WO2000012520A1 - Methods for preparing ruthenium and osmium compounds - Google Patents
Methods for preparing ruthenium and osmium compounds Download PDFInfo
- Publication number
- WO2000012520A1 WO2000012520A1 PCT/US1999/017052 US9917052W WO0012520A1 WO 2000012520 A1 WO2000012520 A1 WO 2000012520A1 US 9917052 W US9917052 W US 9917052W WO 0012520 A1 WO0012520 A1 WO 0012520A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- formula
- solvent system
- group
- complex
- prepared
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 21
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title description 16
- 150000002908 osmium compounds Chemical class 0.000 title description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002904 solvent Substances 0.000 claims abstract description 34
- 239000003446 ligand Substances 0.000 claims abstract description 27
- 230000007935 neutral effect Effects 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000009835 boiling Methods 0.000 claims abstract description 10
- 229910052762 osmium Inorganic materials 0.000 claims abstract description 9
- -1 stibenes Chemical class 0.000 claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical class CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical compound [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical class CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 150000001555 benzenes Chemical class 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical class CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 150000005671 trienes Chemical class 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- 150000001345 alkine derivatives Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical class [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 150000001913 cyanates Chemical class 0.000 claims description 2
- 125000005594 diketone group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical class 0.000 claims description 2
- 150000002527 isonitriles Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 claims description 2
- 150000003567 thiocyanates Chemical class 0.000 claims description 2
- 150000003573 thiols Chemical class 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims 1
- 150000005675 cyclic monoalkenes Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000013638 trimer Substances 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000015654 memory Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 150000005673 monoalkenes Chemical class 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- GWYPDXLJACEENP-UHFFFAOYSA-N 1,3-cycloheptadiene Chemical compound C1CC=CC=CC1 GWYPDXLJACEENP-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cis-cyclohexene Natural products C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000003678 cyclohexadienyl group Chemical group C1(=CC=CCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004971 nitroalkyl group Chemical group 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920005547 polycyclic aromatic hydrocarbon Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004964 sulfoalkyl group Chemical group 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
-
- 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 System
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/002—Osmium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/002—Osmium compounds
- C07F15/0026—Osmium compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
Definitions
- This invention relates to the preparation of ruthenium and osmium compounds, which are particularly useful as chemical vapor deposition precursors.
- Metals and metal oxides are becoming important for a variety of electronic and electrochemical applications.
- high quality RuO 2 thin films deposited on silicon wafers have recently gained interest for use in ferroelectric memories.
- Ruthenium and osmium films are generally unreactive to silicon and metal oxides, resistant to diffusion of oxygen and silicon, and are good conductors. Oxides of these metals also possess these properties, although perhaps to a different extent.
- films of ruthenium and osmium and oxides thereof have suitable properties for a variety of uses in integrated circuits. For example, they can be used in integrated circuits for electrical contacts. They are particularly suitable for use as barrier layers between the dielectric material and the silicon substrate in memory devices, such as ferroelectric memories. Furthermore, they may even be suitable as the plate (i.e., electrode) itself in capacitors.
- ruthenium and osmium compounds that can be used as precursors for the preparation of such films. Many are particularly well suited for use in chemical vapor deposition techniques. See, for example, U.S. Pat. No. 5,372,849 (McCormick et al.), which discloses the use of ruthenium and osmium compounds containing carbonyl ligands and other ligands. Typically, such compounds can be prepared by the thermal or photolytic reaction of Ru 3 (CO) 12 or Os 3 (CO) 12 with a neutral two electron donor ligand in benzene. See, for example, Johnson et al., Nature, 901-902 (1967), and Cowles et al., Chem.
- M is Ru or Os
- each L is indepedently a neutral ligand
- These methods involve the reaction of Ru 3 (CO) 12 or Os 3 (CO) 12 with a neutral ligand in a solvent system having a boiling point higher than that of benzene at atmospheric pressure.
- the solvent system can include one solvent, such as toluene, xylene, substituted benzene, heptane, octane, nonane, or an azeotropic mixture.
- the azeotropic mixture can contain one or more solvents having a boiling point at atmospheric pressure higher than that of benzene.
- the product yields are preferably higher than conventional methods, and the reaction times are shorter than conventional methods.
- a complex of Formula I is prepared in greater than about 90% yield, more preferably, in greater than about 95% yield, and most preferably, in greater than about 99% yield.
- a complex of Formula I is prepared in no greater than about 36 hours, and more preferably, in no greater than about 24 hours.
- the present invention provides methods for the preparation of compounds of the formula (Formula I):
- complexes are neutral complexes and may be liquids or solids at room temperature. Typically, they are liquids. If they are solids, they are sufficiently soluble in an organic solvent to allow for vaporization, they can be flash vaporized or sublimed from the solid state, or they have melting temperatures below their decomposition temperatures.
- complexes described herein are suitable for use in chemical vapor deposition (CVD) techniques, such as flash vaporization techniques, bubbler techniques, and/or microdroplet techniques. Preferred embodiments of the complexes described herein are particularly suitable for low temperature CVD techniques.
- These methods involve the reaction of Ru 3 (CO) 12 or Os 3 (CO) 12 (referred to herein as "trimer”) with a neutral ligand in a solvent system having a boiling point higher than that of benzene at atmospheric pressure.
- the reaction can occur thermally or photolytically.
- the solvent system having a boiling point higher than that of benzene at atmospheric pressure can include one solvent or a mixture of solvents that may form an azeotrope.
- the solvent system includes one or more solvents that are less hazardous to an individual than benzene.
- the solvents that are suitable for this application can be one or more of the following: saturated or unsaturated hydrocarbons (preferably, C 6 -C 20 , cyclic, branched, or linear), aromatic hydrocarbons (preferably, C 6 -C 20 ), halogenated hydrocarbons, silylated hydrocarbons such as alkylsilanes, alkylsilicates, ethers, polyethers, thioethers, esters, lactones, amides, amines (aliphatic or aromatic, primary, secondary, or tertiary), polyamines, nitriles, cyanates, isocyanates, thiocyanates, silicone oils, aldehydes, ketones, diketones, carboxylic acids, alcohols, thiols, or compounds containing combinations of any of the above, or mixtures of one or more of the above.
- saturated or unsaturated hydrocarbons preferably, C 6 -C 20 , cyclic, branched, or linear
- the solvent system preferably includes, for example, toluene, xylene, substituted benzene (e.g., ethylbenzene), heptane, octane, nonane, or mixtures, particularly azeotropic mixtures thereof.
- the mixtures can contain one or more solvents having a boiling point higher than that of benzene at atmospheric pressure.
- the ligands L that are suitable for use in the preparation of compounds of Formula I include neutral ligands.
- Examples of such ligands include phosphines (R 3 P), phosphites ((RO) 3 P), amines (R 3 N), arsines (R 3 As), stibenes (R 3 Sb), ethers (R 2 O), sulfides (R 2 S), nitriles (RCN), isonitriles (RNC), thiocarbonyls (CS), monoalkenes (linear, branched, or cyclic), dienes (linear, branched, or cyclic), trienes (linear, branched, or cyclic), bicyclic alkenes, bicyclic dienes, bicyclic trienes, tricyclic alkenes, tricyclic dienes, tricyclic trienes, and alkynes.
- each of the unsaturated ligands (monoalkenes, dienes, trienes, alkynes, etc.) are not shown, they would also include R groups attached to the main carbon chain.
- the R groups can be hydrogen, a halide (particularly fluorine), or an organic group, which may be substituted or unsubstituted.
- the organic R groups preferably include about 1 to about 8 carbon atoms, and more preferably, about 1 to about 2 carbon atoms.
- the unsaturated ligands preferably include about 4 to about 8 carbon atoms, and more preferably, about 6 to about 8 carbon atoms.
- the neutral ligands are selected from the group of linear, branched, or cyclic dienes, bicyclic dienes, tricyclic dienes, and combinations thereof.
- organic group means a hydrocarbon group (with optional elements other than carbon and hydrogen, such as oxygen, nitrogen, sulfur, and silicon) that is classified as an aliphatic group, cyclic group, or combination of aliphatic and cyclic groups (e.g., alkaryl and aralkyl groups).
- the organic groups are those that do not interfere with the formation of compounds of Formula I.
- aliphatic group means a saturated or unsaturated linear or branched hydrocarbon group. This term is used to encompass alkyl, alkenyl, and alkynyl groups, for example.
- alkyl group means a saturated linear or branched hydrocarbon group including, for example, methyl, ethyl, isopropyl, t-butyl, heptyl, dodecyl, octadecyl, amyl, 2-ethylhexyl, and the like.
- alkenyl group means an unsaturated, linear or branched hydrocarbon group with one or more carbon- carbon double bonds, such as a vinyl group.
- alkynyl group means an unsaturated, linear or branched hydrocarbon group with one or more carbon- carbon triple bonds.
- cyclic group means a closed ring hydrocarbon group that is classified as an alicyclic group, aromatic group, or heterocyclic group.
- alicyclic group means a cyclic hydrocarbon group having properties resembling those of aliphatic groups.
- aromatic group or “aryl group” means a mono- or polynuclear aromatic hydrocarbon group.
- heterocyclic group means a closed ring hydrocarbon in which one or more of the atoms in the ring is an element other than carbon (e.g., nitrogen, oxygen, sulfur, etc.).
- substitution is anticipated on the organic groups of the complexes of the present invention.
- group and “moiety” are used to differentiate between chemical species that allow for substitution or that may be substituted and those that do not allow or may not be so substituted.
- group when the term “group” is used to describe a chemical substituent, the described chemical material includes the unsubstituted group and that group with O, N, Si, or S atoms, for example, in the chain (as in an alkoxy group) as well as carbonyl groups or other conventional substitution.
- moiety is used to describe a chemical compound or substituent, only an unsubstituted chemical material is intended to be included.
- alkyl group is intended to include not only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like, but also alkyl substituents bearing further substituents known in the art, such as hydroxy, alkoxy, alkylsulfonyl, halogen atoms, cyano, nitro, amino, carboxyl, etc.
- alkyl group includes ether groups, haloalkyls, nitroalkyls, carboxyalkyls, hydroxyalkyls, sulfoalkyls, etc.
- alkyl moiety is limited to the inclusion of only pure open chain saturated hydrocarbon alkyl substituents, such as methyl, ethyl, propyl, t-butyl, and the like.
- Complexes of Formula I are disclosed, for example in U.S. Pat. No. 5,372,849 (McCormick et al.) and Applicants' Assignees' copending patent application entitled "Precursor Chemistries for Chemical Vapor Deposition of
- a preferred class of complexes formed by the methods of the present invention include (cyclohexadienyl)Ru(CO) 3 and (cycloheptadienyl)Ru(CO) 3 . These complexes are particularly advantageous because they are volatile liquids.
- the methods of the present invention include using the ligand L in an excess amount (e.g., up to about a 20-fold excess, and preferably, about 3- fold to about 10-fold excess) relative to the ruthenium or osmium trimer, optionally in the presence of CO, at a temperature at which the solvent system refluxes.
- the total amount of ligand L can be added to the trimer initially, or it can be added in portions throughout the reaction. Alternatively, the total amount of trimer or portions thereof may be added to ligand L.
- the reaction can be carried out in air, however, it is preferably carried out in an inert atmosphere (e.g., nitrogen or argon) using refluxing apparatus.
- a solvent or mixture of solvents having a boiling point greater than that of benzene at atmospheric pressure produces a complex of Formula I in relatively high yields (preferably, greater than about 90%) yield, more preferably, greater than about 95%, and most preferably, greater than about 99%) in a relatively short period of time (preferably, in no greater than about 36 hours, and more preferably, in no greater than about 24 hours).
- the present invention can provide significantly shorter reaction times and higher yields.
- the product can be isolated from the reaction mixture in a variety of ways. Typically, it is isolated by removing the solvent(s) and unreacted ligand in vacuo, with optional heating of the reaction mixture. Significantly, once removed from the product, the solvent(s) and unreacted ligand can be reused by adding trimer in the desired amount.
- Tricarbonyl(l,3-cvclohentadiene)ruthenium Under an atmosphere of dry argon, toluene (20 mL) and 1,3- cycloheptadiene (2.0 mL, 1.74 g, 18.4 mmol) are added to triruthenium dodecacarbonyl (1.0 g, 1.56 mmol). The red colored reaction mixture is heated to reflux. After 24 hours, the solution has a red/yellow color and the reflux was stopped. The solvent and the unreacted ligand were removed in vacuo.
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000567541A JP2002523516A (en) | 1998-08-27 | 1999-07-28 | Method for preparing ruthenium and osmium compounds |
AU52365/99A AU5236599A (en) | 1998-08-27 | 1999-07-28 | Methods for preparing ruthenium and osmium compounds |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/141,431 US5962716A (en) | 1998-08-27 | 1998-08-27 | Methods for preparing ruthenium and osmium compounds |
US09/141,431 | 1998-08-27 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000012520A1 true WO2000012520A1 (en) | 2000-03-09 |
Family
ID=22495660
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/017052 WO2000012520A1 (en) | 1998-08-27 | 1999-07-28 | Methods for preparing ruthenium and osmium compounds |
Country Status (7)
Country | Link |
---|---|
US (4) | US5962716A (en) |
JP (1) | JP2002523516A (en) |
KR (1) | KR100554486B1 (en) |
AU (1) | AU5236599A (en) |
MY (1) | MY126518A (en) |
TW (1) | TW452603B (en) |
WO (1) | WO2000012520A1 (en) |
Families Citing this family (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6444264B2 (en) * | 1995-03-31 | 2002-09-03 | Advanced Technology Materials, Inc. | Method for liquid delivery CVD utilizing alkane and polyamine solvent compositions |
US6271131B1 (en) | 1998-08-26 | 2001-08-07 | Micron Technology, Inc. | Methods for forming rhodium-containing layers such as platinum-rhodium barrier layers |
US6197628B1 (en) * | 1998-08-27 | 2001-03-06 | Micron Technology, Inc. | Ruthenium silicide diffusion barrier layers and methods of forming same |
US5962716A (en) * | 1998-08-27 | 1999-10-05 | Micron Technology, Inc. | Methods for preparing ruthenium and osmium compounds |
US6284655B1 (en) | 1998-09-03 | 2001-09-04 | Micron Technology, Inc. | Method for producing low carbon/oxygen conductive layers |
US6239028B1 (en) | 1998-09-03 | 2001-05-29 | Micron Technology, Inc. | Methods for forming iridium-containing films on substrates |
US6323081B1 (en) | 1998-09-03 | 2001-11-27 | Micron Technology, Inc. | Diffusion barrier layers and methods of forming same |
US6319832B1 (en) * | 1999-02-19 | 2001-11-20 | Micron Technology, Inc. | Methods of making semiconductor devices |
US6329286B1 (en) | 1999-04-27 | 2001-12-11 | Micron Technology, Inc. | Methods for forming conformal iridium layers on substrates |
US6380080B2 (en) * | 2000-03-08 | 2002-04-30 | Micron Technology, Inc. | Methods for preparing ruthenium metal films |
US6429127B1 (en) | 2000-06-08 | 2002-08-06 | Micron Technology, Inc. | Methods for forming rough ruthenium-containing layers and structures/methods using same |
US6903005B1 (en) | 2000-08-30 | 2005-06-07 | Micron Technology, Inc. | Method for the formation of RuSixOy-containing barrier layers for high-k dielectrics |
US6461909B1 (en) | 2000-08-30 | 2002-10-08 | Micron Technology, Inc. | Process for fabricating RuSixOy-containing adhesion layers |
US6660631B1 (en) * | 2000-08-31 | 2003-12-09 | Micron Technology, Inc. | Devices containing platinum-iridium films and methods of preparing such films and devices |
JP2002212112A (en) * | 2001-01-22 | 2002-07-31 | Tanaka Kikinzoku Kogyo Kk | Ruthenium compound for chemical vapor deposition and method for chemical vapor deposition of ruthenium thin film and ruthenium compound thin film |
US6399492B1 (en) | 2001-03-15 | 2002-06-04 | Micron Technology, Inc. | Ruthenium silicide processing methods |
KR100727372B1 (en) | 2001-09-12 | 2007-06-12 | 토소가부시키가이샤 | Ruthenium complex, manufacturing process thereof and the method for forming thin-film using the complex |
US6420583B1 (en) * | 2001-09-27 | 2002-07-16 | Praxair Technology, Inc | Methods of synthesizing ruthenium and osmium compounds |
KR100476556B1 (en) * | 2002-04-11 | 2005-03-18 | 삼성전기주식회사 | Piezoelectric transformer, housing for piezoelectric transformer and manufacture thereof |
US7398209B2 (en) * | 2002-06-03 | 2008-07-08 | Voicebox Technologies, Inc. | Systems and methods for responding to natural language speech utterance |
US7910165B2 (en) * | 2002-06-04 | 2011-03-22 | Applied Materials, Inc. | Ruthenium layer formation for copper film deposition |
US7264846B2 (en) * | 2002-06-04 | 2007-09-04 | Applied Materials, Inc. | Ruthenium layer formation for copper film deposition |
US7404985B2 (en) * | 2002-06-04 | 2008-07-29 | Applied Materials, Inc. | Noble metal layer formation for copper film deposition |
US6737313B1 (en) * | 2003-04-16 | 2004-05-18 | Micron Technology, Inc. | Surface treatment of an oxide layer to enhance adhesion of a ruthenium metal layer |
US7429402B2 (en) * | 2004-12-10 | 2008-09-30 | Applied Materials, Inc. | Ruthenium as an underlayer for tungsten film deposition |
US7265048B2 (en) * | 2005-03-01 | 2007-09-04 | Applied Materials, Inc. | Reduction of copper dewetting by transition metal deposition |
US8197898B2 (en) * | 2005-03-29 | 2012-06-12 | Tokyo Electron Limited | Method and system for depositing a layer from light-induced vaporization of a solid precursor |
US20070128862A1 (en) | 2005-11-04 | 2007-06-07 | Paul Ma | Apparatus and process for plasma-enhanced atomic layer deposition |
US7833358B2 (en) * | 2006-04-07 | 2010-11-16 | Applied Materials, Inc. | Method of recovering valuable material from exhaust gas stream of a reaction chamber |
JP5248508B2 (en) * | 2006-09-22 | 2013-07-31 | レール・リキード−ソシエテ・アノニム・プール・レテュード・エ・レクスプロワタシオン・デ・プロセデ・ジョルジュ・クロード | Method for depositing ruthenium-containing films |
US20080152793A1 (en) * | 2006-12-22 | 2008-06-26 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitaion Des Procedes Georges Claude | Method for the deposition of a ruthenium containing film with aryl and diene containing complexes |
EP1935897B1 (en) * | 2006-12-22 | 2011-03-02 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | New organo-Ruthenium compound, the process for its preparation and its use as a ruthenium precursor to manufacture ruthenium based film coated metal electrodes |
KR20100054806A (en) * | 2007-07-24 | 2010-05-25 | 레르 리키드 쏘시에떼 아노님 뿌르 레드 에렉스뿔라따시옹 데 프로세데 조르즈 클로드 | Ruthenium precursor with two differing ligands for use in semiconductor applications |
US7737028B2 (en) * | 2007-09-28 | 2010-06-15 | Applied Materials, Inc. | Selective ruthenium deposition on copper materials |
WO2009057064A2 (en) * | 2007-10-29 | 2009-05-07 | L'air Liquide-Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Ruthenium and osmium precursor synthesis method |
US8124528B2 (en) * | 2008-04-10 | 2012-02-28 | Micron Technology, Inc. | Method for forming a ruthenium film |
US20110045171A1 (en) * | 2009-08-19 | 2011-02-24 | International Business Machines Corporation | Multi-Step Method to Selectively Deposit Ruthenium Layers of Arbitrary Thickness on Copper |
US8357614B2 (en) | 2010-04-19 | 2013-01-22 | L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Ruthenium-containing precursors for CVD and ALD |
JP5992764B2 (en) * | 2012-08-20 | 2016-09-14 | 田中貴金属工業株式会社 | Chemical vapor deposition material comprising ruthenium complex, method for producing the same, and chemical vapor deposition method |
US11913110B2 (en) | 2020-01-31 | 2024-02-27 | Tanaka Kikinzoku Kogyo K.K. | Raw material for chemical deposition containing organoruthenium compound, and chemical deposition method using the raw material for chemical deposition |
CN115003855A (en) | 2020-01-31 | 2022-09-02 | 田中贵金属工业株式会社 | Raw material for chemical vapor deposition comprising organic ruthenium compound and chemical vapor deposition method using the same |
TWI789848B (en) | 2020-08-04 | 2023-01-11 | 嶺南大學校產學協力團 | Method for forming ruthenium thin film |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5372849A (en) * | 1992-07-28 | 1994-12-13 | Minnesota Mining And Manufacturing Company | Chemical vapor deposition of iron, ruthenium, and osmium |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5130172A (en) * | 1988-10-21 | 1992-07-14 | The Regents Of The University Of California | Low temperature organometallic deposition of metals |
KR100325967B1 (en) * | 1992-04-20 | 2002-06-20 | 윌리엄 비. 켐플러 | Electrical connections to dielectric material |
JP3407204B2 (en) * | 1992-07-23 | 2003-05-19 | オリンパス光学工業株式会社 | Ferroelectric integrated circuit and method of manufacturing the same |
US5392189A (en) * | 1993-04-02 | 1995-02-21 | Micron Semiconductor, Inc. | Capacitor compatible with high dielectric constant materials having two independent insulative layers and the method for forming same |
US5352488A (en) * | 1993-05-14 | 1994-10-04 | Syracuse University | Chemical vapor deposition process employing metal pentadienyl complexes |
US5407855A (en) * | 1993-06-07 | 1995-04-18 | Motorola, Inc. | Process for forming a semiconductor device having a reducing/oxidizing conductive material |
US5566045A (en) * | 1994-08-01 | 1996-10-15 | Texas Instruments, Inc. | High-dielectric-constant material electrodes comprising thin platinum layers |
US5555486A (en) * | 1994-12-29 | 1996-09-10 | North Carolina State University | Hybrid metal/metal oxide electrodes for ferroelectric capacitors |
US6133159A (en) | 1998-08-27 | 2000-10-17 | Micron Technology, Inc. | Methods for preparing ruthenium oxide films |
US6074945A (en) | 1998-08-27 | 2000-06-13 | Micron Technology, Inc. | Methods for preparing ruthenium metal films |
US6517616B2 (en) | 1998-08-27 | 2003-02-11 | Micron Technology, Inc. | Solvated ruthenium precursors for direct liquid injection of ruthenium and ruthenium oxide |
US6541067B1 (en) | 1998-08-27 | 2003-04-01 | Micron Technology, Inc. | Solvated ruthenium precursors for direct liquid injection of ruthenium and ruthenium oxide and method of using same |
US5962716A (en) | 1998-08-27 | 1999-10-05 | Micron Technology, Inc. | Methods for preparing ruthenium and osmium compounds |
US6063705A (en) | 1998-08-27 | 2000-05-16 | Micron Technology, Inc. | Precursor chemistries for chemical vapor deposition of ruthenium and ruthenium oxide |
-
1998
- 1998-08-27 US US09/141,431 patent/US5962716A/en not_active Expired - Lifetime
-
1999
- 1999-07-28 JP JP2000567541A patent/JP2002523516A/en active Pending
- 1999-07-28 WO PCT/US1999/017052 patent/WO2000012520A1/en not_active Application Discontinuation
- 1999-07-28 KR KR1020017002581A patent/KR100554486B1/en not_active IP Right Cessation
- 1999-07-28 AU AU52365/99A patent/AU5236599A/en not_active Abandoned
- 1999-08-11 TW TW088113757A patent/TW452603B/en not_active IP Right Cessation
- 1999-08-11 US US09/372,427 patent/US6114557A/en not_active Expired - Lifetime
- 1999-08-13 MY MYPI99003491A patent/MY126518A/en unknown
-
2000
- 2000-08-29 US US09/650,231 patent/US6576778B1/en not_active Expired - Lifetime
-
2003
- 2003-04-21 US US10/419,592 patent/US6872420B2/en not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5372849A (en) * | 1992-07-28 | 1994-12-13 | Minnesota Mining And Manufacturing Company | Chemical vapor deposition of iron, ruthenium, and osmium |
Non-Patent Citations (10)
Title |
---|
BURT, JENNIFER C. ET AL: "Hydrocarbon complexes of ruthenium. III. Reactions of cycloheptatrienes with ruthenium carbonyl", J. CHEM. SOC., DALTON TRANS. (1975), (8), 731-6, XP002118223 * |
CHEMICAL ABSTRACTS, vol. 109, no. 26, 26 December 1988, Columbus, Ohio, US; abstract no. 233267b, CHATZITHEODOROU, G. ET AL.: "low temperature chemical preparation of semiconducting transition metal chalcogenide films for energy conversion and storage, lubrication, and surface protection" XP002118225 * |
DEGANELLO, G. ET AL.: "the reaction of cis-bicyclo(6.2.0)deca-2,4,6-triene with dodecacarbonyltriruthenium", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 90, 1975, pages c31 - c33, XP002118831 * |
EDWARDS, ANDREW J. ET AL: "The photochemical generation of novel neutral mononuclear ruthenium complexes and their reactivity", J. ORGANOMET. CHEM. (1995), 503(1), 15-20, XP002118221 * |
FERRARI, R.P. ET AL.: "reactions of dodecacarbonyltriosmium with dienic ligands", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 182, 1979, pages 245 - 249, XP002118830 * |
MATER. RES. BULL., vol. 23, no. 9, 1988, pages 1261 - 1271 * |
SCHUMANN, H. ET AL.: "tricarbonylbis(tri-t-butylphosphinn)eisen(0) und -ruthenium(0)", JOURNAL OF ORGANOMETALLIC CHEMISTRY, vol. 166, 1979, pages 233 - 239, XP002118829 * |
SIEGL, W.O. ET AL.: "ruthenium(0) and ruthenium(II)complexes with 1,1,1-tris(diphenylphosphinomethyl)ethane", INORGANIC CHEMISTRY, vol. 12, no. 3, 1973, pages 674 - 677, XP002118828 * |
SOSINSKY, BARRIE A. ET AL: "Hydrocarbon complexes of ruthenium. IV. Cyclic dienyl complexes", J. CHEM. SOC., DALTON TRANS. (1975), (16-17), 1633-40, XP002118222 * |
WHITESIDES, THOMAS H. ET AL: "Cleavage of carbon-carbon sigma bonds by dodecacarbonyltriruthenium", J. CHEM. SOC., CHEM. COMMUN. (1973), (3), 87, XP002118224 * |
Also Published As
Publication number | Publication date |
---|---|
MY126518A (en) | 2006-10-31 |
JP2002523516A (en) | 2002-07-30 |
US6576778B1 (en) | 2003-06-10 |
TW452603B (en) | 2001-09-01 |
US6872420B2 (en) | 2005-03-29 |
KR100554486B1 (en) | 2006-03-03 |
KR20010073064A (en) | 2001-07-31 |
AU5236599A (en) | 2000-03-21 |
US5962716A (en) | 1999-10-05 |
US6114557A (en) | 2000-09-05 |
US20030212285A1 (en) | 2003-11-13 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5962716A (en) | Methods for preparing ruthenium and osmium compounds | |
US7973188B2 (en) | Processes for the production of organometallic compounds | |
EP1814892B1 (en) | Organometallic compounds and processes for preparation thereof | |
US20090208670A1 (en) | Organometallic compounds, processes for the preparation thereof and methods of use thereof | |
JP5265570B2 (en) | Method for depositing ruthenium-containing films | |
EP2307589B1 (en) | Method for deposition of transition metal-containing films using heteroleptic cyclopentadienyl transition metal precursors | |
KR20030023484A (en) | Ruthenium complex, manufacturing process thereof and the method for forming thin-film using the complex | |
WO2009094262A1 (en) | Organometallic compounds, processes and methods of use | |
WO2009094263A1 (en) | Organometallic compounds, processes and methods of use | |
US20090202740A1 (en) | Organometallic compounds, processes for the preparation thereof and methods of use thereof | |
US7959986B2 (en) | Organometallic compounds, processes for the preparation thereof and methods of use thereof | |
US20090042041A1 (en) | Pyrrolyl complexes of copper for copper metal deposition |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG UZ VN YU ZA ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SL SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 1020017002581 Country of ref document: KR |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 1020017002581 Country of ref document: KR |
|
122 | Ep: pct application non-entry in european phase | ||
WWR | Wipo information: refused in national office |
Ref document number: 1020017002581 Country of ref document: KR |