JP2023157842A - Ruthenium complex, method for producing the same, and method for producing ruthenium-containing thin film - Google Patents

Abstract

To provide a ruthenium complex which is useful for production of a ruthenium-containing thin film under low temperature conditions in which an oxidizing gas is not used.SOLUTION: The present invention provides a ruthenium complex represented by general formula (1). (In the formula, each of R1 and R2 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; each of R3 and R4 represents a hydrogen atom or combined together to form an alkylene group having 1 to 4 carbon atoms; and each of R5, R6 and R7 independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group.)SELECTED DRAWING: Figure 1

Description

The present invention relates to a ruthenium complex useful as a raw material for manufacturing semiconductor devices, a method for manufacturing the same, and a method for manufacturing a ruthenium-containing thin film using the ruthenium complex.

Ruthenium has features such as high conductivity, the ability to form conductive oxides, a high work function, excellent etching properties, and excellent lattice matching with copper. It is attracting attention as a material for memory electrodes such as DRAM, gate electrodes, copper wiring seed layers/adhesion layers, wiring, etc. Next-generation semiconductor devices are employing highly detailed and three-dimensional designs to further improve storage capacity and responsiveness. Therefore, in order to use ruthenium as a material constituting next-generation semiconductor devices, it is necessary to establish a technology to uniformly form a ruthenium-containing thin film with a thickness of several nanometers to several tens of nanometers on a three-dimensional substrate. is necessary. Technologies for producing metal thin films on three-dimensional substrates include the use of vapor phase deposition methods based on chemical reactions, such as atomic layer deposition (ALD) and chemical vapor deposition (CVD). It is seen as a strong candidate. When ruthenium is used as the next-generation DRAM lower electrode or copper wiring seed layer/adhesion layer, titanium nitride, tantalum nitride, or the like is expected to be used as the underlying barrier metal. If the barrier metal is oxidized during the production of a ruthenium-containing thin film, problems such as deterioration of barrier performance, poor conduction with transistors due to increased resistance, and decreased responsiveness due to increased capacitance between interconnects. occurs. In order to avoid these problems, there is a need for materials that enable the production of ruthenium-containing thin films under conditions that do not use oxidizing gases such as oxygen or ozone. Furthermore, with the recent miniaturization of semiconductor devices, low-temperature film formation (around 200° C.) is required in order to form ultra-thin films with excellent density and continuity.

Patent Document 1 describes tricarbonyl (η ⁴ -buta-1,3-diene)ruthenium, tricarbonyl (η ⁴ -2,3-dimethyl) as compounds having a structure similar to the ruthenium complex (1) of the present invention. but-1,3-diene)ruthenium and tricarbonyl(η ⁴ -cyclohexa-1,3-diene)ruthenium are described. However, there is no description of η ⁴ -diene complexes having a silyloxy group.

International Publication 2009/146423

An object of the present invention is to provide a ruthenium complex useful for producing a ruthenium-containing thin film under low-temperature conditions without using an oxidizing gas, a method for producing the ruthenium complex, and a method for producing a ruthenium-containing thin film.

As a result of intensive studies to solve the above problems, the present inventors found that the ruthenium complex represented by the general formula (1) is useful as a material for producing ruthenium-containing thin films under low-temperature conditions without using oxidizing gas. This discovery led to the completion of the present invention.

That is, the present invention includes the following embodiments.

[1] General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. A ruthenium complex represented by R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group.

[2] R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are a hydrogen atom or a group that together form an alkylene group having 1 to 2 carbon atoms, and R The ruthenium complex according to the above [1], wherein R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms.

[3] R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are a hydrogen atom, and R ⁵ , R ⁶ and R ⁷ are each independently a methyl group or an ethyl group. The ruthenium complex according to [1] or [2] above.

[4] General formula (2)

Dodecacarbonyl triruthenium represented by and general formula (3)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. represents a group to be formed. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group). , general formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group.

[5] R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are hydrogen atoms or a group that together form an alkylene group having 1 to 2 carbon atoms, and R ⁵ , R ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms, the method for producing a ruthenium complex according to [4] above.

[6] R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are hydrogen atoms, and R ⁵ , R ⁶ and R ⁷ are each independently a methyl group or an ethyl group. The method for producing a ruthenium complex according to [4] or [5] above.

[7] General formula (1)

(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group. A method for producing a ruthenium-containing thin film by decomposing a ruthenium complex on a substrate.

[8] The method for producing a ruthenium-containing thin film according to [7] above, which is a method for producing a ruthenium-containing thin film by a vapor phase deposition method based on a chemical reaction.

[9] The method for producing a ruthenium-containing thin film according to [7] or [8] above, which is a method for producing a ruthenium-containing thin film by chemical vapor deposition.

[10] The method for producing a ruthenium-containing thin film according to [7] or [8] above, which comprises decomposing using a reducing gas.

[11] The method for producing a ruthenium-containing thin film according to [7] or [8] above, wherein the ruthenium-containing thin film is a metallic ruthenium thin film.

By using the ruthenium complex (1) of the present invention as a material, a ruthenium-containing thin film can be produced under low temperature conditions without using an oxidizing gas.

1 is a DSC chart of tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) of Evaluation Example 1. 2 is a DSC chart of tricarbonyl[η ⁴ -(3-trimethylsilyloxy)penta-1,3-diene]ruthenium (1-14) of Evaluation Example 2. This is a DSC chart of tricarbonyl[η ⁴ -(2-trimethylsilyloxy)cyclohexa-1,3-diene]ruthenium (1-134) of Evaluation Example 3. 1 is a DSC chart of tricarbonyl(η ⁴ -cyclohexa-1,3-diene)ruthenium of Comparative Example 1. FIG. 2 is a diagram showing the CVD apparatus used in Comparative Examples 2 to 4 and Examples 4 to 7 and 10 to 18. 2 is a DSC chart of tricarbonyl[η ⁴ -(3-isopropyldimethylsilyloxy)penta-1,3-diene]ruthenium (1-17) of Evaluation Example 4. 2 is an AFM image of a thin film obtained from tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) of Example 10. 1 is an AFM image of a thin film obtained from tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) of Example 11. 2 is an AFM image of a thin film obtained from tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) of Example 12. 2 is an AFM image of a thin film obtained from tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) of Example 13. FIG. 7 is a diagram showing an ALD apparatus used in Example 19.

First, the definitions of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ in general formula (1) will be explained.

The alkyl group having 1 to 4 carbon atoms represented by R ¹ and R ² may be linear, branched or cyclic, and specifically includes a methyl group, ethyl group, propyl group, isopropyl group, cyclo Examples include propyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, and cyclobutyl group. In that the ruthenium complex (1) of the present invention has a vapor pressure and thermal stability suitable for use as a CVD material or an ALD material, R ¹ and R ² are each independently preferably a hydrogen atom or a methyl group; preferable.

The alkylene group having 1 to 4 carbon atoms formed by R ³ and R ⁴ may be linear or branched, and may be a methylene group, ethylene group, propylene group, butylene group, trimethylene group, tetra Examples include methylene group. The ruthenium complex (1) of the present invention has vapor pressure and thermal stability suitable as a CVD material or ALD material, and R ³ and R ⁴ are hydrogen atoms or together form a methylene group or an ethylene group. It is preferable to form an ethylene group, more preferably a hydrogen atom or to form an ethylene group together, particularly preferably a hydrogen atom.

The alkyl group having 1 to 4 carbon atoms represented by R ⁵ , R ⁶ and R ⁷ may be linear, branched or cyclic, and specifically includes methyl group, ethyl group, propyl group, isopropyl group. Examples include a cyclopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclobutyl group. Since the ruthenium complex (1) of the present invention has suitable vapor pressure and thermal stability as a CVD material or ALD material, R ⁵ , R ⁶ and R ⁷ are each independently preferably a methyl group or an ethyl group, and methyl More preferred are groups.

Specific examples of the ruthenium complex (1) of the present invention include:

etc. can be mentioned. Note that Me, Et, Pr, ⁱ Pr, Bu, and ^t Bu each represent a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group. The ruthenium complex (1) of the present invention has vapor pressure and thermal stability suitable as a CVD material or an ALD material (1-2), (1-3), (1-8), (1- 14), (1-15), (1-17), (1-20), (1-38), (1-39), (1-44), (1-62), (1-63) , (1-68), (1-74), (1-75), (1-80), (1-86), (1-87), (1-92), (1-134), ( 1-135), (1-140), (1-146), (1-147), (1-152) are preferred, and (1-2), (1-3), (1-8), ( 1-14), (1-15), (1-20), (1-38), (1-39), (1-44), (1-62), (1-63), (1- 68), (1-74), (1-75), (1-80), (1-86), (1-87), and (1-92) are more preferred; -3), (1-8), (1-14), (1-15) and (1-20) are particularly preferred.

Next, a method for producing the ruthenium complex (1) of the present invention will be explained.

The ruthenium complex (1) of the present invention can be manufactured by the following manufacturing method 1.

Production method 1 is a method for producing a ruthenium complex (1) by reacting dodecacarbonyl triruthenium (2) with a silyloxydiene (3).

Manufacturing method 1

(In the formula, R ¹ to R ⁷ have the same meanings as R ¹ to R ⁷ in general formula (1).)

R ¹ to R ⁷ in the silyloxydiene (3) have the same meanings as R ¹ to R ⁷ in the general formula (1), and the ruthenium complex (1) of the present invention has a vapor pressure and a temperature suitable for use as a CVD material or an ALD material. From the viewpoint of thermal stability, R ¹ and R ² are each independently preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom. R ³ and R ⁴ are preferably hydrogen atoms or together form a methylene group or ethylene group, more preferably hydrogen atoms or together form an ethylene group, and a hydrogen atom It is particularly preferable that R ⁵ , R ⁶ and R ⁷ are each independently preferably a methyl group or an ethyl group, more preferably a methyl group.

Specific examples of silyloxydiene (3) include:

etc. can be mentioned. In terms of the good yield of the ruthenium complex (1) of the present invention, (3-2), (3-3), (3-8), (3-14), (3-15), (3-20) ), (3-38), (3-39), (3-44), (3-62), (3-63), (3-68), (3-74), (3-75), (3-80), (3-86), (3-87), (3-92), (3-134), (3-135), (3-140), (3-146), (3 -147), (3-152) are preferred, and (3-2), (3-3), (3-8), (3-14), (3-15), (3-20), (3 -38), (3-39), (3-44), (3-62), (3-63), (3-68), (3-74), (3-75), (3-80 ), (3-86), (3-87), (3-92) are more preferred, and (3-2), (3-3), (3-8), (3-14), (3- 15) and (3-20) are particularly preferred.

Silyloxydiene (3) can be obtained by obtaining commercially available products, as well as in Chemical Communications, Volume 58, Page 1780 (2022), Journal of Organic Chemistry, Volume 54, Page 4553 (1989), Examples include manufacturing methods described in Organic Letters, Volume 11, Page 4842 (2009), Dalton Transactions, Volume 41, Page 13862 (2012), and the like.

Production method 1 is preferably carried out in an inert gas since the yield of ruthenium complex (1) is high. Specific examples of the inert gas include helium, neon, argon, krypton, xenon, and nitrogen gas, with argon or nitrogen gas being more preferred.

Production method 1 is preferably carried out in an organic solvent since the yield of ruthenium complex (1) is good. When manufacturing method 1 is carried out in an organic solvent, specific examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, methylcyclohexane, ethylcyclohexane, and petroleum ether, diethyl ether, and diisopropyl. Ethers such as ether, dibutyl ether, cyclopentyl methyl ether, cyclopentyl ethyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, benzene, toluene, xylene, ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, 2-methylpropylbenzene, Examples include aromatic hydrocarbons such as 1-methylpropylbenzene, tert-butylbenzene, and 1,3,5-trimethylbenzene (mesitylene). One type of these organic solvents can be used alone, or a plurality of them can be used as a mixture in any ratio. As the organic solvent, aromatic hydrocarbons are preferred, and toluene is more preferred, since the yield of the ruthenium complex (1) is high.

Next, the molar ratio of dodecacarbonyl triruthenium (2) and silyloxydiene (3) when carrying out production method 1 will be explained. Ruthenium complex (1) can be produced by using 3 or more moles of silyloxydiene (3) per mole of dodecacarbonyltriruthenium (2). Preferably, by using 10 moles or more of silyloxydiene (3) per mole of dodecacarbonyltriruthenium (2), the ruthenium complex (1) can be produced with good yield.

Further, the reaction temperature and reaction time when implementing manufacturing method 1 will be explained. As a specific example, the ruthenium complex (1) is produced in good yield by selecting an appropriately selected reaction temperature from a temperature range of 50°C to 180°C and a reaction time appropriately selected from a range of 5 hours to 120 hours. I can do it.

The ruthenium complex (1) produced by Production Method 1 can be purified by a metal complex purification method common to those skilled in the art. Specific purification methods include filtration, extraction, centrifugation, decantation, distillation, sublimation, crystallization, column chromatography, and the like.

Next, a method for producing a ruthenium-containing thin film, which is characterized by vaporizing the ruthenium complex (1) and decomposing the ruthenium complex on a substrate, will be described in detail.

Examples of methods for producing the ruthenium-containing thin film include common technical means used by those skilled in the art to produce metal-containing thin films. Specifically, a vapor phase deposition method based on a chemical reaction, and a solution method such as a dip coating method, a spin coating method, or an inkjet method can be exemplified. In this specification, a vapor phase deposition method based on a chemical reaction is a method for producing a ruthenium-containing thin film by vaporizing a ruthenium complex represented by general formula (1) and decomposing it on a substrate. This includes CVD methods such as thermal CVD method, plasma CVD method, and optical CVD method, and ALD method. A vapor phase deposition method based on a chemical reaction is preferred, and a CVD method or an ALD method is more preferred, since it is easy to uniformly form a ruthenium-containing thin film even on the surface of a substrate having a three-dimensional structure. The CVD method is particularly preferred because of its good film formation rate, and the ALD method is particularly preferred because it provides good step coverage. For example, when producing a ruthenium-containing thin film by CVD or ALD, the ruthenium complex (1) is vaporized and supplied to a reaction chamber, and the ruthenium complex (1) is decomposed on a substrate installed in the reaction chamber. A ruthenium-containing thin film can be produced on the substrate. Methods for decomposing the ruthenium complex (1) include the usual technical means used by those skilled in the art to produce metal-containing thin films. Specifically, examples include a method in which the ruthenium complex (1) is reacted with a reaction gas, and a method in which heat, plasma, light, etc. are applied to the ruthenium complex (1).

When using a reactive gas, examples of the reactive gas that can be used include reducing gases and oxidizing gases. Specific examples of reducing gases include hydrogen, ammonia, methylamine, ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, tert-butylamine, dimethylamine, N-ethylmethylamine, diethylamine, N- Methylpropylamine, N-methylisopropylamine, N-ethylpropylamine, trimethylamine, N,N-dimethylethylamine, triethylamine, hydrazine, aniline, methanol, ethanol, propanol, isopropanol, butanol, 2-methyl-1-propanol, tert - Examples include butanol, formic acid, acetic acid, and monosilane. Specific examples of the oxidizing gas include oxygen, ozone, water vapor, hydrogen peroxide, laughing gas, hydrogen chloride, and nitric acid gas. One type of these reactive gases can be used alone, or a plurality of them can be used in a mixture at an arbitrary ratio. Ammonia, hydrogen, formic acid, or ethanol are preferable as the reducing gas, and oxygen, ozone, or water vapor is preferable as the oxidizing gas, since they are less restricted by the specifications of the film forming apparatus and are easy to handle. In order to prevent oxidation of the base, a reducing gas is particularly preferable as the reactive gas, and ammonia, formic acid, hydrogen, or a mixed gas of ammonia and hydrogen is even more preferable in terms of the film formation rate and film quality of the ruthenium-containing thin film. The flow rate of the reaction gas is adjusted as appropriate depending on the reactivity of the material and the capacity of the reaction chamber. For example, when the capacity of the reaction chamber is 1 to 10 L, the flow rate of the reaction gas is not particularly limited, and is preferably 1 to 10,000 sccm for economical reasons.

By appropriately selecting and using these decomposition methods, a ruthenium-containing thin film can be produced. It is also possible to use a combination of multiple decomposition methods. The method for supplying the ruthenium complex (1) to the reaction chamber includes, for example, methods commonly used by those skilled in the art, such as bubbling and liquid vaporization supply systems, and is not particularly limited.

As the carrier gas and diluent gas when producing a ruthenium-containing thin film by the CVD method or the ALD method, rare gases such as helium, neon, argon, krypton, and xenon, or nitrogen gas are preferable.For economical reasons, nitrogen gas and helium are preferable. , neon, and argon are particularly preferred. The flow rates of the carrier gas and diluent gas are adjusted as appropriate depending on the capacity of the reaction chamber. For example, when the capacity of the reaction chamber is 1 to 10 L, the flow rate of the carrier gas is not particularly limited and is preferably 1 to 10,000 sccm for economical reasons. Note that in this specification, sccm is a unit expressing the flow rate of gas, and 1 sccm indicates that gas is moving at a speed of 2.68 mmol/h when converted to ideal gas.

The substrate temperature when producing a ruthenium-containing thin film by the CVD method or the ALD method is appropriately selected depending on whether heat, plasma, light, etc. are used, the type of reaction gas, etc. For example, when ammonia is used as a reactive gas without using light or plasma in combination, there is no particular restriction on the substrate temperature, and for economic reasons, 150° C. to 1000° C. is preferable. The temperature is more preferably 200° C. to 400° C. in terms of film formation rate and film quality.

As the ruthenium-containing thin film obtained by the production method of the present invention, for example, when the ruthenium complex (1) is used alone, a metal ruthenium thin film, a ruthenium oxide thin film, a ruthenium nitride thin film, a ruthenium oxynitride thin film, etc. are obtained. Furthermore, when used in combination with other metal materials, a ruthenium-containing composite thin film can be obtained. For example, when used in combination with a strontium material, a SrRuO ₃ thin film can be obtained. Examples of the strontium material include bis(dipivaloylmethanato)strontium, diethoxystrontium, bis(1,1,1,5,5,5-hexafluoro-2,4-pentanedionato)strontium, bis( Examples include pentamethylcyclopentadienyl) strontium and bis(triisopropylcyclopentadienyl) strontium. Furthermore, it is also possible to obtain a ruthenium-containing composite film containing transition metals such as platinum, iridium, and rhodium, and typical elements such as silicon and aluminum. Furthermore, when producing a ruthenium-containing composite thin film by the CVD method or the ALD method, the ruthenium complex (1) and other metal materials may be supplied into the reaction chamber separately or may be supplied after mixing. .

By using the ruthenium-containing thin film of the present invention as a component, a high-performance semiconductor device with improved storage capacity and responsiveness can be manufactured. Examples of semiconductor devices include semiconductor storage devices such as DRAM, FeRAM, and ReRAM, and field effect transistors. Examples of these components include capacitor electrodes, gate electrodes, copper wiring liners, and wiring.

Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited thereto.

Reference example 1

Under an argon atmosphere, 25.0 g (0.30 mol) of 1-penten-3-one and 33.0 g (0.33 mol) of triethylamine were added to a solution of 28.0 g (0.32 mol) of lithium bromide in 400 mL of tetrahydrofuran at 20°C. , 36.0 g (0.33 mol) of chlorotrimethylsilane were added. After stirring at 20°C for 72 hours, the solvent was distilled off under reduced pressure. 150 mL of hexane was added to the remaining yellow liquid, and the mixture was vigorously stirred at room temperature. After filtering the resulting suspension, the solvent was distilled off from the filtrate under reduced pressure. By distilling the remaining yellow liquid under reduced pressure (heating temperature 70°C/distillation temperature 57°C/back pressure 1800 Pa), (3-trimethylsilyloxy)pent-1,3-diene (3-14) was obtained as a transparent liquid. (3.20 g, yield 7%).
^1H -NMR (400MHz, CDCl ₃ , δ)
6.13-6.21 (m, 1H), 5.21-5.26 (m, 1H), 4.85-4.95 (m, 2H), 1.63-1.65 (m, 3H) ), 0.215 (s, 9H). .

Reference example 2

Under an argon atmosphere, 10.0 g (125 mmol) of 1,3-cyclohexadiene was added to a suspension of 5.00 g (7.82 mmol) of dodecacarbonyltriruthenium in 150 mL of toluene at 20°C. After stirring at 80° C. for 48 hours, the solvent was distilled off under reduced pressure. The remaining yellow solid was distilled under reduced pressure (heating temperature 100°C/back pressure 32 Pa) to obtain tricarbonyl(η ⁴ -cyclohexa-1,3-diene)ruthenium as a yellow liquid (0.32 g, yield 5). %).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
4.78-4.81 (m, 2H), 2.82-2.85 (m, 2H), 1.38-1.46 (m, 4H). .

Example 1

Under an argon atmosphere, 36.0 g (2-trimethylsilyloxy)buta-1,3-diene (3-2) (36.0 g (2-trimethylsilyloxy)buta-1,3-diene (3-2) ( 253 mmol) was added. After stirring at 80° C. for 70 hours, the solvent was distilled off under reduced pressure. By distilling the remaining yellow solid under reduced pressure (heating temperature 100°C/back pressure 77 Pa), tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) was converted into a yellow liquid. (3.40 g, yield 21%).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
4.95-5.00 (m, 1H), 2.02-2.04 (m, 1H), 1.17-1.20 (m, 1H), 0.44-0.45 (m, 1H) ), 0.045 (s, 9H), -0.41 (m, 1H). .

Example 2

Under an argon atmosphere, (3-trimethylsilyloxy)penta-1,3-diene (3 -14) 3.18g (20.3mmol) was added. After stirring at 80° C. for 84 hours, the solvent was distilled off under reduced pressure. By distilling the remaining yellow solid under reduced pressure (heating temperature 80°C/back pressure 40 Pa), tricarbonyl[η ⁴ -(3-trimethylsilyloxy)penta-1,3-diene]ruthenium (1-14) is converted into a yellow liquid. (150 mg, yield 9%).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
4.74-4.78 (m, 1H), 1.60-1.62 (m, 1H), 1.47-1.49 (m, 3H), 1.12-1.15 (m, 1H) ), 0.068 (s, 9H), -0.39 (m, 1H). .

Example 3

Under an argon atmosphere, 5.00 g (2-trimethylsilyloxy)cyclohexa-1,3-diene (3-134) was added to a suspension of 1.00 g (1.56 mmol) dodecacarbonyltriruthenium in 50 mL toluene at 20°C 29.7 mmol) was added. After stirring at 80° C. for 48 hours, the solvent was distilled off under reduced pressure. By distilling the remaining yellow solid under reduced pressure (heating temperature 80°C/back pressure 43 Pa), tricarbonyl[η ⁴ -(2-trimethylsilyloxy)cyclohexa-1,3-diene]ruthenium (1-134) was converted into a yellow liquid. (400 mg, yield 23%).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
5.04-5.06 (m, 1H), 3.36-3.39 (m, 1H), 2.48-2.51 (m, 1H), 1.60-1.65 (m, 2H) ), 1.34-1.38 (m, 2H), 0.048 (s, 9H). .

Evaluation example 1
Thermal analysis of tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2).

As a sample, 7.8 mg of tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) obtained in Example 1 was used by differential scanning calorimetry (DSC). .
FIG. 1 shows the results of DSC, which was measured in a closed container in an argon atmosphere at a temperature increase rate of 10° C./min. A thermal decomposition onset temperature of 174° C. was observed in the DSC curve.

Evaluation example 2
Thermal analysis of tricarbonyl[η ⁴ -(3-trimethylsilyloxy)penta-1,3-diene]ruthenium (1-14).

As a sample, 3.6 mg of tricarbonyl[η ⁴ -(3-trimethylsilyloxy)penta-1,3-diene]ruthenium (1-14) obtained in Example 2 was used in differential scanning calorimetry (DSC). .
FIG. 2 shows the results of DSC, which was measured in a closed container in an argon atmosphere at a temperature increase rate of 10° C./min. A thermal decomposition onset temperature of 157° C. was observed in the DSC curve.

Evaluation example 3
Thermal analysis of tricarbonyl[η ⁴ -(2-trimethylsilyloxy)cyclohexa-1,3-diene]ruthenium (1-134).

As a sample, 4.0 mg of tricarbonyl[η ⁴ -(2-trimethylsilyloxy)cyclohexa-1,3-diene]ruthenium (1-134) obtained in Example 3 was used in differential scanning calorimetry (DSC). .
FIG. 3 shows the results of DSC, which was measured in a closed container in an argon atmosphere at a temperature increase rate of 10° C./min. A thermal decomposition onset temperature of 119° C. was observed in the DSC curve.

The results of Evaluation Examples 1 to 3 show that the ruthenium complex (1) of the present invention is promising as a material for low-temperature film formation around 200°C.

Comparative example 1
Thermal analysis of tricarbonyl(η ⁴ -cyclohexa-1,3-diene)ruthenium.

As a sample, 5.2 mg of tricarbonyl(η ⁴ -cyclohexa-1,3-diene)ruthenium obtained in Reference Example 2 was measured by differential scanning calorimetry (DSC).
FIG. 4 shows the results of DSC, which was measured in a closed container in an argon atmosphere at a temperature increase rate of 10° C./min. A thermal decomposition onset temperature of 162° C. was observed in the DSC curve.
From the results of Evaluation Example 3 and Comparative Example 1, introducing a silyloxy group into the η ⁴ -diene ligand lowers the thermal decomposition initiation temperature, and the ruthenium complex (1) of the present invention is even more promising as a material for low-temperature film formation. I understand that.

Examples of manufacturing ruthenium-containing thin films using reducing gas (Comparative Examples 2 to 4 and Examples 4 to 7).

Comparative example 2
An example of producing a ruthenium-containing thin film on a Si substrate using a known material.
Using tricarbonyl (η ⁴ -methylene-1,3-propanediyl)ruthenium produced by the method described in International Publication No. 2021/153639 as a known material and using ammonia as a reactant, it was deposited on a Si substrate at the substrate temperature. A ruthenium-containing thin film was produced by thermal CVD at 200°C. FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as shown in Table 1, and other conditions are as follows.
Material container temperature: 30° C., total pressure inside the material container: 40.0 kPa, carrier gas flow rate: 10 sccm, ammonia gas flow rate: 50 sccm, diluent gas flow rate: 40 sccm, carrier gas and diluent gas: argon.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were not detected.

Comparative example 3
An example of producing a ruthenium-containing thin film on a Si substrate using a known material.
Using tricarbonyl (η ⁴ -methylene-1,3-propanediyl)ruthenium produced by the method described in International Publication No. 2021/153639 as a known material and using ammonia as a reactant, it was deposited on a Si substrate at the substrate temperature. A ruthenium-containing thin film was produced by thermal CVD at 250°C. FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as shown in Table 1, and the other conditions are the same as in Comparative Example 2.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 4.7 nm.

Comparative example 4
An example of producing a ruthenium-containing thin film on a SiO ₂ substrate using a known material.
Using tricarbonyl (η ⁴ -methylene-1,3-propanediyl)ruthenium produced by the method described in International Publication No. 2021/153639 as a known material and using hydrogen as a reactant, a substrate was formed on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a temperature of 200°C. FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as shown in Table 1, and other conditions are as follows.
Material container temperature: 30° C., total pressure inside the material container: 40.0 kPa, carrier gas flow rate: 10 sccm, hydrogen gas flow rate: 4 sccm, diluent gas flow rate: 86 sccm, carrier gas and diluent gas: argon.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were not detected.

Example 4
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and ammonia as a reactant, on a Si substrate, A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 200°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as shown in Table 1, and other conditions are as follows.
Material container temperature: 50° C., total pressure inside the material container: 26.7 kPa, carrier gas flow rate: 10 sccm, ammonia gas flow rate: 50 sccm, dilution gas flow rate: 40 sccm, carrier gas and dilution gas: argon.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 9.3 nm.

Example 5
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and ammonia as a reactant, on a Si substrate, A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as shown in Table 1, and the other conditions are as in Example 4.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 29.8 nm.

Example 6
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and hydrogen as a reactant, it was deposited on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 200°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as shown in Table 1, and other conditions are as follows.
Material container temperature: 50° C., total pressure inside the material container: 26.7 kPa, carrier gas flow rate: 10 sccm, hydrogen gas flow rate: 4 sccm, diluent gas flow rate: 86 sccm, carrier gas and diluent gas: argon.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 9.3 nm.

Example 7
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and formic acid as a reactant, on a Cu substrate, A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as shown in Table 1, and other conditions are as follows.
Material container temperature: 50° C., total pressure inside the material container: 26.7 kPa, carrier gas flow rate: 10 sccm, formic acid gas flow rate: 3 sccm, diluent gas flow rate: 87 sccm, carrier gas and diluent gas: argon.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 22.3 nm.

From the above Examples 4 to 7, it can be seen that the ruthenium complex (1) of the present invention is a material capable of producing a ruthenium-containing thin film at a low temperature around 200° C. and under reducing gas conditions. Furthermore, from a comparison between Comparative Examples 2 to 4 and Examples 4 to 7, the ruthenium complex (1) of the present invention is better than the known materials despite having three carbonyl ligands in common. It can be seen that this is a material that can be formed into a film at a lower temperature.

Reference example 3

Under an argon atmosphere, 1.8 g (0.021 mol) of 1-penten-3-one and 3.3 g (0.032 mol) of triethylamine were added to a solution of 3.7 g (0.043 mol) of lithium bromide in 30 mL of tetrahydrofuran at 20°C. , 4.4 g (0.032 mol) of chloro(isopropyl)dimethylsilane were added. After stirring at 20° C. for 16 hours, the solvent was distilled off under reduced pressure. 30 mL of hexane was added to the remaining yellow liquid, and the mixture was vigorously stirred at room temperature. After filtering the resulting suspension, the solvent was distilled off from the filtrate under reduced pressure. By distilling the remaining yellow liquid under reduced pressure (heating temperature 90°C/distillation temperature 76-78°C/back pressure 2000Pa), (3-isopropyldimethylsilyloxy)pent-1,3-diene (3-17) was obtained. Obtained as a colorless liquid (1.85 g, yield 47%).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
6.10-6.19 (m, 1H), 5.40-5.45 (m, 1H), 4.90-4.94 (m, 1H), 4.70-4.80 (m, 1H) ), 1.60 (d, J=6.8Hz, 3H), 0.70-1.10 (m, 7H), 0.13 (s, 6H). .

Example 8

Under an argon atmosphere, the (3-isopropyldimethylsilyloxy)penta-1,3-diene synthesized in Reference Example 3 was added to a suspension of 1.00 g (1.56 mmol) of dodecacarbonyltriruthenium in 50 mL of toluene at 20°C. (3-17) 1.85 g (10.0 mmol) was added. After stirring at 80° C. for 48 hours, the solvent was distilled off under reduced pressure. By distilling the remaining yellow solid under reduced pressure (heating temperature 120°C/back pressure 19 Pa), tricarbonyl[η ⁴ -(3-isopropyldimethylsilyloxy)pent-1,3-diene]ruthenium (1-17) was obtained. Obtained as a yellow liquid (70 mg, yield 4%).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
4.74-4.80 (m, 1H), 1.49 (d, J=6.4Hz, 3H), 1.13-1.17 (m, 1H), 1.07-1.13 (m , 1H), 0.68-0.94 (m, 7H), 0.065 (m, 6H), -0.38 (m, 1H). .

Reference example 4

Under an argon atmosphere, a solution of 1.48 g (0.015 mol) of 2-cyclohexen-1-one in 10 mL of tetrahydrofuran was added at -70°C to a solution of lithium diisopropylamide in 10 mL (2 mol/L, 0.020 mol) of tetrahydrofuran, and then chloro( A solution of 1.89 g (0.015 mol) of dimethylsilane in 10 mL of tetrahydrofuran was added. The reaction solution was stirred at -70°C for 30 minutes and then at 20°C for 16 hours. After distilling off the solvent under reduced pressure, 30 mL of hexane was added to the remaining yellow liquid, and the mixture was vigorously stirred at room temperature. After filtering the resulting suspension, the solvent was distilled off from the filtrate under reduced pressure. By distilling the remaining yellow liquid under reduced pressure (heating temperature 85°C/distillation temperature 68-69°C/back pressure 400Pa), (2-ethyldimethylsilyloxy)cyclohexa-1,3-diene (3-135) was obtained. Obtained as a colorless liquid (2.27 g, yield 81%).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
5.88-5.91 (m, 1H), 5.68-5.73 (m, 1H), 4.91-4.94 (m, 1H), 2.02-2.14 (m, 2H) ), 1.85-1.99 (m, 2H), 0.98 (t, J = 8.0Hz, 3H), 0.63 (q, J = 8.0Hz, 2H), 0.16 (s , 6H). .

Example 9

Under an argon atmosphere, the (2-ethyldimethylsilyloxy)cyclohexa-1,3-diene synthesized in Reference Example 4 was added to a suspension of 1.00 g (1.56 mmol) of dodecacarbonyltriruthenium in 50 mL of toluene at 20°C. 2.27 g (12.4 mmol) of (3-135) was added. After stirring at 80° C. for 48 hours, the solvent was distilled off under reduced pressure. By distilling the remaining yellow solid under reduced pressure (heating temperature 100°C/back pressure 21 Pa), tricarbonyl[η ⁴ -(2-ethyldimethylsilyloxy)cyclohexa-1,3-diene]ruthenium (1-135) was obtained. Obtained as a yellow liquid (90 mg, 5% yield).
^1H -NMR (400MHz, C ₆ D ₆ , δ)
5.06-5.10 (m, 1H), 3.36-3.41 (m, 1H), 2.48-2.52 (m, 1H), 1.50-1.70 (m, 2H) ), 1.30-1.50 (m, 2H), 0.85 (t, J = 8.0Hz, 3H), 0.49 (q, J = 8.0Hz, 2H), 0.043 (s , 6H). .

Evaluation example 4
Thermal analysis of tricarbonyl[η ⁴ -(3-isopropyldimethylsilyloxy)penta-1,3-diene]ruthenium (1-17).

As a sample, 3.8 mg of tricarbonyl[η ⁴ -(3-isopropyldimethylsilyloxy)penta-1,3-diene]ruthenium (1-17) obtained in Example 8 was measured by differential scanning calorimetry (DSC). Using.
FIG. 6 shows the results of DSC, which was measured in a closed container in an argon atmosphere at a temperature increase rate of 10° C./min. A thermal decomposition onset temperature of 170° C. was observed in the DSC curve.

Example 10
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and ammonia as a reactant, it was deposited on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 15° C., total pressure inside the material container: 6.7 kPa, carrier gas flow rate: 20 sccm, ammonia gas flow rate: 50 sccm, diluent gas flow rate: 30 sccm, carrier gas and diluent gas: argon, film formation time: 30 minutes.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 16.3 nm.

When the surface of the produced thin film was observed using an atomic force microscope (AFM), it was found that a thin film with extremely high surface smoothness with a root mean square roughness (RMS) of 1.14 nm was formed. The obtained AFM image is shown in FIG.

Example 11
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and formic acid as a reactant, it was deposited on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 15° C., total pressure inside the material container: 6.7 kPa, carrier gas flow rate: 20 sccm, formic acid gas flow rate: 3 sccm, diluent gas flow rate: 57 sccm, carrier gas and diluent gas: argon, film formation time: 30 minutes.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 12.8 nm.

When the surface of the produced thin film was observed using an atomic force microscope (AFM), it was found that a thin film with extremely high surface smoothness with a root mean square roughness (RMS) of 1.24 nm was formed. The obtained AFM image is shown in FIG.

Example 12
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and ammonia as a reactant, it was deposited on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 200°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 50° C., total pressure inside the material container: 26.7 kPa, carrier gas flow rate: 10 sccm, ammonia gas flow rate: 50 sccm, diluent gas flow rate: 40 sccm, carrier gas and diluent gas: argon, film formation time: 90 minutes.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 31.7 nm.

When the surface of the produced thin film was observed using an atomic force microscope (AFM), it was found that a thin film with extremely high surface smoothness with a root mean square roughness (RMS) of 1.37 nm was formed. The obtained AFM image is shown in FIG.

Example 13
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and formic acid as a reactant, it was deposited on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 200°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 50° C., total pressure inside the material container: 26.7 kPa, carrier gas flow rate: 10 sccm, formic acid gas flow rate: 3 sccm, diluent gas flow rate: 87 sccm, carrier gas and diluent gas: argon, film formation time: 360 minutes.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 56.4 nm.

When the surface of the produced thin film was observed using an atomic force microscope (AFM), it was found that a thin film with extremely high surface smoothness with a root mean square roughness (RMS) of 0.93 nm was formed. The obtained AFM image is shown in FIG.

Example 14
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and ammonia and hydrogen as reactants, a SiO ₂ substrate was prepared. A ruthenium-containing thin film was formed thereon by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 15°C, total pressure inside the material container: 6.7 kPa, carrier gas flow rate: 20 sccm, ammonia gas flow rate: 60 sccm, hydrogen gas flow rate: 20 sccm, dilution gas flow rate: 0 sccm, carrier gas and dilution gas: argon, film formation Time: 65 minutes, reaction chamber total pressure: 300 Pa.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 14.0 nm.

Example 15
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and ammonia and hydrogen as reactants, a SiO ₂ substrate was prepared. A ruthenium-containing thin film was formed thereon by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 15°C, total pressure inside the material container: 6.7 kPa, carrier gas flow rate: 20 sccm, ammonia gas flow rate: 40 sccm, hydrogen gas flow rate: 40 sccm, dilution gas flow rate: 0 sccm, carrier gas and dilution gas: argon, film formation Time: 65 minutes, reaction chamber total pressure: 300 Pa.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 13.5 nm.

Example 16
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and ammonia and hydrogen as reactants, a SiO ₂ substrate was prepared. A ruthenium-containing thin film was formed thereon by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 15°C, total pressure inside the material container: 6.7 kPa, carrier gas flow rate: 20 sccm, ammonia gas flow rate: 20 sccm, hydrogen gas flow rate: 60 sccm, dilution gas flow rate: 0 sccm, carrier gas and dilution gas: argon, film formation Time: 65 minutes, reaction chamber total pressure: 300 Pa.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 13.1.

Example 17
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and hydrogen as a reactant, it was deposited on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 250°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 15°C, total pressure inside the material container: 6.7 kPa, carrier gas flow rate: 20 sccm, hydrogen gas flow rate: 90 sccm, diluent gas flow rate: 0 sccm, carrier gas and diluent gas: argon, film formation time: 65 minutes, reaction Chamber total pressure: 300Pa.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 13.1 nm.

Example 18
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a material and hydrogen as a reactant, it was deposited on a SiO ₂ substrate. A ruthenium-containing thin film was produced by thermal CVD at a substrate temperature of 280°C.

FIG. 5 shows a schematic diagram of the apparatus used for producing the thin film. The film forming conditions are as follows.

Material container temperature: 15°C, total pressure inside the material container: 6.7 kPa, carrier gas flow rate: 20 sccm, hydrogen gas flow rate: 50 sccm, diluent gas flow rate: 30 sccm, carrier gas and diluent gas: argon, film formation time: 65 minutes, reaction Chamber total pressure: 300Pa.
When the produced thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 17.4 nm.

Example 19
Using tricarbonyl[η ⁴ -(2-trimethylsilyloxy)buta-1,3-diene]ruthenium (1-2) produced in Example 1 as a raw material, a ruthenium-containing thin film was produced on a SiO ₂ substrate by ALD method. did. FIG. 11 shows an outline of the apparatus used for producing the thin film. The thin film manufacturing conditions are as follows.

Purge gas: argon, reducing gas: ammonia, raw material gas: (1-2), carrier gas: argon 20 sccm, material container temperature: 15°C, material vapor pressure: 6.7 kPa. Raw material vapor vaporized by bubbling. The following steps (a) to (h) were repeated 100 times as one cycle for a total of 50 minutes under the following conditions: substrate temperature: 300° C., reaction chamber total pressure: 1 to 300 Pa.
(a) 80 sccm of purge argon gas and 20 sccm of carrier argon gas containing source gas are introduced into the chamber for 3 seconds, the reaction chamber pressure is set to 300 Pa, and the gas is adsorbed onto the substrate surface.
(b) Stop introducing purge argon gas and carrier argon gas containing source gas, and evacuate the chamber for 4 seconds to remove unreacted gas and byproducts.
(c) Purge Argon gas at 400 sccm is introduced into the chamber for 1 second to increase the reaction chamber pressure.
(d) Purge Argon gas of 100 sccm is introduced into the chamber for 6 seconds, and the reaction chamber pressure is set to 300 Pa.
(e) Purge Stop introducing argon gas, and introduce 100 sccm of ammonia gas into the reaction chamber for 10 seconds.
(f) Stop introducing ammonia gas and evacuate the chamber for 2 seconds to remove unreacted gas and byproducts.
(g) Purging Argon gas at 400 sccm is introduced into the chamber for 1 second to increase the pressure in the reaction chamber.
(h) Purge Argon gas of 100 sccm is introduced into the chamber for 3 seconds, and the reaction chamber pressure is set to 300 Pa.

When the manufactured thin film was confirmed by fluorescent X-ray analysis, characteristic X-rays based on ruthenium were detected. The film thickness was calculated from the intensity of the detected X-rays to be 2.3 nm.

1 Material container 2 Thermostatic chamber 3 Reaction chamber 4 Substrate 5 Reaction gas inlet 6 Dilution gas inlet 7 Carrier gas inlet 8 Mass flow controller 9 Mass flow controller 10 Mass flow controller 11 Oil rotary pump 12 Exhaust

Claims (11)

General formula (1)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. A ruthenium complex represented by R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group. R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are hydrogen atoms or a group that together form an alkylene group having 1 to 2 carbon atoms, and R ⁵ , R The ruthenium complex according to claim 1, wherein ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms. R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are hydrogen atoms, and R ⁵ , R ⁶ and R ⁷ are each independently a methyl group or an ethyl group, The ruthenium complex according to claim 1 or 2. General formula (2)
Dodecacarbonyl triruthenium represented by and general formula (3)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. represents a group to be formed. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group). , general formula (1)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group. R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are hydrogen atoms or a group that together form an alkylene group having 1 to 2 carbon atoms, and R ⁵ , R 5. The method for producing a ruthenium complex according to claim 4, wherein ⁶ and R ⁷ are each independently an alkyl group having 1 to 4 carbon atoms. R ¹ and R ² are each independently a hydrogen atom or a methyl group, R ³ and R ⁴ are hydrogen atoms, and R ⁵ , R ⁶ and R ⁷ are each independently a methyl group or an ethyl group, A method for producing a ruthenium complex according to claim 4 or 5. General formula (1)
(In the formula, R ¹ and R ² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ and R ⁴ represent a hydrogen atom or an alkylene group having 1 to 4 carbon atoms together. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a vinyl group or an allyl group. A method for producing a ruthenium-containing thin film by decomposing a ruthenium complex on a substrate. The method for producing a ruthenium-containing thin film according to claim 7, which is a method for producing a ruthenium-containing thin film by a vapor phase deposition method based on a chemical reaction. The method for producing a ruthenium-containing thin film according to claim 7 or 8, which is a method for producing a ruthenium-containing thin film by chemical vapor deposition. The method for producing a ruthenium-containing thin film according to claim 7 or 8, characterized in that the decomposition is performed using a reducing gas. The method for producing a ruthenium-containing thin film according to claim 7 or 8, wherein the ruthenium-containing thin film is a metallic ruthenium thin film.