Organoruthenium complex, and method for production of ruthenium thin film using the ruthenium complex
View Patent ↗An organoruthenium complex represented by the general formula (1-1), bis(acetylacetonato)(1,5-hexadiene)ruthenium and bis(acetylacetonato)(1,3-pentadiene)ruthenium have low melting points, show excellent stability against moisture, air and heat, and are suitable for the film formation by a CVD method. (1-1) wherein X represents a group represented by the general formula (1-2); Y represent a group represented by the general formula (1-2) or a linear or branched alkyl group having 1 to 8 carbon atoms; Z represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and L represents an unsaturated hydrocarbon compound having at least two double bonds: (1-2) wherein R a and R b independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.
1. An organoruthenium complex comprising a β-diketonato having an alkoxyalkylmethyl group and an unsaturated hydrocarbon compound having at least two double bonds as a ligand, and represented by the general formula (1-1):
wherein X represents a group represented by the general formula (1-2):
wherein R a and R b independently represent a linear or branched alkyl group having 1 to 5 carbon atoms;
Y represents a group represented by the above general formula (1-2), or a linear or branched alkyl group having 1 to 8 carbon atoms;
Z represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms; and
L represents an unsaturated hydrocarbon compound having at least two double bonds.
2. The organoruthenium complex as claimed in claim 1 , wherein the unsaturated hydrocarbon compound having at least two double bonds is 1,5-hexadiene, 1,5-cyclooctadiene, norbornadiene, 4-vinyl-1-cyclohexene or 1,3-pentadiene.
3. A method for producing a ruthenium-containing thin film comprising:
a) providing the organoruthenium complex as claimed in claim 1 or a solvent solution thereof as a ruthenium source, and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
4. A method for producing a ruthenium-containing thin film comprising:
a) providing the organoruthenium complex as claimed in claim 1 or a solvent solution thereof, and a hydrogen source, and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
5. The method for producing a ruthenium-containing thin film as claimed in claim 4 , wherein the hydrogen source is a hydrogen gas.
6. A method for producing a ruthenium-containing thin film comprising:
a) providing the organoruthenium complex as claimed in claim 1 or a solvent solution thereof, and an oxygen source, and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
7. The method for producing a ruthenium-containing thin film as claimed in claim 6 , wherein the oxygen source is an oxygen gas.
8. The method for producing a ruthenium-containing thin film as claimed in claim 6 , wherein the ruthenium-containing thin film produced is a metallic ruthenium film which contains substantially no oxygen atom.
9. The method for producing a ruthenium-containing thin film as claimed in claim 3 , wherein the solvent used is at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and ethers.
10. Bis(acetylacetonato)(1,5-hexadiene)ruthenium represented by the formula (2-1):
11. A method for producing a metallic ruthenium-containing thin film comprising:
a) providing Bis(acetylacetonato)(1,5-hexadiene)ruthenium as claimed in claim 10 , and
b) forming the metallic ruthenium-containing thin film by a chemical vapor deposition method.
12. A method for producing a ruthenium-containing thin film comprising:
a) providing bis(acetylacetonato)(1,5-hexadiene)ruthenium as claimed in claim 10 or a solvent solution thereof as a ruthenium source, and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
13. A method for producing a ruthenium-containing thin film comprising:
a) providing bis(acetylacetonato)(1,5-hexadiene)ruthenium as claimed in claim 10 or a solvent solution thereof, and a hydrogen source and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
14. The method for producing a ruthenium-containing thin film as claimed in claim 13 , wherein the hydrogen source is a hydrogen gas.
15. A method for producing a ruthenium-containing thin film comprising:
a) providing bis(acetylacetonato)(1,5-hexadiene)ruthenium as claimed in claim 10 or a solvent solution thereof, and an oxygen source, and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
16. The method for producing a ruthenium-containing thin film as claimed in claim 15 , wherein the oxygen source is an oxygen gas.
17. The method for producing a ruthenium-containing thin film as claimed in claim 15 , wherein the ruthenium-containing thin film produced is a metallic ruthenium film which contains substantially no oxygen atom.
18. The method for producing a ruthenium-containing thin film as claimed in claim 12 , wherein the solvent used is at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and ethers.
19. Bis(acetylacetonato)(1,3-pentadiene)ruthenium represented by the formula (3-1):
20. A method for producing a metallic ruthenium-containing thin film comprising:
a) providing Bis(acetylacetonato)(1,3-pentadiene}ruthenium as claimed in claim 19 , and
b) forming the metallic ruthenium-containing thin film by a chemical vapor deposition method.
21. A method for producing a ruthenium-containing thin film comprising:
a) providing bis(acetylacetonato)(1,3-pentadiene)ruthenium as claimed in claim 19 or a solvent solution thereof as a ruthenium source, and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
22. A method for producing a ruthenium-containing thin film comprising:
a) providing bis(acetylacetonato)(1,3-pentadiene)ruthenium as claimed in claim 19 or a solvent solution thereof, and a hydrogen source are used and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
23. The method for producing a ruthenium-containing thin film as claimed in claim 22 , wherein the hydrogen source is a hydrogen gas.
24. A method for producing a ruthenium-containing thin film comprising:
a) providing bis(acetylacetonato)(1,3-pentadiene)ruthenium as claimed in claim 19 or a solvent solution thereof, and an oxygen source, and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
25. The method for producing a ruthenium-containing thin film as claimed in claim 24 , wherein the oxygen source is an oxygen gas.
26. The method as claimed in claim 21 , wherein the solvent used is at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and ethers.
27. A method for producing a metallic ruthenium-containing thin film comprising
a) providing a ruthenium source and a hydrogen source
wherein the ruthenium source is an organoruthenium complex comprising a β-diketonato and an unsaturated hydrocarbon compound having at least two double bonds as a ligand, and represented by the general formula (4-1):
wherein X 4 and Y 4 independently represent a linear or branched alkyl group (with the proviso that the sum total of the carbon atoms in the groups represented by X 4 and Y 4 is 2 to 10);
Z 4 represents a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms; and
L 4 represents an unsaturated hydrocarbon compound having at least two double bonds, or a solvent solution thereof; and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
28. The method as claimed in claim 27 , wherein the unsaturated hydrocarbon compound having at least two double bonds is 1,5-hexadiene, 1,5-cyclooctadiene, norbornadiene, 4-vinyl-1-cyclohexene or 1,3-pentadiene.
29. The method as claimed in claim 27 , wherein the hydrogen source is a hydrogen gas.
30. A method for producing a ruthenium-containing thin film comprising:
a) providing a ruthenium source and an oxygen source, wherein the ruthenium source is an organoruthenium complex comprising a 8-diketonato and an unsaturated hydrocarbon compound having at least two double bonds as a ligand, and represented by the above general formula (4-1), or a solvent solution thereof; and
b) forming the ruthenium-containing thin film by a chemical vapor deposition method.
31. The method as claimed in claim 30 , wherein the oxygen source is an oxygen gas.
32. The method as claimed in claim 27 , wherein the solvent used is at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and ethers.
33. The method as claimed in claim 30 , wherein the solvent used comprises at least one selected from the group consisting of aliphatic hydrocarbons, aromatic hydrocarbons, and ethers.