TWI227239B - Ruthenium complex, process for producing the same and process for producing thin film - Google Patents

Abstract

A ruthenium-containing thin film is produced by the chemical vapor deposition method etc. with the use of an organometallic ruthenium compound represented by the general formula (1), specific example of which is (2,4-dimethyl-pentadienyl) (ethylcyclopentadienyl) ruthenium: or an organometallic ruthenium compound represented by the general formula (7), specific example of which is carbonylbis (2-methyl-1,3-pentadiene) ruthenium: as the precursor.

Description

r1227239 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics ______ B7 V. Description of the invention (1) Field of the invention The present invention relates to an organometallic ruthenium complex, which can be used by chemical vapor deposition (hereinafter referred to as CVD method) ), Coating thermal decomposition method and the like to form a thin film containing ruthenium, a manufacturing method thereof, and a method for manufacturing a ruthenium-containing thin film used in electronic devices such as semiconductor memories. BACKGROUND OF THE INVENTION With the advancement of precision processing of memory components and the recent trend towards highly integrated semiconductor memory devices, attempts have been made to use ferroelectric films such as (Ba, Sr) Ti03 as insulating films in capacitors. In a capacitor having a ferroelectric thin film, noble metals such as pt, Ru, and ir are used as electrodes. Among these metals, Ru is predicted to be the most effective electrode material because its oxides have electrical conductivity and superior precision machining properties. Therefore, detection has been performed on electrodes made of Ru thin film or RuCh thin film. In order to form such a ruthenium-containing film in a highly integrated memory device, the CVD method is the most suitable method because of its step coverage and composition control. Organometallic compounds which have a low melting point and can be easily handled in metal compounds are generally considered to be suitable precursors for forming thin films by this CVD method. As for the organometallic compound used for depositing a ruthenium or ruthenium oxide film, a ruthenium complex or tris (di-pentamylmethyl) ruthenium (hereinafter referred to as Ru (DPM) 3) is actually used [Japanese Publication Patent No. 283438/1 994] or tris (octane-2,4-diketo) ruthenium (hereinafter referred to as ru (0D) 3) [Japanese Laid-Open Patent No. 2 0 0 0-2 1 2 7 4 4 ]. The ruthenium complex has a sandwich structure, and the nail system is sandwiched between two cyclopentadiene rings each consisting only of carbon and hydrogen. Because in the atmosphere, this paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) ~ — / i mm (Please read the precautions on the back before filling this page)

1T line 1227239 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (2) Extremely stable and non-toxic, ruthenium complexes are suitable as precursors for CVD. However, the evaporation and transfer of the precursor to the substrate is difficult because it is a solid at normal temperature and has a relatively high melting point of about 200t. For this reason, ruthenium compounds having a lower melting point have been actively investigated in recent years. The melting point of a ruthenium-containing organometallic compound can be lowered by converting it to a ruthenium complex derivative, wherein at least one hydrogen atom in the cyclopentadiene ring of the ruthenium complex is an alkyl group such as methyl or ethyl The replacement. For example, Japanese Patent Publication No. 35589/1 999 discloses bis (alkylcyclopentadienyl) ruthenium, such as bis (ethylcyclopentadienyl) ruthenium (hereinafter referred to as Ru (EtCp) 2) and bis ( Isopropylcyclopentadienyl) ruthenium is a ruthenium complex derivative. In addition, Japanese Laid-Open Patent No. 2000-281694 discloses the use of an alkyl-substituted ruthenium complex as a CVD precursor. It states that these organometallic compounds are in a liquid state at ordinary temperature and have a melting point lower than that of a ruthenium complex, that is, they have characteristics required as precursors for use in a CVD method. However, such bis (alkylcyclopentadienyl) ruthenium basically has a ruthenium complex structure. Because this structure has extremely high stability, these complexes have extremely high decomposition temperatures. Therefore, when the film is formed, it is basically necessary to raise the temperature of the substrate, resulting in a problem that the step coverage is deteriorated. On the other hand, R. Gleiter et al. (Organometallics, 8,298 (1989)) describe that (cyclopentadienyl) (2,4-dimethylcyclopentadienyl) ruthenium is synthesized with cyclopentadienyl Examples of half-sandwich complexes of ligands. However, this complex cannot be considered a suitable CVD precursor because it has a melting point of 1 36 to 13.7 ° C and is a solid at room temperature. According to the record, osmium has not been synthesized at room temperature and is semi-sandwich ruthenium with excellent evaporation properties. This paper is sized to the Chinese National Standard (CNS) A4 (210X297 mm) (Please read the precautions on the back first) (Fill in this page)

1T • M line -5- 1227239 A7 B7 5. Description of the invention (3). Equipment-(Please read the precautions on the back before filling this page) To synthesize semi-sandwich ruthenium complexes, it is generally to add pentadiene derivatives, cyclopentadiene derivatives, zinc and ruthenium halide hydrates at one time. Solvent, and then reacted under appropriate reaction conditions. However, this method cannot be practically used because only very low yields can be achieved. For post-reaction post-treatment, the liquid reaction mixture is also concentrated to produce a paste-like mixture. The target product is extracted from the paste-like mixture using a suitable solvent, and then filtered through calcium ore or column chromatography using an alumina column. Instead, purification is performed to produce the target product. However, this method includes steps that are not conducive to industrialization, such as extraction from the paste-like mixture obtained after concentration after completion of the reaction, and filtration of calcium ore or column chromatography. Therefore, in order to industrially obtain a semi-interlayered organometallic ruthenium compound, it is extremely necessary to establish a manufacturing method capable of obtaining a target product in a stable state at a high yield. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. On the other hand, thin films formed by thermal decomposition of coatings are used to manufacture components with relatively low integration. Since the precursor used in the thermal decomposition method of the coating is dissolved in an organic solvent to control the thickness of the film before use, it is preferable that these precursors are soluble in the organic solvent and decompose at a low temperature. However, very few ruthenium compounds have the aforementioned characteristics. In addition to carbonyl bis (1,3-butadiene) ruthenium (D. Minniti and PL · Timms ,; [.〇1 ^ & 11〇11 ^ 1 (: 1 ^ 111., 258, (: 12 (1983) ), Carbonyl bis (2,3-dimethyl-1,3-butadiene) ruthenium and carbonyl bis (1,3-cyclohexadiene) ruthenium (DN Cox and R · Roulet, Helv · Chim. Acta, Other than 67,1 365 (1 984)), there are no known carbonyl bis (diene) ruthenium complexes. These complexes are prepared by a method that requires reaction at low temperature, that is, Ru and diene Inverted at -196 ° C The paper size is applicable to Chinese National Standard (CNS) A4 (210X297 mm) -6- 1227239 A7 B7 V. Description of the invention (4) should be followed by adding C. In the CVD method, as The complex of the film precursor should be applied as a gas. Among the complexes currently used, Ru (DPM) 3 is evaporated by sublimation because of its high melting point of 168 ° C. This occurs when sublimation is evaporated. The precursor gas concentration changes due to changes in the solid surface area, so the problem of the precursor gas cannot be stably provided. To overcome this problem, Japanese Laid-Open Patent No. 1 32776/1 993 proposes a method The complex is dissolved in an organic solvent before use. However, the precursor is not always supplied stably in this method, because the evaporation of the solvent alone or the difference in the evaporation properties of the solid between the solvent and the complex is generated. There are some problems with deposition. On the other hand, Ru (OD) 3 and Ru (EtCp) 2 do not have the problem of providing precursors steadily because they are liquid at room temperature and have relatively high vapor pressures. However, in these complexes, Ru is stably bonded to individual organic ligands. Therefore, these complexes are difficult to decompose and should be processed at high temperature to form a thin film. The present invention is directed to In order to provide a ruthenium complex, which can be used to form a thin film by the CVD method using a CVD method at a low temperature, and a precursor thereof, a method for manufacturing the same, and a method for manufacturing a ruthenium-containing film can be provided appropriately. Research was conducted to overcome the foregoing problems. As a result, it was found that the decomposition temperature of a known compound having a ruthenium complex structure can be substituted by one of the cyclopentadienyl rings (hereinafter referred to as the Cp ring) with a linear pentadienyl group. While falling Low. As a result of subsequent research, a novel ruthenium complex was successfully developed. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) --------- install-(Please Read the precautions on the back before filling this page) Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1227239 A7 B7 V. Description of the invention (5) It appears at room temperature by introducing a low alkyl group into the Cp ring Below is the melting point of the liquid, and has better evaporation and decomposition properties. It was further found that the foregoing objects can be achieved by a carbonylbis (diene) ruthenium complex having a low molecular weight diene and a carbonyl ligand, and completed the present invention. Therefore, the present invention provides a semi-sandwich type organometallic ruthenium compound, which is characterized by the general formula (1):

--------- Install-(Please read the notes on the back before filling this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where R1, R2, R3 and R4 are the same or different and each indicates The prerequisites for hydrogen, halogen atoms, low-density radicals, low-density radicals, low-oxygen radicals, or low-density radicals do not include the case where R1 to R4 are all hydrogen, and R1 is hydrogen, and R2 to R4 One is hydrogen, and the other is methyl. The present invention further provides a method for manufacturing a ruthenium-containing film, which is characterized by using the aforementioned semi-interlayered organometallic ruthenium compound as a precursor, and forming a ruthenium-containing film on a heated substrate by a chemical vapor deposition method. The present invention further provides a method, which is characterized in that the open-type ruthenium octadecene represented by the following general formula (3):

Among them, R2, R3 and R4 are the same or different, and each represents hydrogen and halogen atoms. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210x297 mm),? Τ -8-1227239 Α7 Β7 V. Description of the invention (6) Low fluorenyl, low alkoxy, low alkoxycarbonyl or low alkyl; react with cyclopentadiene represented by the following general formula (4) in the presence of zinc in a solvent: R1 (4) where R1 Represents a hydrogen, a halogen atom, a lower fluorenyl group, a lower alkoxy group, a lower alkoxycarbonyl group, or a lower alkyl group; to obtain a semi-interlayered organometallic ruthenium compound represented by the general formula (1). In addition, the present invention provides a carbonylbis (diene) ruthenium complex, which is characterized by the following general formula (7):

R5 R8 R6 R7

R8 R5 R7 R6 (7) ί-- (Please read the notes on the back before filling this page), printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R5 to R8 each represent hydrogen, alkyl, or alkane An alkyl group of oxy, alkoxycarbonyl, alkylfluorenyl, hydroxy, carbonyl, halogen atom, carboxyl, amine or aminomethyl, the unsubstituted alkyl group and substituted alkyl group each having 1 to 6 For carbon atoms, the prerequisites do not include the case where R5 to R8 are all hydrogen and the case where R5 and R8 are hydrogen and R6 and RM are methyl. In addition, the present invention provides a method for manufacturing the aforementioned carbonylbis (diene) ruthenium complex, which is characterized by ruthenium chloride η-hydrate (where η is 1 or more)

This paper size applies Chinese National Standard (CNS) A4 specification (210 × 297 mm) -9-1227239 A7 ___ B7 _ 5. Description of the invention (7) Large number) and diene in alcohol in the presence of zinc powder to react. (Please read the notes on the back before filling this page.) In addition, the present invention provides a method for manufacturing a ruthenium-containing film, which is characterized by using the aforementioned carbonylbis (diene) ruthenium complex as a precursor. Brief Description of the Drawings Fig. 1 is a schematic diagram showing a CVD apparatus. FIG. 2 is an MS chart showing the measurement in Example 1. FIG. FIG. 3 is a graph showing the results of decomposition properties (DSC) measured in Example 1. FIG. FIG. 4 is a graph showing the results of the decomposition properties (DSC) measured in Comparative Example 1. FIG. FIG. 5 is a MS chart showing the measurement of Example 2. FIG. Fig. 6 is a graph showing the relationship between the oxygen flow rate and the decomposition rate in Example 3. Fig. 7 is a view showing an X-ray diffraction pattern of a film obtained in Example 3. FIG. 8 is a diagram showing an Arrehenius diagram showing a film growth rate. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 9 is a graph showing the resistivity of the film obtained in Example 4. Fig. 10 is a view showing an X-ray diffraction pattern of the film obtained in Example 5. FIG. 11 is a graph showing the resistivity of the thin film obtained in Example 5. FIG. 12 is a SEM photograph of the thin film obtained in Example 5. 13 are SEM photographs of the film obtained in Comparative Example 2. This paper size applies the Chinese National Standard (CNS) A4 (210X297 mm) -10-1227239 A7 B7 V. Description of the invention (8) Figure 14 is a SEM photograph of the film obtained in Example 5. Fig. 15 is a SEM photograph of the film obtained in Comparative Example 2. (Please read the precautions on the back before filling out this page) Figure 16 is an AFM photo of the film obtained in Example 5. Figure 17 is an AFM photograph of the film obtained in Comparative Example 2. FIG. 18 is an AF M photograph of the film obtained in Example 5. FIG. Figure 19 is an AFM photograph of the film obtained in Comparative Example 2. Fig. 20 is a graph showing the relationship between the carrier gas flow rate and the deposition rate in Example 6. Fig. 21 is a graph showing the relationship between the deposition time and the film thickness. Fig. 22 is a graph showing the DSC curve of Example 9. DESCRIPTION OF SYMBOLS 1: Precursor container 2: Oil bath 3: Reaction tank 4: Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5: Oxidizing gas 6: Relative gas 7: Carrier gas 8: Mass flow controller 9: Mass Flow controller 1 0: Mass flow controller 1 1: Vacuum pump The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -11-1227239 A7 ~ _____ _B? __ V. Description of the invention (9) 12: Exhaust gas detailed description Now, the present invention is described in detail. First, the definitions and special cases of the vocabulary used in this article are described. Unless otherwise stated, the term "low" as used in the present invention means that the group using the term is a straight-chain, branched-chain or cyclic hydrocarbon group having 1 to 6 carbon atoms. Therefore, examples of the lower alkyl group used in R1, R2, R3 or R4 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third Butyl, pentyl (pentyl), isopentyl, neopentyl, third pentyl, 1-methylbutyl, 2-methylbutyl, 1,2-dimethylpropyl, hexyl, isohexyl Base, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 1,1 · difluorenylbutyl, 2,2-dimethylbutyl, 1,3-dimethyl Butyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1 , 2,2-trimethylpropyl, 1-ethyl-1-fluorenylpropyl, 1-ethyl-2-methylpropyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl ' Cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the like. Preferred examples include methyl, ethyl, propyl, isopropyl and cyclopropyl. Examples of the lower alkoxy group used in R1, R2, R3 or R4 include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, and second butylene Oxy, tertiary butoxy, pentyloxy, methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,2-dimethylpropoxy, hexyloxy, 1-methylpentyloxy, 1-ethylpropoxy, 2-fluorenylpentyloxy, 3- This paper is also applicable to the Chinese National Standard (CNS) A4 specification (210 > < 297mm) (please (Please read the notes on the back before filling out this page)

Printed by 1T Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -12-12239239 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (id methylpentyloxy, 4-methylpentyloxy, 1, 2-dimethylbutoxy, ι, 3-dimethylbutoxy, 2,3-dimethylbutoxy, 1,1-dimethylbutoxy, 2,2-dimethylbutoxy Group, 3,3-dimethylbutoxy, etc. Preferred examples include methoxy, ethoxy and propoxy. Examples of lower alkoxycarbonyl groups used in R1, R2, R3 or R4 include Methoxycarbon, ethoxylate, propoxylate, isopropoxyl, cyclopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, second butoxycarbonyl, third butoxycarbonyl, etc. Preferred Examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, and cyclopropoxycarbonyl. Examples of lower fluorenyl groups used in R1, R2, R3, or R4 include formamyl, acetamyl , Propionyl, butylfluorenyl, isobutylfluorenyl, pentamyl, 1-methylpropylcarbonyl, isopentyl, pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methyl Butylcarbonyl , 1-ethylbutylcarbonyl, 2-ethylpropylcarbonyl, etc. Preferred examples include methylamidino, ethylamido, and propylamido. Among R1, R2, R3 or R4, in addition to the aforementioned lower alkyl, In addition to lower alkoxy, lower alkoxycarbonyl and lower fluorenyl groups, it is preferred to use-the same or different-hydrogen or halogen atoms. Specific examples of halogen atoms include fluorine, chlorine, bromine and iodine. Fluorine The present invention relates to a semi-interlayered organometallic ruthenium compound represented by the aforementioned general formula (1). The present invention relates to a semi-interlayered organometallic ruthenium compound represented by the following general formula (2): (Please read first Note on the back, please fill out this page again)-Binding, binding, I, thread, and paper size are applicable to Chinese National Standard (CNS) A4 (210X297 mm) -13- 1227239 A7 ________ B7 V. Description of the invention (1) R1

(Please read the precautions on the back before filling out this page) where R1 and R2 are the same or different, and each represents hydrogen, halogen atom, lower fluorenyl, lower alkoxy, lower alkoxycarbonyl, or lower alkyl. The prerequisite is that the case where R1 is hydrogen and R2 is methyl is not included. Also preferred is that both Ri and R2 are low alkyl, especially R1 is ethyl, and R2 is methyl. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In addition, the present invention relates to a method of borrowing CVD. Method for producing a ruthenium-containing film using the aforementioned semi-interlayered organometallic ruthenium compound. Figure 丨 shows an example of the device. The semi-sandwich organometallic ruthenium compound of the present invention is introduced into the precursor container 1 and maintained therein at 40 to 120 ° C. Thereafter, the carrier gas 7 was bubbled into the liquid under reduced pressure, and the semi-interlayered organometallic ruthenium compound was evaporated and sent to the reaction tank 3. The semi-interlayered organometallic ruthenium compound is then thermally decomposed on the substrate 4 held by heating to 200 to 75 ° C. to form a ruthenium-containing film. The method for forming a CVD film of the present invention can be performed by a bubbling method as shown in FIG. 1. Alternatively, a solution evaporation method may be used, in which the organometallic ruthenium compound of the present invention or a solution thereof in an organic solvent is transported into an evaporation container and converted into a gas therein. The semi-interlayer organic metal used in the CVD method of the present invention The ruthenium compound can be used in its original state, or the semi-sandwich organometallic ruthenium compound. The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm). -14- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1227239 A7 _____ B7 V. Description of the invention (1 It will be used in the form of a solution dissolved in an organic solvent. Examples of organic solvents that can be used in the present invention include alcohols such as methanol, ethanol, and isopropanol, and esters such as ethyl acetate , Butyl acetate and isoamyl acetate, glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether and ethylene glycol monobutyl ether, ethers such as diethylene glycol Ether, Glyme, Diglyme, Triglyme and Tetrahydrofuran, Ketones such as methyl · butyl ketone, methyl · isopropyl ketone, ethyl · butyl ketone, dipropyl Ketones, diisobutyl ketones, methyl-pentyl ketones, and cyclohexanone, and hydrocarbons such as hexane, cyclohexane, heptane, octane, benzene, toluene, and xylene, but the present invention is not limited to these Therefore, the compound represented by the general formula (1) of the present invention can be prepared by reacting an open type ruthenocene represented by the general formula (3) with a cyclopentadiene represented by the general formula (4). In the present invention, the open-type ruthenium metallocene represented by the general formula (3) may exist in zinc through a pentadiene derivative represented by the general formula (5) and a ruthenium halide hydrate represented by the general formula (6). It can be prepared by carrying out the reaction. The reaction formula ⑴ shows these reactions. Many methods used to produce these semi-interlayer organometallic ruthenium compounds include a single addition of a pentadiene derivative and a cyclopentadiene derivative. 'Only a poor yield is obtained. On the contrary, the aforementioned method can obtain the target product at a high yield. (Please read the precautions on the back before filling this page) • Binding · Binding-I · Line This paper size is applicable to Chinese National Standard (CNS) A4 specification (210X297 mm) -15- 1227239 A7 B7 V. Description of invention (佗 (5)

(Please read the notes on the back before filling out this page)-Equipment · Where X is a halogen atom; η is a number from 0 to 10; and R1, R2, R3 and R4 are as defined above. In this production method, the reaction solvent is not particularly limited. Similarly, the method of collecting and purifying the product is not particularly limited. However, the target product can be prepared by industrial methods using methanol as the overall reaction solvent or a part of it. After the reaction is completed, excess zinc is filtered off, and then extracted with a solvent that is not miscible with methanol. The semi-interlayered organometallic ruthenium compound shown is an oily product obtained by concentration and distillation. Examples of solvents which are never miscible with the methanol used therein include aliphatic hydrocarbons such as pentane, hexane, heptane and octane. Among them, pentane and hexane are particularly preferred because of their economic benefits and industrial advantages. Although the amount of zinc used in the reaction of the present invention is not particularly limited, it is preferred to use 1.0 mole or more of zinc per mole of the compound represented by the general formula (6) or the compound represented by the general formula (3) ' 1.5 moles or more is better. There is no economic advantage to using too much zinc. That is, it is preferable to use zinc of from 1.5 to 1,000 moles. The paper standard is applicable to the Chinese National Standard (CNS) A4 specification (210X297 meals). Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs -16-1227239 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy B7. V. Invention ((U) In the step of reacting the compound represented by formula (5) with the compound represented by general formula (6) in the presence of zinc, it is preferred to use 2 moles per mole of compound represented by general formula (6). Or an excess of the compound represented by the general formula (5). It is not economically advantageous to use too much of the compound. That is, it is preferred to use a compound represented by the general formula (5) from 2 to 20 moles. 5) In the step of reacting the compound represented by the general formula (6) with the compound represented by the general formula (6) in the presence of zinc, the reaction temperature is preferably in the range of -20 to 100 ° C, and more preferably -20 to 80 ° C. In the step of reacting the compound represented by the general formula (3) with the compound represented by the general formula (4) in the presence of zinc, the reaction temperature is preferably in the range of -20 to 100 ° C, from -20 More preferably to 80 ° C. Compounds represented by general formula (3) and compounds represented by general formula (4) are stored in zinc. In the step of carrying out the next reaction, it is preferred to use a compound represented by the general formula (4) from 0.8 to 1.0 mole per compound represented by the formula (3). A large amount of the compound represented by the general formula (3) remains unreacted with the compound of the formula (4). If the compound represented by the general formula (4) is used in an amount exceeding 1.0 mol, a large amount of bis (ethylcyclopentane) is formed. Dienyl) ruthenium by-product. Therefore, both of these cases are less favorable. In the present invention, if a compound represented by the general formula (5) is reacted with a compound represented by the general formula (6), The compound represented by the formula (3), the compound represented by the general formula (3) is reacted with the compound represented by the general formula (4) in a single pot as it is without isolation, to synthesize the general formula (1) The compounds shown are preferred. All reactions of the present invention are performed in a nitrogen or inert gas atmosphere (please read the notes on the back before filling this page) National Standard (CNS) A4 specification (210X297 mm) -17-1227239 A7 B7 5. Description of the invention (preferably. Examples of gasses include ammonia, neon, argon, krypton, xenon, and krypton. Among these gases, nitrogen and argon are still preferred because they are more economical. Next, the compounds represented by the general formula (7) will be described. Examples of such carbonylbis (diene) ruthenium complexes include carbonylbis (1,3-hexadiene) ruthenium [R5 to R7 = _h, Rs = -C2H5], carbonylbis (2,4-hexane Diene) Ruthenium [R5, Rk-CH3, R6, R7 = -H], carbonylbis (3-methyl_1,3-pentadiene) ruthenium [R5, R6 = -H, R7, R8 = -CH3 ], Carbonylbis (2,4-hexadienal) ruthenium [R, -CH3, R8 = -C = 〇, R6, R7 = -H], mineral-based bis (2,4-diene-1-ol ) Ruthenium [R = -CH3, R8 = -CH2〇H, R6, R7 = -H], mineral-based bis (1-acetamido-1,3-butadiene) ruthenium [R5 = -〇-C〇 CH3, R6, R7, r8 = _h], carbonylbis (2,4-hexadienoate ruthenium [R5 = -CH3, R8 = -COOH, R6, R7 = _h], carbonylbis (2,4-pentadienoate methyl Esters) Ruthenium [R5 = -CoCH3, R6, R7, r8 = _H] and the like. Other examples include carbonylbis (2,4-heptadienal) ruthenium [R5 = -C2H5, R8 = -C = 〇, R6, R7 = -H], carbonylbis (2,6-dimethyl-2, 4,6-octatriene) ruthenium [R5, R6 = -CH3, R8 = -C = C (CH3) 2, R7 = -H], carbonylbis (2,4-decadienoate ethyl) ruthenium [ R5 = -CH2CH2CH2CH2CH3, R8 = _COOC2H5, R6, R7 = -H], carbonylbis (geranene) ruthenium [R6 = -CH2CH2CH = C (CH3) 2, R5, R6, R7 = -H], carbonylbis ( 2,4-octadienal) ruthenium [R5 = -CH2CH2CH3, R8 = -C = 〇, R6, R7 = -H], carbonylbis (ethyl sorbate) ruthenium [R5 = -CH3, R8 = -C 〇〇C2H5, R6, R7 = -H], carbonylbis (methyl sorbate) ruthenium [R5 = -CH3, R8 = -CO〇CH3, R6, R7 = -H], carbonylbis (2,4- Heptadiene-6-one) ruthenium [foot 5 =-(:; ^, foot 8 = -C0CH3, R6, R7 = -H], etc. From the viewpoint of reducing the evaporation point of the complex, R5 to At least one of R8 is alkyl or contains alkoxy, alkoxycarbonyl, alkanoyl, and hydroxyl groups. The paper size is applicable to China National Standard (CNS) A4 (X297 mm). Clothing-(Please read the back first (Please fill in this page before taking note) Printed by the Consumer Property Cooperative of the Smart Property Bureau -18-1227239 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (1), carbonyl, halogen atom, carboxyl, amine or aminomethyl alkyl Preferably, the unsubstituted alkyl group and the substituted alkyl group each have 1 or 2 carbon atoms' and the rest are hydrogen. At least one of R5 to R8 is 1 or 2 carbon atoms, and The others are preferably hydrogen. Among them, carbonylbis (2 · methyl-1,3-pentadiene) ruthenium is most desirable [R5, R7 = -H, R6, R8 = -CH3]. The present invention is based on the general formula The carbonyl bis (diene) ruthenium complex represented by (7) can be prepared by reacting ruthenium chloride η-hydrate with diene in the presence of zinc in an alcohol. The lack of diene in this reaction leads to the formation of a metal Ruthenium reduces the yield. Therefore, it is preferable to use an excessive amount of diene for the aforementioned reaction. That is, it is preferable to use a diene that is 10 to 20 mol times more than the ruthenium chloride η-hydrate. In order to sufficiently reduce chlorine Ruthenium η-hydrate is preferably used in excess of zinc powder (10 moles or more). If these reactants are mixed, ruthenium chloride η- The alcohol solution of the hydrate was dropped into the diene or the alcohol solution of the diene-zinc powder dispersed therein, to obtain the target carbonyl bis (diene) ruthenium complex in high yield. The diene used in the present invention is not particularly limited as long as it is a compound having two or more double bonds on a continuous carbon chain in its molecule. Because the double bond is transferred during the reaction, non-conjugated diene such as 1,4-hexadiene, 1,5-hexadiene, 2-methyl-1,4-pentadiene, 3-methyl -1,4-pentadiene or 2-fluorenyl-1,5-hexadiene. However, it is preferable to use a conjugated diene represented by the following general formula (8): R6 R7

This paper size applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the precautions on the back before filling out this page) -Packing ', 1T i · line-19- 1227239 A7 B7 V. Description of the invention (( (Please read the notes on the back before filling out this page) where R5 to R8 each represent hydrogen, alkyl, or contain alkoxy, alkoxycarbonyl, alkylfluorenyl, hydroxyl, carbonyl, halogen atom, carboxyl, amine or The amino alkyl groups of the amino group, the unsubstituted alkyl group and the substituted alkyl group each have 1 to 6 carbon atoms, the prerequisites do not include the case where R5 to r8 are all hydrogen and R5 and R8 are In the case where hydrogen and R6 and R7 are fluorenyl groups, in the general formula (8), it is preferable that at least one of R5 to R8 is an alkyl group or contains an alkoxy group, an alkoxycarbonyl group, an alkylfluorenyl group, a hydroxyl group, and a carbonyl group. A halogen atom, a carboxyl group, an amino group, or an aminomethylamino alkyl group is preferred. The unsubstituted alkyl group and the substituted alkyl group each have 1 or 2 carbon atoms, and the rest are hydrogen. The Examples of conjugated dienes include 1,3-hexadiene (R 5 to R 7 =-Η, R8 = -C2H5), 2,4-hexadiene (R5, R8 = -CH3, R6, R7 = -H), 3-methyl-1,3-pentadiene (R5, R6 = -H, R7, R8 = -CH3), 2,4-hexadienal (R5 = -CH3, R8 =- C = 〇, R6, R7 = -H), 2,4-diene · 1-ol (R = -CH3, R8 = -CH2〇H, R6, R7 = -H), 1 · acetamidine-1 3-butadiene (R5 = -0-C0CH3, R6, R7, R8 = -H), 2,4-hexadiene acid (R5 = -CH3, R8 = -COOH, R6, R7 = -H), 2, Methyl 4-pentadienoate (R5 = -CO〇CH3, R6, R7, R8 = -H) and 2,4-heptadienal (R5 = -C2H5, R8 = -C = 0, R6, R7 = -H). Other examples printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs include 2,6-dimethyl-2,4,6-octatriene (R5, R6 = -CH3, R8 = -C = C (CH3) 2, R7 = -H), ethyl 2,4-decadienoate (feet 5 = -CH2CH2CH2CH2CH3, R8 = -CO〇C2H5, R6, R7 = -H), geranene (feet 6 = · CH2CH2CH = C (CH3) 2, R5, R6, R7 = -H), 2,4-octadialdehyde (R5 = -CH2CH2CH3, R8 di-C = 〇, R6, R7 = -H), Ethyl sorbate (R5 = -CH3, R8 = -COOC2H5, R6, R7 = _H), methyl sorbate (R5 = -CH3, R8 = -C00CH3, R6, R7 = _H), 2,4_heptane Olefin_6_ different (R5 = _CH3, R8 = _C〇CH3, this Paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) -20-1227239 A7 B7 V. Description of invention (R6, R7 = -H), etc. Among them, 2-methyl-1,3-pentadiene is most desirable (R5, R7 = -H, R6, R8 = -CH3). The alcohol is not particularly limited as long as it is a liquid at room temperature (251). Since CO as a ligand is formed from an alcohol, it is preferable to use methanol, ethanol, or 1-propanol from the viewpoint of the reaction rate. A single alcohol or a mixture of several alcohols can be used. If an alcohol solution of ruthenium chloride η-hydrate is dropped into an alcohol solution of diene or a diene containing zinc powder, the alcohol used to dissolve the diene and the alcohol used to dissolve the ruthenium chloride η-hydrate The alcohols may be the same or different. The reaction proceeds slowly at low temperatures, while the polymerization of diene increases at high temperatures. Therefore, the reaction temperature is preferably in the range from 0 to 80 ° C. After the reaction was completed, the zinc powder was filtered off. The complex formed can then be extracted directly from the reaction mixture using a solvent such as pentane or hexane, or after removing the alcohol and unreacted diene. Because the extracted complex is contaminated by the diene polymer and those formed during the reaction, it is purified by chromatography, distillation, and other methods. Using these carbonylbis (diene) ruthenium complexes as precursors, ruthenium-containing films can be obtained. If a CVD method is used to produce a thin film containing ruthenium such as ruthenium or ruthenium oxide on a substrate using a carbonylbis (diene) ruthenium complex as a precursor, the carbonylbis (diene) ruthenium complex is evaporated and provided. On the substrate. Examples of the evaporation method include a method in which an inert carrier gas system is introduced into a heated complex in a liquid state, and then the complex is provided together with a carrier gas into a reaction tank in which a substrate is placed; a method in which the The complex is dissolved in an organic solvent to produce a solution. The solution is then supplied to an evaporator, where it is evaporated, and the gas is supplied to a reaction tank where the substrate is placed; etc. The paper dimensions are subject to Chinese national standards (CNS ) A4 size (210X297mm) (Please read the precautions on the back before filling out this page), printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-21-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1227239 A7 ____B7 V. Description of the invention (ο If carbonylbis (diene) ruthenium complex is used in the form of a solution in an organic solvent, an example of an organic solution is Include alcohols, such as alcohols, such as methanol, ethanol, and isopropanol, esters such as ethyl acetate, butyl acetate, and isoamyl acetate, and glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monomethyl ether And ethylene glycol monobutyl ether, ethers such as diethyl ether, glyceme, digremide, trigeminy, and tetrahydrofuran, and ketones such as methyl · butyl ketone, methyl · isopropyl ketone , Ethyl · butyl ketone, dipropyl ketone, diisobutyl ketone, methyl · pentyl ketone and cyclohexanone, and hydrocarbons such as hexane, cyclohexane, heptane, octane, benzene, toluene The present invention is not limited to this. In order to form a thin film containing ruthenium such as ruthenium or ruthenium oxide on the substrate by thermal decomposition of the coating, the carbonyl bis (diene) ruthenium complex is also in solution form. In this case, the aforementioned organic solvent can also be used. For producing the ruthenium-containing film of the present invention The CVD method is not particularly limited, and its prerequisite is that it is a CVD method generally used in the art world, such as thermal CVD, plasma CVD, or photo-CVD. In the thermal decomposition method of coatings, the precursor can be applied by, for example, spin coating. Coating method, dipping method or spray method. When heating, a stove, hot plate or the like can be used. The coating method, heating method and combination method are not particularly limited. The half shown by the general formula (1) of the present invention The interlayer organometallic ruthenium compound is liquid at room temperature, and has sufficient vapor pressure at about loot. Because of these characteristics, it can be provided in large quantities as CVD precursors by gas bubbling. Compared with conventional precursors Below, it can be thermally decomposed at low temperature. Therefore, a ruthenium-containing film with excellent step coverage can be formed on the substrate. This paper size applies to China National Standard (CNS) A4 (210X 297 mm) ( Please read the precautions on the back before filling this page) Binding and binding I · line-22- 1227239 A7 B7 V. Description of the invention (2d According to the present invention, the ruthenium-containing film can be made by the CVD method, and its large capacity is superior. Use of the hair by CVD method It is clear that the organometallic ruthenium compound can form a Ru film or RuO2 film by controlling the oxygen flow rate. The resulting ruthenium-containing film therefore has a high density, is contaminated by a small amount of impurities, and has excellent crystallinity. As a result, it can be obtained A ruthenium-containing film having a preferable resistivity near the bulk level. Compared with a film obtained by using a conventional product, the ruthenium-containing film of the present invention has a high density and a flat film surface. A semi-interlayered organometallic ruthenium compound is manufactured according to the present invention This method can stably obtain the semi-interlayered organometallic ruthenium compound at a high yield. The conventional method can only obtain a low yield. In addition, the target product can be prepared by this method without concentrating the alcohol, which consumes energy. In terms of this, this is an advantage. Therefore, the method for manufacturing the semi-interlayer organometallic ruthenium compound of the present invention can be widely used, not only for the small-scale manufacturing of these products, but also for its industrial specifications. Using the carbonyl bis (diene) ruthenium complex of the present invention, a thin film can be formed at a lower temperature than the complexes currently used for thin film formation by the CVD method, and can be formed under the condition that a precursor is provided in a stable state. Ruthenium-containing film. In addition, the carbonyl bis (diene) ruthenium complex has a low thermal decomposition temperature and high solubility in solvents, making it also useful for forming ruthenium-containing thin films by coating thermal decomposition. It is further predicted that it can be used as a reaction catalyst in a solvent. Compared with the conventional method for producing a carbonylbis (diene) ruthenium complex, it can be produced under mild conditions, and therefore has manufacturing advantages. Now, the present invention will be described in more detail with reference to the following examples. However, this paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm) U3 (Please read the precautions on the back before filling this page), \ 呑 Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-23- 1227239 A7 B7 V. Description of the invention (2) It is known that the present invention is not limited to this. Example 1 Synthesis and thermal decomposition properties of (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium 400 g of zinc was weighed in a four-necked flask. After flushing the container with argon, 205 ml of 2,4-dimethyl-1,3-pentadiene was added to produce a suspension. Then, a solution of 30 g of ruthenium trichloride η-hydrate (η: about 3) dissolved in 1000 ml of methanol was added dropwise at room temperature over 40 minutes. After the dripping was completed, the mixture was stirred at room temperature for 30 minutes, then heated to 60 ° C, and stirred for another 2 hours. The mixture was left to cool before adding 12 ml of ethylcyclopentadiene. The resulting mixture was stirred at room temperature for 30 minutes, then heated to 60 ° C and stirred for another 2 hours. After the reaction was completed, the mixture was cooled to room temperature, and unreacted zinc was removed using a glass filter. Next, it was extracted with hexane (7 50 ml x 1, 300 ml x 4). The extract was concentrated under reduced pressure, and the resulting oily product was distilled under reduced pressure to yield 25.4 g of the standard (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium (yield: 76.3%). Oily yellow product: 'H-NMRCSOOMHz, CDCh, 5 ppm) 5.38 (s, 1H), 4.63 (t, J = 2.0Hz, 2H), 4.52 (t, J = 2.0Hz, 2H), 2.70 (d, J = 2.5Hz, 2H), 2.15 (q, J = 7.5Hz, 2H), 1.93 (s, 6H), 1.12 (t, J = 7.5Hz, 3H), -0.09 (d, J = 2.5Hz, 2H ) IR (pure, cm-1) 3050, 2960, 2910, 1475, 1 445, 1430, 1 375, 1 030, 860, 800, MS (GC / MS, El) This paper standard applies to Chinese National Standard (CNS) A4 specification (210X 297 mm) (Please read the notes on the back before filling this page)-Assembled 'Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by 8 Industrial Consumer Cooperatives-24- 1227239 A7 __B7 V. Invention Description (2 sessions (Please read the precautions on the back before filling this page) (2,4-Dimethylpentadienyl) (ethylcyclopentadienyl) The molecular ion peak of ruthenium is located at 1 () 2Ru: m / z 290. This MS chart is shown in Fig. 2. (Decomposition properties) Fig. 3 shows the measurement results of the decomposition properties of the obtained (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium. Decomposition The property is measured under the following conditions: Measurement method: Energy-compensated differential scanning calorimetry (DSC) measurement Item: Reference: Alumina inert gas: Nitrogen 50ml / min Heating rate: 1 (TC / min Comparative Example 1 Decomposition properties of bis (ethylcyclopentadienyl) ruthenium bis (ethylcyclopentadienyl) The decomposition properties of ruthenium were measured under the same conditions as in Example 1. The exothermic reaction was observed from about 320 ° C. Figure 4 shows the printed fruits of the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Example 2 (2,4 -Synthesis of dimethylpentadienyl) (methylcyclopentadienyl) ruthenium Weigh 8.0 g of zinc into a 50 ml Schlenk test tube. After flushing the container with nitrogen, add 4 ml of 2,4-dimethyl -1,3-Pentaic distillate to produce a suspension. After that, 0.6 g of ruthenium trichloride hydrated in drops at room temperature for 50 minutes. This paper is sized for the Chinese National Standard (CNS) A4 (210X297 mm) -25- 1227239 A7 B7 V. Description of the invention (2 $ (please read the precautions on the back before filling this page) The solution of the substance dissolved in 20 ml of ethanol. After the dropwise addition is complete, the mixture is stirred at room temperature for 30 minutes, and then heated to 70 ° C, stir for another 2 hours. The mixture is left to cool and 240 is added. Liter methyl cyclopentadiene. The formed mixture was stirred at room temperature for 30 minutes' After heating to 70 ° C, and then further stirred for 2 hours. After the reaction was completed, the mixture was cooled to room temperature, and unreacted zinc was removed using a glass filter. After that, it was concentrated to a paste-like mixture. The obtained paste mixture was extracted with pentane, and the extract was subjected to column chromatography using alumina as a carrier and pentane as an eluate. As a result, 0.28 g of the target (2,4-dimethylpentadienyl) (methylcyclopentadienyl) ruthenium was obtained. 1H-NMR (500MHz, CDCh, 5 ppm) 5.36 (s, 1H), 4.61 (t, J = 2.0Hz, 2H), 4.57 (t, J = 2.0Hz, 2H), 2.67 (d, J = 2.5Hz , 2H), 1.93 (s, 6H), 1.83 (s, 3H), -0.07 (d, J = 2.5Hz, 2H) MS (GC / MS, El) Printed by the Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs The molecular ion peak of (2,4-dimethylpentadienyl) (methylcyclopentadienyl) ruthenium is located at 1 () 2Ru: m / z 276. Figure 5 shows this MS picture. Example 3 A ruthenium-containing film was prepared by a CVD method using (2,4-dimethylpentadienyl) (methylcyclopentadienyl) ruthenium as a precursor. Using the apparatus shown in FIG. A Si substrate with a Si02 film (100 nm) formed as a substrate. Approx. 10 g (2,4-dimethylpentadienyl) (This paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) '-26- 1227239 A7 _ B7 V. Description of the invention (24 ( Please read the precautions on the back before filling in this page) Methylcyclopentadienyl) Ruthenium is fed into the precursor container 1 and heated to a constant temperature of 60 ° C in an oil bath. Reaction tank 3 and precursor container The interior of 1 uses vacuum pump 11 and pressure control valve individually controlled at 10 Torr and 100 Torr. Nitrogen is used as the carrier gas 7, and the flow rate is set to 100 seem using the mass flow controller. Oxygen is used as the oxidizing gas 5 And nitrogen is used as the relative gas 6. The flow rate of the oxidizing gas is set at 0, 10, 30, and 300 seem ', and the flow rate of the relative gas is individually set to the level of the sum of the oxidizing gas to 500 seem. The temperature was set at 400 ° C, and the film formation was performed under heating for 60 minutes. Fig. 6 shows a graph of the film thickness of the ruthenium-containing film formed on the substrate with respect to the oxygen flow rate. Fig. 7 shows A and B of Fig. 6 And the X-ray diffraction pattern of the film obtained from C and C. As clearly shown in Fig. 7, at 0 s Ru films were obtained at an oxygen flow rate (A) of eem, and Ru02 films were obtained at an oxygen flow rate greater than 0 sccm (B) or (C). That is, Ru has been found to be produced by controlling the oxygen flow rate in CVD Thin film or RuO2 thin film. Example 4 Printing by (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium as a precursor using the CVD method printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Preparation of a film containing ruthenium Using the apparatus shown in FIG. 1, a Si substrate with a Si02 film (100 nm) formed on the surface was used as the substrate. Approximately 10 g (2,4-dimethyl) Pentadienyl) (ethylcyclopentadienyl) ruthenium was fed into the precursor container 1 and heated to a constant temperature of 60 ° C in an oil bath. The inside of the reaction tank 3 and the precursor container 1 was vacuumed. The pump 11 and the pressure control valve are individually controlled at 10 Torr and 100 Torr. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -27- 1227239 A7 B7 V. Description of the invention (2 $ (please First read the notes on the back before filling this page) ears. Use nitrogen as the carrier gas 7 and its flow rate is set to 100 seem using a mass flow controller Use oxygen as the oxidizing gas 5 and nitrogen as the relative gas 6. The flow rate of the oxidizing gas is set to 300 seem, and the flow rate of the relative gas is set to 200 seem. The temperature of the substrate 4 is set to 170, 200, 200 , 300, 400, 500, and 60 (TC, and the film formation is performed by heating to each temperature for 60 minutes. The closed ring U in Figure 8) is an Arrehenius diagram showing the growth rate of the film. The ruthenium-containing film can be at 200 ° C or higher. Fig. 9 shows the resistivity of the obtained film. A better resistivity near the bulk resistivity (shown by the arrow in Figure 9) is obtained. Example 5 A thin film containing ruthenium was prepared by a CVD method using (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium as a precursor and printed by a consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The device shown in FIG. 1 uses a Si substrate with a SiCh film (100 nm) formed on the surface as a substrate. About 10 g of (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium was fed into the precursor container 1 and heated to a constant temperature of 60 ° C in an oil bath. The inside of the reaction tank 3 and the precursor container 1 are individually controlled at 100 Torr and 100 Torr using a vacuum pump 11 and a pressure control valve. Nitrogen was used as the carrier gas 7 and its flow rate was set at 100 s c c m using a mass flow controller. In the case where no oxidizing gas is used, nitrogen is used as the relative gas 6, and the flow velocity of the relative gas is set at 500 seem. The temperature of the substrate 4 is set at 250, 275, 300, 325 '350, 375, 400, 450, 500, 550, and 600 ° C, and the film is formed by heating to the temperature of the paper and using the National Standard of China ㈧⑽ 丨 Eight-view grid 丨 Training tear mm) " -28- 1227239 A7 B7 V. Description of the invention (60 minutes at 2 degrees. The closed loop (b) in Figure 8 is an Arrehenius diagram showing the growth rate of the film The ruthenium-containing film can be formed at 27 5 ° C or higher temperature. Figure X shows the X-ray diffraction pattern of the obtained film. A film with better crystallinity is obtained at 400 ° C and higher temperature. Figure 11 shows the resistivity of the obtained film. A better resistivity close to the bulk resistivity (shown by the arrow in Figure 11) is obtained. Figures 12 and 14 individually show the formation at 30 ° C and 60CTC substrate temperature. SEM photograph of the cross section of the film. Although dense films are found at various temperatures, the density of the films formed at 600 ° C is better. Figures 16 and 18 individually show the formation at 350 ° C and 600 ° C substrate temperatures AFM image of the cross section of the thin film. '(A) in Table 1 shows the results of measuring surface roughness by AFM The obtained Ra (log average roughness) and Ry (maximum height). Ra and Ry are individually measured according to the methods described in nS B0601-1994 and JIS B003 1-1994. Therefore, each of the ruthenium-containing films of the present invention is known All have a very flat surface. (Please read the precautions on the back before filling out this page.) Equipment--Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Table 1 Substrate temperature (a) Example 6 (b) Imitation 丨 丨 rc) Ra Ry Ra Ry 300 4.75 61.12 20.07 223.26 600 4.14 72.25 26.23 326.45 Comparative Example 2 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -29 · 1227239 A7 B7 V. Description of the invention (2) —-------- Installation— (Please read the precautions on the back before filling out this page) The film formation is performed as in Example 5 using the device shown in Figure 1 'but provides about 10 Grams of commercially available bis (ethylcyclopentadienyl) ruthenium in the precursor container 1. Figures 13 and 15 are SEM photographs showing the cross section of a film formed at a substrate temperature of 300 ° C and 60 ° C, respectively. In each case, the density of the film was poor, and columnar crystals were found to form. 17 and 19 individually show cross-section AFM images of films formed at 350 ° C and 60 ° C substrate temperature. In Table 1, (b) represents Ra and Ry obtained from the surface roughness measurement results of AFM. In comparison with the examples, a high saccharin surface sugar content was found. Example 6 Use of (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium as a precursor to manufacture a ruthenium-containing film by CVD method-Wire · Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The system shown in Fig. 1 was used, and a Si substrate with a Si02 film (100 nm) formed on the surface was used as the substrate. About 10 g of (2,4-dimethylpentadienyl) (ethylcyclopentadienyl) ruthenium was fed into the precursor container 1 and heated in an oil bath to reach a constant temperature of 60 ° C. The inside of the reaction tank 3 and the precursor container were individually controlled at 10 Torr and 1000 Torr using a vacuum pump 11 and a pressure control valve. Nitrogen was used as the carrier gas 7 and its flow rate was set at 30 and 100 seem using a mass flow controller. Oxygen is used as the oxidizing gas 5 and nitrogen is used as the counter gas 6. The flow rate of the oxidizing gas is set at 300 s c c m, and the flow rate of the relative gas is set at 200 seem. The temperature of the substrate 4 was set at 400 ° C, and the film formation was performed under heating for 60 minutes. Figure 20 shows the relationship between the carrier gas flow rate and the deposition rate of the ruthenium-containing film formed on the substrate. The paper size applies the Chinese National Standard (CNS) A4 specification (210X tear mm) -30- 1227239 A7 ___B7 V. Invention Instructions (2). A small amount of carrier gas can be used to form a sufficiently uniform film in this area. Example 7 (Please read the precautions on the back before filling this page) Use (2,4-monomethylpentadienyl) ( Ethylcyclopentadienyl) ruthenium is used as a precursor to produce ruthenium-containing films by CVD. Using the device shown in Figure 1, a Si substrate with a Si02 film (100nm) formed on the surface is used as the base. Approximately 10 grams of (2,4-dimethylpentadienyl) (ethyl pentadienyl) ruthenium was fed into the precursor container 1 and heated in an oil bath to reach 60 ° C. Constant temperature. Vacuum tank 11 and pressure control valve are used to control the reaction tank 3 and the precursor container individually at 100 Torr and 100 Torr. Nitrogen is used as the carrier gas 7, and the flow rate is set to 3 using a mass flow controller. 0 and 1 0 0 sccm. Without using any oxidizing gas 5, Nitrogen is used as the relative gas 6, and the flow rate of the relative gas is set to 500 seem. The temperature of the substrate 4 is set to 350 ° C, and the film formation is performed under heating for 2.5, 5, 10, 20, 60, and 120 minutes. Ministry of Economy Wisdom Printed by the Employees' Cooperative of the Property Bureau. In Figure 21, the closed ring (a) shows the deposition time and film thickness of the ruthenium-containing film formed on the substrate. The ruthenium-containing film was obtained at 2.5 minutes and a longer deposition time. It increases linearly with the increase of the deposition time. The ruthenium-containing film can be easily formed without showing any incubation time (the time when no film is formed on the substrate). Comparative Example 3 The device was run as in Example 7, but about 10 grams of commercially available bis (ethylcyclopentadienyl) ruthenium was fed into the precursor container 1. Box (b) in Fig. 21 shows the formation on the base The paper size on the material applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -31-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1227239 A7 ________B7_ V. Description of the invention (2 $ during the deposition of ruthenium-containing films And the thickness of the film. The incubation time was found before the deposition time reached 20 minutes. Example 8 Synthesis of mineral-based bis (2-methyl-1,3-pentadiene) ruthenium 160 g of zinc powder was introduced into 100 ml of four necks In a flask, after connecting a stirrer, a dropping funnel, a condenser, and a thermometer, the flask was flushed with argon. Thereafter, 60 ml of 2-methyl-1,3-pentadiene was added, and zinc powder was dispersed therein by stirring. Secondly, 10 g of ruthenium chloride η-hydrate dissolved in 400 liters of ethanol was added from the dropping funnel for 1 hour, while maintaining the temperature in the water bath at 25 ° C or lower. After the dripping was completed, the resulting mixture was heated to 70 ° C and stirred for 3 hours. Zinc powder was filtered from the reaction mixture, and ethanol and the like were removed under reduced pressure. The obtained pasty product was extracted with pentane. The extract was purified by column chromatography using alumina as the filling and pentane as the solvent. After removing the solvent, 9.99 g of carbonylbis (2-fluorenyl-1,3-pentadiene) ruthenium was obtained as a yellow liquid (yield: 89%). ^ -NMR (COCh) S 3.91 (d, 2H, J = 7.5Hz), 2.04 (s, 6H), 1.42 (s, 2H), 1.27 (d, 6H, J = 6Hz), 1.17 (dq, 2H, J = 14Hz), 0.30 (s, 2H). 13C-NMR (CDCh) δ 218.88 (CO), 91.51 (〇, 89.47 (CH), 50.51 (CH), 37.58 (CHa), 22.84 (CH3), 18.78 (CH〇IR 1 967 cm'1 (CO) MS 294 (M +) This paper size is applicable to Chinese National Standard (CNS) A4 size (210x297 mm) (Please read the precautions on the back before filling this page). Binding · Binding-Thread • 32- 1227239 A7 B7 V. Invention Explanation (30 Example 9 Thermal decomposition properties of carbonylbis (2-methyl-1,3-pentadiene) ruthenium (measured by DSC) 6.7 mg of the carbonylbis (2-methyl-1, 3-Pentadiene) Ruthenium is introduced into a stainless steel pan and hermetically covers the stainless steel lid. This sample was heated at a rate of 10 ° C / min using 18.8 mg of alumina as a reference 'using a differential scanning calorimeter ( DSC) measures the change in heat during heating. An exothermic reaction was found at about 120 ° C to confirm the decomposition of the complex. The results are shown in Figure 22. Example 10 0 Carbonylbis (2-fluorenyl-1,3-pentane (Ene) ruthenium as a precursor to manufacture ruthenium-containing films by CVD method Using the CVD apparatus shown in FIG. 1 with carbonylbis (2-methyl-1,3-pentadiene) ruthenium as a precursor, At 50 ° C precursor temperature, 100 sccm carrier gas (N2) flow rate, 400 Torr precursor pressure, 200 sccm relative gas (N2) flow rate, 80 ° C tube temperature, 300 ° C substrate temperature, 10 Torr The fj film was formed on a silicon wafer with a Si02 film under an ear groove pressure and a flow rate of 300 seem oxidizing gas (〇2) over 1 hour. By analyzing the X-ray diffractometer, the film was found to contain ru〇2. The thickness of the film measured by SEM was 500 nm. Example 11 A spin-coating method was used to produce a ruthenium-containing film using spinyl bis (2-methyl-1,3-pentadiene) ruthenium as a precursor. Paper size applies Chinese National Standard (CNS) A4 specification (210X297 mm) ---------- Zhuang Yi-(Please read the precautions on the back before filling in this page j -Order · -Line · Economy Printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau -33- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economy 1227239 A7 _B7___ V. Description of the Invention (3) By putting 1 ml of carbonylbis (2-methyl-1,3- Pentadiene) ruthenium was dissolved in 9 ml of heptane to prepare a solution. This solution was spin-coated on a silicon wafer at 500 rpm for 5 seconds and at 100 After 10 seconds at 0 revolutions per minute, it was then heated in a furnace at 150 ° C for 20 minutes. By analysis by X-ray diffraction, the film was found to contain RuO2. The film thickness measured by SEM was 300 nm. Comparative Example 4 The film formation was performed in the same manner as in Example 10, but starting from bis (ethylcyclopentadienyl) ruthenium. As a result, a ruthenium-containing film cannot be obtained. Example 12 2 8.0 grams of zinc was introduced into a Schlenk test tube. After flushing the container with argon, 240 µl of ethylcyclopentadiene and 4 ml of 2,4-dimethyl-1,3-pentadiene were added. Under ice cooling, 608 mg of ruthenium chloride η-hydrate (η: about 3) dissolved in 25 ml of absolute ethanol was added dropwise over 1 hour and 15 minutes. Thereafter, the resulting mixture was stirred under ice cooling for 1 hour and 30 minutes, and then at room temperature for 1 hour. After the reaction was completed, unreacted zinc was removed using a glass filter, and the residue was concentrated under reduced pressure to give a pasty product. This paste product was extracted with pentane, and the extract was subjected to column chromatography (pentane / alumina) to produce 106 mg of the target (2,4-dimethylpentadienyl) (ethylcyclopentadienyl). Ruthenium (yield: 16%). Further, 70 mg of a by-product of bis (ethylcyclopentadienyl) ruthenium was obtained (yield: 11%). Although the present invention has been described in detail with reference to specific specific examples, familiarize yourself with this technique (please read the notes on the back before filling out this page) • Pei-Order I · Threaded paper size applies Chinese National Standard (CNS) A4 Specification (210 × 297 (Mm) -34- 1227239 A7 B7 V. Invention Description (3i artists are known to make various changes and modifications without departing from the spirit and scope of the invention. Equipment— (Please read the precautions on the back before filling out this Page) Ordered by I · Line Ministry of Economic Affairs Intellectual Property Bureau Employees' Cooperatives Printed on this paper Standards applicable to Chinese National Standard (CNS) A4 (210X297 mm) -35-

Claims (1)

1227239 Β8 (Please read the notes on the back before filling out this page) where R, R2, r3, and R4 are the same or different and each represents hydrogen, halogen atom, 'lower oxygen, lower alkoxycarbonyl, or lower alkyl, which are prerequisites The conditions are excluding the case where R1 to R4 are hydrogen, and the case where R1 is hydrogen, one of R2 to R4 is hydrogen, and the other is methyl. 2.% $ Please apply the semi-sandwich type organometallic ruthenium compound in the first item of the patent scope. The semi-sandwich type organometallic ruthenium compound is represented by the following general formula (2): R1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R1 and R2 are the same or different and each represents hydrogen, halogen atom, low fluorenyl, low alkoxy, low alkoxycarbonyl or low alkyl, the prerequisites are: The case where R1 is hydrogen and R2 is methyl is not included. 3. A method for manufacturing a ruthenium-containing thin film, which is characterized in that a semi-sandwich-type organometallic ruthenium compound such as the first item in the scope of patent application is used as a precursor. (%) -36- 1227239 6. Apply for a patent scope of 2 C8 D8 and form a ruthenium-containing film on a heated substrate by chemical vapor deposition. 4. A method for producing a semi-sandwich type organometallic ruthenium compound represented by the following general formula (1), (1) wherein R1 to R4 are the same or different and each represents hydrogen, a halogen atom, a lower fluorenyl group, a lower alkoxy group, a lower alkoxycarbonyl group, or a lower alkyl group, which includes opening up represented by the following general formula (3) Ruthenium type: R2 R2 R3 R4 (3) Please read the precautions on the back first to fill in this note. · 1. Where R, R and R are as defined above; in the presence of zinc in the solvent, the ring represented by the following general formula (4) Pentadiene reacts: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (4) where R1 is as described above. 5 · A method for producing a semi-sandwich-type organometallic ruthenium compound as described in item 4 of the scope of the patent application, wherein the open-type ruthenium system represented by the general formula (3) is obtained by the following general formula (5) The liquid mixture of pentadiene and zinc shown in this paper applies the Chinese National Standard (CNS) A4 «L ^ rf71〇x297 public director_y -37-1227239 Α8 Β8 C8 D8 6. Scope of patent application 3: R2 (5) a lower fluorenyl group, a lower alkoxy group, a lower alkoxycarbonyl group or a lower alkyl group; a solvent-diluted solution of the ruthenium halide hydrate represented by the following general formula (6) is added dropwise: RuXs · nH2O (6) ( Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where X is a halogen atom; and η is a number from 0 to 10; and react with it. 6. A method for manufacturing a semi-sandwich-type organometallic ruthenium compound as described in item 4 of the patent application, wherein methanol is used as the overall solvent or a part thereof 'After the excess zinc is filtered out after the reaction is completed, it is incompatible with methanol The mixed solvent extracts the ruthenium complex represented by the general formula (1). 7 · A method for producing a semi-sandwich-type organometallic ruthenium compound as described in item 4 of the scope of patent application, wherein after extraction with a solvent that is absolutely miscible with methanol, the solution is concentrated and distilled to purify the Formula (1) represents a semi-interlayer organometallic ruthenium compound. 8 · A method for manufacturing a semi-sandwich-type organometallic ruthenium compound as described in item 5 of the patent application, wherein the amount of pentadiene represented by the general formula (5) is 2 to 2 moles of ruthenium halide hydrate To 20 mol. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) • 38-1227239 A8 B8 C8 D8 6. Application for patent scope 4 9. A semi-sandwich-type organometallic nail compound as described in item 4 of the patent scope Method, wherein the amount of zinc added is from ι · 5 to ιοι mol per mol of ruthenium halide hydrate or an open-type ruthenium metalcene represented by the general formula (3). 10 · —A method for manufacturing a semi-sandwich type organometallic ruthenium compound as described in item 4 of the patent application, wherein pentadiene represented by the general formula (5) and ruthenium halide hydrate represented by the general formula (6) The reaction is carried out by synthesizing an open ruthenium metallocene represented by the general formula (3) at a temperature ranging from -20 to 100 ° C. 11. A method for manufacturing a semi-sandwich-type organometallic ruthenium compound according to item 4 of the scope of patent application, wherein the open-type dicene nail represented by the general formula (3) and cyclopentadiene represented by the general formula (4) The reaction of ene to synthesize a semi-sandwich type organometallic ruthenium compound represented by the general formula (1) is carried out at a temperature ranging from -20 to 100. 12. —A method for manufacturing a semi-sandwich type organometallic ruthenium compound as described in item 4 of the scope of patent application, wherein the semi-sandwich type organometallic ruthenium complex shown by the general formula is opened by the formula (3) In a synthesis in which a type of ruthenium is reacted with a cyclopentadiene represented by the general formula (4), the amount of cyclopentadiene storage represented by the general formula (4) is shown by the general formula (3) per mole The open type of ruthenium is from 0.8 to 1 mole. 13. · A method for producing a semi-sandwich-type organometallic ruthenium compound as described in item 4 of the scope of the patent application, wherein 'after obtaining an open ruthenium metallocene represented by the general formula (3)' A single pot is reacted with cyclopentadiene represented by the general formula (4) to synthesize a semi-sandwich type organometallic ruthenium compound represented by the general formula (1). 14. A kind of semi-sandwich type organic paper as in the scope of patent application No. 4 is applicable to China National Standard (CNS) A4 specification (210X297 ^ 3 --- Mr -----_ installation-(Please read first Note on the back, please fill out this page again), ^ 1 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -39-1227239 A8 B8 C8 D8々, Patent Application Method 5 Method of metal ruthenium compounds' where the reaction is under nitrogen or inert It is carried out in a gas atmosphere. 15. The method for manufacturing a ruthenium-containing thin film according to item 3 of the patent application, wherein a method prepared by dissolving a semi-sandwich type organometallic ruthenium compound as described in item 1 of the patent application in an organic solvent is used. Semi-sandwich type organometallic ruthenium compound solution. 16. —A carbonyl bis (diene) ruthenium complex represented by the following general formula (7), (Please read the precautions on the back before filling this page) R6 R7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R5 to R8 each represent hydrogen, alkyl, or contain alkoxy, alkoxycarbonyl, alkylfluorenyl, hydroxyl, carbonyl, halogen atom, carboxyl, amine, or amine The methylformyl alkyl group, the unsubstituted alkyl group and the substituted alkyl group each have 1 to 6 carbon atoms, the prerequisites do not include the case where R5 to R8 are all hydrogen and R5 and R8 are hydrogen When R6 and R7 are methyl groups. 17. The carbonyl bis (diene) ruthenium complex according to item 16 of the application, wherein in the general formula (7), at least one of R5 to R8 is an alkyl group or contains an alkoxy group or an alkoxy group. Carbonyl, alkyl, hydroxy, carbonyl, halogen, carboxy, amine, or aminomethyl alkyl groups, the unsubstituted alkyl group and substituted alkyl group each having 1 or 2 carbon atoms, and The rest is hydrogen, and its paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) -40-1227239 Α8 Β8 C8 D8 VI. Patent application scope 6 The prerequisite is that R5 to R8 are not hydrogen This is the case where R5 and R8 are hydrogen, and R6 and R7 are methyl. 18. The carbonyl bis (diene) ruthenium complex according to item 16 of the application, wherein 'in the general formula (7), R5 and R7 are hydrogen, and R6 and R8 are methyl. 19. A method for producing a carbonyl bis (diene) ruthenium complex as described in item 16 of the scope of patent application, wherein ruthenium chloride η-hydrate-wherein η is 1 or a larger number The reaction proceeds in the presence of zinc powder in the alcohol. 20. The method for manufacturing a carbonylbis (diene) ruthenium complex according to item 19 of the scope of patent application, wherein the diene is represented by the following general formula (8): (Please read the precautions on the back before filling this page ) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, where R5 to R8 each represents hydrogen, alkyl, or contains alkoxy, alkoxycarbonyl, alkylfluorenyl, hydroxyl, carbonyl, halogen atom, carboxyl, amine or The aminomethylamino alkyl group, the unsubstituted alkyl group and the substituted alkyl group each have 1 to 6 carbon atoms, the prerequisites do not include the case where R5 to R8 are all hydrogen and R5 and R8 are When hydrogen and R6 and R7 are methyl. 21. The method for producing a carbonylbis (diene) ruthenium complex as claimed in claim 20, wherein in the general formula (8), at least one of R5 to R8 is an alkyl group or contains an alkoxy group , Alkoxycarbonyl, alkylfluorenyl, hydroxy, carbonyl, halogen, carboxyl, amine or aminomethyl alkyl groups, the unsubstituted alkyl group and substituted alkyl group each having 1 or 2 carbons Atoms, while the rest are hydrogen. The prerequisites are that the cases where R5 to R8 are all hydrogen, and R5. This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) -41-1227239 A8 B8 C8 D8 6. The scope of patent application 7 and R8 are hydrogen, and R6 and R7 are methyl. 22. The method for producing a carbonylbis (diene) ruthenium compound according to item 20 of the application, wherein, in the general formula (8), R5 and R7 are hydrogen, and r6 and R8 are methyl. 23. The method for producing a carbonyl bis (diene) ruthenium complex according to item 19 of the application, wherein the alcohol solution of ruthenium chloride η-hydrate is a diene in which the diene is dropped into the diene or zinc powder is dispersed. It is reacted in an alcohol solution at 0 to 8 ° C. 24. A method for manufacturing a ruthenium-containing film, which comprises using a carbonylbis (diene) ruthenium complex as a precursor as described in item 16 of the patent application. 25. The method for manufacturing a ruthenium-containing thin film as claimed in item 24 of the patent application, wherein ruthenium or ruthenium oxide is grown on a substrate by a chemical vapor deposition method. 26. The method for producing a ruthenium-containing thin film as claimed in item 24 of the patent application Method, in which ruthenium or ruthenium oxide is formed on the substrate by thermal decomposition of the coating. -----------__ Ｍ 装 I — (Please read the precautions on the back before filling this page) The paper size printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs is compliant with China National Standards (CNS) A4 (210X297 mm) -42-