EP1556394A2 - Asymmetric group 8 (viii) metallocene compounds - Google Patents
Asymmetric group 8 (viii) metallocene compoundsInfo
- Publication number
- EP1556394A2 EP1556394A2 EP03810819A EP03810819A EP1556394A2 EP 1556394 A2 EP1556394 A2 EP 1556394A2 EP 03810819 A EP03810819 A EP 03810819A EP 03810819 A EP03810819 A EP 03810819A EP 1556394 A2 EP1556394 A2 EP 1556394A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- integer
- group
- butyl
- flask
- metallocene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 59
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 33
- -1 cyclopentdienyl Chemical group 0.000 claims abstract description 25
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical group C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000001424 substituent group Chemical group 0.000 claims abstract description 14
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 12
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- 229910052794 bromium Inorganic materials 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 229910052740 iodine Inorganic materials 0.000 claims description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 7
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 13
- 125000005843 halogen group Chemical group 0.000 abstract description 11
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- 238000005137 deposition process Methods 0.000 abstract description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000007788 liquid Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- FZHCFNGSGGGXEH-UHFFFAOYSA-N ruthenocene Chemical compound [Ru+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 FZHCFNGSGGGXEH-UHFFFAOYSA-N 0.000 description 16
- 238000010992 reflux Methods 0.000 description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000005229 chemical vapour deposition Methods 0.000 description 14
- 239000004809 Teflon Substances 0.000 description 11
- 229920006362 Teflon® Polymers 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- OXJUCLBTTSNHOF-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene;ruthenium(2+) Chemical compound [Ru+2].CC[C-]1C=CC=C1.CC[C-]1C=CC=C1 OXJUCLBTTSNHOF-UHFFFAOYSA-N 0.000 description 10
- 238000007792 addition Methods 0.000 description 10
- 238000004821 distillation Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 229920001971 elastomer Polymers 0.000 description 9
- 239000010408 film Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 9
- 238000003756 stirring Methods 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 210000003739 neck Anatomy 0.000 description 6
- 238000000526 short-path distillation Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- HCIZCANORNXHEA-UHFFFAOYSA-N C(C)[C-]1C=CC=C1.[CH-]1C=CC=C1.[Ru+2] Chemical compound C(C)[C-]1C=CC=C1.[CH-]1C=CC=C1.[Ru+2] HCIZCANORNXHEA-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical class CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000010189 synthetic method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 238000007306 functionalization reaction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000005499 meniscus Effects 0.000 description 4
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 3
- MCSXGCZMEPXKIW-UHFFFAOYSA-N 3-hydroxy-4-[(4-methyl-2-nitrophenyl)diazenyl]-N-(3-nitrophenyl)naphthalene-2-carboxamide Chemical compound Cc1ccc(N=Nc2c(O)c(cc3ccccc23)C(=O)Nc2cccc(c2)[N+]([O-])=O)c(c1)[N+]([O-])=O MCSXGCZMEPXKIW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 229910019891 RuCl3 Inorganic materials 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- ZBDWUWNQBVXRMA-UHFFFAOYSA-N lithium;5-ethylcyclopenta-1,3-diene Chemical compound [Li+].CC[C-]1C=CC=C1 ZBDWUWNQBVXRMA-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- YAYGSLOSTXKUBW-UHFFFAOYSA-N ruthenium(2+) Chemical compound [Ru+2] YAYGSLOSTXKUBW-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XZORYMHKRROFSA-UHFFFAOYSA-N C(C)(C)[C-]1C=CC=C1.[C-]1(C=CC=C1)C(C)C.[Ru+2] Chemical compound C(C)(C)[C-]1C=CC=C1.[C-]1(C=CC=C1)C(C)C.[Ru+2] XZORYMHKRROFSA-UHFFFAOYSA-N 0.000 description 2
- IZKVHKZVBOXLNW-UHFFFAOYSA-N C[C-]1C=CC=C1.[C-]1(C=CC=C1)C.[Ru+2] Chemical compound C[C-]1C=CC=C1.[C-]1(C=CC=C1)C.[Ru+2] IZKVHKZVBOXLNW-UHFFFAOYSA-N 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001350 alkyl halides Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000007373 indentation Methods 0.000 description 2
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000037361 pathway Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003003 phosphines Chemical class 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- OOFOOWBKEGKSBQ-UHFFFAOYSA-N sodium;5-ethylcyclopenta-1,3-diene Chemical compound [Na+].CC[C-]1C=CC=C1 OOFOOWBKEGKSBQ-UHFFFAOYSA-N 0.000 description 2
- IWYSOVJPHUTFIM-UHFFFAOYSA-N sodium;5-propan-2-ylcyclopenta-1,3-diene Chemical compound [Na+].CC(C)[C-]1C=CC=C1 IWYSOVJPHUTFIM-UHFFFAOYSA-N 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- JLCSUHFRTBWNBX-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene;lithium Chemical compound [Li].CCC1=CC=CC1 JLCSUHFRTBWNBX-UHFFFAOYSA-N 0.000 description 1
- MWQKURVBJZAOSC-UHFFFAOYSA-N 1-propan-2-ylcyclopenta-1,3-diene Chemical compound CC(C)C1=CC=CC1 MWQKURVBJZAOSC-UHFFFAOYSA-N 0.000 description 1
- RZPAXISDLOEXPI-UHFFFAOYSA-N 1-propylcyclopenta-1,3-diene Chemical group CCCC1=CC=CC1 RZPAXISDLOEXPI-UHFFFAOYSA-N 0.000 description 1
- NWFVDKHZNWEXAD-UHFFFAOYSA-N 1-tert-butylcyclopenta-1,3-diene Chemical compound CC(C)(C)C1=CC=CC1 NWFVDKHZNWEXAD-UHFFFAOYSA-N 0.000 description 1
- LJEOEPPSGGLCKY-UHFFFAOYSA-N 2-chlorocyclopenta-1,3-diene Chemical group ClC1=CCC=C1 LJEOEPPSGGLCKY-UHFFFAOYSA-N 0.000 description 1
- DYIPSYFMBOEWDW-UHFFFAOYSA-N 5-ethylcyclopenta-1,3-diene Chemical compound CC[C-]1C=CC=C1 DYIPSYFMBOEWDW-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- TZALOXSTVBCYKQ-UHFFFAOYSA-N C(C)(C)(C)[Ru](C1C=CC=C1)C1C=CC=C1 Chemical compound C(C)(C)(C)[Ru](C1C=CC=C1)C1C=CC=C1 TZALOXSTVBCYKQ-UHFFFAOYSA-N 0.000 description 1
- HDWDVUXQIOWBEP-UHFFFAOYSA-N C(C)C1(C=CC=C1)[Ru] Chemical compound C(C)C1(C=CC=C1)[Ru] HDWDVUXQIOWBEP-UHFFFAOYSA-N 0.000 description 1
- ZPVXWXLIHAIJHD-UHFFFAOYSA-N C(C)[C-]1C=CC=C1.C[C-]1C=CC=C1.[Ru+2] Chemical compound C(C)[C-]1C=CC=C1.C[C-]1C=CC=C1.[Ru+2] ZPVXWXLIHAIJHD-UHFFFAOYSA-N 0.000 description 1
- JJJUETMZNSARBW-UHFFFAOYSA-N C[C-]1C=CC=C1.C(C)(C)[C-]1C=CC=C1.[Ru+2] Chemical compound C[C-]1C=CC=C1.C(C)(C)[C-]1C=CC=C1.[Ru+2] JJJUETMZNSARBW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010022971 Iron Deficiencies Diseases 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229920002274 Nalgene Polymers 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 102000014961 Protein Precursors Human genes 0.000 description 1
- 108010078762 Protein Precursors Proteins 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000006079 antiknock agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- SINKOGOPEQSHQD-UHFFFAOYSA-N cyclopentadienide Chemical class C=1C=C[CH-]C=1 SINKOGOPEQSHQD-UHFFFAOYSA-N 0.000 description 1
- YUYGUQQDGRTJMA-UHFFFAOYSA-M cyclopentane;ruthenium(1+);triphenylphosphane;chloride Chemical compound [Ru]Cl.[CH]1[CH][CH][CH][CH]1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YUYGUQQDGRTJMA-UHFFFAOYSA-M 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000011874 heated mixture Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- KPCHKRNAYPIRSD-UHFFFAOYSA-N lithium;5-methylcyclopenta-1,3-diene Chemical compound [Li+].C[C-]1C=CC=C1 KPCHKRNAYPIRSD-UHFFFAOYSA-N 0.000 description 1
- IEBUJNAGERLHSJ-UHFFFAOYSA-N lithium;5-propan-2-ylcyclopenta-1,3-diene Chemical compound [Li+].CC(C)[C-]1C=CC=C1 IEBUJNAGERLHSJ-UHFFFAOYSA-N 0.000 description 1
- GTLNCANDXCIVJA-UHFFFAOYSA-N magnesium;propylcyclopentane Chemical compound [Mg].CCC[C]1[CH][CH][CH][CH]1.CCC[C]1[CH][CH][CH][CH]1 GTLNCANDXCIVJA-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005199 ultracentrifugation Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/406—Oxides of iron group metals
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- 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
-
- 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
- C23C16/22—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 inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
-
- 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
- C23C16/44—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 method of coating
- C23C16/455—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 method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45523—Pulsed gas flow or change of composition over time
- C23C16/45525—Atomic layer deposition [ALD]
- C23C16/45553—Atomic layer deposition [ALD] characterized by the use of precursors specially adapted for ALD
Definitions
- Chemical vapor deposition (CVD) methods are employed to form films of material on substrates such as wafers or other surfaces during the manufacture or processing of semiconductors.
- a CVD precursor also known as a CVD chemical compound, is decomposed thermally, chemically, photochemically or by plasma activation, to form a thin film having a desired composition.
- a vapor phase CVD precursor can be contacted with a substrate that is heated to a temperature higher than the decomposition temperature of the precursor, to form a metal or metal oxide film on the substrate.
- Thin films that include ruthenium (Ru) , ruthenium oxide (Ru0 2 ) or iron (Fe) have good electrical conductivity, high work function, are chemically and thermally stable, resistant to inter-layer chemical diffusion and are compatible with many dielectric substrate materials. Ru and Ru0 2 films, for instance, have been investigated as film electrode material for semiconductor devices such as DRAM (Dynamic Random Access Memory) devices. Bis (pentai ⁇ aptocyclopentadienyl) ruthenium
- ruthenocene and the symmetrical, diethyl-substituted ruthenocene (1, 1' -diethylruthenocene) have been investigated as possible precursors for forming ruthenium-based thin films by CVD techniques. These compounds have been prepared by several synthetic routes.
- One existing method for forming ruthenocene includes the reaction of RuCl 3 -XH 2 0 with cyclopentadiene, in the presence of Zn, to produce ruthenocene, ZnCl 2 and HCl , as shown in Fig. 1A.
- a similar approach, using ethyl- substituted cyclopentadiene has been employed to produce 1, 1' -diethylruthenocene, as shown in Fig. IB.
- yields obtained by this method are about 70%.
- unsubstituted ruthenocene also has been prepared by the reaction of cyclopentadiene, chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium( II) and sodium hydride (NaH) in benzene.
- Chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium ( II) precursor has been synthesized by reacting ruthenium trichloride and triphenylphosphine in ethanol .
- Another method that has been investigated for the synthesis of ruthenocene includes the transmetallation reactions of a bis (alkylcyclopentadienyl) iron compound with RuCl 3 -XH 2 0 and results in the formation of low yield 1, 1' -dialkylruthenocene, iron trichloride (FeCl 3 ) and difficult to separate iron species.
- these synthetic approaches include a one step addition of both cyclopentadienyl rings and thus are suitable for preparing unsubstituted ruthenocene or the symmetrically substituted 1,1' -diethylruthenocene.
- Monosubstituted ruthenocene e.g., 1 - ethylruthenocene
- Another monosubstituted ruthenocene, tert- butyl (cyclopentadienyl) (cyclopentadienyl) ruthenium has been prepared by reacting a heated mixture of bis (cyclopentadienyl) ruthenium, aluminum chloride and polyphosphoric acid, with tert-butyl alcohol, followed by distillation.
- Both ruthenocene and 1, 1' -diethylruthenocene have relatively low vapor pressure (less than 10 Torr at 100 °C) .
- ruthenocene is a solid and 1, 1' -diethylruthenocene is a liquid.
- more volatile CVD precursors are preferred, as are precursors that are liquid at room temperature, rather than solid.
- desired CVD precursors also are heat decomposable and capable of producing uniform films under suitable CVD conditions. Therefore, a need exists for developing new ruthenocenes that are liquid at room temperature and have relatively high vapor pressure and for exploring their potential as CVD precursors for film depositions.
- a need also exists for developing other Group 8 (VIII) metallocene compounds that can be used as CVD precursors for forming osmium- or iron-based films .
- the invention generally is related to asymmetric Group 8 (VIII) metallocenes . More specifically, the invention is directed to a compound of the general formula CpMCp' , where M is a metal selected from the group consisting of Ru, Os and Fe; Cp is a first substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group D x ; and Cp' is a second substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group Di' .
- M is a metal selected from the group consisting of Ru, Os and Fe
- Cp is a first substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group D x
- Cp' is a second substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group Di' .
- Di can be : X; CalHblXcl
- X is a halogen atom or a nitro (N0 2 ) group; al is an integer from 2 to 8 ; bl is an integer from 0 to 2(al)+l-cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2--is an -integer -from J-l-to .2_(a2_)_+_l_ -_b2... can be: X;
- X is a halogen atom or N0 2 ; al is an integer from 1 to 8 ; bl is an integer from 0 to 2(al)+l-cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2 is an integer from 0 to 2(a2) + 1 - b2.
- a metallocene compound of the invention is 1-methyl-l' -ethylruthenocene .
- At least one of Cp or Cp' can include one or more additional substituents, e.g., D 2 , D 3 , D 4 , D 5 , D 2 ' , D 3 ' , D 4 ' , and D 5 ' .
- the invention has several advantages.
- the compounds of the invention provide additional options and flexibility to existing methods for producing Ru- , Os-, or Fe-based thin films by CVD. Some of these compounds are liquid at room temperature.
- 1-methyl-l' -ethylruthenocene has a higher vapor pressure than 1, 1' -diethylruthenocene.
- each of the cyclopentadienyl rings in the compounds of the invention is believed to modify properties such as solubility, vapor pressure, decomposition, combustion and other reaction pathways, reduction/oxidation potentials, geometry, preferred orientations and electron density distribution through modification of the cyclopentadienyl rings.
- Functionalization of the cyclopentadienyl ring allows tailoring or optimization of the metallocene for a desired application.
- Fig. 1A depicts a prior art synthetic route for forming unsubstituted ruthenocene.
- Fig. IB depicts a prior art synthetic route for forming 1, 1' -diethylruthenocene .
- Fig. 1C depicts another prior art method that has been used to form unsubstituted ruthenocene.
- Fig. 2A shows the molecular formula of a metallocene in a staggered conformation.
- Fig. 2B shows the molecular formula of a metallocene in an eclipsed conformation.
- Fig. 3 shows a structural formula of a disubstituted asymmetric metallocene compound of the invention.
- Fig. 4 shows a generalized structural formula of a metallocene compound of the invention.
- Fig. 5 shows illustrative asymmetric ruthenocene compounds of the invention.
- Fig. 6 shows a synthetic method that can be employed to form a metallocene compound of the invention.
- Fig. 7 shows a synthetic method for forming 1- methyl-1' -ethylruthenocene .
- the invention generally relates to Group 8 (VIII) asymmetric metallocenes .
- metallocene refers to an organometallic coordination compound, having a sandwich-type structure similar to that of ferrocene, in which a transition metal is believed to be ⁇ -bonded (electrons are moving in orbitals extending above and below the ring) to cyclic moieties.
- the cyclic moieties are cyclopentadienyl or indenyl. If all 5 carbon atoms in the cyclopentadienyl ring are bonding to the transition metal, cyclopentadienyl or indenyl (a cyclopentadienyl ring fused to a phenyl ring) moieties also can be described as ⁇ 5 -coordinated moieties. Thus a complete description of ferrocene would be ( ⁇ 5 -C 5 H 5 ) 2 Fe .
- Fig 2A Shown in Fig 2A is a staggered conformation of an unsubstituted metallocene, where M is a group 8 (VIII) metal, e.g., ruthenium, osmium or iron. Metallocenes also can have an eclipsed conformation, as shown in Fig. 2B. As used herein, molecular formulae are not intended to depict a particular metallocene conformation.
- the invention relates to Group 8 (VIII) asymmetric metallocenes of the general formula CpMCp' , where M is Ru, Os or Fe .
- Cyclopentadienyl and indenyl moieties are abbreviated- herei-n--as Cp-.
- -both Cp--and Cp' are cyclopentadienyl moieties.
- both Cp and Cp' are indenyl moieties.
- one of Cp and Cp' is cyclopentadienyl, while the other is indenyl .
- At least one hydrogen (H) atom is replaced by a substituent group, e.g. D x and D x ' .
- the two groups, Di and Di' are different from each other and are independently selected.
- X is a halogen atom, e.g., fluorine (F) , chlorine (Cl) , bromine (Br) or iodine (I) ; or N0 2 ; al is an integer from 2 to 8 ; bl is an integer from 0 to 2(al)+l - cl cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2 is an integer from 0 to 2(a2) + 1 - b2.
- Di' can be: X;
- X is a halogen atom,- e.g., F,--C1-, J3r or_ ⁇ I; or N0 2 ; al is an integer from 1 to 8 ; bl is an integer from 0 to 2(al)+l-cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1 ; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2 is an integer from 0 to 2(a2) + 1 - b2.
- Di and Di' can be employed.
- Di and/or Di' can be a straight or branched C1-C8 alkyl group.
- D x is selected from the following: C a ⁇ HbiX c ⁇ ;
- X is a halogen atom, e.g., F, Cl, Br or I; al is an integer from 1 to 8; bl is an integer from 0 to 2(al)+l - cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is equal to or greater than 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2)+l - c2; c2 is an integer from 0 to 2(a2)+l - b2; b2 + c2 is equal to or greater than 1 ; and Di' is selected from the following:
- X is a halogen atom, e.g., F, Cl, Br or I ; al is an integer from 1 to 8 ; bl is an integer from 0 to 2(al)+l - cl cl is an integer from 0 to 2(al)+l - bl bl + cl is equal to or greater than 1 a2 is an integer from 0 to 8 b2 is an integer from 0 to 2(a2)+l - c2 c2 is an integer from 0 to 2(a2)+l - b2 b2 + c2 is equal to or greater than 1.
- D x is a halogen atom, X, e.g., F, Cl, Br, I; or N0 2 and D x ' is selected from:
- X is a halogen atom, e . g . , F, Cl , Br, I ; or N0 2 ; al is an integer from 2 to 8 ; bl is an integer from 0 to 2 (al ) +l - cl cl is an integer from 0 to 2 (al) +l - bl bl + cl is equal to or greater than 1 a2 is an integer from 0 to 8 b2 is an integer from 0 to 2(a2)+l - c2 c2 is an integer from 0 to 2(a2)+l - b2 b2 + c2 is equal to or greater than 1.
- CpMCp' One example of the structural formula of a metallocene compound (CpMCp' ) of the invention is shown in Fig 3.
- Cp and Cp' moieties of the metallocene compounds of the invention further include one or more additional substituent group, D x .
- D x is a ulti- -substituted cyclopentadienyl or -indenyl—moiet .-
- a generalized structural formula of a CpMCp' metallocene compound of the invention is shown in Fig 4.
- Di and Di' are independently selected as described above.
- D 2/ D 3 , D 4 , D 5 , D 2 ' , D 3 ' , D 4 ' , and D 5 ' are independently selected from: X,
- X is a halogen atom, e.g., F, Cl , Br, I; or N0 2 ; al is an integer from 0 to 8 bl is an integer from 0 to 2(al)+l - cl cl is an integer from 0 to 2(al)+l - bl bl + cl is greater to or equal to 1 a2 is an integer from 0 to 8 b2 is an integer from 0 to 2(a2)+l - c2 c2 is an integer from 0 to 2(a2)+l - b2 b2 + c2 is greater to or equal to 1
- Specific examples of ruthenium-based metallocene compounds of the invention are shown in Table 1 and in Fig. 5.
- the metallocene compounds of the invention also include osmium-based and iron-based compounds similar to those shown in Table 1 or Fig. 6.
- a suitable synthetic method for preparing metallocene compounds of the invention is disclosed in U.S. Patent Application, by David M. Thompson and Cynthia A. Hoover with the title Methods for Making Metallocene Compounds, filed concurrently herewith, under Attorney Docket Number D-21245, the entire teachings of which are incorporated herein by reference .
- the method includes the steps of combining a metal salt compound, a ligand (L) compound and a first Cp compound, for example a substituted cyclopentadiene (HCp) , to form an intermediate compound; and reacting the intermediate compound with a second (Cp' ) compound, for instance, a compound including a cyclopentadienyl anion, such as a cyclopentadienide salt, to form CpMCp' .
- the metal salt can be a metal (III) salt, such as, for example, a metal halide (e.g., chloride, bromide, iodide, fluoride), a metal nitrate and other suitable metal salts.
- M is a Group 8 (VIII) metal, e.g., Ru, Os or Fe .
- the metal salt is abbreviated as MX n .
- MX n does not exclude metal salt compounds that include water of hydration and that, as known in the art, can be more specifically represented by the formula MX n QDH 2 0, D being other than 0.
- the abbreviation FeX 3 used herein includes anhydrous as well as hydrated iron salts that can be employed to form ferrocenes or ferrocene-like compounds.
- Ligand (L) generally is an electron pair donor compound.
- a neutral electron pair donor such as, for example, triphenylphosphine (PPh 3 ) is employed in one example .
- P(OR) 3 Tricyclohexylphosphine and other phosphines of the general formula PR 3 , as well as phosphite triesters, P(OR) 3 , where R is phenyl, cyclohexyl, alkyl or branched alkyl, e.g., t-butyl, group, also can be employed.
- Other suitable electron pair donors include amines, phosphates, carbonyl compounds, olefins, polyolefins, chelating phosphines, chelating amines and others.
- the Cp compound is a precursor of the Cp moiety in the CpMCp' compound described above.
- the Cp compound is HCp, e.g., cyclopentadiene or indene .
- the Cp compound " also “" can " Be " a ⁇ saT.Tt ⁇ " of ⁇ ' a " ⁇ c ⁇ clope ⁇ fiadi ⁇ nyl ⁇ r indenyl anion, e.g., potassium cyclopentadienyl (KCp) , sodium cyclopentadienyl (NaCp) , lithium cyclopentadienyl (LiCp) and others.
- Suitable cations for use with a cyclopentadienyl anion in the synthetic method described herein include trimethylsilyl (TMS) , Na, Li, K, Mg, Ca and Tl.
- At least one hydrogen atom in the Cp moiety is replaced by a group Di, as described above.
- HCp include, methylcyclopentadiene, ethylcyclopentadiene, n-propyl- or isopropylcyclopentadiene, n-butyl-, sec-butyl- or tert- butylcyclopentadiene, halo-cyclopentadiene and others.
- the Cp compound also can be di- or multi-substituted, e.g., it can be a di-, tri-, tetra- and penta-substituted- cyclopentadiene .
- substituent groups D 2 , D 3 , D 4 and D 5 are described above.
- Each of the MX n , L and HCp components can be provided in neat form or can optionally include a suitable solvent.
- Preferred solvents that can be employed in the method of the invention include alcohols, such as, for instance, ethanol, methanol, isopropanol and other alcohols.
- Ethyl acetate, tetrahydrofuran (THF) saturated or unsaturated hydrocarbons, aromatic heterocycles, alkyl halides, silylated hydrocarbons, ethers, polyethers thioethers, esters, lactones, amides, amines, polyamines, nitriles, silicone oils and other aprotic solvents also can be employed.
- Combinations of solvents also can be employed.
- concentrations of MX n , L and Cp are selected as “ ⁇ k ⁇ own " in “ the " a t “ . ⁇ ⁇
- the molar " c ⁇ ncent ationT of MX n in a suitable solvent can be in the range of from about 0.1 M to neat. That of L in a suitable solvent can be in the range of from about 0.1 M to neat .
- the molar concentration of Cp in a suitable solvent can be in the range of from about 0.1 to neat. If neat phosphine is employed it is believed that the reaction would be highly exothermic. Methods and systems for dissipating substantial amounts of heat of reaction per unit volume are known in the art .
- the three components can be combined in any order.
- the metal component and the HCp component are added concurrently to the L component .
- the metal component and the HCp component are combined to form a mixture and then the mixture is combined with the L component, for instance by adding the L component to the mixture.
- all components are combined at the same time.
- the molar ratio of HCp to MX n used is in the range from about 50 to about 1, preferably from about 12 to about 2 and most preferably in the range from about 7 to about 5.
- the molar ratio of L to MX n is in the range of from about 8 to about 0 , preferably from about 6 to about 2 and most preferably from about 5 to about 3.5. If a large excess amount of HCp component is employed, the reaction is driven to forming (Cp) 2 M product.
- the reaction temperature preferably is around the boiling point of the solvent employed or the boiling point of the ⁇ ⁇ ⁇ eactTon " mixture .
- Ot " her ⁇ suita “ ble ⁇ tempe : ratTures ⁇ ” can " be determined by routine experimentation.
- the reaction can be conducted at a temperature that is in the range of from above the freezing point to about the boiling point of the reaction composition.
- the reaction can be conducted at a temperature in the range of from about -100DC to about 150DC.
- the time of reaction generally depends on temperature, and concentration of the various reactants, and can range, for example, from about 5 minutes to about 96 hours.
- CpML f X is isolated, e.g., as a solid, by methods known in the art, such as filtration, centrifugation or recrystallization.
- Intermediate compound, CpML f X is then reacted with a Cp' compound, preferably in the presence of a solvent.
- Cp' preferably is an anion of the Cp' moiety in the compounds of the invention described above.
- Counterions can include trimethylsilyl (TMS), Na, Li, K, Mg, Ca, Tl .
- cyclopentadienyl compounds that can be used include, but are not limited to sodium or lithium ethylcyclopentadienide, sodium or lithium methylcyclopentadienide, sodium or lithium isopropylcyclopentadienide and others.
- Di- or multi- substituted anions of the Cp' moiety also can be employed (e.g., di-, tri-, tetra- or penta-substituted cycl ⁇ penta ' dienyl anions) .
- Anions " o " f unsubst ⁇ tuT-Ted indenes also can be employed, as described above.
- the intermediate compound is CpRu(PPh 3 ) 2 C1. It is reacted with a salt of Cp' .
- Recommended salts of Cp' include NaCp' , LiCp' , (Cp') 2 Mg, TMS(Cp') and (Cp')Tl.
- suitable solvents include benzene, toluene, xylenes, pentanes, hexanes, petroleum ether, aromatic heterocycles, saturated or unsaturated hydrocarbons, alkyl halides, silylated hydrocarbons, ethers, polyethers, thioethers, esters, lactones, amides, amines, polyamines, nitriles, silicones, and others.
- the molar concentrations of the Cp' component in a solvent can be in the range of from about 0.1 M to about 3.5 M, preferably in the range of from about 0.5 M to about 2.5 M and most preferably in the range of from about 1.4 to about 1.8 M.
- the molar ratio of Cp' relative to the CpML f X is in the range from about 50 to about 1, preferably from about 6 to about 1 and most preferably from about 1.6 to about 1.2.
- the intermediate CpML f X component is not isolated.
- a Cp' compound such as described above, is added to the solution that includes CpML f X.
- the time of reaction generally depends ⁇ o ⁇ ⁇ t " e ⁇ mperature, and concentration of the various reactants, and can range from about 15 minutes to about 6 days.
- the product of the reaction can be isolated and/or or purified by methods known in the art, such as, for example, solvent, e.g., hexane, extraction followed by distillation, sublimation or chromatography or directly by distillation, sublimation or chromatography. Recrystallization, ultracentrifugation and other techniques also can be employed. Alternatively, the product can be further employed in the reaction mixture, without further isolation and or purification.
- solvent e.g., hexane
- Recrystallization, ultracentrifugation and other techniques also can be employed.
- the product can be further employed in the reaction mixture, without further isolation and or purification.
- a method for forming the compounds of the invention is described by the chemical reaction shown in Fig. 6.
- MC1 3 D XH 2 0, triphenylphosphine and a cyclopentadiene react in ethanol, under reflux, to form intermediate compound CpM (PPh 3 ) 2 C1, which then reacts with a sodium ethylcyclopentadienide to form CpMCp' .
- Cp and/or Cp' can include additional substituent groups, D x , such as, for instance, groups described above.
- Cp and/or Cp' can be a di-, tri-, tetra- or penta-substituted cyclopentadiene moiety.
- asymmetric ruthenocenes can be prepared by first preparing an intermediate of CpRu (PPh 3 ) 2 C1 , followed by the reaction of this intermediate with a salt of Cp' .
- the most highly recommended salts of Cp' include NaCp' , LiCp', (Cp') 2 Mg, TMS(Cp') and (Cp')Tl.
- Examples of techniques that can be employed to characterize the compounds formed by the synthetic methods described above include, but are not limited to, analytical gas chromatography, nuclear magnetic resonance (NMR) , thermogravimetric analysis (TGA) , inductively coupled plasma mass spectrometry (ICPMS) , vapor pressure and viscosity measurements.
- each of the Cp and Cp' rings modifies properties such as solubility, vapor pressure, decomposition, combustion and other reaction pathways, reduction/oxidation potentials, geometry, preferred orientations and electron density distribution.
- example " , i ⁇ "” is believed-tha " larger substituent D ⁇ and/or Di' contribute to an increase in molecular entropy and that metallocene compounds of the invention are more likely to be liquid at room temperature in comparison to previously disclosed compounds.
- asymmetric metallocenes of the invention are believed to be useful in scientific research, for example, in the study and understanding of organometallic chemistry of ferrocene and ferrocene-like molecules and in chemical reactions.
- the compounds of the invention also can be employed as combustion modifiers for solid propellants.
- functionalization of the parent ferrocene may prevent migration of the ferrocene from the rubber like binder matrix of the solid propel1ant into the surrounding insulation material .
- the metallocene compounds of the invention may find uses as catalysis, for instance, in zeolite-impregnated metallocene catalysts for the reduction of nitrogen oxides or as catalysts in chiral organic synthesis.
- the compounds of the invention may also find uses as iron deficiency supplements for animals and plants; antioxidants and antiknock agents; additives for motor fuels and oils; color pigments; radiation absorberes; and as insecticides and fungicides.
- the asymmetric metallocenes of the invention are particularly useful as precursors in processes for forming films, coatings or powders, particularly in film deposition ⁇ processes " , " s ⁇ ch “” as ⁇ CVD " processesT " Such " processes ⁇ a”re described in the U.S. Patent Application by David M. Thompson and Cynthia A. Hoover, John Peck and Mike Litwin, entitled Deposition Processes Using Group 8 (VIII) Metallocene Precursors , filed concurrently herewith, under Attorney Docket No. D-21267, the entire teachings of which are incorporated herein by reference.
- a 5 L five-necked round bottomed flask was equipped with a mechanical stirring paddle through the central neck. It was then charged with ethanol (2.0 L) and PPh3 (420 g, 1.6 mol) .
- Two 500 mL three necked flasks, were connected to two necks of the 5 L four-necked flask via Teflon ® (perfluorinated polymer, DuPont Corp.) tubing through positive displacement pumps.
- the remaining neck of the 5 L flask was equipped with a condenser.
- a heating mantle was placed beneath the 5 L flask and the solution was stired and heated to reflux. At reflux all of the triphenylphosphine dissolved in the ethanol .
- the system was purged with nitrogen for 30 minutes while at reflux. While this was taking place one of the 500 mL round- bottomed flasks was charged with RuCl 3 'XH 2 0 (100 g, 0.40 mol) , ethanol (300 mL) and a Teflon ® (perfluorinated polymer, DuPont Corp.) coated magnetic stirring bar. The ethanolic solution immediately developed a brown/orange colour. To dissolve all of the RuCl 3 "XH 2 0 it was necessary to heat the solution. This solution was sparged with nitrogen for 30 minutes by inserting a needle connected to a 1-2 pounds per square inch gauge (psig) nitrogen source through the septum and into the solution and by piercing the septum with another needle to allow for relief of excess pressure.
- psig pounds per square inch gauge
- a 2 L three-necked round bottomed flask was charged with a Teflon ® (perfluorinated polymer, DuPont Corp.) stirring bar, ethanol (1.0 L) and PPh 3 (263 g, 1.0 mol, 5 eq) .
- a 250 mL dropping funnel, a 150 mL bath-jacketed dropping funnel, and a condenser were attached to the three necks of the 2L flask. It is important to note that both dropping funnels were equipped with Teflon (perfluorinated polymer, DuPont Corp.) valves that permitted their isolation from the atmosphere of the round-bottomed flask.
- a rubber septum was connected to the top of the 150 mL bath-jacketed dropping funnel.
- the top of the condenser was fitted with an T junction adapter and connected to an inert atmosphere.
- a heating mantle was placed beneath the 2 L three-necked round-bottomed flask and the solution was stirred and heated to reflux. At reflux all of the triphenylphosphine dissolved in the ethanol.
- the system was purged with nitrogen for 3 hours while at reflux. While this was taking place a 500 mL Erlenmyer flask was charged with RuCl 3 -XH 2 0 (50 g, 0.20 mol), ethanol (150 mL, 1 eq) and a Teflon" (perfluorinated polymer, DuPont Corp.) coated magnetic stirring bar.
- the ethanolic solution immediately developed a brown/orange colour.
- This solution was poured into the 250 mL dropping funnel and the dropping funnel was fitted with a rubber septum. This solution was sparged with nitrogen for 30 minutes by inserting a needle connected to a 1-2 psig nitrogen source through the septum and into the solution and by piercing the septum with another needle to allow for relief of excess pressure.
- a piece of tubing with a coarse porous frit attached to one end was attached to a positive displacement pump.
- the fritted end of the tubing was immersed in the reactor and all of the liquids were pumped out of the 2 L round- bottomed flask. At this stage the dropping funnels were removed from the reactor.
- One side was fitted with a K- Head distillation adapter and the other side was fitted with a rubber septum.
- the flask was evacuated and refilled with nitrogen three times. Working under nitrogen, anhydrous toluene (1.0 L) was cannulated into the 5 L flask through the rubber septum.
- the dark opaque solution was heated to reflux and the K-head distillation adapter was opened to distill off a fraction of the solvent .
- the remaining liquid (approximately 400 mL) was decanted into a 1.0 L round-bottomed flask. This round- bottomed flask was fitted with a short path distillation adapter with vigreux indentations and distilled. The liquid collected from the vigreux column was distilled again using spinning band distillation under vacuum and 44 g of a clear yellow liquid, 1-methyl, 1' -ethylruthenocene was obtained in >99% purity (GCMS) . TGA studies showed that this liquid had less than 0.01% nonvolatile residue.
- Lithium(ethylcyclopentadienide) was produced as follows. A 2 L three-necked jacketed round bottomed flask was charged with a Teflon" (perfluorinated polymer, DuPont Corp.) stirring bar. A stopcock adapter, a thermowell adapter with thermowell and a rubber septum were fitted to the three necks of the flask. A nitrogen/vacuum manifold was connected to the stopcock adapater and the flask was evacuated and refilled with nitrogen 3 times. Anhydrous toluene (1.0 L) was then cannulated into the flask through the rubber septum and stirring was initiated.
- Teflon perfluorinated polymer, DuPont Corp.
- a cold fluid circulator was connected to the outer jacket of the jacketed flask with nalgene tubing and a cold fluid (-15 °C) was circulated through the outside wall of the jacketed flask.
- a cold fluid 15 °C
- freshly distilled ethylcyclopentadiene (middle cut distilled on a vigreux column) was cannulated into the flask (127 g, 1.35 mol) .
- n-butyllithium 800 mL, 1.6 M in hexanes, 1.28 mol
- n-butyllithium a fine white precipitate (lithium ethylcyclopentadienide) became evident in the solution.
- This material could be used as a suspension or isolated as a solid via filtration and removal of solvent.
- the THF solvent was then removed from the flask under reduced pressure.
- the 250 mL flask was fitted with a vacuum jacketed short path distillation adapter and the contents of the flask were distilled under reduced pressure ( ⁇ 0.1 torr) .
- a pale yellow liquid was collected (0.72 g) .
- This liquid was then purified via chromatography.
- a silica gel in pentane solution was used.
- the column had a diameter of 0.75" and a 6" length. 0.53 g of 99+% pure 1-ethyl-l' -isopropylruthenocene were isolated via chromatography (41% yield) .
- the THF solvent was then removed from the flask under reduced pressure.
- the 250 mL flask was fitted with a vacuum jacketed short path distillation adapter and the contents of the flask were distilled under reduced pressure ( ⁇ 0.1 torr) .
- a pale yellow liquid was collected ( 1.78 g) .
- This liquid was then purified via chromatography.
- a silica gel in pentane solution was used.
- the column had a diameter of 0.75" and a 6" length. 1.03 g of 98+% pure 1- methyl-1' -isopropylruthenocene were obtained after chromatography (53% yield) .
- the toluene solvent was then removed from the flask under reduced pressure .
- the toluene solvent was removed under reduced pressure and the flask was fitted with a short path distillation adapter.
- the distillate was collected and the GC/MS revealed that the main cut from the short path distillation was 88.7% pure 1-propyl-l'- ethylruthenocene . ' ' -
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Abstract
Asymmetric, disubstituted metallocene compounds have the general formula CpMCp' where M is a metal selected from the group consisting of Ru, Os and Fe; Cp is a first substituted cyclopentdienyl or indenyl moiety that includes at least one substituent group D1; Cp' is a second substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group D1'. D1 is different from D1'. D1 is X; Ca1Hb1Xc1; Ca2Hb2Xc2(C=O) Ca1Hb1Xc1; or Ca2Hb2Xc2O Ca1Hb1Xc1, where X is a halogen atom or nitro group; a1 is an integer between 2 and 8; b1 is an integer between 0 and 2 (a1)+1-c1; c1 is an integer between 0 and 2 (a1) + 1 - b1; b1 + c1 is at least 1; a2 is an integer between 0 and 8; b2 is an integer between 0 and 2 (a2) + 1 - c2; and c2 is an integer between 0 and 2 (a2) + 1 - b2; and D1' is X; Ca1Hb1Xc1; Ca2Hb2Xc2(C=O) Ca1Hb1Xc1; or Ca2Hb2Xc2O Ca1Hb1Xc1, where X is a halogen atom or nitro group; a1 is an integer between 1 and 8; b1 is an integer between 0 and 2 (a1) +1 -c1; c1 is an integer between 0 and 2 (a1) +1 -b1; b1 + c1 is at least 1; a2 is an integer between 0 and 8; b2 is an integer between 0 and 2 (a2) + 1 - c2; and c2 is an integer between 0 and 2 (a2) + 1 - b2. The compounds can be employed as precursors in film deposition processes.
Description
ASYMMETRIC GROUP 8 (VIII) METALLOCENE COMPOUNDS
BACKGROUND OF THE INVENTION Chemical vapor deposition (CVD) methods are employed to form films of material on substrates such as wafers or other surfaces during the manufacture or processing of semiconductors. In CVD, a CVD precursor, also known as a CVD chemical compound, is decomposed thermally, chemically, photochemically or by plasma activation, to form a thin film having a desired composition. For instance, a vapor phase CVD precursor can be contacted with a substrate that is heated to a temperature higher than the decomposition temperature of the precursor, to form a metal or metal oxide film on the substrate.
Thin films that include ruthenium (Ru) , ruthenium oxide (Ru02) or iron (Fe) have good electrical conductivity, high work function, are chemically and thermally stable, resistant to inter-layer chemical diffusion and are compatible with many dielectric substrate materials. Ru and Ru02 films, for instance, have been investigated as film electrode material for semiconductor devices such as DRAM (Dynamic Random Access Memory) devices. Bis (pentaiαaptocyclopentadienyl) ruthenium
(ruthenocene) and the symmetrical, diethyl-substituted ruthenocene (1, 1' -diethylruthenocene) have been investigated as possible precursors for forming ruthenium-based thin films by CVD techniques. These compounds have been prepared by several synthetic routes. One existing method for forming ruthenocene includes the reaction of RuCl3-XH20 with cyclopentadiene, in the
presence of Zn, to produce ruthenocene, ZnCl2 and HCl , as shown in Fig. 1A. A similar approach, using ethyl- substituted cyclopentadiene, has been employed to produce 1, 1' -diethylruthenocene, as shown in Fig. IB. Generally, yields obtained by this method are about 70%.
As shown in Fig. 1C, unsubstituted ruthenocene also has been prepared by the reaction of cyclopentadiene, chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium( II) and sodium hydride (NaH) in benzene. Chloro (cyclopentadienyl) bis (triphenylphosphine) ruthenium ( II) precursor has been synthesized by reacting ruthenium trichloride and triphenylphosphine in ethanol .
Another method that has been investigated for the synthesis of ruthenocene includes the transmetallation reactions of a bis (alkylcyclopentadienyl) iron compound with RuCl3-XH20 and results in the formation of low yield 1, 1' -dialkylruthenocene, iron trichloride (FeCl3) and difficult to separate iron species.
As seen in Figs. 1A and IB, these synthetic approaches include a one step addition of both cyclopentadienyl rings and thus are suitable for preparing unsubstituted ruthenocene or the symmetrically substituted 1,1' -diethylruthenocene.
Monosubstituted ruthenocene, e.g., 1 - ethylruthenocene, is formed as an impurity during the synthesis of 1,1' -diethylruthenocene. Another monosubstituted ruthenocene, tert- butyl (cyclopentadienyl) (cyclopentadienyl) ruthenium has been prepared by reacting a heated mixture of bis (cyclopentadienyl) ruthenium, aluminum chloride and polyphosphoric acid, with tert-butyl alcohol, followed by distillation.
Both ruthenocene and 1, 1' -diethylruthenocene have relatively low vapor pressure (less than 10 Torr at 100 °C) . At room temperature, ruthenocene is a solid and 1, 1' -diethylruthenocene is a liquid. Generally, more volatile CVD precursors are preferred, as are precursors that are liquid at room temperature, rather than solid. In addition, desired CVD precursors also are heat decomposable and capable of producing uniform films under suitable CVD conditions. Therefore, a need exists for developing new ruthenocenes that are liquid at room temperature and have relatively high vapor pressure and for exploring their potential as CVD precursors for film depositions. A need also exists for developing other Group 8 (VIII) metallocene compounds that can be used as CVD precursors for forming osmium- or iron-based films .
SUMMARY OF THE INVENTION The invention generally is related to asymmetric Group 8 (VIII) metallocenes . More specifically, the invention is directed to a compound of the general formula CpMCp' , where M is a metal selected from the group consisting of Ru, Os and Fe; Cp is a first substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group Dx; and Cp' is a second substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group Di' .
The two groups, D and Di' , are different from each other and are independently selected. Di can be : X;
CalHblXcl
Ca2Hb2 c2 ( C=0 ) CaiHbiXci ; or
Ca2Hb2Xc2θCaιH iXci . where
X is a halogen atom or a nitro (N02) group; al is an integer from 2 to 8 ; bl is an integer from 0 to 2(al)+l-cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2--is an -integer -from J-l-to .2_(a2_)_+_l_ -_b2... can be: X;
CalHblXcl /"
Ca2Hb2Xc2 ( C=0) CaiHbiXci ; or Ca2Hb2X OCaιHbiXci / where
X is a halogen atom or N02; al is an integer from 1 to 8 ; bl is an integer from 0 to 2(al)+l-cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2 is an integer from 0 to 2(a2) + 1 - b2. One specific example of a metallocene compound of the invention is 1-methyl-l' -ethylruthenocene .
At least one of Cp or Cp' can include one or more additional substituents, e.g., D2, D3, D4, D5, D2' , D3' , D4' , and D5' .
The invention has several advantages. The compounds of the invention provide additional options and flexibility to existing methods for producing Ru- , Os-, or Fe-based thin films by CVD. Some of these compounds are liquid at room temperature. In addition, it has been found that 1-methyl-l' -ethylruthenocene has a higher vapor pressure than 1, 1' -diethylruthenocene. Independent functionalization of each of the cyclopentadienyl rings in the compounds of the invention is believed to modify properties such as solubility, vapor pressure, decomposition, combustion and other reaction pathways, reduction/oxidation potentials, geometry, preferred orientations and electron density distribution through modification of the cyclopentadienyl rings. Functionalization of the cyclopentadienyl ring allows tailoring or optimization of the metallocene for a desired application.
BRIEF DESCRIPTION OF THE DRAWINGS
Fig. 1A depicts a prior art synthetic route for forming unsubstituted ruthenocene.
Fig. IB depicts a prior art synthetic route for forming 1, 1' -diethylruthenocene . Fig. 1C depicts another prior art method that has been used to form unsubstituted ruthenocene.
Fig. 2A shows the molecular formula of a metallocene in a staggered conformation.
Fig. 2B shows the molecular formula of a metallocene in an eclipsed conformation.
Fig. 3 shows a structural formula of a disubstituted asymmetric metallocene compound of the invention.
Fig. 4 shows a generalized structural formula of a metallocene compound of the invention.
Fig. 5 shows illustrative asymmetric ruthenocene compounds of the invention. Fig. 6 shows a synthetic method that can be employed to form a metallocene compound of the invention.
Fig. 7 shows a synthetic method for forming 1- methyl-1' -ethylruthenocene .
DETAILED DESCRIPTION OF THE INVENTION
The foregoing and other objects, features and advantages of the invention will be apparent -from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention. The invention generally relates to Group 8 (VIII) asymmetric metallocenes . As used herein, the term "metallocene" refers to an organometallic coordination compound, having a sandwich-type structure similar to that of ferrocene, in which a transition metal is believed to be π-bonded (electrons are moving in orbitals extending above and below the ring) to cyclic moieties. In the asymmetric metallocenes described herein, the cyclic moieties are cyclopentadienyl or indenyl. If all 5 carbon atoms in the cyclopentadienyl ring are bonding to the transition metal, cyclopentadienyl or indenyl (a cyclopentadienyl ring fused to a phenyl ring) moieties
also can be described as η5-coordinated moieties. Thus a complete description of ferrocene would be (η5-C5H5) 2Fe . Shown in Fig 2A is a staggered conformation of an unsubstituted metallocene, where M is a group 8 (VIII) metal, e.g., ruthenium, osmium or iron. Metallocenes also can have an eclipsed conformation, as shown in Fig. 2B. As used herein, molecular formulae are not intended to depict a particular metallocene conformation.
The invention relates to Group 8 (VIII) asymmetric metallocenes of the general formula CpMCp' , where M is Ru, Os or Fe . Cyclopentadienyl and indenyl moieties are abbreviated- herei-n--as Cp-. -In one example, -both Cp--and Cp' are cyclopentadienyl moieties. In another example, both Cp and Cp' are indenyl moieties. In yet another example, one of Cp and Cp' is cyclopentadienyl, while the other is indenyl .
In each of the Cp and Cp' moiety of the compounds of the invention, at least one hydrogen (H) atom is replaced by a substituent group, e.g. Dx and Dx' . The two groups, Di and Di' , are different from each other and are independently selected.
X;
CalHbl cl ; Ca2Hb2Xo2 ( C=0) CaiHbiXci ; or
Ca2Hb2Xc20CalHblXcl where
X is a halogen atom, e.g., fluorine (F) , chlorine (Cl) , bromine (Br) or iodine (I) ; or N02; al is an integer from 2 to 8 ; bl is an integer from 0 to 2(al)+l - cl
cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2 is an integer from 0 to 2(a2) + 1 - b2.
Di' can be: X;
CaιHbiXcι;
Ca2Hb2Xc2 ( C=0) CaiH iXci ; or Ca2Hb2Xc2θCaιHbiXci / where
X is a halogen atom,- e.g., F,--C1-, J3r or_~I; or N02; al is an integer from 1 to 8 ; bl is an integer from 0 to 2(al)+l-cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1 ; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2) + 1 - c2; c2 is an integer from 0 to 2(a2) + 1 - b2.
As used herein, integer ranges are inclusive. Straight as well as branched substituent groups Di and Di' can be employed. For example, Di and/or Di' can be a straight or branched C1-C8 alkyl group. In one embodiment of the invention, Dx is selected from the following: CaιHbiXcι;
Ca2Hb2Xc2 (C=0) CaiHbiXci ; or Ca2H 2Xc2OCaιH iXci i where
X is a halogen atom, e.g., F, Cl, Br or I; al is an integer from 1 to 8;
bl is an integer from 0 to 2(al)+l - cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is equal to or greater than 1; a2 is an integer from 0 to 8 ; b2 is an integer from 0 to 2(a2)+l - c2; c2 is an integer from 0 to 2(a2)+l - b2; b2 + c2 is equal to or greater than 1 ; and Di' is selected from the following:
CalHblXcl / Ca2Hb2Xc2 (C=0) CaiHbiXci , or
Ca2Hb2 c2θCaiHbi ci •where ,
X is a halogen atom, e.g., F, Cl, Br or I ; al is an integer from 1 to 8 ; bl is an integer from 0 to 2(al)+l - cl cl is an integer from 0 to 2(al)+l - bl bl + cl is equal to or greater than 1 a2 is an integer from 0 to 8 b2 is an integer from 0 to 2(a2)+l - c2 c2 is an integer from 0 to 2(a2)+l - b2 b2 + c2 is equal to or greater than 1. In another embodiment, Dx is a halogen atom, X, e.g., F, Cl, Br, I; or N02 and Dx' is selected from:
CalHblXcl / Ca2Hb2 c2 (C=0) CaiHbiXci or
Ca2Hb2Xc2θCaιHbiXci / where ,
X is a halogen atom, e . g . , F, Cl , Br, I ; or N02 ; al is an integer from 2 to 8 ; bl is an integer from 0 to 2 (al ) +l - cl cl is an integer from 0 to 2 (al) +l - bl bl + cl is equal to or greater than 1
a2 is an integer from 0 to 8 b2 is an integer from 0 to 2(a2)+l - c2 c2 is an integer from 0 to 2(a2)+l - b2 b2 + c2 is equal to or greater than 1. One example of the structural formula of a metallocene compound (CpMCp' ) of the invention is shown in Fig 3.
Optionally, either or both Cp and Cp' moieties of the metallocene compounds of the invention further include one or more additional substituent group, Dx. In one example, at least one of Cp and Cp' is a ulti- -substituted cyclopentadienyl or -indenyl—moiet .-
A generalized structural formula of a CpMCp' metallocene compound of the invention is shown in Fig 4. Di and Di' are independently selected as described above. D2/ D3, D4, D5, D2' , D3' , D4' , and D5' are independently selected from: X,
CalHblXcl / Ca2Hb2Xc2 ( C=0 ) CaiHbiXci ,
Ca2Hb2Xc2θCaiHbi cl ,
Ca2Hb2Xc2 ( C=0) OCaiHbiXci . or
Ca2H 2Xc2θ (C=0) CalHblXcl where , X is a halogen atom, e.g., F, Cl , Br, I; or N02; al is an integer from 0 to 8 bl is an integer from 0 to 2(al)+l - cl cl is an integer from 0 to 2(al)+l - bl bl + cl is greater to or equal to 1 a2 is an integer from 0 to 8 b2 is an integer from 0 to 2(a2)+l - c2 c2 is an integer from 0 to 2(a2)+l - b2
b2 + c2 is greater to or equal to 1 Specific examples of ruthenium-based metallocene compounds of the invention are shown in Table 1 and in Fig. 5.
The metallocene compounds of the invention also include osmium-based and iron-based compounds similar to those shown in Table 1 or Fig. 6.
A suitable synthetic method for preparing metallocene compounds of the invention is disclosed in U.S. Patent Application, by David M. Thompson and Cynthia A. Hoover with the title Methods for Making Metallocene Compounds, filed concurrently herewith, under Attorney Docket Number D-21245, the entire teachings of which are incorporated herein by reference .
The method includes the steps of combining a metal salt compound, a ligand (L) compound and a first Cp compound, for example a substituted cyclopentadiene (HCp) , to form an intermediate compound; and reacting the intermediate compound with a second (Cp' ) compound, for instance, a compound including a cyclopentadienyl anion, such as a cyclopentadienide salt, to form CpMCp' . The metal salt can be a metal (III) salt, such as, for example, a metal halide (e.g., chloride, bromide, iodide, fluoride), a metal nitrate and other suitable metal salts. M is a Group 8 (VIII) metal, e.g., Ru, Os or Fe . Generally, the metal salt is abbreviated as MXn. As used herein, the abbreviation MXn does not exclude metal salt compounds that include water of hydration and that, as known in the art, can be more specifically represented by the formula MXnQDH20, D being other than 0. Thus in specific examples, the abbreviation FeX3 used herein includes anhydrous as well as hydrated iron salts that can be employed to form ferrocenes or ferrocene-like compounds.
Ligand (L) generally is an electron pair donor compound. A neutral electron pair donor, such as, for example, triphenylphosphine (PPh3) is employed in one
example . Tricyclohexylphosphine and other phosphines of the general formula PR3, as well as phosphite triesters, P(OR)3, where R is phenyl, cyclohexyl, alkyl or branched alkyl, e.g., t-butyl, group, also can be employed. Other suitable electron pair donors include amines, phosphates, carbonyl compounds, olefins, polyolefins, chelating phosphines, chelating amines and others.
The Cp compound is a precursor of the Cp moiety in the CpMCp' compound described above. Preferably the Cp compound is HCp, e.g., cyclopentadiene or indene . The Cp compound" also""can "Be" a~saT.Tt~"of~'a"~cγclopeϊfiadi^nyl~ r indenyl anion, e.g., potassium cyclopentadienyl (KCp) , sodium cyclopentadienyl (NaCp) , lithium cyclopentadienyl (LiCp) and others. Suitable cations for use with a cyclopentadienyl anion in the synthetic method described herein include trimethylsilyl (TMS) , Na, Li, K, Mg, Ca and Tl.
At least one hydrogen atom in the Cp moiety is replaced by a group Di, as described above. Specific examples of HCp include, methylcyclopentadiene, ethylcyclopentadiene, n-propyl- or isopropylcyclopentadiene, n-butyl-, sec-butyl- or tert- butylcyclopentadiene, halo-cyclopentadiene and others.
The Cp compound also can be di- or multi-substituted, e.g., it can be a di-, tri-, tetra- and penta-substituted- cyclopentadiene . Specific examples of substituent groups D2, D3, D4 and D5 are described above.
Each of the MXn, L and HCp components can be provided in neat form or can optionally include a suitable solvent.
Preferred solvents that can be employed in the method of the invention include alcohols, such as, for instance, ethanol, methanol, isopropanol and other alcohols. Ethyl acetate, tetrahydrofuran (THF) , saturated or unsaturated hydrocarbons, aromatic heterocycles, alkyl halides, silylated hydrocarbons, ethers, polyethers thioethers, esters, lactones, amides, amines, polyamines, nitriles, silicone oils and other aprotic solvents also can be employed. Combinations of solvents also can be employed. Generally, concentrations of MXn, L and Cp are selected as"~kήown "in "the" a t". ~ ~For example-, " the molar "cόncent ationT of MXn in a suitable solvent can be in the range of from about 0.1 M to neat. That of L in a suitable solvent can be in the range of from about 0.1 M to neat . The molar concentration of Cp in a suitable solvent can be in the range of from about 0.1 to neat. If neat phosphine is employed it is believed that the reaction would be highly exothermic. Methods and systems for dissipating substantial amounts of heat of reaction per unit volume are known in the art .
The three components can be combined in any order. In one example, the metal component and the HCp component are added concurrently to the L component . In another embodiment, the metal component and the HCp component are combined to form a mixture and then the mixture is combined with the L component, for instance by adding the L component to the mixture. In yet another embodiment, all components are combined at the same time.
Typically the molar ratio of HCp to MXn used is in the range from about 50 to about 1, preferably from about 12 to about 2 and most preferably in the range from about 7 to about 5. Typically, the molar ratio of L to MXn is in the range of from about 8 to about 0 , preferably from about 6 to about 2 and most preferably from about 5 to about 3.5. If a large excess amount of HCp component is employed, the reaction is driven to forming (Cp) 2M product.
The reaction temperature preferably is around the boiling point of the solvent employed or the boiling point of the^ ~±eactTon "mixture . Ot"her~~suita"ble~tempe:ratTures~"can" be determined by routine experimentation. Generally, the reaction can be conducted at a temperature that is in the range of from above the freezing point to about the boiling point of the reaction composition. For instance, the reaction can be conducted at a temperature in the range of from about -100DC to about 150DC.
The time of reaction generally depends on temperature, and concentration of the various reactants, and can range, for example, from about 5 minutes to about 96 hours.
The intermediate component formed by the reaction of the metal salt (MXn) component, ligand (L) component and HCp can be represented by the formula CpMLfX, where f = 1 or 2. In one example, CpMLfX is isolated, e.g., as a solid, by methods known in the art, such as filtration, centrifugation or recrystallization. Intermediate compound, CpMLfX, is then reacted with a Cp' compound, preferably in the presence of a solvent. Cp' preferably is
an anion of the Cp' moiety in the compounds of the invention described above. Counterions can include trimethylsilyl (TMS), Na, Li, K, Mg, Ca, Tl . Specific examples of cyclopentadienyl compounds that can be used include, but are not limited to sodium or lithium ethylcyclopentadienide, sodium or lithium methylcyclopentadienide, sodium or lithium isopropylcyclopentadienide and others. Di- or multi- substituted anions of the Cp' moiety also can be employed (e.g., di-, tri-, tetra- or penta-substituted cyclόpenta'dienyl anions) . "Anions" o"f unsubstϊtuT-Ted indenes also can be employed, as described above.
In a specific example, the intermediate compound is CpRu(PPh3) 2C1. It is reacted with a salt of Cp' . Recommended salts of Cp' include NaCp' , LiCp' , (Cp')2Mg, TMS(Cp') and (Cp')Tl.
Examples of suitable solvents include benzene, toluene, xylenes, pentanes, hexanes, petroleum ether, aromatic heterocycles, saturated or unsaturated hydrocarbons, alkyl halides, silylated hydrocarbons, ethers, polyethers, thioethers, esters, lactones, amides, amines, polyamines, nitriles, silicones, and others.
Generally, the molar concentrations of the Cp' component in a solvent can be in the range of from about 0.1 M to about 3.5 M, preferably in the range of from about 0.5 M to about 2.5 M and most preferably in the range of from about 1.4 to about 1.8 M.
Typically, the molar ratio of Cp' relative to the CpMLfX is in the range from about 50 to about 1, preferably
from about 6 to about 1 and most preferably from about 1.6 to about 1.2.
In another example the intermediate CpMLfX component is not isolated. Following its formation in solution, a Cp' compound, such as described above, is added to the solution that includes CpMLfX.
The reaction between Cp' and the intermediate CpMLfX (whether isolated or not) is conducted at a temperature such as generally described above and results in the formation of CpMCp' product.
The time of reaction generally depends ~oΗ~t"e~mperature, and concentration of the various reactants, and can range from about 15 minutes to about 6 days.
The product of the reaction, CpMCp' , can be isolated and/or or purified by methods known in the art, such as, for example, solvent, e.g., hexane, extraction followed by distillation, sublimation or chromatography or directly by distillation, sublimation or chromatography. Recrystallization, ultracentrifugation and other techniques also can be employed. Alternatively, the product can be further employed in the reaction mixture, without further isolation and or purification.
A method for forming the compounds of the invention is described by the chemical reaction shown in Fig. 6. In the method depicted in Fig. 6, MC13D XH20, triphenylphosphine and a cyclopentadiene react in ethanol, under reflux, to form intermediate compound CpM (PPh3) 2C1, which then reacts with a sodium ethylcyclopentadienide to form CpMCp' .
Either or both Cp and/or Cp' can include additional
substituent groups, Dx, such as, for instance, groups described above. Thus either or both Cp and/or Cp' can be a di-, tri-, tetra- or penta-substituted cyclopentadiene moiety. In general, asymmetric ruthenocenes can be prepared by first preparing an intermediate of CpRu (PPh3) 2C1 , followed by the reaction of this intermediate with a salt of Cp' . The most highly recommended salts of Cp' include NaCp' , LiCp', (Cp')2Mg, TMS(Cp') and (Cp')Tl. When trying to synthesize structures of the type CpRuCp' and when one of "Cp or 'Cp' colϊtains a ke'tone", es~te"r"~or ether" functionaTity" it is preferred that the ring with the greater number of ketones, esters or ethers is identified as the Cp' ring, and that it is added to the intermediate as a TMS salt . A synthetic scheme that can be employed to form a specific di-substituted asymmetric ruthenocene, i.e., 1- methyl, 1' -ethylruthenocene or (methyl- cycplopentadienyl) (ethylcyclopentadienyl) ruthenium, is shown in Fig. 7. As shown in Fig. 7, RuCl3DXH20, triphenylphosphine and methylcyclopentadiene react in ethanol, under reflux, to form intermediate compound chloro (methylcyclopentadienyl) bis (triphenylphosphine) ruthen ium(II) or (η5-C5H4C2H5) Ru (PPh3) 2C1, which then reacts with a sodium ethylcyclopentadienide to form l-methyl,l'- ethylruthenocene .
Examples of techniques that can be employed to characterize the compounds formed by the synthetic methods described above include, but are not limited to, analytical gas chromatography, nuclear magnetic resonance (NMR) ,
thermogravimetric analysis (TGA) , inductively coupled plasma mass spectrometry (ICPMS) , vapor pressure and viscosity measurements.
Without being held to a particular mechanism to interpret the invention, it is believed that specific functionalization of each of the Cp and Cp' rings modifies properties such as solubility, vapor pressure, decomposition, combustion and other reaction pathways, reduction/oxidation potentials, geometry, preferred orientations and electron density distribution. For
"example", iύ""is believed-tha " larger substituent D~and/or Di' contribute to an increase in molecular entropy and that metallocene compounds of the invention are more likely to be liquid at room temperature in comparison to previously disclosed compounds.
The asymmetric metallocenes of the invention are believed to be useful in scientific research, for example, in the study and understanding of organometallic chemistry of ferrocene and ferrocene-like molecules and in chemical reactions.
It is believed that the compounds of the invention also can be employed as combustion modifiers for solid propellants. In some cases, functionalization of the parent ferrocene may prevent migration of the ferrocene from the rubber like binder matrix of the solid propel1ant into the surrounding insulation material .
The metallocene compounds of the invention may find uses as catalysis, for instance, in zeolite-impregnated
metallocene catalysts for the reduction of nitrogen oxides or as catalysts in chiral organic synthesis.
It is believed that the compounds of the invention may also find uses as iron deficiency supplements for animals and plants; antioxidants and antiknock agents; additives for motor fuels and oils; color pigments; radiation absorberes; and as insecticides and fungicides.
The asymmetric metallocenes of the invention are particularly useful as precursors in processes for forming films, coatings or powders, particularly in film deposition ~ processes", " sύch""as~CVD" processesT" Such" processes~a"re described in the U.S. Patent Application by David M. Thompson and Cynthia A. Hoover, John Peck and Mike Litwin, entitled Deposition Processes Using Group 8 (VIII) Metallocene Precursors , filed concurrently herewith, under Attorney Docket No. D-21267, the entire teachings of which are incorporated herein by reference.
EXEMPLIFICATION EXAMPLE 1 STEP A
A 5 L five-necked round bottomed flask was equipped with a mechanical stirring paddle through the central neck. It was then charged with ethanol (2.0 L) and PPh3 (420 g, 1.6 mol) . Two 500 mL three necked flasks, were connected to two necks of the 5 L four-necked flask via Teflon® (perfluorinated polymer, DuPont Corp.) tubing through positive displacement pumps. The remaining neck of the 5 L flask was equipped with a condenser. A heating mantle was
placed beneath the 5 L flask and the solution was stired and heated to reflux. At reflux all of the triphenylphosphine dissolved in the ethanol . The system was purged with nitrogen for 30 minutes while at reflux. While this was taking place one of the 500 mL round- bottomed flasks was charged with RuCl3'XH20 (100 g, 0.40 mol) , ethanol (300 mL) and a Teflon® (perfluorinated polymer, DuPont Corp.) coated magnetic stirring bar. The ethanolic solution immediately developed a brown/orange colour. To dissolve all of the RuCl3"XH20 it was necessary to heat the solution. This solution was sparged with nitrogen for 30 minutes by inserting a needle connected to a 1-2 pounds per square inch gauge (psig) nitrogen source through the septum and into the solution and by piercing the septum with another needle to allow for relief of excess pressure.
An acetonitrile/dry ice bath was made up and the other 500 mL flask was immersed into this bath. Freshly distilled methylcyclopentadiene (190 g, 270 mL, 2.4 mol, freshly distilled under a nitrogen atmosphere) was then cannulated into the cooled flask.
After the nitrogen sparging of the ethanolic solutions of triphenylphosphine and ruthenium trichloride had completed, the contents of the two 500 mL flasks were pumped into the 5.0 L flask by positive displacement pumps at independent rates so that both additions completed after 5 minutes. To accomplish this the ethylcyclopentadiene was pumped in at a rate of 45 mL/min and the ethanolic ruthenium trichloride was pumped in at a rate of 50
mL/min .
After the addition had been completed the solution was left to reflux for an additional 2 hours. During this time small orange crystals could be seen accumulating above the meniscus of the solution on the walls of the 2 L flask.
STEP B
The two positive displacement pumps and Teflon0 (perfluorinated polymer, DuPont Corp.) lines were disconnected from the 5 L flask after the 2 hours of
"stiffing": "' A~ distillation "sid'earπv was -connected one of the necks of the flask and approximately 1 L of ethanol was removed via distillation. Mechanical stirring was discontinued and the orange crystals settled to the bottom of the flask. The solution cooled to room temperature over 3 hours. The solution was then removed from the flask by inserting a piece of glass tubing with a coarse frit attached to the end of it and using reduced pressure to draw the solution through the frit and out of the flask. The crystals were washed with heptane (300 mL) and the heptane was removed in a similar fashion. The washing was carried out three times.
STEP C
All of the open ports to the flask were sealed with rubber septa and the flask was evacuated and refilled with nitrogen three times. THF (500 mL, anhydrous) was cannulated into the flask and mechanical stirring was initiated. A THF solution of lithium ethylcyclopentadiene (500 mL, 1.2 M, 0.60 mol) was then cannnulated into the 5 L
flask. The contents were heated to reflux and stirred for 4 hours .
After the 4 hours of reflux, stirring was discontinued and the solution was transferred to a 2 L one necked round bottomed flask. This solution was concentrated to a volume of approximately 200 mL on a rotary evaporator. The viscous liquid was then transferred to a 250 mL round bottomed flask.
The 250 mL round-bottomed flask was fitted with a short path distillation adapter with vigreux indentations aricTaT ΪOO'TαT storage"" "flask "feceptacle . "" The liquid was distilled under vacuum and a clear yellow liquid, 1-methyl, 1 ' -ethylruthenocene containing some triphenylphosphine (determined by GCMS) . Spinning band distillation of the yellow liquid afforded 84.6 g (82% yield) of triphenylphosphine free 1-methyl, 1 ' -ethylruthenocene in >99% purity (GCMS, IH NMR) , with the remaining impurities being attributable to 1, 1 ' -dimethylruthenocene and 1,1'- diethylruthenocene . TGA studies showed that this liquid had less than 0.01% nonvolatile residue. EXAMPLE 2
A 2 L three-necked round bottomed flask was charged with a Teflon® (perfluorinated polymer, DuPont Corp.) stirring bar, ethanol (1.0 L) and PPh3 (263 g, 1.0 mol, 5 eq) . A 250 mL dropping funnel, a 150 mL bath-jacketed dropping funnel, and a condenser were attached to the three necks of the 2L flask. It is important to note that both dropping funnels were equipped with Teflon (perfluorinated polymer, DuPont Corp.) valves that permitted their
isolation from the atmosphere of the round-bottomed flask. A rubber septum was connected to the top of the 150 mL bath-jacketed dropping funnel. The top of the condenser was fitted with an T junction adapter and connected to an inert atmosphere. A heating mantle was placed beneath the 2 L three-necked round-bottomed flask and the solution was stirred and heated to reflux. At reflux all of the triphenylphosphine dissolved in the ethanol. The system was purged with nitrogen for 3 hours while at reflux. While this was taking place a 500 mL Erlenmyer flask was charged with RuCl3-XH20 (50 g, 0.20 mol), ethanol (150 mL, 1 eq) and a Teflon" (perfluorinated polymer, DuPont Corp.) coated magnetic stirring bar. The ethanolic solution immediately developed a brown/orange colour. To dissolve all of the RuCl3-XH20 it was necessary to gently heat the solution. This solution was poured into the 250 mL dropping funnel and the dropping funnel was fitted with a rubber septum. This solution was sparged with nitrogen for 30 minutes by inserting a needle connected to a 1-2 psig nitrogen source through the septum and into the solution and by piercing the septum with another needle to allow for relief of excess pressure.
A methanol/dry ice bath was made up in the 150 mL bath-jacketed dropping funnel. The interior of this droppping funnel was purged with nitrogen for 30 minutes in a similar fashion to which the other dropping funnel was sparged. Methylcyclopentadiene (96.2 g, 1.2 mol, 6 eq, doubly distilled under a nitrogen atmosphere) was then
cannulated into the cooled dropping funnel through the rubber septum.
After the 3 hours of purging the 2 L-round bottomed flask had elapsed, the Teflon® (perfluorinated polymer, DuPont Corp.) valves isolating the dropping funnels from the rest of the system were both opened and dropwise addition of the two solutions commenced simultaneously. Over the course of 20 minutes the two solutions were both added to the ethanolic PPh3 solution. During this entire time the solution was at reflux. The solution quickly developed a deep orange brown color. After "the "addition had been completed the solution was left to reflux for an additional 2 hours. During this time small orange crystals of CpRu(PPh3) 2C1 could be seen accumulating above the meniscus of the solution on the walls of the 2 L flask.
A piece of tubing with a coarse porous frit attached to one end was attached to a positive displacement pump. The fritted end of the tubing was immersed in the reactor and all of the liquids were pumped out of the 2 L round- bottomed flask. At this stage the dropping funnels were removed from the reactor. One side was fitted with a K- Head distillation adapter and the other side was fitted with a rubber septum. The flask was evacuated and refilled with nitrogen three times. Working under nitrogen, anhydrous toluene (1.0 L) was cannulated into the 5 L flask through the rubber septum. The dark opaque solution was heated to reflux and the K-head distillation adapter was opened to distill off a fraction of the solvent . Distillate was collected until the head temperature reached
109 °C (It is important to note that in different experiments this consumes different volumes of solvent - typically 400-600 mL of liquid) . The solution was then cooled to below reflux. The flask was then charged with additional toluene to obtain a volume of approximately 600 mL toluene. A lithium ethylcyclopentadienide slurry of toluene (35 g, 0.35 mol, 400 mL) was then cannulated into the reaction pot. Following this addition the solution was stirred for 4 hours at 80 °C. At this stage the flask was removed from the glovebox and the majority of toluene" "was removed using a K-head distillation adapter.
The remaining liquid (approximately 400 mL) was decanted into a 1.0 L round-bottomed flask. This round- bottomed flask was fitted with a short path distillation adapter with vigreux indentations and distilled. The liquid collected from the vigreux column was distilled again using spinning band distillation under vacuum and 44 g of a clear yellow liquid, 1-methyl, 1' -ethylruthenocene was obtained in >99% purity (GCMS) . TGA studies showed that this liquid had less than 0.01% nonvolatile residue.
EXAMPLE 3 Lithium(ethylcyclopentadienide) was produced as follows. A 2 L three-necked jacketed round bottomed flask was charged with a Teflon" (perfluorinated polymer, DuPont Corp.) stirring bar. A stopcock adapter, a thermowell adapter with thermowell and a rubber septum were fitted to
the three necks of the flask. A nitrogen/vacuum manifold was connected to the stopcock adapater and the flask was evacuated and refilled with nitrogen 3 times. Anhydrous toluene (1.0 L) was then cannulated into the flask through the rubber septum and stirring was initiated. A cold fluid circulator was connected to the outer jacket of the jacketed flask with nalgene tubing and a cold fluid (-15 °C) was circulated through the outside wall of the jacketed flask. Once the toluene reached -10 °C, freshly distilled ethylcyclopentadiene (middle cut distilled on a vigreux column) was cannulated into the flask (127 g, 1.35 mol) . While stirring, n-butyllithium (800 mL, 1.6 M in hexanes, 1.28 mol) was slowly cannulated at a rate that kept the temperature below 0 °C (approximately 2 hours) . During the addition of the n-butyllithium a fine white precipitate (lithium ethylcyclopentadienide) became evident in the solution.
This material could be used as a suspension or isolated as a solid via filtration and removal of solvent.
EXAMPLE 4
In a nitrogen glovebox, a 250 mL flask was charged with THF (50 mL, anhydrous, inhibitor free) , chloro (ethylcyclopentadienyl) bis (triphenylphosphine) rutheni urn (II) (3.22 g, 0.004 mol, 1 equivalent) and a Teflon®
(perfluorinated polymer, DuPont Corp.) stirring bar. The solution was stirred and a burgundy colored THF solution of sodium isopropylcyclopentadienide was slowly added (0.20 M, 30 mL, 1.5 equivalents) . Following the addition the
solution developed a deep red color. Within 30 minutes, the meniscus appeared yellow in color. The solution was stirred overnight.
An aliquot (1.0 mL) was taken from the solution and was analyzed by GC/MS . A peak with a mass of 301 g/mol was observed consistent with the 1-ethyl-l'- isopropylruthenocene . Other peaks with masses consistent with the presence of alkylcyclopentadiene di ers, 1,1'- diethylruthenocene, 1, 1' -diisopropylruthenocene and triphenylphosphine were also observed.
The THF solvent was then removed from the flask under reduced pressure. The 250 mL flask was fitted with a vacuum jacketed short path distillation adapter and the contents of the flask were distilled under reduced pressure (~ 0.1 torr) . A pale yellow liquid was collected (0.72 g) . This liquid was then purified via chromatography. A silica gel in pentane solution was used. The column had a diameter of 0.75" and a 6" length. 0.53 g of 99+% pure 1-ethyl-l' -isopropylruthenocene were isolated via chromatography (41% yield) .
EXAMPLE 5
In a nitrogen glovebox, a 250 mL flask was charged with THF (50 mL, anhydrous, inhibitor free) , chloro (methylcyclopentadienyl) bis (triphenylphosphine) ruthen ium(II) (5.02 g, 0.007 mol, 1 equivalent) and a Teflon® (perfluorinated polymer, DuPont Corp.) stirring bar. The solution was stirred and a burgundy colored THF solution of sodium isopropylcyclopentadienide was slowly added (0.20 M,
50 mL, 1.5 equivalents). Following the addition the solution developed a deep red color. Within 30 minutes, the meniscus appeared yellow in color. The solution was stirred overnight. An aliquot (1.0 mL) was taken from the solution and was analyzed by GC/MS. A peak with a mass of 287 g/mol was observed consistent with 1-methyl-l' -isopropylruthenocene . Other peaks with masses consistent with the presence of alkylcyclopentadiene dimers, 1, 1' -dimethylruthenocene, 1, 1' -diisopropylruthenocene and triphenylphosphine were also observed.
The THF solvent was then removed from the flask under reduced pressure. The 250 mL flask was fitted with a vacuum jacketed short path distillation adapter and the contents of the flask were distilled under reduced pressure (~ 0.1 torr) . A pale yellow liquid was collected ( 1.78 g) . This liquid was then purified via chromatography. A silica gel in pentane solution was used. The column had a diameter of 0.75" and a 6" length. 1.03 g of 98+% pure 1- methyl-1' -isopropylruthenocene were obtained after chromatography (53% yield) .
EXAMPLE 6
In a nitrogen glovebox, a 250 mL flask was charged with bis (propylcyclopentadienyl) magnesium (5.15 g, 0.02 mol, 1 equivalent) , chloro (methylcyclopentadienyl) bis (triphenylphosphine) ruthen ium(II) (5.02 g, 0.007 mol, 1 equivalent) and a Teflon® (perfluorinated polymer, DuPont Corp.) stirring bar.
Toluene (120 mL, anhydrous, inhibitor free) was cannulated into the 250 mL round-bottomed flask and the contents were stirred. Following the addition of solvent the solution developed a deep red color. The toluene solvent was then removed from the flask under reduced pressure . The toluene solvent was removed under reduced pressure and the flask was fitted with a short path distillation adapter. The distillate was collected and the GC/MS revealed that the main cut from the short path distillation was 88.7% pure 1-propyl-l'- ethylruthenocene . ' ' -
EQUIVALENTS
While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention encompassed by the appended claims .
Claims
What is claimed is :
1. An asymmetric Group 8 (VIII) metallocene of the general formula CpMCp' , where
M is a metal selected from the group consistinc of Ru, Os and Fe;
Cp is a first substituted cyclopentadienyl or indenyl moiety that includes at least one substituent group Di;
Cp' is a second substituted cyclopentadienyl o: indenyl moiety that includes at least one substituent group Di' ; wherein
D is different from Di' ;
D is selected from the group consisting of: X;
CalHblXcl /" Ca2Hb2Xc2 (C=0) CaiHbiXci ; and
Ca2Hb Xc2θCalHblXcl / where
X is F, Cl, Br, I or N02; al is an integer from 2 to 8; bl is an integer from 0 to 2(al)+l - cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2(a2) + 1 - c2
c2 is an integer from 0 to 2(a2) + 1 - b2; and Dl' is selected from the group consisting of: X; CaiHbiXci;
Ca2Hb2Xc2 ( C=0) CaiHbiXci ; and
Ca2H 2Xc2θCaιHblXcl / where ,
X is FI, Cl, Br or I or N02; al is an integer from 1 to 8; bl is "an integer from 'to 2 (al)-+T -- -cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is equal to or greater than 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2(a2)+l - c2; c2 is an integer from 0 to 2(a2)+l - b2; and b2 + c2 is equal to or greater than 1.
2. The asymmetric metallocene of Claim 1 wherein either or both of Cp and Cp' includes at least one additional substituent, Dx, selected from the group consisting of: X;
CalHblXcl /"
Ca2H 2Xc2 ( C=0) CalHblXcl /' Ca2Hb2Xc2θCaιHbiXcι ;
Ca2H 2 c2 (C=0) OCaiHbiX i ; and
C 2Hb2Xc20 (C=0) CalHblXcl / where ,
X is Fl , Cl , Br or I or N02 ;
al is an integer from 0 to 8 ,- bl is an integer from 0 to 2(al)+l - cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is equal to or greater than 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2(a2)+l - c2; c2 is an integer from 0 to 2(a2)+l - b2; and b2 + c2 is. greater to or equal to 1.
A metallocene compound represented by the following molecular formula:
where
M is selected from the group consisting of Ru, Os and Fe;
Di is different from Di' and Di and Dl' are independently selected from the group consisting of:
X ;
CalHbl cl /'
Ca2Hb2Xc2 ( C=0 ) CaiHbiXci ; and
Ca2Hb2 c2θCaιHblXcl /
where
X is F, Cl, Br, I or N02; al is an integer from 1 to 8; bl is an integer from 0 to 2(al)+l-cl cl is an integer from 0 to 2(al)+l - bl; bl + cl is at least 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2(a2) + 1 - c2; and c2 is an integer from 0 to 2(a2) + 1 - b2.
4. The metallocene compound of Claim 3, wherein Di is methyl and Di' is selected from the group consisting of ethyl, propyl, isopropyl, n-butyl, sec-butyl and tert- butyl .
5. The metallocene compound of Claim 3, wherein Di is ethyl and Dx' is selected from the group consisting of propyl, isopropyl, n-butyl, sec-butyl and tert-butyl.
6. The metallocene compound of Claim 3, wherein Di is propyl and Dx' is selected from the group consisting of isopropyl, n-butyl, sec-butyl and tert-butyl.
7. The metallocene compound of Claim 3, wherein Dx is isopropyl and Di' is selected from the group consisting of n-butyl, sec-butyl and tert-butyl.
8. The metallocene compound of Claim 3, wherein Dx is n- butyl and Dx' is selected from the group consisting of sec-butyl and tert-butyl.
9. The metallocene compound of Claim 3, wherein Dx is sec- butyl and Di' is tert-butyl.
10. A compound of the general formula,
where Dx and D2 are different and each is independently selected from the group consisting of: X;
CalHblXcl /
Ca2Hb2Xc2 ( C=0) CaiHbiXci ; and Ca2H 2 c2θCaιHbiXci ■ where
X is F , Cl , Br I or N02 ; al is an integer from 1 to 8; bl is an integer from 0 to 2(al)+l - cl cl is an integer from 0 to 2(al)+l - bl;
bl + cl is at least 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2(a2) + 1 - c2; c2 is an integer from 0 to 2(a2) + 1 - b2; and each of D2, D3, D4, D5, D2' , D3' , D4' , and D5' is independently selected from the group consisting of: X;
CaιHiXι ;
Ca2H 2Xc2 (C=0) CaiH iXci ; Ca2Hb2Xc2OCaιHbiXci ;
" Ca ~ 2Hb2Xc2 ( C=0 ) OCaiHbiXci ; and ■
Ca2Hb2Xc2θ ( C=0) CalHblXcl / where,
X is F, Cl, Br, I or N02; al is an integer from 0 to 8; bl is an integer from 0 to 2(al)+l - cl; cl is an integer from 0 to 2(al)+l - bl; bl + cl is equal to or greater than 1; a2 is an integer from 0 to 8; b2 is an integer from 0 to 2(a2)+l - c2; c2 is an integer from 0 to 2(a2)+l - b2; b2 + c2 is equal to or greater than 1.
Applications Claiming Priority (23)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US685777 | 1991-04-16 | ||
| US42294702P | 2002-10-31 | 2002-10-31 | |
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| US45371703P | 2003-04-18 | 2003-04-18 | |
| US45371903P | 2003-04-18 | 2003-04-18 | |
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| US453718P | 2003-04-18 | ||
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| US10/685,785 US7927658B2 (en) | 2002-10-31 | 2003-10-16 | Deposition processes using group 8 (VIII) metallocene precursors |
| US10/685,777 US6884901B2 (en) | 2002-10-31 | 2003-10-16 | Methods for making metallocene compounds |
| US685785 | 2003-10-16 | ||
| US10/686,254 US6919468B2 (en) | 2002-10-31 | 2003-10-16 | Asymmetric group 8 (VIII) metallocene compounds |
| US686254 | 2003-10-16 | ||
| PCT/US2003/034497 WO2004041832A2 (en) | 2002-10-31 | 2003-10-30 | Asymmetric group 8 (viii) metallocene compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1556394A2 true EP1556394A2 (en) | 2005-07-27 |
| EP1556394A4 EP1556394A4 (en) | 2008-02-20 |
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| EP03810820.5A Expired - Lifetime EP1556395B1 (en) | 2002-10-31 | 2003-10-30 | Methods for making metallocene compounds |
| EP03810819A Withdrawn EP1556394A4 (en) | 2002-10-31 | 2003-10-30 | Asymmetric group 8 (viii) metallocene compounds |
| EP03810818A Expired - Lifetime EP1556527B1 (en) | 2002-10-31 | 2003-10-30 | Deposition processes using group 8 (viii) metallocene precursors |
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| EP03810818A Expired - Lifetime EP1556527B1 (en) | 2002-10-31 | 2003-10-30 | Deposition processes using group 8 (viii) metallocene precursors |
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|---|---|
| EP (3) | EP1556395B1 (en) |
| JP (3) | JP4542506B2 (en) |
| KR (3) | KR100997838B1 (en) |
| AU (3) | AU2003301874A1 (en) |
| TW (1) | TWI274082B (en) |
| WO (3) | WO2004041753A2 (en) |
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| US7048968B2 (en) | 2003-08-22 | 2006-05-23 | Micron Technology, Inc. | Methods of depositing materials over substrates, and methods of forming layers over substrates |
| US6987063B2 (en) | 2004-06-10 | 2006-01-17 | Freescale Semiconductor, Inc. | Method to reduce impurity elements during semiconductor film deposition |
| US7816550B2 (en) * | 2005-02-10 | 2010-10-19 | Praxair Technology, Inc. | Processes for the production of organometallic compounds |
| US7485338B2 (en) * | 2005-03-31 | 2009-02-03 | Tokyo Electron Limited | Method for precursor delivery |
| JP2009007270A (en) * | 2007-06-27 | 2009-01-15 | Tosoh Corp | Ruthenium compound production method and thin film production method |
| KR101598485B1 (en) * | 2014-06-20 | 2016-02-29 | 주식회사 유진테크 머티리얼즈 | Precursor compositions and Method for forming a thin film using thereof |
| KR101636491B1 (en) | 2014-07-09 | 2016-07-05 | 한국화학연구원 | Ruthenium precursors, preparation method thereof and process for the formation of thin films using the same |
| KR102486128B1 (en) | 2020-12-30 | 2023-01-06 | 에스케이트리켐 주식회사 | Precursor comprising organometal halide, deposition method of film and semiconductor device of the same |
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| US3294685A (en) * | 1952-04-21 | 1966-12-27 | Gulf Research Development Co | Organic compositions containing a metallo cyclopentadienyl |
| US3035978A (en) * | 1957-08-12 | 1962-05-22 | Ici Ltd | Ferrocene hematinic compositions and therapy |
| GB864198A (en) * | 1959-01-07 | 1961-03-29 | Ici Ltd | A process for the manufacture of ferrocene derivatives |
| NL284400A (en) * | 1961-10-18 | |||
| US3535356A (en) * | 1968-06-11 | 1970-10-20 | Gulf Research Development Co | Process for producing dicyclopentadienyliron compounds |
| US4066569A (en) * | 1975-12-30 | 1978-01-03 | Hughes Aircraft Company | Dopants for dynamic scattering liquid crystals |
| PL124360B1 (en) * | 1980-02-27 | 1983-01-31 | Politechnika Gdanska | Process for preparing ruthenocene |
| JPH02250892A (en) * | 1989-03-24 | 1990-10-08 | Idemitsu Kosan Co Ltd | New ferrocene derivative, surfactant containing the same and production of organic thin film |
| JPH1125589A (en) * | 1997-07-04 | 1999-01-29 | Matsushita Electric Ind Co Ltd | Magnetic recording / reproducing device |
| JP3371328B2 (en) * | 1997-07-17 | 2003-01-27 | 株式会社高純度化学研究所 | Method for producing bis (alkylcyclopentadienyl) ruthenium complex and method for producing ruthenium-containing thin film using the same |
| JP2000281694A (en) * | 1999-03-29 | 2000-10-10 | Tanaka Kikinzoku Kogyo Kk | Organometallic compounds for metalorganic vapor phase epitaxy |
| JP2001122887A (en) * | 1999-10-25 | 2001-05-08 | Tanaka Kikinzoku Kogyo Kk | Organometallic compound for chemical vapor deposition, method for producing the organometallic compound, and method for producing a thin film using the organometallic compound |
| JP4162366B2 (en) * | 2000-03-31 | 2008-10-08 | 田中貴金属工業株式会社 | CVD thin film forming process and CVD thin film manufacturing apparatus |
| US6921712B2 (en) * | 2000-05-15 | 2005-07-26 | Asm International Nv | Process for producing integrated circuits including reduction using gaseous organic compounds |
| JP4512248B2 (en) * | 2000-09-26 | 2010-07-28 | 田中貴金属工業株式会社 | Method for producing bis (alkylcyclopentadienyl) ruthenium and method for chemical vapor deposition of bis (alkylcyclopentadienyl) ruthenium and ruthenium thin film or ruthenium compound thin film produced by the method |
| JP4759126B2 (en) * | 2000-10-11 | 2011-08-31 | 田中貴金属工業株式会社 | Organometallic compound for chemical vapor deposition, method for producing organometallic compound for chemical vapor deposition, noble metal thin film, and chemical vapor deposition method for noble metal compound thin film |
| JP3598055B2 (en) * | 2000-11-08 | 2004-12-08 | 田中貴金属工業株式会社 | Method for producing bis (alkylcyclopentadienyl) ruthenium and method for producing bis (alkylcyclopentadienyl) ruthenium and ruthenium thin film or ruthenium compound thin film produced by the method |
| US20020161253A1 (en) * | 2001-04-30 | 2002-10-31 | Boulder Scientific Company | Synthesis of bis (cyclopentadienyl) and bis (indenyl) ruthenium complexes |
| US6521772B1 (en) * | 2001-09-27 | 2003-02-18 | Praxair Technology, Inc. | Synthesis of substituted ruthenocene complexes |
| US6653236B2 (en) * | 2002-03-29 | 2003-11-25 | Micron Technology, Inc. | Methods of forming metal-containing films over surfaces of semiconductor substrates; and semiconductor constructions |
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2003
- 2003-10-29 TW TW092130102A patent/TWI274082B/en not_active IP Right Cessation
- 2003-10-30 WO PCT/US2003/034494 patent/WO2004041753A2/en not_active Ceased
- 2003-10-30 EP EP03810820.5A patent/EP1556395B1/en not_active Expired - Lifetime
- 2003-10-30 JP JP2005502215A patent/JP4542506B2/en not_active Expired - Fee Related
- 2003-10-30 KR KR1020057007504A patent/KR100997838B1/en not_active Expired - Lifetime
- 2003-10-30 EP EP03810819A patent/EP1556394A4/en not_active Withdrawn
- 2003-10-30 KR KR1020057007501A patent/KR101150551B1/en not_active Expired - Fee Related
- 2003-10-30 KR KR1020057007554A patent/KR100995223B1/en not_active Expired - Fee Related
- 2003-10-30 JP JP2005502216A patent/JP4538407B2/en not_active Expired - Fee Related
- 2003-10-30 WO PCT/US2003/034498 patent/WO2004042354A2/en not_active Ceased
- 2003-10-30 AU AU2003301874A patent/AU2003301874A1/en not_active Abandoned
- 2003-10-30 EP EP03810818A patent/EP1556527B1/en not_active Expired - Lifetime
- 2003-10-30 JP JP2005502217A patent/JP4560484B2/en not_active Expired - Fee Related
- 2003-10-30 WO PCT/US2003/034497 patent/WO2004041832A2/en not_active Ceased
- 2003-10-30 AU AU2003301884A patent/AU2003301884A1/en not_active Abandoned
- 2003-10-30 AU AU2003301873A patent/AU2003301873A1/en not_active Abandoned
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