RAW MATERIAL FOR CHEMICAL DEPOSITION CONTAINING ORGANORUTHENIUM COMPOUND, AND CHEMICAL DEPOSITION METHOD USING THE RAW MATERIAL FOR CHEMICAL DEPOSITION
20230348511 · 2023-11-02
Assignee
Inventors
- Ryosuke HARADA (Tsukuba-shi, JP)
- Tomohiro TSUGAWA (Tsukuba-shi, JP)
- Shigeyuki OOTAKE (Tsukuba-shi, JP)
- Seung-Joon LEE (Tsukuba-shi, JP)
- Yohei KOTSUGI (Tsukuba-shi, JP)
Cpc classification
International classification
Abstract
The present invention relates to an organoruthenium compound raw material for a chemical deposition method. An organoruthenium compound is represented by the following Formula 1 in which a trimethylenemethane-based ligand (L.sub.1), and two carbonyl ligands and a ligand X coordinate to divalent ruthenium. In Formula 1, the trimethylenemethane-based ligand (L.sub.1) is represented by the following Formula 2. Besides, the ligand X is any one of an isocyanide ligand, a pyridine ligand, an amine ligand, an imidazole ligand, a pyridazine ligand, a pyrimidine ligand, and a pyrazine ligand.
##STR00001## wherein a substituent R of the ligand L.sub.1 is hydrogen, or any one of an alkyl group, a cyclic alkyl group, an alkenyl group, an alkynyl group, and an amino group having a predetermined number of carbon atoms.
Claims
1. A raw material for chemical deposition for producing a ruthenium thin film or a ruthenium compound thin film by a chemical deposition method, the raw material comprising: an organoruthenium compound represented by the following Formula 1 in which a trimethylenemethane-based ligand (L.sub.1), and two carbonyl ligands and a ligand X coordinate to divalent ruthenium:
RuL.sub.1(CO).sub.2X [Formula 1] wherein the trimethylenemethane-based ligand (L.sub.1) is represented by the following Formula 2, and the ligand X is any one of an isocyanide ligand (L.sub.2), a pyridine ligand (L.sub.3), an amine ligand (L.sub.4), an imidazole ligand (L.sub.5), a pyridazine ligand (L.sub.6), a pyrimidine ligand (L.sub.7), and a pyrazine ligand (L.sub.8) represented by the following Formula 3 to Formula 9: ##STR00038## wherein a substituent R of the ligand L.sub.1 is any one of hydrogen, a linear or branched alkyl group having 1 or more and 8 or less carbon atoms, a cyclic alkyl group having 3 or more and 9 or less carbon atoms, a linear or branched alkenyl group having 2 or more and 8 or less carbon atoms, a linear or branched alkynyl group having 2 or more and 8 or less carbon atoms, a linear or branched amino group having 2 or more and 8 or less carbon atoms, and an aryl group having 6 or more and 9 or less carbon atoms; ##STR00039## wherein a substituent R.sub.1 of the ligand L.sub.2 is any one of hydrogen, a linear or branched alkyl group having 1 or more and 8 or less carbon atoms, a cyclic alkyl group having 3 or more and 9 or less carbon atoms, a linear or branched amino group having 1 or more and 8 or less carbon atoms, an aryl group having 6 or more and 9 or less carbon atoms, a linear or branched alkoxy group having 1 or more and 8 or less carbon atoms, a linear or branched cyano group having 1 or more and 8 or less carbon atoms, a linear or branched nitro group having 1 or more and 8 or less carbon atoms, and a linear or branched fluoroalkyl group having 1 or more and 8 or less carbon atoms; ##STR00040## wherein each of substituents R.sub.2 to R.sub.6 of the ligand L.sub.3 is any one of hydrogen, a linear or branched alkyl group or fluoroalkyl group having 1 or more and 5 or less carbon atoms, a fluoro group, a linear or branched alkoxy group having 1 or more and 5 or less carbon atoms, a linear or branched cyano group having 1 or more and 5 or less carbon atoms, and a linear or branched nitro group having 1 or more and 5 or less carbon atoms; ##STR00041## wherein each of substituents R.sub.7 to R.sub.9 of the ligand L.sub.4 is a linear or branched alkyl group having 1 or more and 5 or less carbon atoms; ##STR00042## wherein a substituent R.sub.10 of the ligand L.sub.5 is any one of hydrogen, a linear or branched alkyl group having 1 or more and 8 or less carbon atoms, a cyclic alkyl group having 3 or more and 8 or less carbon atoms, and a linear or branched fluoroalkyl group having 1 or more and 8 or less carbon atoms, and each of substituents R.sub.11 to R.sub.13 is any one of hydrogen, a linear or branched alkyl group having 1 or more and 5 or less carbon atoms, a linear or branched amino group having 1 or more and 5 or less carbon atoms, a linear or branched alkoxy group having 1 or more and 5 or less carbon atoms, a linear or branched cyano group having 1 or more and 5 or less carbon atoms, a linear or branched nitro group having 1 or more and 5 or less carbon atoms, a fluoro group, and a linear or branched fluoroalkyl group having 1 or more and 5 or less carbon atoms; ##STR00043## wherein each of substituents R.sub.14 to R.sub.17 of the ligand L.sub.6 is any one of hydrogen, a linear or branched alkyl group having 1 or more and 5 or less carbon atoms, a linear or branched fluoroalkyl group having 1 or more and 5 or less carbon atoms, a fluoro group, a linear or branched alkoxy group having 1 or more and 5 or less carbon atoms, a linear or branched cyano group having 1 or more and 5 or less carbon atoms, and a linear or branched nitro group having 1 or more and 5 or less carbon atoms; ##STR00044## wherein each of substituents R.sub.18 to R.sub.21 of the ligand L.sub.7 is any one of hydrogen, a linear or branched alkyl group having 1 or more and 5 or less carbon atoms, a linear or branched fluoroalkyl group having 1 or more and 5 or less carbon atoms, a fluoro group, a linear or branched alkoxy group having 1 or more and 5 or less carbon atoms, a linear or branched cyano group having 1 or more and 5 or less carbon atoms, and a linear or branched nitro group having 1 or more and 5 or less carbon atoms; and ##STR00045## wherein each of substituents R.sub.22 to R.sub.25 of the ligand L.sub.8 is any one of hydrogen, a linear or branched alkyl group having 1 or more and 5 or less carbon atoms, a linear or branched fluoroalkyl group having 1 or more and 5 or less carbon atoms, a fluoro group, a linear or branched alkoxy group having 1 or more and 5 or less carbon atoms, a linear or branched cyano group having 1 or more and 5 or less carbon atoms, and a linear or branched nitro group having 1 or more and 5 or less carbon atoms.
2. The raw material for chemical deposition according to claim 1, wherein the substituent R of the trimethylenemethane-based ligand (L.sub.1) is any one of hydrogen, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, and a neopentyl group.
3. The raw material for chemical deposition according to claim 1, wherein the ligand X is the isocyanide ligand (L.sub.2), and R.sub.1 is any one of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a trifluoromethyl group, and a pentafluoroethyl group.
4. The raw material for chemical deposition according to claim 1, wherein ligand X is the pyridine ligand (L.sub.3), and all of R.sub.2 to R.sub.6 are hydrogen, all of R.sub.2, R.sub.4 and R.sub.6 are methyl groups, and R.sub.3 and R.sub.5 are hydrogen, or all of R.sub.2, R.sub.3, R.sub.5 and R.sub.6 are hydrogen, and R.sub.4 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a trifluoromethyl group, a methoxy group, a cyano group, and a nitro group.
5. The raw material for chemical deposition according to claim 1, wherein the ligand X is the amine ligand (L.sub.4), and all of R.sub.7 to R.sub.9 are any one of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, and a n-butyl group, or both R.sub.7 and R.sub.8 are any one of a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, and a tert-butyl group, and R.sub.9 is hydrogen.
6. The raw material for chemical deposition according to claim 1, wherein the ligand X is the imidazole ligand (L.sub.5), and all of R.sub.10 to R.sub.13 are hydrogen, R.sub.10 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a trifluoromethyl group, and R.sub.11 to R.sub.13 are any one of hydrogen, a methyl group and an ethyl group, or R.sub.10 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, and a trifluoromethyl group, and all of R.sub.11 to R.sub.13 are any one of hydrogen, a methyl group, and an ethyl group.
7. The raw material for chemical deposition according to claim 1, wherein the ligand X is the pyridazine ligand (L.sub.6), and all of R.sub.14 to R.sub.17 are hydrogen, R.sub.14 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a trifluoromethyl group, a fluoro group, a methoxy group, a cyano group, and a nitro group, and R.sub.15 to R.sub.17 are any one of hydrogen, a methyl group, and an ethyl group, R.sub.15 is any one of a methyl group, an ethyl group, an isopropyl group, and a tert-butyl group, and all of R.sub.14, R.sub.16 and R.sub.17 are any one of hydrogen, a methyl group, and an ethyl group, or both R.sub.15 and R.sub.16 are methyl groups, and both R.sub.14 and R.sub.17 are hydrogen.
8. The raw material for chemical deposition according to claim 1, wherein the ligand X is the pyrimidine ligand (L.sub.7), and all of R.sub.18 to R.sub.21 are hydrogen, all of R.sub.19 to R.sub.21 are methyl groups, and R.sub.18 is hydrogen, R.sub.18 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a trifluoro group, a fluoro group, a methoxy group, a cyano group, and a nitro group, and R.sub.19 to R.sub.21 are any one of hydrogen, a methyl group, and an ethyl group, or R.sub.20 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a trifluoro group, a fluoro group, a methoxy group, a cyano group, and a nitro group, and all of R.sub.18, R.sub.19 and R.sub.21 are any one of hydrogen, a methyl group and an ethyl group.
9. The raw material for chemical deposition according to claim 1, wherein the ligand X is the pyrazine ligand (L.sub.8), and all of R.sub.22 to R.sub.25 are hydrogen, R.sub.22 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a trifluoromethyl group, a fluoro group, a methoxy group, a cyano group, and a nitro group, and R.sub.23 to R.sub.25 are any one of hydrogen, a methyl group, and an ethyl group, or R.sub.23 is any one of a methyl group, an ethyl group, an isopropyl group, a tert-butyl group, a trifluoromethyl group, a fluoro group, a methoxy group, a cyano group, and a nitro group, and all of R.sub.22, R.sub.24 and R.sub.25 are any one of hydrogen, a methyl group, and an ethyl group.
10. A chemical deposition method for a ruthenium thin film or a ruthenium compound thin film, comprising vaporizing a raw material containing an organoruthenium compound to obtain a raw material gas, and introducing the raw material gas together onto a substrate surface while heating the gas, wherein the method uses the raw material for chemical deposition according to claim 1 as the raw material, and uses hydrogen as a reaction gas.
11. The chemical deposition method according to claim 10, wherein the method comprises: applying a reducing gas as the reaction gas, and introducing the raw material gas onto the substrate surface together with the reaction gas, and heating the gases.
12. The chemical deposition method according to claim 11, wherein the reducing gas is a gas of any one of hydrogen, ammonia, hydrazine, formic acid, and an alcohol.
13. The chemical deposition method according to claim 10, wherein the method comprises: applying either of an oxidizing gas and a gas of an oxygen-containing reactant as the reaction gas, and introducing the raw material gas onto the substrate surface together with the reaction gas, and heating the gases.
14. The chemical deposition method according to claim 13, wherein the oxidizing gas is a gas of any one of oxygen and ozone, and the gas of an oxygen-containing reactant is a gas of any one of water and an alcohol.
15. The chemical deposition method according to claim 10, wherein a film forming temperature is 150° C. or more and 350° C. or less.
16. A chemical deposition method for a ruthenium thin film or a ruthenium compound thin film, comprising vaporizing a raw material containing an organoruthenium compound to obtain a raw material gas, and introducing the raw material gas together onto a substrate surface while heating the gas, wherein the method uses the raw material for chemical deposition according to claim 2 as the raw material, and uses hydrogen as a reaction gas.
17. A chemical deposition method for a ruthenium thin film or a ruthenium compound thin film, comprising vaporizing a raw material containing an organoruthenium compound to obtain a raw material gas, and introducing the raw material gas together onto a substrate surface while heating the gas, wherein the method uses the raw material for chemical deposition according to claim 3 as the raw material, and uses hydrogen as a reaction gas.
18. A chemical deposition method for a ruthenium thin film or a ruthenium compound thin film, comprising vaporizing a raw material containing an organoruthenium compound to obtain a raw material gas, and introducing the raw material gas together onto a substrate surface while heating the gas, wherein the method uses the raw material for chemical deposition according to claim 4 as the raw material, and uses hydrogen as a reaction gas.
19. A chemical deposition method for a ruthenium thin film or a ruthenium compound thin film, comprising vaporizing a raw material containing an organoruthenium compound to obtain a raw material gas, and introducing the raw material gas together onto a substrate surface while heating the gas, wherein the method uses the raw material for chemical deposition according to claim 5 as the raw material, and uses hydrogen as a reaction gas.
20. A chemical deposition method for a ruthenium thin film or a ruthenium compound thin film, comprising vaporizing a raw material containing an organoruthenium compound to obtain a raw material gas, and introducing the raw material gas together onto a substrate surface while heating the gas, wherein the method uses the raw material for chemical deposition according to claim 6 as the raw material, and uses hydrogen as a reaction gas.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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[0077]
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[0080]
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[0084]
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0085] First Embodiment: A most preferable embodiment of the present invention will now be described. In the present embodiment, it was confirmed whether or not an organoruthenium compound of the present invention could be synthesized. Then, the synthesized organoruthenium compound was evaluated for a physical property, and a film formation test of a ruthenium thin film was performed.
[0086] In the organoruthenium compounds synthesized in the present embodiment, trimethylenemethane (R=hydrogen) was used as a trimethylenemethane-based ligand (L.sub.1). In addition, it was confirmed whether or not various organoruthenium compounds such as organoruthenium compounds in which an isocyanide ligand (L.sub.2) coordinated as a ligand X (Examples 1 to 6), organoruthenium compounds in which a pyridine ligand (L.sub.3) coordinated (Examples 7 and 8), an organoruthenium compound in which an amine ligand (L.sub.4) coordinated (Example 9), organoruthenium compounds in which an imidazole ligand (L.sub.5) coordinated (Examples 10 and 11), an organoruthenium compound in which a pyridazine ligand (L.sub.6) coordinated (Example 12), an organoruthenium compound in which a pyrimidine ligand (L.sub.7) coordinated (Example 13), and an organoruthenium compound in which a pyrazine ligand (L.sub.8) coordinated (Example 14) could be synthesized.
[0087] [Synthesis of Organoruthenium Compounds]
[0088] Example 1: To a flask containing 700 ml of tetrahydrofuran, 16.8 g (70.0 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 14.5 g (75.0 mmol) of (2-isocyano-2-methylpropane), and 7.89 g (105 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 12 hours. To a residue obtained by distilling off the solvent under reduced pressure, n-pentane was added for extraction, and the thus obtained solution was distilled off under reduced pressure. The thus obtained yellow solid was purified by sublimation to obtain 18.8 g (63.8 mmol) of a white solid as a target (yield: 91%). The synthesis reaction performed in this example is as follows:
##STR00023##
[0089] Example 2: To a flask containing 40 ml of tetrahydrofuran, 1.0 g (4.2 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.50 g (7.2 mmol) of (2-isocyanopropane), and 3.0 g (9.2 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 16 hours. To a residue obtained by distilling off the solvent under reduced pressure, n-pentane was added for extraction, and the thus obtained solution was distilled off under reduced pressure. The thus obtained solid was purified with an alumina column to obtain 0.68 g (2.5 mmol) of a white solid as a target (yield: 61%). The synthesis reaction performed in this example is as follows:
##STR00024##
[0090] Example 3: To a flask containing 40 ml of tetrahydrofuran, 1.0 g (4.2 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.69 g (8.4 mmol) of 2-isocyanobutane, and 3.0 g (9.2 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 18 hours. To a residue obtained by distilling off the solvent under reduced pressure, n-pentane was added for extraction, and the thus obtained solution was distilled off under reduced pressure. The thus obtained residue was purified with an alumina column to obtain 0.25 g (0.84 mmol) of a colorless liquid as a target (yield: 20%). The synthesis reaction performed in this example is as follows:
##STR00025##
[0091] Example 4: To a flask containing 40 ml of tetrahydrofuran, 1.0 g (4.2 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.87 g (8.0 mmol) of isocyanocyclohexane, and 3.0 g (9.2 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 10 hours. To a residue obtained by distilling off the solvent under reduced pressure, n-pentane was added for extraction, and the thus obtained solution was distilled off under reduced pressure. The thus obtained residue was purified with an alumina column to obtain 0.55 g (1.7 mmol) of a white solid as a target (yield: 41%). The synthesis reaction performed in this example is as follows:
##STR00026##
[0092] Example 5: To a flask containing 100 ml of tetrahydrofuran, 3.67 g (15.3 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 2.15 g (26.8 mmol) of 3-isocyanopropionitrile, and 2.0 g (18.4 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 12 hours. A solid obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 2.38 g (8.2 mmol) of a white solid as a target (yield: 53%). The synthesis reaction performed in this example is as follows:
##STR00027##
[0093] Example 6: To a flask containing 150 ml of tetrahydrofuran, 4.0 g (15.0 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 3.78 g (30.0 mmol) of 3-(N-diethylamino)propionitrile, and 1.70 g (22.5 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 18 hours. An oil obtained by distilling off the solvent was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 3.03 g (8.98 mmol) of a colorless liquid as a target (yield: 60%). The synthesis reaction performed in this example is as follows:
##STR00028##
[0094] Example 7: To a flask containing 40 ml of tetrahydrofuran, 1.0 g (4.2 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 3.3 g (42 mmol) of pyridine, and 3.0 g (9.2 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was stirred at room temperature 18 hours. A residue obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.66 g (2.3 mmol) of a yellow solid as a target (yield: 55%). The synthesis reaction performed in this example is as follows:
##STR00029##
[0095] Example 8: To a flask containing 25 ml of tetrahydrofuran, 0.60 g (2.5 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.52 g (5.0 mmol) of 4-cyanopyridine, and 0.30 g (3.8 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 12 hours. A solid obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.39 g (1.3 mmol) of a yellow solid as a target (yield: 50%). The synthesis reaction performed in this example is as follows:
##STR00030##
[0096] Example 9: To a flask containing 25 ml of tetrahydrofuran, 0.66 g (2.5 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], and 0.56 g (5.0 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 1 hour. A solid obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.27 g (1.0 mmol) of a white solid as a target (yield: 40%). The synthesis reaction performed in this example is as follows:
##STR00031##
[0097] Example 10: To a flask containing 25 ml of tetrahydrofuran, 0.66 g (2.5 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.34 g (5.0 mmol) of imidazole, and 0.19 g (2.5 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 3 hours. A solid obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.21 g (0.75 mmol) of a yellow solid as a target (yield: 30%). The synthesis reaction performed in this example is as follows:
##STR00032##
[0098] Example 11: To a flask containing 50 ml of tetrahydrofuran, 1.2 g (5.0 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 1.44 g (15 mmol) of (1-ethylimidazole), and 0.60 g (7.5 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 1 hour. A residue obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.99 g (3.2 mmol) of a yellow liquid as a target (yield: 65%). The synthesis reaction performed in this example is as follows:
##STR00033##
[0099] Example 12: To a flask containing 40 ml of tetrahydrofuran, 0.66 g (2.5 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.40 g (5.0 mmol) of pyridazine, and 0.19 g (5.0 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 3 hours. A solid obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.23 g (0.80 mmol) of a yellow solid as a target (yield: 32%). The synthesis reaction performed in this example is as follows:
##STR00034##
[0100] Example 13: To a flask containing 40 ml of tetrahydrofuran, 0.66 g (2.5 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.40 g (5.0 mmol) of pyrimidine, and 0.19 g (5.0 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 3 hours. A solid obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.22 g (0.75 mmol) of a yellow solid as a target (yield: 30%). The synthesis reaction performed in this example is as follows:
##STR00035##
[0101] Example 14: To a flask containing 40 ml of tetrahydrofuran, 0.66 g (2.5 mmol) of [tricarbonyl-(η4-methylene-1,3-propanediyl)ruthenium], 0.40 g (5.0 mmol) of pyrazine, and 0.19 g (5.0 mmol) of trimethylamine N-oxide/dihydrate were added, and the resultant was heated at 60° C. for 3 hours. A solid obtained by distilling off the solvent under reduced pressure was dissolved in n-hexane, and the resultant was purified with an alumina column. The thus obtained solution was distilled off under reduced pressure to obtain 0.22 g (0.75 mmol) of a yellow solid as a target (yield: 30%). The synthesis reaction performed in this example is as follows:
##STR00036##
[0102] As described in the respective Examples, it could be confirmed in the present embodiment that the organoruthenium compounds in which the trimethylenemethane-based ligand (L.sub.1) and the various ligands X (the isocyanide ligand (L.sub.2), the pyridine ligand (L.sub.3), the amine ligand (L.sub.4), the imidazole ligand (L.sub.5), the pyridazine ligand (L.sub.6), the pyrimidine ligand (L.sub.7), and the pyrazine ligand (L.sub.8)) coordinated to ruthenium could be synthesized.
[0103] [Evaluation of Physical Properties]
[0104] Among the organorutheniums produced in the present embodiment, the organoruthenium compounds of Example 1 (dicarbonyl-(2-isocyano-2-methylpropane)-(η4-methylene-1,3-propanediyl)ruthenium: ligand X=L.sub.2, R.sub.1=tert-butyl), Example 3 (dicarbonyl-(2-isocyano-2-butyl)-(η4-methylene-1,3-propanediyl: ligand X=L.sub.2, R.sub.1=sec-butyl group), and Example 6 (dicarbonyl-(2-isocyano-2-methyl)-(η4-methylene-1,3-propanediyl)ruthenium: ligand X=L.sub.3, all of R.sub.2 to R.sub.6=hydrogen) were evaluated for thermal stability and vaporization property.
[0105] Besides, in the present embodiment, for comparison with the Examples described above, (η4-methylene-1,3-propanediyl)tricarbonyl ruthenium in which trimethylenemethane (R=hydrogen) coordinated as the trimethylenemethane-based ligand (L.sub.1) and three carbonyl groups coordinated was synthesized as Reference Example 1 as follows.
[0106] Reference Example 1: 50.0 g (97.5 mmol) of tricarbonyl-dichlororuthenium dimer was suspended in 1700 ml of tetrahydrofuran, and 300 ml of a solution of 29.2 g of (231.6 mmol) of 3-chloro-2-(chloromethyl)-1-propene in tetrahydrofuran was added thereto. To the resultant, 19.7 g (800 mmol) of magnesium turnings were slowly added, followed by stirring at room temperature for 3 hours. To the resultant reaction mixture, 5 mL of methanol was added for quenching, and the solvent was distilled off under reduced pressure. The thus obtained residue was extracted with 30 mL of pentane three times, and the solvent was distilled off under reduced pressure. The thus obtained oil was purified by sublimation to obtain 16.3 g (68.3 mmol) of a colorless liquid as a target (yield: 35%). The synthesis reaction is as follows:
##STR00037##
[0107] Study of Thermal Stability
[0108] The evaluation of thermal stability was performed by measuring a decomposition starting temperature by differential scanning calorimetry (DSC). In the DSC, DSC3500-ASC manufactured by NETZSCH was used as a measurement apparatus, and the measurement was performed with the weight of a sample set to 1.0 mg, nitrogen used as a carrier gas, at a scanning rate of 5° C./min in a range of −50° C. to 400° C.
[0109] In this study, the DSC was performed also on (1,3-cyclohexadiene)tricarbonyl ruthenium (Formula 2) described above as the conventional technique (Comparative Example 1). The decomposition temperatures of the respective organoruthenium compounds measured by DSC are shown in Table 1. Besides, DSC results of the organoruthenium compounds of Example 1, Example 3, Example 6, Reference Example 1 and Comparative Example 1 are illustrated in
TABLE-US-00001 TABLE 1 Decomposition Temperature Example 1 231.6° C. Example 3 240.0° C. Example 6 200.0° C. Reference 282.2° C. Example 1 Comparative 190.1° C. Example 1
[0110] As described above, the decomposition temperature of (1,3-cyclohexadiene)tricarbonyl ruthenium (Formula 2) of Comparative Example 1 was 190.1° C. On the contrary, the decomposition temperatures of the organoruthenium compounds of Examples 1, 3, and 6 were 200° C. or more, and thus, it is deemed that the thermal stability is higher than that of Comparative Example. It is noted that the organoruthenium compound of Reference Example 1 also had a decomposition temperature higher than that of Comparative Example 1, and is deemed to be favorable from the viewpoint of the thermal stability.
[0111] Study of Vaporization Property
[0112] Next, regarding the organoruthenium compounds of Examples 1, 3, and 6 and Reference Example 1, the vaporization property was comparatively studied by thermogravimetric-differential thermal analysis (TG-DTA). In the TG-DTA, TG-DTA2000SA manufactured by BRUKER was used, a sample with a weight of 5 mg was filled in an aluminum cell, and change in a calorific value and a weight was observed in a nitrogen atmosphere at a temperature increase rate of 5° C./min in a measurement temperature range of from room temperature to 500° C.
[0113] The organoruthenium compound of Reference Example 1 (in which the three carbonyl ligands coordinate) started to vaporize substantially at the same time as the start of the measurement at around normal temperature. Thus, the vapor pressure of the organoruthenium compound of Reference Example 1 is deemed to be high, but is deemed to be too high. In other words, it is deemed that the organoruthenium compound of Reference Example 1 has favorable thermal stability but is rather disadvantageous in the vaporization property (vapor pressure).
[0114] On the contrary, the organoruthenium compound of Example 1 (ligand X=isocyanide ligand) was inhibited from vaporizing and stable up to about 60° C. Besides, based on the inclination of the TG curve, rapid vaporization occurred in Example 1. It is deemed, based on this result, that the vaporization property was adjusted by introducing the ligand X (isocyanide ligand) into the compound of Reference Example in which only the carbonyl ligands coordinated. In Example 1, the vaporization is inhibited under room temperature environment, and hence, it is presumed that temperature control and quality control in film formation of a raw material for chemical deposition are further eased. Besides, in Example 1, vaporization occurs rapidly at the time of film formation, and the organoruthenium compound easily vaporizes to a raw material gas.
[0115] It was confirmed also in Examples 3 and 6 that the organoruthenium compounds did no vaporize at normal temperature but easily vaporized when heated.
[0116] [Film Formation Test]
[0117] The organoruthenium compound of Example 1 of the present embodiment (dicarbonyl-(2-isocyano-2-methylpropane)-(η4-methylene-1,3-propanediyl)ruthenium) was subjected to a film formation test to study the film formability. Besides, for comparison, dicarbonyl-bis(5-methyl-2,4-hexanediketonato)ruthenium (Formula 5, Patent Document 4) corresponding to a conventional raw material for chemical deposition was also subjected to the film formation test (Comparative Example 2).
[0118] With the organoruthenium compound of the present embodiment used as a raw material, a ruthenium thin film was formed with a CVD apparatus (hot wall CVD film forming apparatus). Film forming conditions were as follows: [0119] Substrate material: Si [0120] Carrier gas (nitrogen gas): 10 sccm, 200 sccm [0121] Reaction gas (hydrogen gas): 10 sccm, 200 sccm [0122] Film forming pressure: 50 torr [0123] Film forming time: 15 min, 30 min [0124] Film forming temperature: 260° C., 250° C.
[0125] A ruthenium thin film was formed under the above-described conditions, and a thickness and a resistance value of the resultant were measured. The thickness of the ruthenium thin film was obtained by measuring thicknesses in a plurality portions based on a result of XRF (X-ray reflection fluorescence) using EA1200VX manufactured by Hitachi High-Tech Science Corporation, and calculating an average of the thicknesses. Besides, the resistance value was measured by a four point probe method. Results of the measurement are shown in Table 2.
TABLE-US-00002 TABLE 2 Film Film Nitrogen Hydrogen Forming Forming Film Forming Ru Film Specific Substrate Gas Gas Pressure Time Temperature Thickness Resistance Sample Material (sccm) (sccm) (torr) (min) (° C.) (nm) (μΩ .Math. cm) Example 1 Si 10 200 50 15 260 18.7 20.1 200 5.9 33.9 10 5.8 55.8 Comparative 10 200 30 250 17.8 65.3 Example 2
[0126] As illustrated in
[0127] Besides, regarding the quality of the thin film, it can be confirmed that a high quality ruthenium thin film having largely lower specific resistance as compared with that of Comparative Example 2 is formed. Differently from the compound of Comparative Example 2, the organoruthenium compound of the present invention does not contain an oxygen atom capable of directly coordinating to ruthenium, and has favorable reactivity with hydrogen or the like. Therefore, a possibility of oxygen mixture in the ruthenium thin film is low, and hence a high quality ruthenium thin film having low specific resistance can be formed.
[0128] Second Embodiment: In the present embodiment, a film formation test of a ruthenium thin film was performed with the organoruthenium compounds of Example 1 and Comparative Example 2 of First Embodiment used as raw materials, and with oxygen applied as the reaction gas. For the film formation, the same CVD apparatus (hot wall CVD film forming apparatus) as that used in First Embodiment was used. Film forming conditions were as follows: [0129] Substrate material: Si [0130] Carrier gas (nitrogen gas): 50 sccm [0131] Reaction gas (oxygen gas): 10 sccm [0132] Film forming pressure: 2 torr [0133] Film forming time: 30 min [0134] Film forming temperature: 260° C., 250° C.
[0135] A ruthenium thin film was formed under the above-described conditions, and a thickness and a resistance value of the resultant were measured. The methods for measuring the thickness and the resistance value of the ruthenium thin film were the same as those employed in First Embodiment. Results of the measurement are shown in Table 3. Besides,
TABLE-US-00003 TABLE 3 Film Film Nitrogen Oxygen Forming Forming Film Forming Ru Film Specific Substrate Gas Gas Pressure Time Temperature Thickness Resistance Sample Material (sccm) (sccm) (torr) (min) (° C.) (nm) (μΩ .Math. cm) Example 1 Si 50 10 2 30 260 36.5 43.7 Comparative 250 21.6 46.4 Example 2
[0136] It is understood, based on Table 3 and
INDUSTRIAL APPLICABILITY
[0137] An organoruthenium compound contained in a raw material for chemical deposition of the present invention has high thermal stability, and can form a ruthenium thin film even with a reducing gas such as hydrogen used as a reaction gas. Besides, even when oxygen is used as the reaction gas, it can form a good ruthenium thin film. The raw material for chemical deposition of the present invention has a favorable vapor pressure, and is good also in handleability. The present invention is suitable for use as a wiring/electrode material of a semiconductor device such as a DRAM.