WO2024218468A1 - Ruthenium complexes and process for producing ruthenium film - Google Patents
Ruthenium complexes and process for producing ruthenium film Download PDFInfo
- Publication number
- WO2024218468A1 WO2024218468A1 PCT/GB2024/050908 GB2024050908W WO2024218468A1 WO 2024218468 A1 WO2024218468 A1 WO 2024218468A1 GB 2024050908 W GB2024050908 W GB 2024050908W WO 2024218468 A1 WO2024218468 A1 WO 2024218468A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- ruthenium
- formula
- complex
- dmopd
- complexes
- Prior art date
Links
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- 150000003303 ruthenium Chemical class 0.000 title abstract description 6
- 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 7
- 238000005234 chemical deposition Methods 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 7
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 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 description 5
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims description 5
- -1 ruthenium (II) tetrafluoroborate Chemical compound 0.000 claims description 5
- 238000000231 atomic layer deposition Methods 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- IDEYZABHVQLHAF-GQCTYLIASA-N (e)-2-methylpent-2-enal Chemical compound CC\C=C(/C)C=O IDEYZABHVQLHAF-GQCTYLIASA-N 0.000 claims description 2
- IDEYZABHVQLHAF-UHFFFAOYSA-N 2-Methyl-2-pentenal Natural products CCC=C(C)C=O IDEYZABHVQLHAF-UHFFFAOYSA-N 0.000 claims description 2
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 claims description 2
- 239000010408 film Substances 0.000 description 22
- BZORFPDSXLZWJF-UHFFFAOYSA-N N,N-dimethyl-1,4-phenylenediamine Chemical compound CN(C)C1=CC=C(N)C=C1 BZORFPDSXLZWJF-UHFFFAOYSA-N 0.000 description 21
- 238000000151 deposition Methods 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- 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
- 239000000758 substrate Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 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
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000005086 pumping Methods 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
- 239000012327 Ruthenium complex Substances 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
- 239000000376 reactant Substances 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
- 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
- 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
- 150000003839 salts Chemical class 0.000 description 1
- 239000000523 sample Substances 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
- 239000010409 thin film Substances 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
Definitions
- the present invention relates to ruthenium complexes for use in preparing ruthenium films.
- DMPD DM-dimethylpentadienyl
- DMOPD DMO-dimethyl-1-oxa-pentadienyl
- 3,5-DMOPD 3,5-DMOPD
- the analogous complex Ru(DMOPD)2 is also known.
- the complex Ru(DMOPD)2 does not appear to have been used previously as a precursor for producing ruthenium films.
- US9349601 B2 describes ruthenium complexes with various general structures, including a family of formula (1a) containing a substituted or unsubstituted Cp ligand and a DMOPD-type ligand.
- the examples include preparation of the complexes Ru(CsH5)(DMOPD) [Example 7], Ru(C 5 H 4 Me)(DMOPD) [Example 8], Ru(C 5 H 4 Et)(DMOPD) [Examples 9, 12, 13], Ru(C 5 Me 5 )(DMOPD) [Example 11],
- 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.
- the invention relates to complex of Formula (I): (Formula I) wherein R 2 and R 4 are each independently selected from a Ci to Ce hydrocarbyl group; on the condition that the total number of carbon atoms within groups R 2 and R 4 combined is 2-7.
- the invention in a second aspect relates to a complex of Formula (II): (Formula II) wherein R 3 and R 5 are each independently selected from a Ci to Ce hydrocarbyl group; on the condition that the total number of carbon atoms within groups R 3 and R 5 combined is 2-7.
- the substituents R 2 and R 4 (in the case of Formula (I)) or groups R 3 and R 5 (in the case of Formula (II)) are each independently selected from a Ci to Ce hydrocarbyl group.
- 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.
- a particularly preferred complex of Formula (I) is (n 5 -2,4-dimethylpentadienyl)(r
- a particularly preferred complex of Formula (II) is (n 5 -2,4-dimethylpentadienyl)(r
- the invention in a third aspect 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).
- the a,p-unsaturated carbonyl compound is mesityl oxide.
- the a,p-unsaturated carbonyl compound is 2-methyl-2-pentenal.
- Suitable (n 5 -2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) salts include perchlorate, tetrafluoroborate, hexafluorophosphate, triflate, bis(trifluoromethanesulfonyl)imidate (bistriflimide), etc.
- a preferred salt is (n 5 -2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) tetrafluoroborate.
- a 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.
- 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.
- 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.
- the complex Ru(DMPD)(DMOPD) is a low melting solid with a melting point of ⁇ 70 °C, and volatilises without decomposition below 220 °C.
- Both Ru(DMPD)(DMOPD) and Ru(DMPD)2 were used as precursors for deposition of ruthenium thin films in a Beneq TFS-200 ALD tool. Following the deposition, the thickness of the films and their resistivity were measured. The film thickness was measured using a FISCHERSCOPETM X-RAY XDV TM -SDD from Fischer. Film resistivity was measured by a four- point probe method using a Loresta-GX from Nittoseiko Analytech. Deposition conditions are summarised below. Deposition results are shown in Table 1.
- Substrate Si with native oxide
- Ru(DMPD)(DMOPD) produced a thicker film of lower resistivity compared with the film produced using Ru(DMPD)2.
- Ru(DMPD)(DMOPD) ruthenium films were deposited in the temperature range from 165 to 220 °C. Films were analysed as described above. Deposition results are shown in Table 2.
- conductive ruthenium films can be deposited in the 165 - 220 °C temperature range.
Landscapes
- 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
The invention relates to ruthenium complexes of Formula (I) or (II), a process for producing a ruthenium film by a chemical deposition method using the complexes, and a method for preparing the complexes from a (η5-2,4-dimethylpentadienyl)(CH3CN)3 ruthenium (II) salt.
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 (n5-2,4-dimethylpentadienyl) is abbreviated to DMPD, (n5-2,4-dimethyl-1-oxa- pentadienyl) is abbreviated to DMOPD and (n5-3,5-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 O.ITorr @ 82 °C; decomposition temperature (DSC) of 210 °C.
The analogous complex Ru(DMOPD)2 is also known. The article “Bis[r|5-(2,4-dimethyl-1- oxapentadienyl)] ruthenium(ll): the First Homoleptic Open Ruthenocenes with Nonhydrocarbon Ligands” J. Chem. Soc., Chem. Common., 1991 , 1427-1429 describes the preparation of this complex from RuCh 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)CI]4: Syntheses, Characterizations, and Solid-State Structures” Organometallics 1992, 11, 1686-1692 describes the complex Ru(CsMe5)(DMOPD). This complex was prepared by the reaction between [Ru(CsMe5)CI]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.
US9349601 B2 describes ruthenium complexes with various general structures, including a family of formula (1a) containing a substituted or unsubstituted Cp ligand and a DMOPD-type ligand. The examples include preparation of the complexes Ru(CsH5)(DMOPD) [Example 7], Ru(C5H4Me)(DMOPD) [Example 8], Ru(C5H4Et)(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 (I):
(Formula I)
wherein R2 and R4 are each independently selected from a Ci to Ce hydrocarbyl group; on the condition that the total number of carbon atoms within groups R2 and R4 combined is 2-7.
For the avoidance of doubt, as an example if R2 = 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 (II):
(Formula II) wherein R3 and R5 are each independently selected from a Ci to Ce 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(DMPD)2 and Ru(DMOPD)2and, 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 (I)) or groups R3 and R5 (in the case of Formula (II)) are each independently selected from a Ci to Ce 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 (n5-2,4-dimethylpentadienyl)(r|5-2,4-dimethyl- 1-oxa-pentadienyl) ruthenium (II) “Ru(DMPD)(DMOPD)”, i.e. where R2 = R4 = Me.
A particularly preferred complex of Formula (II) is (n5-2,4-dimethylpentadienyl)(r|5-3,4- dimethyl-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,p-unsaturated carbonyl compound of formula R2C(=O)CH=CR4CH3 in the case of Formula (I) or of formula
CH(=O)CR3=CHCH2R5 in the case of Formula (II).
In a preferred embodiment the a,p-unsaturated carbonyl compound is mesityl oxide.
In a preferred embodiment the a,p-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 (n5-2,4-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)3][BF4]
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 [Ru(DMPD)(DMOPD)]
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.
Ruthenium film deposition
Both Ru(DMPD)(DMOPD) and Ru(DMPD)2 were used as precursors for deposition of ruthenium thin films in a Beneq TFS-200 ALD tool. Following the deposition, the thickness of the films and their resistivity were measured. The film thickness was measured using a FISCHERSCOPE™ X-RAY XDVTM-SDD from Fischer. Film resistivity was measured by a four- point probe method using a Loresta-GX from Nittoseiko Analytech. Deposition conditions are summarised below. Deposition results are shown in Table 1.
Deposition conditions:
Substrate: Si with native oxide
Deposition temperature: 220 °C
Precursor temperature: 75 °C
Oxygen pressure: 4 mbar
Deposition cycle: Ru pulse (5s); Oxygen pulse (20 s)
Number of cycles: 300
Table 1.
After the same number of cycles, Ru(DMPD)(DMOPD) produced a thicker film of lower resistivity compared with the film produced using Ru(DMPD)2.
Using Ru(DMPD)(DMOPD), ruthenium films were deposited in the temperature range from 165 to 220 °C. Films were analysed as described above. Deposition results are shown in Table 2.
Table 2.
Using Ru(DMPD)(DMOPD) and oxygen as a co-reactant, conductive ruthenium films can be deposited in the 165 - 220 °C temperature range.
Claims
1. A complex of Formula
(Formula I) wherein R2 and R4 are each independently selected from a Ci to Ce 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 = R4 = Me.
4. A complex of Formula (II):
(Formula II) wherein R3 and R5 are each independently selected from a Ci to Ce 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 = R5 = 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 a,p-unsaturated carbonyl compound of formula R2C(=O)CH=CR4CH3 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 (n5-2,4-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,p-unsaturated carbonyl compound is mesityl oxide.
13. A method according to claim 10 or claim 11, wherein the a,p-unsaturated carbonyl compound is 2-methyl-2-pentenal.
Applications Claiming Priority (2)
| 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 |
| GB2305643.5 | 2023-04-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024218468A1 true WO2024218468A1 (en) | 2024-10-24 |
Family
ID=86497227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2024/050908 WO2024218468A1 (en) | 2023-04-18 | 2024-04-03 | Ruthenium complexes and process for producing ruthenium film |
Country Status (2)
| Country | Link |
|---|---|
| GB (1) | GB2629153A (en) |
| WO (1) | WO2024218468A1 (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US884044A (en) | 1907-08-16 | 1908-04-07 | William T Rice | Device for cleaning combs. |
| US8884044B2 (en) | 2008-04-01 | 2014-11-11 | Umicore Ag & Co. Kg | Ruthenium complexes having (P—P)—coordinated diphosphorus donor ligands and processes for preparing them |
| US9349601B2 (en) | 2012-12-07 | 2016-05-24 | Tosoh Corporation | Ruthenium complex, method for producing same, and method for producing ruthenium-containing thin film |
| WO2021187485A1 (en) * | 2020-03-18 | 2021-09-23 | 東ソー株式会社 | Method for producing metal-containing thin film, and metal-containing thin film |
Family Cites Families (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 |
-
2023
- 2023-04-18 GB GB2305643.5A patent/GB2629153A/en active Pending
-
2024
- 2024-04-03 WO PCT/GB2024/050908 patent/WO2024218468A1/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US884044A (en) | 1907-08-16 | 1908-04-07 | William T Rice | Device for cleaning combs. |
| US8884044B2 (en) | 2008-04-01 | 2014-11-11 | Umicore Ag & Co. Kg | Ruthenium complexes having (P—P)—coordinated diphosphorus donor ligands and processes for preparing them |
| US9349601B2 (en) | 2012-12-07 | 2016-05-24 | Tosoh Corporation | Ruthenium complex, method for producing same, and method for producing ruthenium-containing thin film |
| WO2021187485A1 (en) * | 2020-03-18 | 2021-09-23 | 東ソー株式会社 | Method for producing metal-containing thin film, and metal-containing thin film |
Non-Patent Citations (5)
| Title |
|---|
| "Bis[ηs-(2,4-dimethyl-1-oxapentadienyl)] ruthenium(II): the First Homoleptic Open Ruthenocenes with Non-hydrocarbon Ligands", J. CHEM. SOC., CHEM. COMMUN., 1991, pages 1427 - 1429 |
| "Half-Open Ruthenocenes Derived from [Ru(C Me )CI] : Syntheses, Characterizations, and Solid-State Structures", ORGANOMETALLICS, vol. 11, 1992, pages 1686 - 1692 |
| "Low-Temperature Preparation of Metallic Ruthenium Films by MOVCD Using Bis(2,4-dimethylpentadienyl) ruthenium", ELECTROCHEMICAL AND SOLID-STATE LETTERS, vol. 10, no. 6, 2007, pages D60 - D62 |
| J. CHEM. SOC., CHEM. COMMUN., 1991, pages 1427 - 1429 |
| SIDDIQI M. ASLAM ET AL: "Thermal Stability and Sublimation Pressures of Some Ruthenocene Compounds", MATERIALS, vol. 3, no. 2, 1 February 2010 (2010-02-01), CH, pages 1172 - 1185, XP093183294, ISSN: 1996-1944, DOI: 10.3390/ma3021172 * |
Also Published As
| Publication number | Publication date |
|---|---|
| GB202305643D0 (en) | 2023-05-31 |
| TW202444732A (en) | 2024-11-16 |
| GB2629153A (en) | 2024-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5136576B2 (en) | Organoruthenium compound and method for producing the same | |
| RU2705362C2 (en) | Novel complexes of metals with n-aminoguanidine, intended for use in making thin films and for catalysis | |
| US7442407B2 (en) | Tantalum and niobium compounds and their use for chemical vapour deposition (CVD) | |
| KR100988973B1 (en) | Metal Complexes of Tridentate Betapyketoiminate | |
| KR102040043B1 (en) | Ruthenium complex and method for producing same, and method for producing ruthenium-containing thin film | |
| EP2069373A1 (en) | Organometallic precursor compounds | |
| WO2011007323A1 (en) | Deposition of group iv metal-containing films at high temperature | |
| WO2009105668A1 (en) | Bicyclic guanidines, metal complexes thereof and their use in vapor deposition | |
| WO2009094262A1 (en) | Organometallic compounds, processes and methods of use | |
| JP4097979B2 (en) | Chemical source vapor deposition method for CVD and ruthenium or ruthenium compound thin film | |
| US20090202740A1 (en) | Organometallic compounds, processes for the preparation thereof and methods of use thereof | |
| TWI454463B (en) | Complexes of imidazole ligands | |
| KR101623142B1 (en) | Titanium complex, method for production of the complex, titanium-containing thin film, and method for production of the thin film | |
| EP3202949A1 (en) | Chemical vapor deposition raw material comprising organic ruthenium compound and chemical vapor deposition method using chemical vapor deposition raw material | |
| TWI652274B (en) | Alkoxy compound, raw material for film formation, method for producing film, and alcohol compound | |
| WO2024218468A1 (en) | Ruthenium complexes and process for producing ruthenium film | |
| KR100997838B1 (en) | Asymmetric Group 8 (VI) Metallocene Compounds | |
| TWI888075B (en) | Ruthenium complexes and process for producing ruthenium film | |
| Su et al. | Bis (β-ketoiminate) dioxo tungsten (VI) complexes as precursors for growth of WOx by aerosol-assisted chemical vapor deposition | |
| KR20060131874A (en) | High Density Nucleated Organometallic Compound | |
| EP3178808B1 (en) | Alkoxide compound, thin film-forming starting material, thin film formation method and alcohol compound | |
| Maudez et al. | New dimethyl (norbornadienyl) platinum (II) precursors for platinum MOCVD | |
| JP3379315B2 (en) | Raw materials for forming platinum thin films by metal organic chemical vapor deposition | |
| KR101126141B1 (en) | Organoiridium compound, process for producing the same, and process for producing film | |
| KR102735110B1 (en) | Novel Organo-Molybdenum Compounds, Preparation method thereof, and Method for deposition of thin film using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 24719265 Country of ref document: EP Kind code of ref document: A1 |