is an oxygen atom, and R ⁴ is methyl (in the above specific examples, the compound No. .1 to No. 6) are solid but have a low melting point or are liquid at room temperature. For example, Compound No. 1 and no. 2 has the characteristic of being liquid at room temperature.

Among the zinc compounds represented by the general formula (1), at least one of R ² and R ³ is an alkyl group having 1 to 4 carbon atoms. 7 to No. 15, No. 22 to No. 30, No. 32, No. 33, No. 35, and No. 36) have characteristics that are more likely to volatilize than those in which both are hydrogen atoms.

  Among the zinc compounds represented by the general formula (1), those in which X is a nitrogen atom (in the above specific examples, compounds No. 16 to No. 36) are those in which X is an oxygen atom. Compared with, it has the characteristic that it is easy to evaporate.

Among the zinc compounds represented by the general formula (1), those in which X is nitrogen and R ⁵ is —CH ₂ —CH ₂ —NR ⁶ R ⁷ (in the above specific example, the compound No. .31 to No. 36) have a particularly low melting point (100 ° C. or less).

Among the zinc compounds represented by the general formula (1), those in which R ¹ is methyl or ethyl (in the above specific examples, compounds No. 1, No. 2, No. 7 to No. 17). , No. 22 to No. 36) have characteristics that are easily volatilized.

The zinc compound represented by the general formula (1) according to the present invention is not particularly limited by the production method, and is produced by applying a known reaction. As manufacturing methods include a method of reacting an alcohol represented by (R ¹⁾ HO-CR ² in dialkylzinc represented by _{^{2 Zn R 3 CH 2 XR 4}} (R 5) m.

  The thin film forming raw material of the present invention is a thin film precursor made of the zinc compound represented by the general formula (1), and the form thereof is a method for producing a thin film to which the thin film forming raw material is applied ( For example, the MOD method such as a coating pyrolysis method or a sol-gel method, or a CVD method including an ALD method) is appropriately selected. The thin film forming raw material of the present invention is particularly useful as a CVD raw material having a step of vaporizing a zinc compound due to its physical properties.

  When the thin film forming raw material of the present invention is a chemical vapor deposition (CVD) raw material, the form thereof is appropriately selected depending on the method of transport and supply of the CVD method used.

  As the transport and supply method described above, the CVD raw material is vaporized by heating and / or depressurizing in the raw material container, and introduced into the deposition reaction section together with a carrier gas such as argon, nitrogen, and helium used as necessary. There is a gas transport method and a liquid transport method in which a CVD raw material is transported to a vaporization chamber in a liquid or solution state, vaporized by heating and / or decompressing in the vaporization chamber, and introduced into a deposition reaction section. In the case of the gas transport method, the zinc compound itself represented by the general formula (1) is a raw material for CVD, and in the case of the liquid transport method, the zinc compound itself represented by the general formula (1) or the zinc compound is used. A solution dissolved in an organic solvent becomes a raw material for CVD.

  In the multi-component CVD method for producing a multi-component thin film, a CVD raw material is vaporized and supplied independently for each component (hereinafter sometimes referred to as a single source method), a multi-component raw material There is a method of vaporizing and supplying a mixed raw material prepared by mixing in advance with a desired composition (hereinafter sometimes referred to as a cocktail sauce method). In the case of the cocktail sauce method, a mixture of only the metal compound represented by the general formula (1) or a mixed solution obtained by adding an organic solvent medium to these mixtures, the metal compound represented by the general formula (1) and other precursors Or a mixture solution obtained by adding an organic solvent to these mixtures is a raw material for CVD.

  The organic solvent used for the above-mentioned CVD raw material is not particularly limited and a known general organic solvent can be used. Examples of the organic solvent include: acetates such as ethyl acetate, butyl acetate and methoxyethyl acetate; ethers such as tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, dibutyl ether and dioxane Ketones such as methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, methylcyclohexanone; hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, Hydrocarbons such as toluene and xylene; 1-cyanopropane, 1-cyanobutane, 1- Hydrocarbons having a cyano group such as ananohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene Pyridine and lutidine, which are used alone or as a mixed solvent of two or more depending on the solubility of the solute, the relationship between the use temperature and boiling point, the flash point, etc. When these organic solvents are used, the total amount of the precursor components in the organic solvent is preferably 0.01 to 2.0 mol / liter, particularly 0.05 to 1.0 mol / liter. .

  Further, in the multi-component CVD method using the single source method or the cocktail source method, the other precursor used together with the zinc compound represented by the general formula (1) according to the present invention is not particularly limited. Well-known general precursors used for CVD raw materials can be used.

  The other precursor is one or more selected from the group consisting of compounds used as organic ligands such as alcohol compounds, glycol compounds, β-diketone compounds, cyclopentadiene compounds, and organic amine compounds. A compound with silicon, boron, phosphorus and a metal is mentioned. Metal species include group 1 elements such as lithium, sodium, potassium, rubidium and cesium, group 2 elements such as beryllium, magnesium, calcium, strontium and barium, scandium, yttrium and lanthanoid elements (lanthanum, cerium, praseodymium, neodymium, Promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium), group 3 elements such as actinoid elements, group 4 elements of titanium, zirconium, hafnium, group 5 elements of vanadium, niobium, tantalum , Chromium, molybdenum, tungsten group 6 elements, manganese, technetium, rhenium group 7 elements, iron, ruthenium, osmium group 8 elements, cobalt, rhodium, iridium Group 9 elements, nickel, palladium, platinum group 10 elements, copper, silver, gold group 11 elements, cadmium, mercury group 12 elements, aluminum, gallium, indium, thallium group 13 elements, germanium, tin, lead 14 group elements, arsenic, antimony, group 15 elements of bismuth, and group 16 elements of polonium.

  In the case of the single source method, the above-mentioned other precursors are preferably compounds having similar thermal decomposition and / or oxidative decomposition behavior, and in the case of the cocktail source method, the thermal decomposition and / or oxidative decomposition behavior is similar. In addition to these, those which do not cause alteration due to chemical reaction during mixing are preferred.

  In addition, the CVD raw material of the present invention may contain a nucleophilic reagent as needed to impart the stability of the zinc compound of the present invention and other precursors. Examples of the nucleophile include ethylene glycol ethers such as glyme, diglyme, triglyme and tetraglyme, 18-crown-6, dicyclohexyl-18-crown-6, 24-crown-8, dicyclohexyl-24-crown-8, Crown ethers such as dibenzo-24-crown-8, ethylenediamine, N, N′-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4,7,7-penta Polyamines such as methyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine and triethoxytriethyleneamine, cyclic polyamines such as cyclam and cyclen, pyridine, pyrrolidine and piperidy , Morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, thiazole, oxathiolane and other heterocyclic compounds, methyl acetoacetate, ethyl acetoacetate, Β-ketoesters such as acetoacetate-2-methoxyethyl or β-diketones such as acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3,5-heptanedione, and dipivaloylmethane These stabilizers are used in an amount of 0.1 to 10 moles, preferably 1 to 4 moles per mole of the precursor.

  The raw material for forming a thin film of the present invention contains as little impurities metal elements as possible, impurities such as impurity chlorine, and impurity organics other than the components constituting the thin film forming raw material. The impurity metal element content is preferably 100 ppb or less and more preferably 10 ppb or less for each element. The total amount is preferably 1 ppm or less, and more preferably 100 ppb or less. The total amount of impurity organic components is preferably 500 ppm or less, preferably 50 ppm or less, and more preferably 10 ppm or less. In addition, since moisture causes particles in the CVD raw material and particles generated by the CVD method, metal compounds, organic solvents, and nucleophilic reagents should be used as much moisture as possible before use to reduce their moisture content. Should be removed. The water content is preferably 10 ppm or less, and more preferably 1 ppm or less.

  In addition, the raw material for forming a thin film of the present invention can be used to reduce or prevent particle contamination of a thin film to be produced. In the particle measurement by a light scattering submerged particle detector in a liquid phase, The number of particles is preferably 100 or less, more preferably 1000 or less in 1 ml of the liquid phase, and more than 1000 particles in 1 ml of the liquid phase. More preferably, it is 100 or less.

  The method for producing a thin film of the present invention includes the zinc compound represented by the general formula (1) according to the present invention, vapor obtained by vaporizing another precursor used as necessary, and reactivity used as necessary. This is by a CVD method in which a gas is introduced onto the substrate and then a precursor is decomposed and / or reacted on the substrate to grow and deposit a thin film on the substrate. There are no particular restrictions on the method of transporting and supplying the raw material, the deposition method, the production conditions, the production apparatus, etc., and well-known general conditions and methods can be used.

  Examples of the reactive gas used as necessary include oxygen, ozone, nitrogen dioxide, nitric oxide, water vapor, hydrogen peroxide, formic acid, acetic acid, acetic anhydride, etc. Examples of reducing substances include hydrogen, and examples of those that produce nitrides include organic amine compounds such as monoalkylamines, dialkylamines, trialkylamines, and alkylenediamines, hydrazine, ammonia, and the like. A thing which manufactures a thing includes hydrogen sulfide.

  Examples of the transport and supply method include the gas transport method, the liquid transport method, the single source method, and the cocktail sauce method described above.

  In addition, the above deposition methods include thermal CVD in which a raw material gas or a raw material gas and a reactive gas are reacted only by heat to deposit a thin film, plasma CVD using heat and plasma, photo CVD using heat and light, heat Examples include optical plasma CVD using light and plasma, and ALD (Atomic Layer Deposition) in which the deposition reaction of CVD is divided into elementary processes and deposition is performed stepwise at the molecular level.

  Moreover, as said manufacturing conditions, reaction temperature (substrate temperature), reaction pressure, a deposition rate, etc. are mentioned. About reaction temperature, 160 degreeC or more which is the temperature which the said compound based on this invention fully reacts is preferable, and 250 to 800 degreeC is more preferable. The reaction pressure is preferably from atmospheric pressure to 10 Pa, more preferably from atmospheric pressure to 100 Pa. The combination of the deposition method and the reaction pressure is arbitrary, and low pressure thermal CVD, low pressure plasma CVD, low pressure light CVD, low pressure light plasma CVD, atmospheric pressure thermal CVD, atmospheric pressure plasma CVD, atmospheric pressure light CVD, and atmospheric pressure light plasma CVD. Can be mentioned. The deposition rate can be controlled by the raw material supply conditions (vaporization temperature, vaporization pressure), reaction temperature, and reaction pressure. When the deposition rate is large, the properties of the obtained thin film may be deteriorated. When the deposition rate is small, productivity may be problematic. Therefore, the deposition rate is preferably 0.5 to 5000 nm / min, and more preferably 1 to 1000 nm / min. In the case of ALD, the number of cycles is controlled so as to obtain a desired film thickness.

  Further, in the method for producing a thin film of the present invention, after the thin film is deposited, an annealing treatment may be performed to obtain better electrical characteristics, and a reflow process may be provided if step filling is necessary. . The temperature in this case is 500-1200 degreeC, and 600-1000 degreeC is preferable.

  The thin film produced by the method for producing a thin film of the present invention using the raw material for forming a thin film of the present invention can be prepared by appropriately selecting a precursor of other components, a reactive gas, and production conditions, so that a metal, an alloy, a sulfide, Desired types of thin films such as oxide ceramics, nitride ceramics, and glass can be obtained. The types of thin films produced include, for example, zinc, ZnSe, zinc oxide, zinc sulfide, zinc-indium composite oxide, lithium-added zinc oxide, zinc-added ferrite, lead-zinc composite oxide, lead-zinc-niobium composite. Oxides, bismuth-zinc-niobium composite oxides, barium-zinc-tantalum composite oxides, tin-zinc composite oxides, and the use of these thin films include, for example, transparent conductors, light emitters, phosphors , Photocatalyst, magnetic material, conductor, high dielectric material, ferroelectric material, piezoelectric material, microwave dielectric material, optical waveguide, optical amplifier, optical switch, electromagnetic wave shield, solar cell and the like.

  Hereinafter, the present invention will be described in more detail with examples, evaluation examples, and comparative examples. However, the present invention is not limited by the following examples.

Example 1 Compound No. 1 Preparation of 15 A reaction flask substituted with dry argon was charged with 50 ml of a hexane solution of 1.0 mol / liter of diethyl zinc, and 8.77 g of 3-ethoxymethyl-2,4-dimethyl-2-propanol and 50 ml of hexane were added thereto at room temperature. Was slowly added dropwise. Thereafter, the mixture was stirred overnight at room temperature in an argon atmosphere. Solvent removal was performed to obtain 9.7 g of a white solid. The obtained solid was analyzed as follows to confirm that it was the target product.
(analysis)
(1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP)
Carbon 49.5 mass% (theoretical value 53.8%), hydrogen 9.2 mass% (theoretical value 9.8%), zinc 24.3% mass (theoretical value 24.3%)
(2) ¹ H-NMR (solvent: heavy benzene)
A chart is shown in FIG.

Example 2 Compound No. Preparation of No. 23 A reaction flask substituted with dry argon was charged with 50 ml of a 1.0 mol / liter hexane solution of dimethylzinc, and a mixture of 5.86 g of 1-dimethylamino-2-methyl-2-propanol and 50 ml of hexane at room temperature. Was slowly added dropwise. Thereafter, the mixture was stirred overnight at room temperature in an argon atmosphere. Solvent removal was performed to obtain 6.9 g of a white solid. The obtained solid was analyzed as follows to confirm that it was the target product.
(analysis)
(1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP)
Carbon 42.7 mass% (theoretical value 42.77%), hydrogen 8.5 mass% (theoretical value 8.72%), nitrogen 6.7 mass% (theoretical value 7.12%), zinc 31.5 mass% % (Theoretical value 33.25%)
(2) ¹ H-NMR (solvent: heavy benzene)
A chart is shown in FIG.

Example 3 Compound No. Preparation of No. 24 A reaction flask substituted with dry argon was charged with 50 ml of a hexane solution of diethyl zinc 1.0 mol / liter, and a mixture of 5.16 g of 1-dimethylamino-2-propanol and 5050 ml of hexane was slowly added dropwise thereto at room temperature. . Thereafter, the mixture was stirred overnight at room temperature in an argon atmosphere. Solvent removal was performed to obtain 7.7 g of a transparent solid. The obtained solid was analyzed as follows to confirm that it was the target product.
(analysis)
(1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP)
Carbon 42.7 mass% (theoretical value 42.77%), hydrogen 8.5 mass% (theoretical value 8.72%), nitrogen 6.8 mass% (theoretical value 7.12%), zinc 32.0 mass% % (Theoretical value 33.25%)
(2) ¹ H-NMR (solvent: heavy benzene)
A chart is shown in FIG.

Example 4 Compound No. Preparation of 25 A reaction flask substituted with dry argon was charged with 50 ml of a hexane solution of diethyl zinc 1.0 mol / liter, and a mixture of 5.86 g of 1-dimethylamino-2-methyl-2-propanol and 50 ml of hexane at room temperature. Was slowly added dropwise. Thereafter, the mixture was stirred overnight at room temperature in an argon atmosphere. Solvent removal was performed to obtain 7.3 g of a white solid. About the obtained solid, the following analysis was conducted and it confirmed that it was the target object.
(analysis)
(1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP)
Carbon 44.9 mass% (theoretical value 45.6%), hydrogen 8.7 mass% (theoretical value 9.1%), nitrogen 6.2 mass% (theoretical value 6.6%), zinc 30.3 mass% % (Theoretical value 31.0%)
(2) ¹ H-NMR (solvent: heavy benzene)
A chart is shown in FIG.

Example 5 Compound no. Preparation of No. 33 A reaction flask substituted with dry argon was charged with 50 ml of a 1.0 mol / liter hexane solution of dimethylzinc, and 1-[(2-dimethylamino-ethyl) -methylamino] -2-methyl-2 was added thereto at room temperature. -A solvent mixture of 8.72 g of propanol and 50 ml of hexane was slowly added dropwise. And after completion | finish of dripping, it stirred at normal temperature overnight in argon atmosphere. Then, a hexane solvent was removed, and the residue was distilled under reduced pressure to obtain 11.3 g of a white solid from a 0.4 Torr / 137 ° C. fraction. About the obtained substance, the following analysis was conducted and it confirmed that it was the target object.
(analysis)
(1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP)
Carbon 46.6% by mass (theoretical value 47.35%), hydrogen 9.1% by mass (theoretical value 9.54%), nitrogen 10.8% by mass (theoretical value 11.04%), zinc 25.5% by mass % (Theoretical value: 25.77%)
(2) ¹ H-NMR (solvent: heavy benzene)
A chart is shown in FIG.

Example 6 Compound no. Preparation of 36 A reaction flask substituted with dry argon was charged with 150 ml of a hexane solution of 1.0 mol of diethyl zinc, and 1-[(2-dimethylamino-ethyl) -methylamino] -2-methyl-2-propanol was added thereto at room temperature. A mixed solvent of 26.14 g and hexane 80 ml was slowly added dropwise. And after completion | finish of dripping, it stirred at normal temperature overnight in argon atmosphere. Then, a hexane solvent was removed, and the residue was distilled under reduced pressure to obtain 3.8 g of a white solid from a 0.37 Torr / 143 ° C. fraction. About the obtained solid, the following analysis was conducted and it confirmed that it was the target object.
(analysis)
(1) Elemental analysis (CHN: CHN analyzer, metal analysis: ICP)
Carbon 48.5 mass% (theoretical value 49.3%), hydrogen 9.3 mass% (theoretical value 9.8%), nitrogen 9.8 mass% (theoretical value 10.5%), zinc 24.1 mass% % (Theoretical value 24.4%)
(2) ¹ H-NMR (solvent: heavy benzene)
A chart is shown in FIG.

[Evaluation Example 1] Evaluation of liquid or low melting point zinc compound Since the liquid or melting point is low, compound No. 1 which is a zinc compound that easily changes phase from liquid to gas. 2, No. 15, no. 33, no. 36, bis (octane-2,4-dionato) zinc (Comparative Compound 1), bis (2,2-dimethyl-6-ethyldecane-3,5-dionato) zinc (Comparative Compound 2) The vapor temperature near the liquid surface was fixed and measured, and the vapor temperature was measured at four points by changing the pressure of the system, and the vapor pressure equation was obtained from the Clausius-Clapeyron plot. The vapor pressure was calculated, and the oxidative degradation was evaluated by TG measurement with the sample amounts shown in Table 1 under the conditions of oxygen 100 ml / min and 10 ° C./min. The balance was ZnO, and the evaluation was performed based on the ratio (%) with respect to the theoretical value in the case where all of the samples were oxides.

  From the above results, the compound No. which is the zinc compound according to the present invention is shown. 2, No. 15, no. 33 and no. It was confirmed that 36 has a higher vapor pressure and better oxidative decomposability than Comparative Compounds 1 and 2.

[Evaluation Example 2] Evaluation of solid zinc compound 23, no. 24 and no. 25 and CH ₃ —CH ₂ —Zn—OCH (CH ₃ ) ₂ (Comparative Compound 3) were measured for TG-DTA. The measurement conditions were Ar 100 ml / min, 10 ° C./min temperature increase, and the measurement sample amounts are shown in Table 2. The 50% weight loss temperature is shown in Table 2.

  From Table 2, compound No. which is a zinc compound according to the present invention is shown. 23, no. 24 and no. No. 25 was confirmed to have better volatility characteristics than Comparative Compound 3, and better thermal stability in an inert atmosphere.

[Example 7] Production of zinc oxide thin film 1
A zinc oxide thin film was manufactured on a sapphire substrate under the following conditions using the CVD apparatus shown in FIG. About the manufactured thin film, the film thickness and film | membrane composition were confirmed with the fluorescent X ray.
(Production conditions)
Zinc CVD raw material: Compound No. 2. Source temperature: 120 ° C., source pressure: 500-1000 Pa, carrier gas: argon 150 sccm, oxidizing gas: oxygen 1000 sccm, reaction pressure 600 Pa, reaction temperature (base temperature): 500 ° C., film formation time: 60 minutes.
(result)
Film thickness: 496 nm, film composition: zinc oxide

[Example 8] Production of zinc oxide thin film 2
A zinc oxide thin film was manufactured on a sapphire substrate under the following conditions using the CVD apparatus shown in FIG. About the manufactured thin film, the film thickness and film | membrane composition were confirmed with the fluorescent X ray.
(Production conditions)
Zinc CVD raw material: Compound No. 33, source temperature: 120 ° C., source pressure: 500-1000 Pa, carrier gas: argon 150 sccm, oxidizing gas: oxygen 1000 sccm, reaction pressure 600 Pa, reaction temperature (base temperature): 500 ° C., film formation time: 60 minutes.
(result)
Film thickness: 1325 nm, film composition: zinc oxide

[Example 9] Production of zinc oxide thin film 3
A zinc oxide thin film was manufactured on the sapphire substrate under the following conditions using the CVD apparatus shown in FIG. About the manufactured thin film, the film thickness and film | membrane composition were confirmed with the fluorescent X ray.
(Production conditions)
Zinc CVD raw material: Compound No. 23, 0.25 mol / kg ethylcyclohexane solution, raw material flow rate: 0.4 sccm, vaporizing chamber temperature; 220 ° C., vaporizer pressure; 800 Pa, carrier gas; argon 150 sccm, oxidizing gas: oxygen 1000 sccm, reaction pressure to 800 Pa, Reaction temperature (base temperature): 500 ° C., film formation time: 60 minutes.
(result)
Film thickness: 1735 nm, film composition: zinc oxide

  The novel zinc compound of the present invention is used as a raw material for forming a thin film by a CVD method having a vaporization step, as well as a raw material for forming a thin film by a MOD method such as a coating pyrolysis method or a sol-gel method, an organic synthesis catalyst, a polymer compound It can be used as a synthesis catalyst.

1 shows a ¹ H-NMR chart of the zinc compound of the present invention (Compound No. 15) obtained in Example 1. FIG. 2 shows the ¹ H-NMR chart of the zinc compound of the present invention (Compound No. 23) obtained in Example 2. 3 shows a ¹ H-NMR chart of the zinc compound of the present invention (Compound No. 24) obtained in Example 3. 4 shows a ¹ H-NMR chart of the zinc compound of the present invention (Compound No. 25) obtained in Example 4. FIG. 5 shows a ¹ H-NMR chart of the zinc compound of the present invention (Compound No. 33) obtained in Example 5. FIG. 6 shows a ¹ H-NMR chart of the zinc compound of the present invention (Compound No. 36) obtained in Example 6. FIG. 7 is a schematic diagram showing a CVD apparatus used in the thin film manufacturing method of the present invention used in Examples 7 and 8. FIG. 8 is a schematic diagram showing a CVD apparatus used in the thin film manufacturing method of the present invention used in Example 9.

Claims (9)

A raw material for forming a thin film comprising a zinc compound represented by the following general formula (1).

(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to ⁴ carbon atoms, and R ⁴ represents 1 carbon atom. R 4 represents an alkyl group having 1 to 4 carbon atoms, R ⁵ represents an alkyl group having 1 to 4 carbon atoms or —CH ₂ —CH ₂ —NR ⁶ R ⁷ , and R ⁶ and R ⁷ represent an alkyl group having 1 to 4 carbon atoms. X represents an oxygen atom or a nitrogen atom, and m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom.) The raw material for forming a thin film according to claim 1, wherein, in the general formula (1), R ² and R ³ are hydrogen atoms, X is an oxygen atom, and R ⁴ is a methyl group. The raw material for forming a thin film according to claim 1, wherein in the general formula (1), at least one of R ² and R ³ is an alkyl group having 1 to 4 carbon atoms.   The raw material for forming a thin film according to claim 1 or 3, wherein, in the general formula (1), X is a nitrogen atom. The raw material for forming a thin film according to claim 4, wherein in the general formula (1), R ⁵ is —CH ₂ —CH ₂ —NR ⁶ R ⁷ . In the general formula (1), material for thin film formation according to any one of claims 1 to 5 R ¹ is a methyl group or an ethyl group. The vapor containing the zinc compound obtained by vaporizing the thin film-forming material according to any one of claims 1 to 6 is introduced into the substrate, a thin film degradation and / or chemical reacted with the substrate to which A method for producing a thin film to be formed. In lower following general formula (1), a zinc compound at least one of R ² and R ³ is an alkyl group having 1 to 4 carbon atoms.

(In the formula, R ¹ represents an alkyl group having 1 to 4 carbon atoms, R ² and R ³ each independently represents a hydrogen atom or an alkyl group having 1 to ⁴ carbon atoms , and R ⁴ represents 1 carbon atom. R 4 represents an alkyl group having 1 to 4 carbon atoms , R ⁵ represents an alkyl group having 1 to 4 carbon atoms or —CH ₂ —CH ₂ —NR ⁶ R ⁷ , and R ⁶ and R ⁷ represent an alkyl group having 1 to 4 carbon atoms. X represents an oxygen atom or a nitrogen atom, and m is 0 when X is an oxygen atom, and 1 when X is a nitrogen atom.) In the above general formula (1), X is a nitrogen atom, R ⁴ is a methyl group or an ethyl group, R ⁵ is a methyl group or —CH ₂ —CH ₂ —NR ⁶ R ⁷ , R ⁶ and The zinc compound according to claim 8, wherein R ⁷ is a methyl group or an ethyl group.

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