GB2629153A - Ruthenium complexes and process for producing ruthenium film - Google Patents
Ruthenium complexes and process for producing ruthenium film Download PDFInfo
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- GB2629153A GB2629153A GB2305643.5A GB202305643A GB2629153A GB 2629153 A GB2629153 A GB 2629153A GB 202305643 A GB202305643 A GB 202305643A GB 2629153 A GB2629153 A GB 2629153A
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- Prior art keywords
- ruthenium
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- complex
- dimethylpentadienyl
- dmopd
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- 238000000034 method Methods 0.000 title claims abstract description 18
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 17
- 150000003303 ruthenium Chemical class 0.000 title description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 13
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical class [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001728 carbonyl compounds Chemical class 0.000 claims abstract description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 7
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005234 chemical deposition Methods 0.000 claims abstract description 6
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 4
- IDEYZABHVQLHAF-GQCTYLIASA-N (e)-2-methylpent-2-enal Chemical compound CC\C=C(/C)C=O IDEYZABHVQLHAF-GQCTYLIASA-N 0.000 claims abstract description 3
- IDEYZABHVQLHAF-UHFFFAOYSA-N 2-Methyl-2-pentenal Natural products CCC=C(C)C=O IDEYZABHVQLHAF-UHFFFAOYSA-N 0.000 claims abstract description 3
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- -1 ruthenium (II) tetrafluoroborate Chemical compound 0.000 claims description 5
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 abstract description 16
- 239000012327 Ruthenium complex Substances 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- AHXNYDBSLAVPLY-UHFFFAOYSA-M 1,1,1-trifluoro-N-(trifluoromethylsulfonyl)methanesulfonimidate Chemical compound [O-]S(=O)(=NS(=O)(=O)C(F)(F)F)C(F)(F)F AHXNYDBSLAVPLY-UHFFFAOYSA-M 0.000 description 1
- WYILUGVDWAFRSG-UHFFFAOYSA-N 2,4-dimethylpenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC(C)=CC(C)=[CH-].CC(C)=CC(C)=[CH-] WYILUGVDWAFRSG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- FOBPTJZYDGNHLR-UHFFFAOYSA-N diphosphorus Chemical compound P#P FOBPTJZYDGNHLR-UHFFFAOYSA-N 0.000 description 1
- CEIPQQODRKXDSB-UHFFFAOYSA-N ethyl 3-(6-hydroxynaphthalen-2-yl)-1H-indazole-5-carboximidate dihydrochloride Chemical compound Cl.Cl.C1=C(O)C=CC2=CC(C3=NNC4=CC=C(C=C43)C(=N)OCC)=CC=C21 CEIPQQODRKXDSB-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 1
- LABTWGUMFABVFG-UHFFFAOYSA-N methyl propenyl ketone Chemical compound CC=CC(C)=O LABTWGUMFABVFG-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A complex of Formula (I) or Formula (II) is provided: wherein R2-R5 are each independently selected from a C1 to C6 hydrocarbyl group on the condition that the total of R2 and R4 combined is 2-7 and the total of R3 and R5 combined is 2-7. R2, R3, R4 and R5 are preferably methyl. A chemical deposition process for producing a ruthenium film using the ruthenium complex as a precursor is provided. The chemical deposition method may be either a chemical vapor deposition or an atomic layer deposition method. A method of preparing the complex comprising the step of reacting together a (η5-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) salt and an α,β-unsaturated carbonyl compound of the formula R2C(=O)CH=CR4CH3 or CH(=O)CR3=CHCH2R5 is provided. The compound (η5-2,4-dimethylpentadienyl)( η5-2,4-dimethyl-1-oxa-pentadienyl) ruthenium (II) [Ru(DMPD)(DMOPD)] is prepared using mesityl oxide as the α,β-unsaturated carbonyl compound. The compound (η5-2,4-dimethylpentadienyl)( η5-3,4-dimethyl-1-oxa-pentadienyl) ruthenium (II) [Ru(DMPD)(3,5-DMOPD)] is prepared using 2-methyl-2-pentenal as the α,β-unsaturated carbonyl compound.
Description
Ruthenium complexes and process for producing ruthenium film
Technical field
The present invention relates to ruthenium complexes for use in preparing ruthenium films.
Background art
In the following (q5-2,4-dimethylpentadienyl) is abbreviated to DMPD, (115-2,4-dimethy1-1-oxapentadienyl) is abbreviated to DMOPD and (r15-3,5-dimethyl-1-oxa-pentadienyl) is abbreviated to 3,5-DMOPD.
The article "Low-Temperature Preparation of Metallic Ruthenium Films by MOVCD Using Bis(2,4-dimethylpentadienyl) ruthenium" Electrochemical and Solid-State Letters, 10 (6) D60-D62 (2007) describes the deposition of crystalline ruthenium films onto thermally oxidized Si substrates by MOCVD using the ruthenium complex Ru(DMPD)2. The complex was reported to have the following properties: melting point of 89 °C; vapor pressure of 0.1Torr @ 82 °C; decomposition temperature (DSC) of 210 °C.
The analogous complex Ru(DMOPD)2 is also known. The article "Bis[ri5-(2,4-dimethyl-1-oxapentadienyl)] ruthenium(II): the First Homoleptic Open Ruthenocenes with Non-hydrocarbon Ligands" J. Chem. Soc., Chem. Commun., 1991, 1427-1429 describes the preparation of this complex from RuC13. aq and 4-methylbut-3-en-2-one in absolute ethanol with reduction using zinc dust as reducing agent. The reaction produces a mixture of isomers in approximately 1:1 ratio. The complex Ru(DMOPD)2 does not appear to have been used previously as a precursor for producing ruthenium films.
Mixed ruthenium complexes which contain a single DMOPD ligand are also known.
The article "Half-Open Ruthenocenes Derived from [Ru(C5Me5)C1]4: Syntheses, Characterizations, and Solid-State Structures" Organometallics 1992, 11, 1686-1692 describes the complex Ru(C5Me5)(DMOPD). This complex was prepared by the reaction between [Ru(C5Me5)C1]4 and mesityl oxide in K2CO3/THF, as part of an isomeric mixture. These complexes were not investigated for use in ruthenium film production.
US8884044B2 describes complexes of formula Ru(DMPD)(P) where P is a chiral diphosphorus donor ligand. These complexes are described for use in catalytic hydrogenation but have not been investigated for use in ruthenium film production.
US9349601B2 describes ruthenium complexes with various general structures, including a family of formula (la) containing a substituted or unsubstituted Cp ligand and a DMOPD-type ligand. The examples include preparation of the complexes Ru(C5H5)(DMOPD) [Example 7], Ru(C5H4Me)(DMOPD) [Example 8], Ru(C5H4E0(DMOPD) [Examples 9, 12, 13], Ru(C5Me5)(DMOPD) [Example 11].
While Ru(DMPD)2 and Ru(DMOPD)2 are both known, only the former has previously been explored for producing ruthenium films. The absence of any discussion about using Ru(DMOPD)2 for film production may indicate that this complex is not suitable, perhaps due to its insufficient thermal stability.
A ruthenium complex used for producing ruthenium films should ideally satisfy some or all of the following criteria. Firstly, the complex should have a high vapour pressure. Secondly, the complex should be stable enough to be vaporised and transported onto a substrate, yet reactive enough to react with a reactant gas to produce a ruthenium film on the substrate. Thirdly, the complex should be simple to manufacture.
The present invention provides complexes which offer a balance of the above-mentioned requirements.
Description of the invention
In a first aspect the invention relates to complex of Formula (0: (Formula I) wherein IR2 and 54 are each independently selected from a Ci to C6 hydrocarbyl group; on the condition that the total number of carbon atoms within groups 52 and 54 combined is 2-7.
For the avoidance of doubt, as an example if 52 = R4 = Et then the total number of carbon atoms within groups R2 and R4 combined is 4.
In a second aspect the invention relates to a complex of Formula (ID: RS (Formula II) wherein 53 and 55 are each independently selected from a Ci to C6 hydrocarbyl group; on the condition that the total number of carbon atoms within groups R3 and R5 combined is 2-7.
Mixed complexes of Formula (I) or (II), containing a DMPD ligand and a second non-identical ligand described herein are expected to have stability in-between that of Ru(DMOPD) and Ru(DMOPD)2 and, therefore, suitable for film production.
The skilled person will appreciate that conformational isomers may be possible in complexes of Formula (I) or (II), particularly given known conformational isomers in the related complex Ru(DMOPD)2 (see J. Chem. Soc., Chem. Commun., 1991, 1427-1429). For the avoidance of doubt, Formula (I) and (II) are not intended to indicate a specific conformer and should be understood in their broadest sense.
The substituents R2 and R4 (in the case of Formula (0) or groups R3 and R5 (in the case of Formula (ID) are each independently selected from a Ci to Cs hydrocarbyl group. By "hydrocarbyl group" herein we mean a group that contains carbon and hydrogen atoms only. Each group may be saturated or unsaturated, preferably saturated. Preferred groups are Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, sec-Bu, t-Bu, n-pentyl, cyclo-pentyl, n-hexyl.
It will be appreciated that the greater the number of carbon atoms within groups R2 and R4 (Formula (I)) or within groups R3 and R5 (Formula (II)), the less volatile the complex and the higher the temperature required to volatilise the complex. It is preferred that the volatilisation temperature is low in order to minimise the risk of prematurely decomposing the complex. It is therefore preferred that the total number of carbon atoms within groups R2 and R4 combined or within groups R3 and R5 combined is 2 to 6, preferably 2 to 5, preferably 2 to 4, preferably 2 to 3, most preferably 2.
A particularly preferred complex of Formula (I) is (q5-2,4-dimethylpentadienyl)(1-15-2,4-dimethyl1-oxa-pentadienyl) ruthenium (I I) "Ru(DMPD)(DMOPD)", i.e. where R2= R4= Me.
A particularly preferred complex of Formula (II) is (q5-2,4-dimethylpentadienyl)(q5-3,4-dimethy1-1-oxa-pentadienyl) ruthenium (II) "Ru(DMPD)(3,5-DMOPD" i.e. where R3= R5= Me.
In a third aspect the invention relates to a process for producing a ruthenium film by a chemical deposition method, wherein the ruthenium precursor is of Formula (I) or (II). Preferred methods include chemical vapour deposition (CVD) and atomic layer deposition (ALD).
In a fourth aspect the invention relates to a method for the preparation of a complex according to Formula (I) or (II), comprising the step of reacting together a (q5-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) salt and an a,(3-unsaturated carbonyl compound of formula R2C(=O)CH=CR4CH3 in the case of Formula (I) or of formula CH(=0)CR3=CHCH2R5 in the case of Formula (I I).
In a preferred embodiment the a,(3-unsaturated carbonyl compound is mesityl oxide.
In a preferred embodiment the a,(3-unsaturated carbonyl compound is 2-methyl-2-pentenal.
Suitable (n5-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) salts include perchlorate, tetrafluoroborate, hexafluorophosphate, triflate, bis(trifluoromethanesulfonyl)imidate (bistriflimide), etc. A preferred salt is (q5-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) tetrafluoroborate.
Any suitable solvent may be used for the reaction. A preferred solvent is THF, preferably THF at -78 °C.
The reaction according to the fourth and fifth aspects of the invention is preferably carried out in the presence of a base. The base preferably contains an amine functionality. A preferred base is triethylamine.
Example
Ru(DMPD)(DMOPD) was prepared by the reaction between [Ru(DMPD)(CH3CN)3][BF4] and mesityl oxide. [Ru(DMPD)(CH3CN)3][BF4] in turn was prepared following a procedure adapted from US884044B2.
Preparation of (Ru(DMPD)(CH3CN)30F4] In an Argon glovebox, a 100 ml Schlenk flask was charged with 0.681 g Ru(DMPD)2 (2.34 mmol) followed by 31 mL anhydrous diethyl ether and stirring. Within 10 min, 0.32 mL HBF4-Et20 (2.33 mmol) were added dropwise causing precipitation of a pale-yellow solid. The mixture was filtered using an air-free filtration funnel attached to a 200 mL receiving Schlenk flask. The solid was briefly pumped on to remove ether, scraped out of the filtration funnel and weighed: 0.813 g. The solid was placed back into the 100 mL Schlenk flask and dissolved in 23 mL anhydrous acetonitrile. The solution was stirred briefly, and the flask was removed from the glovebox to remove volatiles by pumping on the stirred solution through a cold trap. A warm water bath was used. When pressure reached 0.27 mbar, the flask containing orange solid was isolated and brought back into the glovebox.
Preparation of pu(DMPD)(DMOPE)J Next day, dry THF (13 mL) was added to the remaining orange solid. The flask was removed from the glovebox and placed in a -78 °C bath. With stirring, mesityl oxide (distilled from 3A MS; 0.60 mL; 5.2 mmol) was added followed by triethylamine (distilled from 3A MS; 0.45 mL, 3.27 mmol). After 10 min, the flask was removed from the cold bath and placed in a heating block, which was heated to 40 °C over 1 h. This block temperature was maintained for 3 h. After cooling to ambient temperature, volatiles were removed by pumping on the stirred solution through a cold trap. A warm water bath was used. When pressure reached to 0.18 mbar, the flask was isolated and brought into the glove box. Next day, the residue was extracted with 20 mL anhydrous hexane followed by filtration using an air-free filtration funnel attached to a 200 mL receiving Schlenk flask. The flask was removed from the glovebox to remove volatiles by pumping on the stirred solution through a cold trap. A warm water bath was used. When pressure reached 0.14 mbar, the flask was isolated and brought into the glovebox. The crude product was purified by vacuum sublimation @45 °C / 0.1 mbar. The cold finger was water-cooled. At the end of sublimation, yellow crystals were observed on the cold finger. The sublimation apparatus the flask was isolated and brought in the glove box, where most of the yellow solid was scraped off the cold finger into a pre-weighed vial. Mass: 0.0654 g. Yield: 10%.
The complex Ru(DMPD)(DMOPD) is a low melting solid with a melting point of -70 °C, and volatilises without decomposition below 220 °C.
Claims (13)
- A complex of Formula (0: (Formula I) Claims wherein R2 and R4 are each independently selected from a Ci to C6 hydrocarbyl group; on the condition that the total number of carbon atoms within groups R2 and R4 combined is 2-7.
- 2. A complex according to claim 1, wherein the total number of carbon atoms within groups R2 and R4 combined is 2 or 3.
- 3. A complex according to claim 1, wherein R2 = = Me.
- 4. A complex of Formula (10: Ru (Formula II) wherein R3 and R5 are each independently selected from a Ci to C6 hydrocarbyl group; on the condition that the total number of carbon atoms within groups R3 and R5 combined is 2-7.
- 5. A complex according to claim 4, wherein the total number of carbon atoms within groups R3 and R5 combined is 2 or 3.
- 6. A complex according to claim 4, wherein R3 = RS = Me.
- 7. A process for producing a ruthenium film using a ruthenium precursor by a chemical deposition method, wherein the ruthenium precursor is as claimed in any of claims 1 to 6.
- 8. A process according to claim 7, where the chemical deposition method is a chemical vapour deposition method.
- 9. A process according to claim 7, where the chemical deposition method is an atomic layer deposition method.
- 10. A method for the preparation of a complex according to any of claims 1 to 6, comprising the step of reacting together a (n5-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) salt and an 0,13-unsaturated carbonyl compound of formula R2C(=0)CH=CIR4CH3 in the case of Formula (I) or of formula CH(=O)CR3=CHCH2R5 in the case of Formula (II).
- 11. A method according to claim 10, wherein the (15-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) salt is (n5-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) tetrafluoroborate.
- 12. A method according to claim 10 or claim 11, wherein the a,(3-unsaturated carbonyl compound is mesityl oxide.
- 13. A method according to claim 10 or claim 11, wherein the a,(3-unsaturated carbonyl compound is 2-methyl-2-pentenal.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2305643.5A GB2629153A (en) | 2023-04-18 | 2023-04-18 | Ruthenium complexes and process for producing ruthenium film |
| TW113111397A TW202444732A (en) | 2023-04-18 | 2024-03-27 | Ruthenium complexes and process for producing ruthenium film |
| PCT/GB2024/050908 WO2024218468A1 (en) | 2023-04-18 | 2024-04-03 | Ruthenium complexes and process for producing ruthenium film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB2305643.5A GB2629153A (en) | 2023-04-18 | 2023-04-18 | Ruthenium complexes and process for producing ruthenium film |
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| Publication Number | Publication Date |
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| GB202305643D0 GB202305643D0 (en) | 2023-05-31 |
| GB2629153A true GB2629153A (en) | 2024-10-23 |
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Country Status (3)
| Country | Link |
|---|---|
| GB (1) | GB2629153A (en) |
| TW (1) | TW202444732A (en) |
| WO (1) | WO2024218468A1 (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352488A (en) * | 1993-05-14 | 1994-10-04 | Syracuse University | Chemical vapor deposition process employing metal pentadienyl complexes |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US884044A (en) | 1907-08-16 | 1908-04-07 | William T Rice | Device for cleaning combs. |
| EP2107065A1 (en) | 2008-04-01 | 2009-10-07 | Umicore AG & Co. KG | Ruthenium complexes with (P-P)-coordinated di-phosphor donor ligands and method for production of same |
| TWI610932B (en) | 2012-12-07 | 2018-01-11 | 東曹股份有限公司 | Ruthenium complex and method for producing the same, cationic tris(nitrile) complex and method for producing the same, and method for producing ruthenium-containing film |
| JPWO2021187485A1 (en) * | 2020-03-18 | 2021-09-23 |
-
2023
- 2023-04-18 GB GB2305643.5A patent/GB2629153A/en active Pending
-
2024
- 2024-03-27 TW TW113111397A patent/TW202444732A/en unknown
- 2024-04-03 WO PCT/GB2024/050908 patent/WO2024218468A1/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5352488A (en) * | 1993-05-14 | 1994-10-04 | Syracuse University | Chemical vapor deposition process employing metal pentadienyl complexes |
Non-Patent Citations (2)
| Title |
|---|
| Journal of the Chemical Society, Chemical Communications, no.20, 1991, 1427-1429 * |
| Organometallics, vol. 31, no. 20, 2012, pages 7125-7145 * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB202305643D0 (en) | 2023-05-31 |
| TW202444732A (en) | 2024-11-16 |
| WO2024218468A1 (en) | 2024-10-24 |
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