Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C257/00—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines
  • C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
  • C07C257/14—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to acyclic carbon atoms
• • 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
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
• • 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
  • C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
• • 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
  • C07F9/00—Compounds containing elements of Groups 5 or 15 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
  • C23C16/22—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
  • C23C16/34—Nitrides
• • 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
  • C23C16/405—Oxides of refractory metals or yttrium

Definitions

• This invention relates to novel compounds containing metals in the +4 oxidation state bonded to four amidinate ligands. This invention also relates to the use of these compounds as precursors for vapor deposition of metal-containing layers.
• high-k dielectrics electrically insulating materials with high dielectric constants
• DRAMs dynamic random access memories
• Aluminum oxide and tantalum oxide are currently in commercial use in DRAMs 5 and oxides, nitrides and silicates of hafnium and zirconium are being tested as alternatives for future use.
• These high-k materials may also be used as insulators in future transistors in microelectronic devices.
• Electrode conductive nitrides of metals such as tantalum, tungsten, hafnium, zirconium, titanium, niobium and molybdenum have a variety of applications and potential applications, such as barriers against the diffusion of copper, and as electrodes for capacitors and transistors in microelectronic devices. These refractory metals also find use as adhesion-promoting layers for copper, and as electrodes or electrical interconnections.
• Vapor deposition is a preferred method for making these materials.
• Vapor deposition is a generic term that comprises chemical vapor deposition (CVD) and atomic layer deposition (ALD).
• CVD chemical vapor deposition
• ALD atomic layer deposition
• a CVD process one or more vapors are delivered to a surface on which solid material is deposited; the chemical reactions that convert the vapor to a solid are initiated by means such as heat, light or electrical excitation (plasma activation).
• plasma activation atomic layer deposition
• ALD atomic layer deposition
• two or more vapors are delivered alternately to the surface on which reactions take place to deposit a solid product.
• ALD is capable of depositing these materials inside the very narrow structures in modern DRAMs.
• CVD generally provides higher deposition rates than ALD, but with less uniform deposition inside very narrow holes.
• One aspect of the invention includes novel compounds containing metals in the +4 oxidation state bonded to four amidinate ligands.
• these Hgands comprise ⁇ yV' -dialkylamidinate ligands.
• Preferred metals include hafnium, zirconium, tantalum, niobium, tungsten, molybdenum, tin, tellurium and uranium.
• the compound has the structural formula
• each of R 1 through R 12 are independently selected from the group consisting of hydrogen, hydrocarbon groups, substituted hydrocarbon groups, and other groups of non-metallic atoms.
• the hydrocarbon group is selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl and cycloalkynyl groups and the substituted hydrocarbon group consisting of fluoride derivatives of hydrocarbons, or the group comprising non-metallic atoms are selected from the group consisting of alkylsilyl and alkyl amino groups.
• the metal M is selected from the group consisting of zirconium, hafnium, tin, tantalum, niobium, tungsten, molybdenum, uranium, rhenium, platinum, osmium, indium, ruthenium, palladium, titanium, rhodium, vanadium, cerium and lead, or the metal M is selected from the group consisting of hafnium, zirconium, tantalum, niobium, tungsten, molybdenum, tin, tellurium and uranium.
• At least one of R 1 through R 12 is a lower alkyl having 5 or less carbons.
• R 1 through R 12 is selected from the group consisting of lower alkyls having 5 or less carbons and hydrogen.
• R 1 , R 3 , R 4 , R 6 , R 7 , R 9 , R 10 and R 12 are alkyl groups that are un-branched at the ⁇ -position.
• Another aspect of the present invention includes a process for depositing films comprising metals using the novel compounds according to one or more embodiments of the invention.
• the process includes exposing a heated surface to the vapor of one or more volatile metal tetra-amidinate compounds.
• Exemplary deposition methods include
• CVD Chemical Vapor Deposition
• ALD Atomic Layer Deposition
• the process includes exposing the substrate to a source of oxygen, and the thin film comprises a metal oxide.
• the source of oxygen comprises water vapor, or dioxygen, or ozone.
• the process includes exposing the substrate to a source of nitrogen, and the thin film comprises a metal nitride.
• the source of nitrogen comprises ammonia.
• the vapor is obtained by vaporizing a solid metal tetra-amidinate compound, or by vaporizing a liquid metal tetra-amidinate compound.
• the vapor is obtained by vaporizing a metal tetra-amidinate at a temperature in the range of 100 to 250 0 C.
• the surface is at a temperature in the range of about 200 to 500 0 C.
• Fig. 1 is a schematic cross-sectional drawing of an ALD apparatus that can be used in some embodiments of the invention
• Fig. 2 is a drawing of the molecular structure of tetra ⁇ s(NJsf'-di-iso- butylacetamidinato) zirconium(IV);
• Fig. 3 is a drawing of the molecular structure of tetrakis(iV " ,/V'- dimethylpropionamidinato) hafnium(IV).
• Fig. 4 is a graph of the evaporation rates of 4 hafnium amidinates. Detailed Description of the Invention
• the present invention provides thermally stable, volatile metal compounds that are suitable for use in vapor deposition processes, including chemical vapor deposition and atomic layer deposition.
• Preferred compounds include volatile metal(IV) tetrakis(JV,iV" ⁇ d ⁇ alkylamidinates) complexes. Typically, these compounds are described by a monomelic formula 1,
• R n 1 12
• R n applies equally to each of R 1 through R 12 , unless otherwise specified.
• R n are lower alkyl groups containing 5 or less carbons.
• R" are a mixture of hydrogen and lower alkyl groups.
• R" are chosen from the group comprising methyl, ethyl and /j-propyl. These small alkyl groups are preferred because they are small enough to fit into the structure 1 with very stable chelate binding.
• one or more of R 1 , R 3 , R 4 , R 6 , R 7 , R 9 , R 10 , or R 12 are hydrocarbon groups lacking a branched ⁇ -carbon. As used herein, an ⁇ -carbon is a carbon bound directly to one nitrogen of an amidinate ligand.
• Alkyl groups that branch at the ⁇ -carbon are less preferred because they are likely to cause too much crowding to fit into structure 1.
• the branched alkyl groups will generally provide less stable metal amidinates. Nonetheless, branched groups are contemplated according to one or more embodiments, in particular, where a larger metal center is used or the branching occurs beyond the ⁇ -carbon.
• Exemplary tetravalent metals that may be used in one or more embodiments of the invention include zirconium, hafnium, tin, tantalum, niobium, tungsten, molybdenum, uranium, rhenium, platinum, osmium, iridium, ruthenium, palladium, titanium, rhodium, vanadium, cerium, tellurium and lead.
• Tetravalent metal ions having relatively larger ionic radii form tetra-amidinate complexes that are particularly stable; those metals include zirconium, hafnium, tin, tantalum, niobium, tungsten, molybdenum, tellurium and uranium.
• Tetravalent metal ions having relatively smaller ionic radii that form tetra- amidinate include rhenium, platinum, osmium, indium, ruthenium, palladium, titanium, rhodium and vanadium.
• the amidinate ligand is symmetric, e.g., the N- bound R groups such as R 1 and R 3 or R 4 and R 6 , etc., are the same in formula 1.
• the amidinate ligand is asymmetric, e.g., R 1 and R 3 are different in formula 1.
• the carbon-bound R group, e.g., R 2 in formula 1 can be the same or different.
• metal tetrakis(-YiV-dialkylaniidmate) compounds are prepared using i ⁇ f,N'-dialkylamidines.
• Symmetric amidines may be formed by condensation of amines with nitriles catalyzed by lanthanum trifluoromethanesulfonate (also known as lanthanum triflate), La(CF 3 SO 3 ) 3 :
• Metal amidinates can be prepared by exchange reactions in which a metal dialkylamide is reacted with an amidine.
• the amidine can be converted to its alkali salt by reaction with butyllithium or with sodium amide or with potassium hydride.
• the alkali amidinate can then undergo a salt metathesis reaction with a metal chloride to form the metal amidinate.
• a more commonly-used method to form lithium amidinates is to react a carbodiimide with a lithium alkyl. This conventional synthetic route is more effective when the R 1 and R 3 alkyl groups are branched at the ⁇ -position, because the corresponding carbodiimides are more stable.
• the metal tetra-amidinate compounds may be used to form metal-containing films in a vapor deposition process.
• Vapors of the compounds according to one or more embodiments may be used to deposit materials such as metals, metal oxides, metal nitrides, metal oxynitrides, metal sulfides and the like.
• These vapor deposition processes include CVD and ALD.
• CVD a vapor of the metal tetra-amidinate is supplied to the surface, optionally along with a co-reactant gas or vapor.
• ALD a vapor of the metal tetra-amidinate and a co-reactant are supplied to the surface in alternating time periods.
• CVD processing is described, for example, in US Patent 5,139,999, which is hereby incorporated by reference, and in the "Handbook of Chemical Vapor Deposition: Principles, Technology and Applications” by Hugh O. Pierson (2 nd edition, Noyes Publications, 1999).
• ALD processing is described in US Patent 6,969,539, which is hereby incorporated by reference, and in the article "Atomic Layer Deposition” by M. Ritala and M. Leskela, vol. 1, p. 103 of the Handbook of Thin Film Materials (Ed. H. Nalwa, Academic Press, 2002).
• Oxides may be formed using co-reactants such as water vapor, dioxygen, ozone, hydrogen peroxide and alcohols or a plasma formed from an oxygen-containing gas or vapor.
• Nitrides may be formed using co-reactants such as ammonia, a hydrazine or a plasma formed from a nitrogen-containing gas or vapor.
• Sulfides may be formed using co-reactants such as hydrogen sulfide or a plasma formed from a sulfur-containing gas or vapor.
• FIG. 1 An apparatus for carrying out ALD is shown schematically in cross-section in Fig. 1.
• carrier gas such as nitrogen
• a tetra-amidinate precursor 21 is held in vessel 11 that is heated in oven 41 to a temperature sufficient to form its vapor 31.
• Vapor 31 of the tetravalent amidinate precursor flows into evacuated chamber 61 in oven 81 when valve 51 is opened.
• Valve 51 is then closed and valve 71 opened to allow an aliquot of precursor vapor to flow over the substrate 130 inside heated furnace 120.
• Valve 71 is then closed and time is allowed for excess unreacted precursor to be purged from chamber 110 along with volatile reaction byproducts.
• the second reagent 22, such as water or ammonia, is placed in vessel 12, usually kept at room temperature. Vapor 32 of the second reagent is allowed to flow into vapor space 62 by opening valve 52, which is then closed. Valve 72 is opened to allow an aliquot of the second reagent to flow into the deposition chamber 110. Valve 72 is then closed and time is allowed for unreacted excess of the second reagent to be purged from the deposition chamber 110 along with volatile reaction byproducts. This cycle of operations is then repeated to build up the desired thickness of coating on substrate 130.
• An apparatus for carrying out CVD includes many similar features.
• the apparatus may include a vessel housing a tetra-amidinate precursor that is heated to a temperature to form its vapor.
• the tetra-amidinate precursor vapor flows from the vessel and into a heated furnace housing the substrate. Additional co-reactant vapors may be introduced into the heated furnace with the tetra-amidinate precursor, or the co-reactant vapors may be premixed with the tetra-amidinate vapor prior to their exposure to the heated substrate.
• An exhaust system removes by-products and unreacted reactants from the furnace.
• the tetra-amidinate precursor may be used as a neat liquid, in solution in the appropriate solvent, or as a solid.
• Suitable deposition conditions such as temperatures for vaporization and deposition, pressures, flow rates, and co-reactants may be readily determined by one of skill in the art.
• Exemplary ALD and CVD conditions include substrate temperatures of 200 to 500 0 C, and more preferably 300 to 400 0 C, vapor pressures in the range of 0.1 to 10 Torr, and more preferably 1 to 5 Torr, vaporization temperatures of about 100 to 25O 0 C, and more preferably 150 to 200 0 C, ALD doses of 1 to 100 nmol cm "2 of deposited surface, and more preferably 2 to 20 nmol cm "2 , and ALD exposures of 0.01 Torr-sec to 10 Torr-sec, and more preferably 0.1 to 1 Torr-sec.
• the ALD exposures needed to cover features with high aspect ratios increase approximately as the square of the aspect ratio. Examples
• This compound was prepared in a way similar to that described in Example 2 for Zr( 1 Bu-AMD) 4 , starting from 3 mmol of tetrakis(dimethylamido)hafnium(IV), Hf(NMe 2 ) 4 .
• the product was isolated as a white powder. Yield: 2.17g (85%).
• the lithium salt of A ⁇ TV-dimethylacetamidine was prepared by dissolving one volume of ⁇ W-dimethylacetamidine in 5 volumes of dry ether and cooling the solution to -78°C. An equal molar amount of butyllithium dissolved in hexanes was added slowly while stirring. The reaction mixture was allowed to warm to room temperature. The ether and pentane were removed under reduced pressure. Then the white solid residue was dissolved in dry dioxane. The resulting solution of ⁇ f ⁇ f'-dimethylacetamidinato-lithium in dioxane was used in some of the following examples.
• This compound was prepared by ligand exchange in a way similar to that described in Example 2 for Zr( 1 Bu-AMD) 4 , using iVyV'-dimethylacetamidine in place of iv " ,iV'-dw.so-butylacetamidine.
• ZrCl 4 was reacted with the lithium salt of NjAT-dimethylacetamidine dissolved in dioxane (salt metathesis reaction). This reaction mixture was heated to reflux for 8 hours. After evaporation of the dioxane, the solid residue was extracted with pentane.
• Example 6 Synthesis of tetrakis(MN'-dimethylacetarnidinato)hafniurn(IV). [0045] This compound was prepared from HfCl 4 by the salt metathesis reaction described in Example 5. 1 H NMR (benzene- ⁇ i 6 , ppm): 3.07 (s, 24, NCH 3 ), 1.55 (s, 12, CCH ⁇ ). 13 C NMR (benzene-d ⁇ , ppm): 175.69 (s, CCH 3 ), 34.31 (s, NCH 3 ), 10.09 (s, CCH 3 ). Anal. Calcd. for Ci 6 H 36 HfN 8 : C 37.03, H 6.99, N 21.59.
• a dioxane solution of lithium A ⁇ V'-dimethylpropionarnidinate was prepared by the method described in Example 4, using propionitrile in place of acetonitrile. This solution was then used with ZrCl 4 in the salt metathesis method described in Example 5 to prepare tetrakis(jV,N'-dimethylpropionamidinato)zirconium(IV). This compound may also be prepared by a ligand exchange reaction similar to the one described in Example 2.
• a dioxane solution of lithium iVyV'-dimethylbutyramidinate was prepared by the method described in Example 4, using butyronitrile in place of acetonitrile. This- solution was then used with ZrCU in the salt metathesis method described in Example 5 to prepare tetrakis( ⁇ , ⁇ A'-dimethylbutyramidinato)zirconium(IV).
• This compound may also be prepared by a ligand exchange reaction similar to the one described in Example 1. The compound is a liquid at room temperature, so it was purified by distillation instead of sublimation.
• Example 10 Synthesis of tetrakisfT/JV-dimethylbutyramidinato ⁇ afniumflV).
• This compound was prepared from HfCU by the salt metathesis reaction described in Example 9. It may also be prepared by a ligand exchange reaction similar to the one described in Example 1. The compound is a liquid at room temperature, so it was purified by distillation instead of sublimation.
• a dioxane solution of lithium iVyV'-diethylacetamidinate was prepared by the method described in Example 4, using ethylamine in place of methylamine. This solution was then used with ZrCl 4 in the salt metathesis method described in Example 5 to prepare tetrakis( ⁇ N'-diethylacetamidinato)zirconium(IV). It may also be prepared by a ligand exchange reaction similar to the one described in Example 1.
• Example 12 Synthesis of tetrakisfM//'-diethylacetamidinato)hafhi ⁇ mfrV).
• This compound was prepared from HfCl 4 by the salt metathesis method described in Example 11. It may also be prepared by a ligand exchange reaction similar to the one described in Example 1.
• the first step involved the addition under nitrogen at -78 0 C of an ether solution of tantalum pentachloride (0.95 mmol, 331 mg in 20 mL ether) to a solution of lithium N,N'- di ethyl acetamidinate (2 mmol in 20 mL ether, prepared in situ from the amidine and a hexanes solution (2.6 M) of n-butyl lithium).
• the intermediate tentatively described as trischloro-bis ⁇ yW'-diethylacetamidinato ⁇ antalumCV) was partially soluble in ether, giving an orange solution.
• Compounds containing other metal centers can be prepared in ways similar to those described in Example 3, by using a suitable metal source in place of ZrCLj.
• tetrakis ⁇ W-dimethylacctamidinato) tungsten(IV) is prepared using tungsten(IV) chloride, WCU;
• tetrakis( ⁇ N'-dimethylacetamidinato)tin(IV) is prepared using tin(IV) chloride, SnCU;
• tetrakis(iV,A/"-dimethylacetamidinato)telIurium(IV) is prepared from TeCl 4 ;
• tetrakis(N y /V'-dimethylacetamidinato)uranium(IV) is prepared in using uranium(IV) chloride, UCl 4 .
• Example 15 Atomic layer deposition of hafnium oxide from tetrakisfA/JV- dimethylbutyramidinato)hafnium(TV " ) and ozone.
• 10 nmol cm " doses of the vapor of tetrakis( ⁇ v " '- dimethylpropionamidinato)hafnium(rV) from a direct liquid injection system at 200 0 C are introduced with an exposure of 10 Torr-sec in to an ALD reactor at 400 0 C, alternately with 20 nmol cm '2 doses of ozone at an exposure of 10 Torr-sec.
• a film of hafnium oxide is deposited conformally inside narrow holes with high aspect ratio of 80: 1.
• Example 16 Atomic layer deposition of hafnium oxide from tetrakisfM,7y'- dimethylbutyramidinato)hafniumfrSO and water vapor.
• thermogravimetric analyses of evaporation rates are compared in Fig. 4 for 4 different hafnium arnidinates (from Examples 6, 8, 10 and 19). These measurements show that at each temperature tetrakis( ⁇ V"- dimethylformidinato)hafnium(rV) (Ex. 20) has the highest evaporation rate. At bubbler temperatures above 142 0 C (its melting point) it is a liquid, so that its high evaporation rate is very reproducible. Thus in many applications, tetrakis(Ayv " '- dimethylformidinato)hafnium(rV) is a preferred precursor for vapor deposition of hafnium-containing materials.
• a liquid at room temperature In applications for which a liquid at room temperature is required, it may be supplied as a liquid solution in a solvent with a similar boiling point. Suitable solvents include polyethers, such as triglyme or tetraglyme. Alternatively, the room-temperature liquid tetrakis( ⁇ VV'-dimethylbutyramidinato)hafnium(rV) may be used for neat liquid delivery to a vaporization system.
• Example 21 Synthesis of tetrakisfJVJV '-dimethylformamidinato)zirconium(IV) .

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Chemical Vapour Deposition (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Formation Of Insulating Films (AREA)

Priority Applications (3)

Applications Claiming Priority (4)

Publications (1)

Family

ID=40328880

Family Applications (1)

Country Status (5)

Cited By (30)

Families Citing this family (8)

Citations (2)

Family Cites Families (5)

• 2007
  • 2007-06-26 KR KR1020097001242A patent/KR101467587B1/ko active Active
  • 2007-06-26 EP EP07796442A patent/EP2032529B1/en active Active
  • 2007-06-26 WO PCT/US2007/014768 patent/WO2008002546A1/en not_active Ceased
  • 2007-06-26 JP JP2009518210A patent/JP5555872B2/ja active Active
  • 2007-06-26 CN CN2012104614215A patent/CN102993050A/zh active Pending
  • 2007-06-26 CN CN2007800298108A patent/CN101500989B/zh active Active
• 2013
  • 2013-04-09 JP JP2013081411A patent/JP2013209375A/ja active Pending

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events