JP2011106008A - Raw material for chemical vapor deposition and ruthenium compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a raw material for chemical vapor deposition, containing a (1,5-cyclooctadiene)(η<SP>6</SP>-arene)ruthenium compound which has improved thermostability and is a liquid in a room temperature range. <P>SOLUTION: The (1,5-cyclooctadiene)(η<SP>6</SP>-arene)ruthenium compound shown by general formula (1) (wherein R<SP>1</SP>is a hydrogen atom or a methyl group; R<SP>2</SP>is a methyl group or an ethyl group when R<SP>1</SP>is the hydrogen atom and R<SP>2</SP>is the methyl group when R<SP>1</SP>is the methyl group) is used as the raw material for chemical vapor deposition. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a raw material for chemical vapor deposition comprising a (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound having a specific structure and a novel ruthenium compound.

  Ruthenium-containing thin films such as ruthenium and ruthenium oxide are mainly useful as electrode materials for electronic devices because they can be dry-etched. As a method for forming such a ruthenium-containing thin film, a chemical vapor deposition method (hereinafter referred to as a CVD method) or an atomic layer deposition method (hereinafter referred to as an ALD method) is excellent in composition controllability and step coverage and suitable for mass production. In addition, it has many advantages such as being capable of hybrid integration, which is effective.

  In the CVD method and ALD method, various volatile ruthenium compounds are used as precursors for supplying ruthenium to the thin film, and cyclic unsaturated hydrocarbons such as cyclopentadiene, cyclooctadiene, and arene are used as organic ligands. Various ruthenium compounds have been reported.

  For example, Non-Patent Document 1 discloses a MOCVD method using (1,5-octadiene) (toluene) as a method for producing a ruthenium thin film at a low temperature. Further, Patent Document 1 discloses that (1,5-cyclooctadiene) (1) which decomposes at 240 ° C. or less as an additive for shortening incubation in a CVD method using bis (ethylcyclopentadienyl) ruthenium. , 3,5-cyclooctatriene) ruthenium, (1,5-cyclooctadiene) (1,3,5-cycloheptatriene) ruthenium, (toluene) (1,5-cyclooctadiene) ruthenium Yes.

  Ruthenium compounds containing cyclic unsaturated hydrocarbons as organic ligands are known as polymers and catalysts for organic synthesis. Patent Document 2 discloses (η-cyclooctadiene) (η-cyclooctatriene) ruthenium, (η-benzene) (η-1,3) as a catalyst for the method of producing 2-hexene-1,6-dial. -Cyclohexadiene) ruthenium, bis (ethene) (η-hexamethylbenzene) ruthenium, (η-cyclooctadiene) (η-hexamethylbenzene) ruthenium, (η-benzene) (η-cyclooctadiene) ruthenium, η-benzene) (η-norbornadiene) ruthenium, (η-cyclooctadiene) (η-1,3,5-trimethylbenzene) ruthenium, (η-norbornadiene) (η-1,3,5-trimethylbenzene) ruthenium , (Η-cyclooctadiene) (η-toluene) ruthenium, (η-cyclooctadiene) (η-xylene) ruthe (Η-cyclooctadiene) (η-cycloheptatriene) ruthenium, (η-cycloheptadiene) (η-cycloheptatriene) ruthenium, bis (cyclohexadienyl) ruthenium, bis (hexamethylbenzene) ruthenium It is disclosed.

  However, (1,5-octadiene) (toluene) ruthenium is low-temperature decomposable and can be formed at a low temperature, but its thermal stability is poor, and CVD and ALD methods (hereinafter referred to as the present invention). In the chemical vapor deposition method, there are problems such as generation of particles. In addition, (1,5-octadiene) (toluene) ruthenium is a solid at room temperature.

JP 2007-169725 A (particularly claim 3) JP-A-5-97759 (particularly [0009] paragraph)

Chem. Vap. Deposition 2005, 11, No. 2, p99-105

An object of the present invention is to provide a raw material for chemical vapor deposition comprising a (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound having improved thermal stability. Another object of the present invention is to provide a chemical vapor deposition raw material containing a (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound which is liquid at room temperature.

As a result of repeated studies, the present inventors have achieved the above object by using a (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound having a specific structure as a raw material for chemical vapor deposition. The present invention has been found out.

The present invention provides a raw material for chemical vapor deposition comprising a (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound represented by the following general formula (1).

（式中、Ｒ¹は、水素原子又はメチル基を表し、Ｒ²は、Ｒ¹が水素原子の場合は、メチル基又はエチル基を表し、Ｒ¹がメチル基の場合は、メチル基を表す。）

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group when R ¹ is a hydrogen atom, and represents a methyl group when R ¹ is a methyl group. .)

The present invention also provides a novel (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound represented by the following formula (2).

According to the present invention, the (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound having improved thermal stability, and (1,5-cyclooctadiene) (η ⁶ − It is possible to provide a raw material for chemical vapor deposition containing an arene) ruthenium compound.

1 shows a ¹ H-NMR chart of a ruthenium compound (Compound No. 1) according to the present invention obtained in Example 1. FIG. 2 shows the ¹ H-NMR chart of the ruthenium compound (Compound No. 2) obtained in Example 2 according to the present invention. 3 shows the ¹ H-NMR chart of the ruthenium compound (Compound No. 3) according to the present invention obtained in Example 3. FIG. FIG. 4 is a schematic view showing an example of a CVD apparatus used for forming a ruthenium thin film according to the present invention.

  The raw material for chemical vapor deposition of the present invention contains the ruthenium compound represented by the general formula (1) as a thin film precursor. Specifically, the ruthenium compound represented by the general formula (1) is compound No. 1 represented by the following formula. 1, compound no. 2 and compound no. 3 (compound represented by the above formula (2)).

  Among the ruthenium compounds, the compound No. 1 and compound no. 2 has particularly good thermal stability.

  Among the ruthenium compounds, the compound No. 3 is a novel compound that is liquid at room temperature. Compound No. 3 can be used as various synthetic catalysts and polymerization catalysts in addition to the precursor of the chemical vapor deposition raw material.

These ruthenium compounds can be produced by applying known chemical reactions. As a production method, for example, ruthenium trichloride is added to and reacted with a mixed system of zinc, 1,5-cyclooctadiene and methanol to obtain an intermediate (1,5-cyclooctadiene) (1,3,3). A method for producing a ruthenium compound according to the present invention is prepared by synthesizing 5-cyclooctatriene) ruthenium, adding η ⁶ -arene thereto, and stirring in the presence of hydrogen.

  The raw material for chemical vapor deposition of the present invention contains the above-mentioned ruthenium compound, and the form thereof is appropriately selected according to a method such as a transport supply method of the chemical vapor deposition method used.

  As a method for transporting and supplying the chemical vapor deposition raw material of the present invention (raw material introduction step), the chemical vapor deposition raw material is vaporized by heating and / or depressurizing in the raw material container and used as necessary. A gas transport method for introducing into a deposition reaction section together with a carrier gas such as argon, nitrogen, helium, etc., transporting a raw material for chemical vapor deposition to a vaporization chamber in a liquid or solution state, and heating and / or decompressing in the vaporization chamber. And a liquid transport method in which the gas is vaporized and introduced into the deposition reaction part. In the case of the gas transport method, the ruthenium compound itself is a raw material for chemical vapor deposition, and in the case of the liquid transport method, the ruthenium compound itself or a solution obtained by dissolving this in an organic solvent is a raw material for chemical vapor deposition. It becomes.

  In the multi-component chemical vapor deposition method for forming a multi-component thin film, a method for vaporizing and supplying a chemical vapor deposition raw material independently for each component (hereinafter referred to as a single source method), a multi-component method, and the like. There is a method of vaporizing and supplying a mixed raw material prepared by mixing raw materials in a desired composition in advance (hereinafter referred to as a cocktail sauce method). In the case of the cocktail sauce method, a mixture of the ruthenium compound represented by the general formula (1) and another precursor or a mixed solution obtained by adding an organic solvent to these mixtures is a raw material for chemical vapor deposition.

  In addition, the ruthenium compound represented by the general formula (1) is added to a raw material for chemical vapor deposition mainly composed of another ruthenium compound having a structure different from that of the ruthenium compound represented by the general formula (1). The chemical vapor deposition material of the present invention is also used in a necessary amount (preferably 0.0001 to 0.05 mole part of the ruthenium compound represented by the general formula (1) with respect to 1 mole part of the other ruthenium compound). It is. As one of such other ruthenium compounds, for example, bis (ethylcyclopentadiene) ruthenium described in Patent Document 1 (Japanese Patent Laid-Open No. 2007-169725) can be given.

  The organic solvent used for the chemical vapor deposition material of the present invention is not particularly limited and may be a well-known general organic solvent that does not react with the ruthenium compound according to the present invention. Examples of the organic solvent include acetates such as ethyl acetate, butyl acetate, and methoxyethyl acetate; methyl butyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dipropyl ketone, diisobutyl ketone, methyl amyl ketone, cyclohexanone, and methylcyclohexanone. Ketones such as hexane, cyclohexane, methylcyclohexane, dimethylcyclohexane, ethylcyclohexane, heptane, octane, toluene, xylene, etc .; tetrahydrofuran, tetrahydropyran, morpholine, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, Ethers such as dibutyl ether and dioxane; acetonitrile, 1-cyanopropane, 1-silane Cyanogens such as nobutane, 1-cyanohexane, cyanocyclohexane, cyanobenzene, 1,3-dicyanopropane, 1,4-dicyanobutane, 1,6-dicyanohexane, 1,4-dicyanocyclohexane, 1,4-dicyanobenzene Hydrocarbons having a group; organic amides such as N-methyl-2-pyrrolidinone, N-ethyl-2-pyrrolidinone, N-cyclohexyl-2-pyrrolidinone; pyridine and lutidine, which are soluble in solutes Depending on the relationship between operating temperature, boiling point, flash point, etc., it is used alone or as a mixture of two or more. When these organic solvents are used, the total amount of the precursor component containing the ruthenium compound according to the present invention in the organic solvent is 0.01 to 2.0 mol / liter, particularly 0.05 to 1.0 mol / liter. It is preferable to make it liter. The boiling point of the organic solvent used is preferably 60 ° C. or higher.

  The precursor other than the ruthenium compound represented by the general formula (1) is a group consisting of compounds used as organic ligands such as alcohol compounds, glycol compounds, β-diketone compounds, cyclopentadiene compounds, and organic amine compounds. Or a compound of one or more selected from the above and a metal element. Precursor 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, Group 3 elements such as neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, ruthenium) and actinoid elements; group 4 elements of titanium, zirconium, hafnium; vanadium, niobium, tantalum 5 Group elements; chromium, molybdenum, tungsten group 6 elements; manganese, technetium, rhenium group 7 elements; iron, ruthenium, osmium group 8 elements; cobalt, logistic Group 9 elements of nickel, palladium and platinum; Group 11 elements of copper, silver and gold; Group 12 elements of zinc, cadmium and mercury; Group 13 elements of aluminum, gallium, indium and thallium; Group 14 elements of silicon, germanium, tin, and lead; Group 15 elements of arsenic, antimony, and bismuth; Group 16 elements of polonium.

  Examples of the alcohol compound used as the organic ligand include methanol, ethanol, propanol, isopropanol, butanol, 2-butanol, isobutanol, tertiary butanol, amyl alcohol, isoamino alcohol, and tertiary amino alcohol. Alkyl alcohols; 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2- (2-methoxyethoxy) ethanol, 2-methoxy-1-methylethanol, 2-methoxy-1,1-dimethylethanol, 2 Isopropoxy-1,1-dimethylethanol, 2-butoxy-1,1-dimethylethanol, 2- (2-methoxyethoxy) -1,1-dimethylethanol, 2-propoxy-1,1-diethylethanol, 2 -Second butoxy Ether alcohols such as 1,1-diethylethanol and 3-methoxy-1,1-dimethylpropanol; N, N-dimethylaminoethanol, 1,1-dimethylamino-2-propanol, 1,1-dimethylamino-2 -Dialkylamino alcohols such as methyl-2-propanol.

  Examples of the glycol compound used as the organic ligand include 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 2,4-hexanediol, and 1,2-propanediol. 1,3-propanediol, 2,4-hexanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,3-butanediol, 2, 4-butanediol, 2,2-diethyl-1,3-butanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-pentanediol, 2-methyl-1,3-propanediol 2-methyl-2,4-pentanediol, 2,4-hexanediol, 2,4-dimethyl-2,4-pentanediol and the like.

  Examples of the β-diketone compound used as the organic ligand include acetylacetone, hexane-2,4-dione, 5-methylhexane-2,4-dione, heptane-2,4-dione, 2- Methylheptane-3,5-dione, 5-methylheptane-2,4-dione, 6-methylheptane-2,4-dione, 2,2-dimethylheptane-3,5-dione, 2,6-dimethylheptane -3,5-dione, 2,2,6-trimethylheptane-3,5-dione, 2,2,6,6-tetramethylheptane-3,5-dione, octane-2,4-dione, 2, 2,6-trimethyloctane-3,5-dione, 2,6-dimethyloctane-3,5-dione, 2,2-dimethyl-6-ethyloctane-3,5-dione, 2,2,6,6 -Tetramethyl Kutan-3,5-dione, 2,9-dimethylnonane-4,6-dione, 2,2,6,6-tetramethyl-3,5-nonanedione, 2-methyl-6-ethyldecane-3,5- Alkyl-substituted β-diketones such as dione and 2,2-dimethyl-6-ethyldecane-3,5-dione; 1,1,1-trifluoropentane-2,4-dione, 1,1,1-trifluoro -5,5-dimethylhexane-2,4-dione, 1,1,1,5,5,5-hexafluoropentane-2,4-dione, 1,3-diperfluorohexylpropane-1,3-dione Fluorine-substituted alkyl β-diketones such as 1,1,5,5-tetramethyl-1-methoxyhexane-2,4-dione, 2,2,6,6-tetramethyl-1-methoxyheptane-3 , 5-dione, 2,2,6 - ether substituted β- diketones such as tetramethyl-1- (2-methoxyethoxy) heptane-3,5-dione can be cited.

  Examples of the cyclopentadiene compound used as the organic ligand include, for example, cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, propylcyclopentadiene, isopropylcyclopentadiene, butylcyclopentadiene, second butylcyclopentadiene, isobutylcyclopentadiene, And tertiary butylcyclopentadiene, dimethylcyclopentadiene, tetramethylcyclopentadiene, propyltetramethylcyclopentadiene, and the like.

  Examples of the organic amine compound used as the organic ligand include methylamine, ethylamine, propylamine, isopropylamine, butylamine, secondary butylamine, tertiary butylamine, isobutylamine, dimethylamine, diethylamine, dipropylamine, Examples include diisopropylamine, ethylmethylamine, propylmethylamine, isopropylmethylamine, and bis (trimethylsilyl) amine.

  Further, the chemical vapor deposition raw material of the present invention is required to provide stability to the ruthenium compound represented by the general formula (1) and other precursors (hereinafter also referred to as precursor components) as necessary. A nuclear reagent may be included. Examples of the nucleophilic reagent 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; pyridine, pyrrolidine, piperidine, morpholine, N-methylpyrrolidine, N-methylpiperidine, N-methylmorpholine, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, oxazole, Heterocyclic compounds such as thiazole and oxathiolane; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, and 2-methoxyethyl acetoacetate; acetylacetone, 2,4-hexanedione, 2,4-heptanedione, 3, - heptanedione, beta-diketones such as dipivaloylmethane and the like. Other nucleophilic reagents that impart stability to the precursor component include ethylenediamine, N, N′-tetramethylethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 1,1,4 , 7,7-pentamethyldiethylenetriamine, 1,1,4,7,10,10-hexamethyltriethylenetetramine, polyamines such as triethoxytriethyleneamine; and cyclic polyamines such as cyclam and cyclen. The amount of these nucleophilic reagents used is in the range of 0.05 mol to 10 mol, preferably 0.1 to 5 mol, relative to 1 mol of the precursor component.

  The raw material for chemical vapor deposition of the present invention is made to contain as little impurities metal elements as possible other than the components constituting it, impurity halogens such as impurity chlorine, and impurity organics as much as possible. The impurity metal element content is preferably 100 ppb or less for each element, more preferably 10 ppb or less, and the total amount is preferably 1 ppm or less, more preferably 100 ppb or less. In particular, when used as an electrode film, conductive film, or barrier layer for LSI, the content of alkali metal elements, alkaline earth metal elements, and related elements that affect the electrical characteristics of the obtained electrothin film may be reduced. is necessary. The impurity halogen content is preferably 100 ppm or less, more preferably 10 ppm or less, and still more preferably 1 ppm or less. The total amount of impurity organic components is preferably 500 ppm or less, more preferably 50 ppm or less, and still more preferably 10 ppm or less. In addition, since moisture causes generation of particles in the chemical vapor deposition raw material and generation of particles during thin film formation, each of the precursor component, organic solvent, and nucleophilic reagent reduces the water content. Therefore, it is better to remove moisture as much as possible before use. The moisture content of each of the precursor component, the organic solvent, and the nucleophilic reagent is preferably 10 ppm or less, and more preferably 1 ppm or less.

  Moreover, it is preferable that the chemical vapor deposition material of the present invention does not contain particles that are solid impurity particles as much as possible in order to reduce or prevent particle contamination of the thin film to be formed. Specifically, in the particle measurement by the light scattering liquid particle detector in the liquid phase, the number of particles larger than 0.3 μm is preferably 100 or less in 1 ml of the liquid phase, and larger than 0.2 μm. The number of particles is more preferably 1000 or less in 1 ml of the liquid phase, and the number of particles larger than 0.2 μm is further preferably 100 or less in 1 ml of the liquid phase.

  The method for producing a ruthenium thin film by chemical vapor deposition using the chemical vapor deposition raw material of the present invention vaporizes the ruthenium compound represented by the general formula (1) and other precursors used as necessary. Then, a reactive gas used as needed is introduced onto the substrate, and then the ruthenium compound and other precursor used as needed are decomposed and / or reacted on the substrate to form a desired thin film on the substrate. It grows and deposits on it. 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.

  As the reactive gas used as necessary, for example, for producing an oxide such as ruthenium oxide, oxygen, ozone, nitrogen dioxide, nitrogen monoxide, water vapor, hydrogen peroxide, which is an oxidizing gas, Examples include formic acid, acetic acid, acetic anhydride and the like, and those that produce metallic thin films such as ruthenium include hydrogen, which is a reducing gas, and those that produce nitrides such as ruthenium nitride include mono Examples thereof include organic amine compounds such as alkylamine, dialkylamine, trialkylamine, and alkylenediamine, hydrazine, ammonia, and nitrogen. These reactive gases may be mixed and used.

  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, as the above deposition method, the ruthenium compound (and other precursor gas) represented by the general formula (1) or the ruthenium compound (and other precursor gas) and the reactive gas are reacted only with heat to form a thin film. Thermal CVD to deposit, plasma CVD using heat and plasma, photo-CVD using heat and light, photo-plasma CVD using heat, light and plasma, the deposition reaction of CVD is divided into elementary processes and staged at the molecular level For example, an ALD method in which deposition is performed is used.

  Moreover, as said manufacturing conditions, reaction temperature (substrate temperature), reaction pressure, a deposition rate, etc. are mentioned. About reaction temperature, 100 degreeC or more which is the temperature which a ruthenium compound fully reacts is preferable, and 150-450 degreeC is more preferable. The reaction pressure is preferably from atmospheric pressure to 100 Pa, and when plasma is used, it is preferably from 50 to 100 Pa. The deposition rate can be controlled by the raw material supply conditions (vaporization temperature and pressure), reaction temperature and reaction pressure. If the deposition rate is large, the properties of the obtained thin film may be deteriorated. If the deposition rate is small, the productivity may be problematic. / Min is more preferable. In the case of the ALD method, the number of cycles is controlled so as to obtain a desired film thickness.

  For example, when the ruthenium thin film is formed by the ALD method, the precursor thin film is formed on the substrate by the ruthenium compound represented by the general formula (1) introduced into the deposition reaction part after the raw material introduction step described above. Is deposited (precursor thin film deposition step). At this time, heat may be applied by heating the substrate or heating the deposition reaction part. The precursor thin film formed in this step is the ruthenium compound thin film, or a thin film formed by decomposition and / or reaction of a part thereof, and has a composition different from the target thin film composition. The temperature at which this step is performed is preferably room temperature to 250 ° C.

  Next, unreacted precursor gas and by-produced gas are exhausted from the deposition reaction part (exhaust process). Ideally, unreacted precursor gas and by-produced gas are completely exhausted from the deposition reaction part, but it is not always necessary to exhaust completely. Examples of the exhaust method include a method of purging the system with an inert gas such as helium and argon, a method of exhausting the system by depressurizing the system, a method combining these, and the like. The degree of reduced pressure when the pressure is reduced is preferably 10 to 200 Pa.

  Next, a reducing gas is introduced into the deposition reaction part, and a ruthenium thin film is formed from the precursor thin film obtained in the previous precursor thin film forming step by the action of the reducing gas, the reducing gas, and heat (ruthenium thin film). Forming step). If the temperature at which heat is applied in this step is lower than 100 ° C., the ruthenium thin film may contain a large amount of impurities, and even if the temperature exceeds 500 ° C., the film quality of the obtained thin film is improved. Since there is no, 100-500 degreeC is preferable. The ruthenium compound according to the present invention has good reactivity, and a ruthenium thin film with good film quality can be obtained at 150 to 450 ° C.

  A thin film deposition by a series of operations including the above-described raw material introduction process, precursor thin film formation process, exhaust process, and ruthenium thin film formation process is defined as one cycle, and this cycle is repeated a plurality of times until a thin film having a required film thickness is obtained. May be. In this case, after one cycle is performed, the unreacted precursor gas, reducing gas, and further by-produced gas are exhausted from the deposition reaction portion, and then the next one cycle is performed in the same manner as in the exhaust process. It is preferable.

  In the formation of the ruthenium thin film by the ALD method, energy such as plasma, light, or voltage may be applied. The timing of applying these energies is not particularly limited. For example, when introducing a ruthenium precursor in the raw material introduction step, heating in the precursor thin film formation step, exhausting in the system in the exhaust step, ruthenium thin film formation step It may be at the time of introduction of the reducing gas, or during each of the above steps.

  In the thin film forming method according to the present invention, after thin film deposition, annealing may be performed in an inert atmosphere or a reactive gas atmosphere in order to obtain better film quality. May provide a reflow process. The temperature in this case is preferably 400 to 1200 ° C, particularly 500 to 800 ° C.

  Examples of the ruthenium-containing thin film formed and manufactured using the chemical vapor deposition raw material of the present invention include ruthenium, ruthenium oxide, and strontium ruthenate thin films. Applications of these thin films include electrode films, Electronic parts such as barrier films and electronic members can be mentioned.

  Hereinafter, the present invention will be described in more detail with examples and evaluation examples. However, the present invention is not limited by the following examples. In the text, “part” or “%” is based on mass unless otherwise specified.

Example 1 Compound No. 1 Production of Chemical Vapor Deposition Material Composed of 1 In an argon atmosphere, 1 mol part of ruthenium (III) chloride trihydrate is dissolved in methanol. Ruthenium (III) chloride prepared in advance to a slurry of 6.7 times (mass) zinc powder with 14 mol parts of 1,5-cyclooctadiene added to ruthenium (III) chloride trihydrate A methanol solution was added dropwise at room temperature, and the mixture was stirred at room temperature for 30 minutes. The reaction solution was filtered and the solvent was removed, followed by extraction with hexane, 10 mol parts of m-xylene was added, and the mixture was stirred at room temperature for 12 hours in a hydrogen atmosphere. After the reaction solution was filtered and concentrated, the crystals obtained by purification with alumina column chromatography (developing solvent hexane) were recrystallized with hexane to obtain the target compound No.1. 1 was obtained with a yield of 2.2%. About the obtained compound, the < ¹ > H-NMR measurement in the heavy benzene solvent was performed. The results are shown in FIG.

Example 2 Compound No. Production of Chemical Vapor Deposition Raw Material Composed of Compound No. 2 by the same procedure as in Example 1 except that m-xylene was changed to 1,2,4-trimethylbenzene. 2 was obtained in 1.3% yield. The result of ¹ H-NMR measurement in heavy benzene is shown in FIG.

Example 3 Compound No. Production of Chemical Vapor Deposition Raw Material Composed of Compound 3 According to the same procedure as in Example 1 except that m-xylene was changed to m-ethyltoluene and no recrystallization was performed. 3 was obtained in a yield of 7.1%. The result of ¹ H-NMR measurement in deuterium benzene is shown in FIG.

[Evaluation Examples 1 to 8] Evaluation of Volatility Compound Nos. Obtained in Examples 1 to 3 above. The chemical vapor deposition raw material consisting of 1 to 3 and the comparative compounds 1 to 5 represented by the following formulas were evaluated for melting point, volatility and thermal stability by TG-DTA. The measurement conditions were argon 100 ml / min, 10 ° C./min, and the volatility was evaluated at the temperature at which the weight reduction ended and became a constant weight, and the thermal stability was the residue at the constant temperature. The sample amount was 8 mg to 12 mg.

  From Table 1 above, Compound No. 1 and compound no. 2 was confirmed to show better thermal stability than any of Comparative Compounds 1 to 5, which are similar compounds. In addition, Compound No. 3 showed better thermal stability than Comparative Compounds 1, 2, 4, and 5, which are similar compounds, and was confirmed to show thermal stability equivalent to that of Comparative Compound 3. Compound No. 3 was confirmed to have better thermal stability and volatility than Comparative Compound 2 and Comparative Compound 4 which are liquids.

[Evaluation Example 9] Production of Ruthenium Thin Film A ruthenium thin film was produced on a silicon 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)
Chemical Vapor Deposition Raw Material: Compound No. 1. Raw material temperature: 100 ° C., raw material flow rate: 100 sccm, carrier gas: argon 200 sccm, reducing gas: hydrogen 300 sccm, reaction pressure 600 Pa, reaction temperature (base temperature): 300 ° C., film formation time: 30 minutes.
(result)
Film thickness: 50 nm, film composition: ruthenium

[Evaluation Example 10] Production of Ruthenium Thin Film A ruthenium thin film was produced on a silicon 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)
Chemical Vapor Deposition Raw Material: Compound No. 3. Raw material temperature: 100 ° C., raw material flow rate: 100 sccm, carrier gas: argon 200 sccm, reducing gas: hydrogen 300 sccm, reaction pressure 600 Pa, reaction temperature (base temperature): 300 ° C., film formation time: 30 minutes.
(result)
Film thickness: 45 nm, film composition: ruthenium

Claims (2)

A raw material for chemical vapor deposition comprising a (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound represented by the following general formula (1).

(In the formula, R ¹ represents a hydrogen atom or a methyl group, R ² represents a methyl group or an ethyl group when R ¹ is a hydrogen atom, and represents a methyl group when R ¹ is a methyl group. .) A novel (1,5-cyclooctadiene) (η ⁶ -arene) ruthenium compound represented by the following formula (2).

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