Film forming material and production method

Abstract

To provide a method that enables the stable supply of raw materials by, for example, preventing solidification and clogging during transportation or through pipelines, thereby forming a high-quality ruthenium-based film.SOLUTION: The present invention provides a material for forming a ruthenium-based film, the material comprising Ru[i-C3H7-N-C(n-C3H7)-N-i-C3H7]2.

Description

[Technical field]

[0001] The present invention relates to a film formation technique. [Background technology]

[0002] Ruthenium-based films (e.g., films of metallic ruthenium, ruthenium alloy, ruthenium oxide, or ruthenium nitride. These films are also referred to simply as ruthenium films (Ru films) below) are in demand in various fields. For example, they are used as conductive materials, magnetic materials, or catalytic materials. In recent years, Ru films have been attracting attention, particularly as an LSI wiring material.

[0003] The following methods have been proposed for forming a Ru film. This is a chemical vapor deposition method (CVD method) or an atomic layer deposition method (ALD method) using a cyclopentadienyl-based ruthenium complex (for example, bisethylcyclopentadienyl ruthenium). When using a cyclopentadienyl-based ruthenium complex in the CVD method (or the ALD method), oxygen is required as a reactant. Therefore, it is difficult to form a film on a substrate that does not like oxygen. Furthermore, the CVD method requires a long incubation time. The ALD method requires many incubation cycles (e.g., at least 500 cycles or more). The thin film wiring used in recent LSIs is thin (e.g., a few nm). When the incubation time is long (many incubation cycles), it is difficult to grasp the point in time when film deposition began. Therefore, it is difficult to control the film thickness. This is particularly difficult when forming a thin film (e.g., a few nm).

[0004] Other than the cyclopentadienyl ruthenium complex, other compounds have been proposed. For example, there is a compound in which two carbonyl groups and one amidinate group are bonded to ruthenium. Another example is Ru2{μ2-η3-N(t-Bu)-C(H)-C(i-Pr)}(CO)6. However, all of these require oxygen as a reactant.

[0005] There is a demand for a film formation technique that requires no or little incubation time (no or little incubation cycle) and does not use oxygen as a reactant. To achieve this, a compound different from the above-mentioned compounds (the cyclopentadienyl-based ruthenium complexes and the carbonyl-based ruthenium complexes) is required.

[0006] A trivalent amidinate complex {Ru[i-C3H7-NC(CH3)-Ni-C3H7]3} has been proposed. This amidinate complex has a large molecular weight. The sublimation temperature is reported to be 85°C / 0.05 torr. The vapor pressure is too low for practical use. The trivalent amidinate complex is a solid. Therefore, it is difficult to use. [Prior art documents] [Non-patent literature]

[0007] [Non-Patent Document 1] Huazhi Li, Titta Aaltonen, Zhengwen Li, Booyong S. Lim4 and Roy G. Gordon, Synthesis and Characterization of Ruthenium Amidinate Complexes as Precursors for Vapor Deposition, The Open Inorganic Chemistry Journal, 2008, 2, 11-17. [Non-Patent Document 2] Hye-Mi Kim, Jung-Hoon Lee, Seung-Hwan Lee, Ryosuke Harada, Toshiyuki Shigetomi, Seungjoon Lee, Tomohiro Tsugawa, Bonggeun Shong, and Jin-Seong Park, “Area-Selective Atomic Layer Deposition of Ruthenium Using a Novel Ru Precursor and H2O as a Reactant”, Chem. Mater. 2021, 33, 12, 4353-4361. [Patent documents]

[0008] [Patent Document 1] WO2004 / 046417A2 Summary of the Invention [Problem to be solved by the invention]

[0009] The problem to be solved by the present invention is to solve the above problems. For example, it is to provide a film formation technique that does not use oxygen as a reactant (or is not in an oxidizing atmosphere). And / or it is to provide a film formation technique with a short (or no) incubation time (or incubation cycle). Alternatively, it is to provide a liquid (25°C (1 atm)) raw material used for film formation. In other words, it is to provide a technique that allows a stable supply of raw material (for example, solidification and clogging during transportation (midway through piping) is unlikely to occur) and allows the formation of a high-quality ruthenium film. [Means for solving the problem]

[0010] The present invention relates to Ru[R 1 -NC(R 3 )-NR 2 ]2(R 1 ,R 2 ,R 3 is an alkyl group having 1 to 5 carbon atoms.1 ,R 2 ,R 3 may be the same or different, Li[R 1 -NC(R 3 )-NR 2 ](R 1 ,R 2 ,R 3 is an alkyl group having 1 to 5 carbon atoms. 1 ,R 2 ,R 3 may be the same or different.) is reacted with a divalent ruthenium complex. Suggest a method.

[0011] The present invention relates to Ru[R 1 -NC(R 3 )-NR 2 ]2(R 1 ,R 2 ,R 3 is an alkyl group having 1 to 5 carbon atoms. 1 ,R 2 ,R 3 may be the same or different, R 1 -N=C=NR 2 (R 1 ,R 2 is an alkyl group having 1 to 5 carbon atoms. 1 ,R 2 may be the same or different.) and R 3 Li(R 3 is an alkyl group having 1 to 5 carbon atoms.) is reacted with a divalent ruthenium complex. Suggest a method.

[0012] The present invention proposes said process, wherein said divalent ruthenium complex is preferably a divalent ruthenium chloride complex.

[0013] The present invention proposes the above-mentioned method, wherein the divalent ruthenium complex is preferably one or more selected from the group consisting of ruthenium(II) chloride·1,5-cyclooctadiene complex, bis[(benzene)ruthenium(II) chloride], bis[(mesitylene)ruthenium(II) chloride], and (p-cymene)ruthenium(II) chloride dimer.

[0014] The present invention relates to A material for forming a ruthenium-based film, Ru〔i-C3H7-NC(CH3)-Ni-C3H7〕2 Suggest materials.

[0015] The present invention relates to A material for forming a ruthenium-based film, Ru〔i-C3H7-NC(C2H5)-Ni-C3H7〕2 Suggest materials.

[0016] The present invention relates to A material for forming a ruthenium-based film, Ru〔i-C3H7-NC(n-C3H7)-Ni-C3H7〕2 Suggest materials.

[0017] The present invention relates to A material for forming a ruthenium-based film, Ru〔i-C3H7-NC(R 3 )-Ni-C3H7〕2(R 3 is an alkyl group having 1 to 5 carbon atoms. Suggest materials. Effect of the Invention

[0018] The ruthenium-based film-forming material of the present invention was a liquid (under 25°C (1 atm)). The boiling point was, for example, 96°C to 120°C / 0.1 torr. The vapor pressure was high. Therefore, a high-quality ruthenium film could be stably and easily formed by the CVD method (or the ALD method). The ruthenium-based film-forming materials of the present invention were easily synthesized. [Brief description of the drawings]

[0019] [Figure 1] Schematic diagram of the deposition device DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0020] The first aspect of the present invention is a method for producing Ru[R 1 -NC(R 3 )-NR 2 ]2(R 1 ,R 2 ,R 3 is an alkyl group having 1 to 5 carbon atoms. 1 ,R 2 ,R 3 may be the same or different.) For example, the method is a method for producing Ru[i-C3H7-NC(CH3)-Ni-C3H7]2, Ru[i-C3H7-NC(C2H5)-Ni-C3H7]2, or Ru[i-C3H7-NC(n-C3H7)-Ni-C3H7]2. The method includes the steps of: 1 -NC(R 3 )-NR 2 ](R 1 ,R 2 ,R 3 is an alkyl group having 1 to 5 carbon atoms. 1 ,R 2 ,R 3 may be the same or different.) with a divalent ruthenium complex. For example, R 1 -N=C=NR 2 and R 3 Li(R 1 ,R 2 ,R 3 is an alkyl group having 1 to 5 carbon atoms. 1 ,R 2 ,R 3 may be the same or different. 1 ,R 2 is, for example, an isopropyl group. 3is, for example, a methyl group, an ethyl group, or an n-propyl group.) is reacted with a divalent ruthenium complex. The reaction is carried out, for example, by mixing.

[0021] The divalent ruthenium complex is preferably a divalent ruthenium chloride complex. For example, it is a complex selected from the group consisting of ruthenium chloride (II)·1,5-cyclooctadiene complex, bis[(benzene)ruthenium chloride (II)], bis[(mesitylene)ruthenium chloride (II)], and (p-cymene)ruthenium chloride (II) dimer. It is any one of them. Basically, it is any one of them, but two or more of them may be used.

[0022] The second invention is a material for forming a ruthenium-based film. The material is Ru[i-C3H7-NC(R 3 )-Ni-C3H7]2 (R3 is an alkyl group having 1 to 5 carbon atoms). 3 was preferably a linear alkyl group. Among them, it was an alkyl group having 1 to 3 carbon atoms. Among the above compounds, particularly preferred was Ru[i-C3H7-NC(CH3)-Ni-C3H7]2. Alternatively, it was Ru[i-C3H7-NC(C2H5)-Ni-C3H7]2. Alternatively, it was Ru[i-C3H7-NC(n-C3H7)-Ni-C3H7]2. Most preferred was Ru[i-C3H7-NC(CH3)-Ni-C3H7]2 from the viewpoint of film formability, and Ru[i-C3H7-NC(n-C3H7)-Ni-C3H7]2 from the viewpoint of productivity. The above ruthenium-based film forming material may contain the above compound in a solution.

[0023] The above-mentioned patent document (WO2004 / 046417A2) discloses the following. "Divalent metal precursors include volatile metal(II) bis-amidinates [M(II)(AMD)2]x, where x=1,2. These compounds may have the following monomeric structures: JPEG2024104710000001.jpg4673In formula, R 1 ,R2 ,R 3 ,R 1 ',R 2 ' and R 3 In one or more embodiments, dimers of this structure may be used, such as [M(II)(AMD2]2. In some embodiments, R 1 ,R 2 ,R 3 ,R 1 ',R 2 ' and R 3 ' may be independently selected from hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl or fluoroalkyl groups or other non-metallic atoms or groups. In some embodiments, R 1 ,R 2 ,R 3 ,R 1 ',R 2 ' and R 3 Each ' is independently an alkyl or fluoroalkyl or silylalkyl group having 1 to 4 carbon atoms. Suitable divalent metals include cobalt, iron, nickel, manganese, ruthenium, zinc, titanium, vanadium, chromium, europium, magnesium, and calcium. In one or more embodiments, the metal(II) amidinate is a cobalt amidinate. The cobalt amidinate may include a cobalt amidinate having R as the isopropyl group in the general formula. 1 ,R 2 ,R 1 ' and R 2 ', R as a methyl group 3 and R 3 ' is taken, which corresponds to cobalt (II) bis (N,N'-diisopropylacetamidinate).

[0024] However, the above-mentioned patent document does not specifically disclose the above compound proposed by the present invention. 1 ,R 2 ,R 3 ,R 1 ',R 2 ' and R 3' is hydrogen, alkyl, aryl, alkenyl, alkynyl, trialkylsilyl or fluoroalkyl group or other nonmetallic atom or group. However, there is no specific disclosure of the above compound proposed by the present invention. Moreover, there is no disclosure of a method for producing the above compound proposed by the present invention.

[0025] Incidentally, bis(N,N'-ditertiarybutylacetamidinate)ruthenium is included in the above general formula disclosed in the above patent document (WO2004 / 046417A2). However, this compound was a solid (below 25°C). The sublimation temperature was 130°C. It did not meet the physical properties of the above compound proposed by the present invention. Therefore, it was not suitable as a film-forming material for Ru films. Bis(N-ethyl-N'-tertiarybutylacetamidinate)ruthenium is also included in the above general formula disclosed in the above patent document (WO2004 / 046417A2). However, this compound was a solid (below 25°C). It does not meet the physical properties of the above compound proposed by the present invention. Therefore, this compound included in the general formula disclosed in the above patent document (WO200 / 046417A2) was also not suitable as a film-forming material for Ru films. In other words, it cannot be said that a compound suitable as a Ru film-forming material was disclosed in the above patent document (WO2004 / 046417A2). Bis(N,N'-diisopropyl-2-methylpropionamidinate)ruthenium is also included in the above general formula disclosed in the above patent document (WO2004 / 046417A2). However, this compound was a solid (below 25°C). It does not meet the physical properties of the above compound proposed by the present invention. Therefore, this compound included in the general formula disclosed in the above patent document (WO2004 / 046417A2) was also not suitable as a film-forming material for a Ru film. In other words, it cannot be said that a compound suitable as a Ru film-forming material was disclosed in the above patent document (WO2004 / 046417A2).

[0026] Specific examples are given below. However, the present invention is not limited to the following examples. Various modifications and applications are also included in the present invention as long as the features of the present invention are not significantly impaired.

[0027] [Example 1] [Synthesis of bis(N,N'-diisopropylacetamidinate)ruthenium] All reactions were carried out under an inert gas atmosphere. 25g of N,N'-diisopropylcarbodiimide was dissolved in 200ml of diethyl ether. The solution was cooled to -30℃. An ether solution of methyllithium (0.197mol) was slowly added dropwise to this solution. Stirring was then continued for 4 hours (at room temperature). This reaction mixture was slowly added dropwise to a suspension of 28.8g of (p-cymene)ruthenium(II) chloride dimer in 350ml of tetrahydrofuran, which had been cooled to -40℃. The temperature was then gradually returned to room temperature. Stirring was continued for 4 hours. The solvent was distilled off. The remaining oily material was dissolved in 450ml of n-hexane. Insoluble materials were removed (filtered). The solvent was distilled off again. A dark brown liquid was obtained by vacuum distillation at 0.1torr. This material was bis(N,N'-diisopropylacetamidinate)ruthenium. The boiling point was 96°C. The obtained bis(N,N'-diisopropylacetamidinate)ruthenium was hydrolyzed. Solvent extraction was carried out in an alkaline state. High-purity N,N'-diisopropylacetamidine was obtained. Component analysis showed that the ruthenium contained in the obtained bis(N,N'-diisopropylacetamidinate)ruthenium was 26-26.5%. This demonstrated that the obtained dark brown liquid was divalent bis(N,N'-diisopropylacetamidinate)ruthenium.

[0028] [Comparative Example 1] [Synthesis of bis(N,N'-ditertiarybutylacetamidinate)ruthenium] All reactions were carried out under an inert gas atmosphere. 30 g of N,N'-ditertiarybutylcarbodiimide was dissolved in 200 ml of diethyl ether. The solution was cooled to -30°C. An ether solution of methyllithium (0.197 mol) was slowly added dropwise to this solution. Stirring was then continued for 4 hours (at room temperature). This reaction mixture was slowly added dropwise to a suspension [28.8 g of (p-cymene)ruthenium(II) chloride dimer suspended in 350 ml of tetrahydrofuran] cooled to -40°C. The temperature was then gradually returned to room temperature. Stirring was continued for 4 hours. The solvent was distilled off. The remaining oil was then dissolved in 450 ml of n-hexane. Insoluble matter was removed (filtered). The solvent was distilled off again. Bis(N,N'-ditertiarybutylacetamidinate)ruthenium was obtained by sublimation under reduced pressure of 0.1 torr. This compound was a solid (25°C (1 atm)). The sublimation temperature was 130°C.

[0029] [Comparative Example 2] The procedure was the same as in Comparative Example 1. Bis(N-ethyl-N'-tertiary butylacetamidinate)ruthenium was obtained. This compound was a solid (25°C (1 atm)). The sublimation temperature was 130°C.

[0030] [Comparative Example 3] [Synthesis of tris(N,N'-diisopropylpropionamidinate)ruthenium] All reactions were carried out under an inert gas atmosphere. 45g of N,N'-diisopropylcarbodiimide was dissolved in 400ml of diethyl ether. The solution was cooled to -30°C. An ether solution of ethyllithium (0.353mol) was slowly dripped into the solution. Stirring was then continued for 4 hours (at room temperature). The reaction mixture was slowly dripped into a suspension [30g of ruthenium trichloride-tridimethylsulfur adduct suspended in 150ml of tetrahydrofuran]. The temperature was then gradually returned to room temperature. Stirring was continued for 4 hours. The solvent was distilled off. The remaining oil was then dissolved in 1000ml of n-hexane. Insoluble matter was removed (filtered). The solvent was distilled off again. Sublimation was carried out under reduced pressure (0.1 torr). The temperature of the oil bath was raised to 150°C. However, nothing was collected. Tris(N,N'-diisopropylpropionamidinate)ruthenium was not obtained.

[0031] [Example 2] The procedure was carried out in accordance with Example 1, except that bis[(benzene)ruthenium(II) chloride] was used instead of (p-cymene)ruthenium(II) chloride dimer. The results were the same as in Example 1.

[0032] [Example 3] The procedure was carried out similarly to Example 1, except that bis[(mesitylene)ruthenium(II) chloride] was used instead of (p-cymene)ruthenium(II) chloride dimer. The results were the same as in Example 1.

[0033] [Example 4] The procedure was carried out in accordance with Example 1, except that ruthenium(II) chloride·1,5-cyclooctadiene complex was used instead of (p-cymene)ruthenium(II) chloride dimer. The results were the same as in Example 1.

[0034] [Example 5] [Synthesis of bis(N,N'-diisopropylpropionamidinate)ruthenium] All reactions were carried out under an inert gas atmosphere. 31.5 g of N,N'-diisopropylcarbodiimide was dissolved in 200 ml of diethyl ether. The solution was cooled to -30°C. An ether solution of ethyllithium (0.25 mol) was slowly dripped into the solution. Stirring was then continued for 4 hours (at room temperature). The reaction mixture was slowly dripped into a suspension of 31.8 g of (p-cymene)ruthenium(II) chloride dimer in 400 ml of tetrahydrofuran, which had been cooled to -40°C. The temperature was then gradually returned to room temperature. Stirring was continued for 4 hours. The solvent was distilled off. The remaining oil was then dissolved in 500 ml of n-hexane. Insoluble matter was removed (filtered). The solvent was distilled off again. A dark brown liquid was obtained by vacuum distillation at 0.1 torr. This substance was bis(N,N'-diisopropylpropionamidinate)ruthenium. The boiling point was 115°C. The obtained bis(N,N'-diisopropylpropionamidinate)ruthenium was hydrolyzed. Solvent extraction was carried out in an alkaline state. High-purity N,N'-diisopropylpropionamidine was obtained. The ruthenium contained in the obtained bis(N,N'-diisopropylpropionamidinate)ruthenium was found to be 24.5-24.7% by component analysis. This demonstrated that the obtained dark brown liquid was divalent bis(N,N'-diisopropylpropionamidinate)ruthenium. The same procedure was repeated using bis[(benzene)ruthenium(II)] chloride, bis[(mesitylene)ruthenium(II)] chloride, and ruthenium(II)·1,5-cyclooctadiene chloride complexes instead of the (p-cymene)ruthenium(II) chloride dimer to give bis(N,N'-diisopropylpropionamidinate)ruthenium.

[0035] [Example 6] [Synthesis of bis(N,N'-diisopropylbutanamidinato)ruthenium] All reactions were carried out under an inert gas atmosphere. 33.2 g of N,N'-diisopropylcarbodiimide was dissolved in 200 ml of diethyl ether. The solution was cooled to -30°C. An ether solution of n-propyllithium (0.252 mol) was slowly dripped into the solution. Stirring was then continued for 4 hours (at room temperature). The reaction mixture was slowly dripped into a suspension of 31.5 g of (p-cymene)ruthenium(II) chloride dimer in 300 ml of tetrahydrofuran, which had been cooled to -40°C. The temperature was then gradually returned to room temperature. Stirring was continued for 4 hours. The solvent was distilled off. The remaining oil was then dissolved in 450 ml of n-hexane. Insoluble matter was removed (filtered). The solvent was distilled off again. A dark brown liquid was obtained by vacuum distillation at 0.1 torr. This substance was bis(N,N'-diisopropylbutanamidinate)ruthenium. The boiling point was 120°C. The obtained bis(N,N'-diisopropylbutanamidinate)ruthenium was hydrolyzed. Solvent extraction was carried out in an alkaline state. High-purity N,N'-diisopropylbutanamidine was obtained. Component analysis showed that the ruthenium contained in the obtained bis(N,N'-diisopropylbutanamidinate)ruthenium was 22.9-23.2%. This demonstrated that the obtained dark brown liquid was divalent bis(N,N'-diisopropylbutanamidinate)ruthenium. The same procedure was repeated using bis[(benzene)ruthenium(II)] chloride, bis[(mesitylene)ruthenium(II)] chloride, and ruthenium(II)·1,5-cyclooctadiene chloride complexes instead of the (p-cymene)ruthenium(II) chloride dimer to give bis(N,N'-diisopropylbutanamidinato)ruthenium.

[0036] [Example 7] [Formation of Ruthenium-Based Thin Films] Figure 1 is a schematic diagram of a film formation apparatus, in which 1 is a source container, 2 is a heater, 3 is a decomposition reactor, 4 is a substrate, 5 is a flow rate controller, 6 is a shower head, 7 is a carrier gas (argon), and 8 is a reaction gas (ammonia, hydrogen). The apparatus used was shown in Figure 1. A ruthenium-based film was formed by CVD. Bis(N,N'-diisopropylacetamidinate)ruthenium was placed in the raw material container 1. Ar gas (carrier gas) was bubbled at a rate of 10 ml / min. The evaporated bis(N,N'-diisopropylacetamidinate)ruthenium was introduced into the decomposition reactor 3 together with Ar. Ammonia and hydrogen (reaction gas) were also introduced into the decomposition reactor 3. The raw material container 1 and piping were heated to 90-95°C. At this time, the system was evacuated to a vacuum. The substrate 4 was heated to 300°C. As a result, a film was formed on the substrate 4. The same procedure was repeated. Thin films of 20 nm thickness were produced almost simultaneously each time. There was almost no incubation time. The film was examined by XPS and was confirmed to be a ruthenium film.

[0037] [Comparative Example 4] The apparatus shown in FIG. 1 was used, and the experiment was carried out in accordance with Example 7. Bis(ethylcyclopentadienyl)ruthenium was placed in the raw material container 1. Ar gas (carrier gas) was bubbled at a rate of 10 ml / min. The vaporized bis(ethylcyclopentadienyl)ruthenium was introduced into the decomposition reactor 3 together with Ar. Ammonia and hydrogen (reaction gases) were also introduced into the decomposition reactor 3. The raw material container 1 and piping were heated to 110-115°C. At this time, the system was evacuated to a vacuum. The substrate 4 was heated to 300°C. No film was formed on the substrate 4. Oxygen was introduced into the decomposition reactor 3 instead of ammonia and hydrogen. As a result, a ruthenium film was formed. However, it took 20 minutes for the film formation to start (long incubation time). The same thing happened over and over again. The time required for deposition to begin was not consistent. For example, it varied from 17 to 25 minutes. It was not possible to create a 20 nm-thick thin film every time.

[0038] [Example 8] The procedure was carried out in accordance with Example 7, except that bis(N,N'-diisopropylacetamidinate)ruthenium was replaced with bis(N,N'-diisopropylpropionamidinate)ruthenium, and the raw material container 1 and piping were heated to 105 to 110°C. The same procedure was repeated. Thin films of 20 nm thickness were produced almost simultaneously each time. There was almost no incubation time. The film was examined by XPS and was confirmed to be a ruthenium film.

[0039] [Example 9] The procedure of Example 7 was repeated except that bis(N,N'-diisopropylbutanamidinate)ruthenium was used instead of bis(N,N'-diisopropylacetamidinate)ruthenium, and the raw material container 1 and piping were heated to 110 to 115°C. The same procedure was repeated. Thin films of 20 nm thickness were produced almost simultaneously each time. There was almost no incubation time. The film was examined by XPS and was confirmed to be a ruthenium film.

[0040] [Example 10] The apparatus used was shown in Figure 1. Ruthenium-based films were deposited by the ALD method. Bis(N,N'-diisopropylacetamidinate)ruthenium was placed in the raw material container 1. Ar gas (carrier gas) was bubbled at a rate of 10 ml / min. The evaporated bis(N,N'-diisopropylacetamidinate)ruthenium was introduced into the decomposition reactor 3 together with Ar for 20 seconds. The system was evacuated to a vacuum. After the decomposition reactor was evacuated to a vacuum for 20 seconds, ammonia and hydrogen (reaction gas) were introduced into the decomposition reactor 3 for 20 seconds. After the decomposition reactor was evacuated to a vacuum for 20 seconds, bis(N,N'-diisopropylacetamidinate)ruthenium was again introduced into the decomposition reactor 3 together with the bubbling gas and argon gas for 20 seconds. This operation was repeated 200 times. The raw material container 1 and piping were heated to 90 to 95°C. The substrate 4 was heated to 220°C. As a result, a film was formed on the substrate 4. The film was examined by XPS and was confirmed to be a ruthenium film.

[0041] [Comparative Example 6] The apparatus used was shown in Figure 1. Ruthenium-based films were deposited by the ALD method. Bis(ethylcyclopentadienyl)ruthenium was placed in the raw material container 1. Ar gas (carrier gas) was bubbled at a rate of 10 ml / min. The volatilized bis(ethylcyclopentadienyl)ruthenium was introduced into the decomposition reactor 3 together with Ar for 20 seconds. The system was evacuated to a vacuum. After the decomposition reactor was evacuated to a vacuum for 20 seconds, ammonia and hydrogen (reaction gas) were introduced into the decomposition reactor 3 for 20 seconds. After the decomposition reactor was evacuated to a vacuum for 20 seconds, bis(ethylcyclopentadienyl)ruthenium was again introduced into the decomposition reactor 3 together with the bubbling gas and argon gas for 20 seconds. This operation was repeated 200 times. The raw material container 1 and piping were heated to 110-115°C. The substrate 4 was heated to 275°C. However, no film was formed on the substrate 4. Instead of ammonia and hydrogen, oxygen was introduced into the decomposition reactor 3. After 1000 ALD cycles, film formation was finally observed. It turns out that many incubation cycles are required.

[0042] [Comparative Example 7] The apparatus used was shown in Figure 1. Ruthenium-based films were deposited by the ALD method. Tris(N,N'-diisopropylacetamidinate)ruthenium was placed in the raw material container 1. Ar gas (carrier gas) was introduced at a rate of 10 ml / min. The sublimated tris(N,N'-diisopropylacetamidinate)ruthenium was introduced into the decomposition reactor 3 together with Ar for 20 seconds. The system was evacuated to a vacuum. The decomposition reactor was evacuated to a vacuum for 20 seconds. After this, ammonia and hydrogen (reaction gas) were introduced into the decomposition reactor 3 for 20 seconds. The decomposition reactor was evacuated to a vacuum for 20 seconds. After this, tris(N,N'-diisopropylacetamidinate)ruthenium was again introduced into the decomposition reactor 3 together with the bubbling gas and argon gas for 20 seconds. This operation was repeated 200 times. The raw material container 1 and piping were heated to 105-110°C. The substrate 4 was heated to 220° C. A film was formed on the substrate 4. However, the film thickness in this case was only about 20% of the film thickness when bis(N,N′-diisopropylacetamidinate)ruthenium was used. The same process was repeated, but sometimes the piping became clogged during the film formation (during the transport route).

[0043] [Example 11] Bis(N,N'-diisopropylpropionamidinate)ruthenium was used instead of bis(N,N'-diisopropylacetamidinate)ruthenium, and the procedure was carried out in accordance with Example 10. The source container 1 and piping were heated to 105 to 110° C. As a result, a film was formed on the substrate 4 in the same manner. The film was examined by XPS and was confirmed to be a ruthenium film.

[0044] [Example 12] Bis(N,N'-diisopropylbutaneamidinate)ruthenium was used instead of bis(N,N'-diisopropylacetamidinate)ruthenium, and the procedure was carried out in accordance with Example 10. The source container 1 and piping were heated to 110 to 115° C. As a result, a film was formed on the substrate 4 in the same manner. The film was examined by XPS and was confirmed to be a ruthenium film. [Explanation of symbols]

[0045] 1 Raw material container 2 Heater 3. Decomposition reactor 4. Board 5 Flow Controller 6. Shower head 7 Carrier gas (argon) 8 Reactive gases (ammonia, hydrogen)

Claims

1. Ru[R １ -N-C(R ３ )-N-R ２ ] ２ (R 1 and R 2 are i-C 3 H 7, R ３ is an alkyl group having 1 to 5 carbon atoms. １ , R ２ , R ３ may be the same or different, Li[R １ -N-C(R ３ )-N-R ２ ] (R 1 and R 2 are i-C 3 H 7, R ３ is an alkyl group having 1 to 5 carbon atoms. １ , R ２ , R ３ may be the same or different.) and a divalent ruthenium complex. method.

2. R １ -N=C=N-R ２ and R ３ Li(R 1 , R 2 are i-C 3 H 7,R ３ is an alkyl group having 1 to 5 carbon atoms. １ , R ２ , R ３ may be the same or different.) and a divalent ruthenium complex are reacted.

10. The method of claim 1.

3. The divalent ruthenium complex is a divalent ruthenium chloride complex. The method of claim 1 or claim 2.

4. The divalent ruthenium complex is one or more selected from the group consisting of ruthenium(II) chloride / 1,5-cyclooctadiene complex, bis[(benzene)ruthenium(II)] chloride, bis[(mesitylene)ruthenium(II)] chloride, and (p-cymene)ruthenium(II) chloride dimer. The method of claim 1 or claim 2.

5. The R 3 is any one selected from the group consisting of a methyl group, an ethyl group, and an n-propyl group. The method of claim 1 or claim 2.

6. The divalent ruthenium complex is (p-cymene)ruthenium(II) chloride dimer. The method of claim 4.

7. A material for forming a ruthenium-based film, Ru[i-C], which is liquid at 25°C (1 atmosphere) ３ H ７ -N-C(CH ３ )-N-i-C ３ H ７ 〕 ２ Equipped with material.

8. A material for forming a ruthenium-based film, Ru[i-C], which is liquid at 25°C (1 atmosphere) ３ H ７ -N-C(C ２ H ５ )-N-i-C ３ H ７ 〕 ２ Equipped with material.

9. A material for forming a ruthenium-based film, Ru[i-C], which is liquid at 25°C (1 atmosphere) ３ H ７ -N-C (n-C ３ H ７ )-N-i-C ３ H ７ 〕 ２ Equipped with material.

10. A method for forming a ruthenium-based film, comprising: Ru[i-C 3 H 7 —N—C(CH 3 )—N—i-C 3 H 7 ] 2 , which is liquid at 25° C. (1 atmosphere), is supplied into the film formation chamber; A ruthenium-based film is formed on the substrate in the film-forming chamber by ALD or CVD. method.

11. A method for forming a ruthenium-based film, comprising: Ru[i-C 3 H 7 —N—C(C 2 H 5 )—N—i-C 3 H 7 ] 2 , which is liquid at 25° C. (1 atmosphere), is supplied into the film formation chamber; A ruthenium-based film is formed on the substrate in the film-forming chamber by ALD or CVD. method.

12. A method for forming a ruthenium-based film, comprising: Ru[i-C 3 H 7 -N-C(n-C 3 H 7 )-N-i-C 3 H 7 ] 2 , which is liquid at 25° C. (1 atmosphere), is supplied into a film formation chamber; A ruthenium-based film is formed on the substrate in the film-forming chamber by ALD or CVD. method.

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