Classifications

• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/04—Hydrides of silicon
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/08—Compounds containing halogen
  • C01B33/107—Halogenated silanes
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/08—Compounds containing halogen
• • 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
  • C07F7/02—Silicon compounds
  • C07F7/025—Silicon compounds without C-silicon linkages
• • 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
  • C07F7/02—Silicon compounds
  • C07F7/21—Cyclic compounds having at least one ring containing silicon, but no carbon in the ring
• • 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
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/54—Quaternary phosphonium compounds
  • C07F9/5442—Aromatic phosphonium compounds (P-C aromatic linkage)

Definitions

• Cyclohexasilane can be employed as a liquid precursor for electronics grade silicon materials and devices.
• Cyclohexasilane is a relatively benign, liquid phase alternative to gaseous SiH 4 and/or corrosive trichlorosilane (HS1CI 3 ) in the various processes and technologies adopted in silicon-based electronic industries.
• Existing methods of producing theY 2 Si 6 Cli 4 intermediate salt typically use nucleophilic organic amines as ligands. Such syntheses are prone to extensive side reactions that deplete useful starting materials and give low yields of the intermediate Y 2 Si 6 Cli 4 salt (typically approximately 10%).
• the present application is directed to a method of preparing a cyclohexasilane compound from trichlorosilane.
• the method includes contacting trichlorosilane with a reagent composition to produce a compound containing a tetradecahalocyclohexasilane dianion, e.g., a tetradecachlorocyclohexasilane dianion.
• the reagent composition typically comprises (a) tertiary polyamine ligand, e.g., alkyl substituted polyalkylenepolyamme; and (b) deprotonating reagent, which includes a compound other than a polyamine ligand.
• the deprotonating reagent may include a tertiary amine having a pKa of at least about 10.5 and often 11 or higher. Depending on the reaction components and conditions, reaction times of 1 to 72 hours may commonly be employed, with relatively short reaction times (e.g., 2-10 hours) being desirable.
• the present method can provide greatly enhanced yields of the tetradecachlorocyclohexasilane dianion product.
• the reagent composition may comprise (a) tertiary polyalkylenepolyamme; and (b) deprotonating reagent, such as a trialkyl amine having a pKa of at least about 10.5.
• the tertiary polyamine ligand may be a polyamine containing nitrogen atoms with only alkyl, aryl and/or aralkyl substituents (desirably alkyl and/or aralkyl). Examples of suitable tertiary polyalkylenepolyamines include
• pentaalkyldiethylenetriamines and tetraalkylethylenediamines such as ⁇ , ⁇ , ⁇ ', ⁇ '- tetraethylethylenediamine (TEED A) and N,N,N',N",N"-pentaethyldiethylenetriamine (PEDETA), as well as N,N,N',N'-tetraalkyl-N"-benzyldiethylenetriamines, such as
• the reagent composition may desirably include tertiary amine having a pKa of at least about 10.5. Suitable examples include tertiary amines having a pKa of at least about 10.5, where the tertiary amine is substituted with three alkyl, aryl and/or aralkyl substituent groups.
• the reagent composition may include N,N-diisopropylalkylamine and/or N,N-diisobutylalkylamine, where the alkyl group is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and/or other branched/linear alkyl groups (desirably having no more than 6 carbon atoms).
• the tertiary amine may also be substituted with one or more aralkyl groups such as a benzyl and/or phenethyl.
• the reagent composition may include a tri-n-alkylamine, where the n-alkyl groups typically have no more than 6 carbon atoms (e.g., triethylamine, tri-(n-propyl)amine and/or tn-(n- butyl)amine).
• a tri-n-alkylamine where the n-alkyl groups typically have no more than 6 carbon atoms (e.g., triethylamine, tri-(n-propyl)amine and/or tn-(n- butyl)amine).
• tertiary amines include NNN',N'-tetraalkyl-l,8- naphalenedi amines where the alkyl groups are desirably Ci— C 6 alkyl and preferably methyl (e.g., NNN',N'-tetramethyl-l,8-naphthalenediamine and/or NNN',N'-tetraethyl-l,8- naphthalenediamine) .
• a deprotonating reagent such as a high pKa tertiary amine (e.g., a trialkylamine having a pKa of at least about 10.5) gives improved yields of tetradecahalocyclohexasilane dianion salt, e.g., tetradecachlorocyclohexasilane dianion salt, when used in combination with PEDETA as the polyamine ligand.
• a high pKa tertiary amine is used with TEEDA as the polyamine ligand in combination with a quaternary salt, such as a tetraarylphosphonium salt.
• a sterically-hindered, tertiary amine e.g., EDIPA ®
• EDIPA ® a sterically-hindered, tertiary amine
• the absence of a deprotonating reagent (e.g., a sterically-hindered, tertiary amine) in the reagent composition often gives low product yield (commonly ⁇ 10%) due largely to the occurrence of unwanted side reactions.
• Methods of converting the tetradecahalocyclohexasilane dianion-containing compound to cyclohexasilane or a dodecaorganocyclohexasilane are also provided.
• the tetradecahalocyclohexasilane dianion-containing compound produced by the present method may be converted into cyclohexasilane through reaction with a metal hydride reducing agent.
• the tetradecahalocyclohexasilane dianion-containing compound may also be reacted with a reagent having a formula RMgX (wherein R is alkyl or aryl and X is a halide) to produce a dodecaorganocyclohexasilane compound.
• a reagent having a formula RMgX wherein R is alkyl or aryl and X is a halide
• the present application relates to the use of a deprotonating reagent, such as a relatively high pKa tertiary amine (e.g., N,N-diisopropylamine (EDIPA ® ) - a sterically- hindered, non-nucleophilic amine) and may also employ a quaternary counterion material, such as a phosphonium counterion material to decrease side-reactions and facilitate efficient precipitation of the desired tetradecachlorocyclohexasilane dianion product.
• a deprotonating reagent such as a relatively high pKa tertiary amine (e.g., N,N-diisopropylamine (EDIPA ® ) - a sterically- hindered, non-nucleophilic amine) and may also employ a quaternary counterion material, such as a phosphonium counterion material to decrease side
• TEED A as the polyamine ligand and EDIPA ® as the deprotonating reagent leads to a 7 X or higher enhancement in the yield of tetradecachlorocyclo-hexasilane dianion salt (Y 2 S1 6 CI 14 ) when PI1 4 PCI is used to introduce the counterion material.
• a suitable quaternary salt is a quaternary ammonium salt.
• a high pKa tertiary amine e.g., EDIPA ® or triethylamine (TEA)
• TEEDA triethylamine
• Suitable tertiary polyamine ligands include tertiary
• polyalkylpoly-alkeneamines tertiary polyalkylenepolyalkeneamines, tertiary
• Suitable tertiary polyamine ligands may also include tertiary polyalkylenepolyamines that are substituted with a mixture of alkyl and/or aralkyl substituent groups on the nitrogen atoms.
• Examples include, but are not limited to, N,N,N',N'-tetraalkyl-N"-benzyldiethylene-triamines, such as NNN',N'-tetraethyl-N"- benzyldiethylenetriamine and related derivatives where the alkyl and/or benzyl groups are replaced with hydrocarbon or organosilicon groups.
• Sterically-hindered tertiary amines such as EDIPA ® are suitable for use as deprotonating reagents when used in combination with polyamines according to the present method.
• the sterically-encumbered nature and relatively high pKa (i.e., 11.3) of EDIPA ® can enhance the efficiency of proton abstraction while limiting its role to act as a nucleophile. Both features are believed to limit the formation of unwanted side products such as silicon tetrachloride.
• the yields of the tetradecachlorocyclohexasilane dianion product may also be enhanced through the use of other tertiary amines to act as a high pKa, proton abstractor (i.e., deprotonating reagent) thereby allowing the tertiary polyamine (e.g., PEDETA) to function as a polydentate ligand.
• tertiary polyamine e.g., PEDETA
• Suitable high pKa tertiary amines include N,N-diisopropyl- aralkylamines, N,N-isopropyldiaralkylamines, N,N-diisopropylarylamines, N,N-diarylalkyl- amines, N,N,N-triarylamines and/or N,N,N-triaralkylamines, where such tertiary amines preferably have a pKa of at least about 10.5.
• Suitable high pKa tertiary amines include alkylated cyclic amines such as N-alkyl piperazines, N-aralkyl-substituted piperazines, N-alkyl pyrrolidines and N-aralkyl-substituted pyrrolidines.
• the N-alkyl piperazines and N-alkyl pyrrolidines may desirably include a bulky alkyl group as a substituent on the nitrogen atom (e.g., N- isopropyl, N-isobutyl or N-cyclohexyl).
• the carbon atom(s) immediately adjacent the nitrogen atom in the cyclic amine may be substituted with one or more alkyl groups.
• N-alkyl pyrrolidines examples include N-isopropylpyrrolidine, N-ethyl-2- methylpyrrolidine and N-benzyl-pyrrolidine.
• suitable N-alkyl piperazines include N-isopropylpiperazine, N-ethyl-2-methylpiperazine and N-phenethylpiperazine.
• Such tertiary, alkylated cyclic amines desirably have a pKa of at least about 10.5.
• deprotonating reagents include metal hydride reagents.
• metal hydrides such as LiH, NaH, KH, MgH 2 , CaH 2 , SrH 2 and BaH 2 are known to be good deprotonating agents and may be used in place of or in conjunction with tertiary amine deprotonating reagents.
• Typical examples of such metal amides are lithium diisopropylamide (LiN(i-Pr) 2 ) and sodium hexamethyldisilazide (NaN(SiMe 3 ) 2 ).
• the trichlorosilane can be contacted with the reagent composition in any standard reactor suitable for contacting a chlorosilane with another reactant.
• the reactor can be, for example, a continuous-stirred batch type reactor, a semi- batch type reactor or a continuous type reactor.
• the use of a sealed reactor can also allow the reaction to be run at temperatures above the boiling point of the solvent or other components of the reaction mixture (e.g., HS1CI 3 , bp 32°C).
• the present method is preferably carried out under substantially anhydrous conditions. This can be accomplished by purging the reactor with a dry inert gas such as nitrogen or argon and thereafter maintaining a blanket of such inert gas in the reactor. Often all glassware items are cleaned and dried at 140-150 °C for at least several hours prior to use. All procedures may be performed under nitrogen and/or argon atmosphere using standard Schlenk techniques.
• a dry inert gas such as nitrogen or argon
• Y 2 S1 6 CI 14 can be prepared via the present method in the absence of a diluent, the step of contacting trichlorosilane with the reagent composition is typically carried out in the presence of an organic solvent.
• organic solvent Any organic solvent or mixture of organic solvents that does not interfere with the coupling reaction of trichlorosilane to form the tetradecachlorocyclohexasilane dianion can be used.
• the organic solvent may include haloorganic solvents such as chloroform, dichloromethane and/or 1,2-dichloroethane. Quite often, the organic solvent is dichloromethane and/or 1,2-dichloroethane.
• the amount of organic solvent is typically 0.01-100 (preferably 0.5-10) times the volume of all combined reagents.
• the trichlorosilane may be contacted with the reagent composition at temperatures from 0 to 120°C with common reaction temperatures from 20 to 75°C (preferably ⁇ 40 to 65°C). Higher temperatures may be achieved under elevated pressures or in a higher boiling point solvent under reflux conditions. Trichlorosilane may be contacted with the reagent composition at a temperature of 15 to 75°C and often about 25 to 65°C. In some embodiments, the trichlorosilane may be introduced into the reaction mixture at relatively low temperatures, e.g., from -40 to 25°C. After the addition of trichlorosilane is complete, the reaction is typically allowed to proceed at the higher temperatures noted above.
• the compound containing the tetradecachlorocyclohexasilane dianion may be isolated from the reaction mixture by crystallization/precipitation.
• recovery of the compound containing the tetradecachlorocyclohexasilane dianion can be achieved by adding sufficient quantities of organic solvents that promote crystallization. Crystallization may take place at or below room temperature.
• the compound containing the tetradecachlorcyclohexasilane dianion can be recovered from the reaction mixture by adding sufficient quantities of organic solvents that aid precipitation of the compound (e.g., by adding a hydrocarbon non-solvent to a solution of tetradecachlorocyclohexasilane dianion salt in chlorinated organic solvent).
• organic solvents e.g., by adding a hydrocarbon non-solvent to a solution of tetradecachlorocyclohexasilane dianion salt in chlorinated organic solvent.
• Such mixtures would utilize a chlorinated organic solvent (e.g., CH 2 CI 2 and/or C 2 H 4 CI 2 ) and/or an aliphatic hydrocarbon (e.g., pentane, hexane and/or cyclohexane), and/or an ether (e.g., diethyl ether and/or tetrahydrofuran) and/or an aromatic hydrocarbon (e.g., benzene and/or toluene) solvent.
• a chlorinated organic solvent e.g., CH 2 CI 2 and/or C 2 H 4 CI 2
• an aliphatic hydrocarbon e.g., pentane, hexane and/or cyclohexane
• an ether e.g., diethyl ether and/or tetrahydrofuran
• aromatic hydrocarbon e.g., benzene and/or toluene
• Any organic solvent or mixture of such solvents that effects crystallization or precipitation of the compound containing the tetradecachlorocyclohexasilane dianion from the reaction mixture and does not react with the compound being recovered may be used in the present method.
• suitable organic solvents include hydrocarbons such as pentane, hexane, heptane, octane and nonane as well as ethers such as diethyl ether and tetrahydrofuran.
• the organic solvents used for effecting crystallization or precipitation of the compounds produced by the present method are pentane, hexane, heptane, octane or nonane.
• a particularly suitable solvent is pentane.
• tetradecachlorocyclohexasilane dianion can be chemically reduced to cyclohexasilane.
• the reduction reaction can be carried out by contacting the compound containing the tetradecahalocyclohexasilane dianion with a metal hydride reducing agent in an organic solvent at temperatures from -110 to 150 °C.
• Suitable reducing agents include lithium aluminum hydride and diisobutylaluminum hydride.
• tetradecachlorocyclohexasilane dianion can also be contacted with a Grignard reagent to form a dodecaorganocyclohexasilane.
• the Grignard reagent is represented by the formula PvMgX wherein R is alkyl or aryl and X is CI, Br or I. Suitable R groups include, but are not limited to, methyl, ethyl, propyl, tert-butyl and phenyl.
• reaction of the compound containing the tetradecahalocyclohexasilane dianion with Grignard reagents can be performed by standard methods known in the art for reacting chlorosilanes with Grignard reagents.
• a 3L three neck round-bottomed flask (previously dried in an oven at 140 °C) equipped with a magnetic stirrer and a Friedrichs condenser was flushed with nitrogen.
• the flask was charged with dichloromethane (400 mL) followed by N,N,N',N",N"- pentaethyldiethylenetriamine (PEDETA, 115.4 g, 474 mmol). To this mixture,
• a blended solvent system Such mixtures would utilize a chlorinated organic solvent (e.g., CH 2 CI 2 and/or C 2 H 4 CI 2 ) and/or an aliphatic hydrocarbon (e.g., pentane, hexane and/or cyclohexane), and/or an ether (e.g., diethyl ether and/or tetrahydrofuran) and/or an aromatic hydrocarbon (e.g., benzene and/or toluene). Reactions were performed using dichloromethane-based mixtures with benzene, tetrahydrofuran and cyclohexane.
• a chlorinated organic solvent e.g., CH 2 CI 2 and/or C 2 H 4 CI 2
• an aliphatic hydrocarbon e.g., pentane, hexane and/or cyclohexane
• an ether e.g., diethyl ether and
• the time for producing Si 6 Cli 4 salts can be reduced from the usual 42-72 h described in the examples above to about 7 h using a number of alternate reaction conditions.
• the general approach was to conduct the reaction in a sealed reaction vessel capable of withstanding medium pressures (up to about 20 bar). Energy/heat was introduced to the reaction mixture using a variety of methods as described below with control reactions performed at room temperature for 5 days.
• the general reaction scheme unless otherwise specified, is as given below:
• the resulting solution was cooled to - 30 °C and the septum on the reaction vial was quickly replaced with a medium pressure (20 bar) crimp cap.
• the solution was heated for various periods using an oil bath maintained at 60 °C for conventional thermal reactions.
• similar solutions were placed in a Biotage Initiator microwave or a conventional ultrasonic cleaning bath.
• TEEDA and PPh 4 Cl as the ligand and the counter ion source, respectively, instead of PEDETA.
• the product mixtures were cooled to -30 °C for 23 h after the reaction period. Sonochemical reactions and room temperature control experiments were performed at one-quarter scale using -0.5 g PEDETA, -0.8 g EDIPA ® and -1.0 g trichlorosilane.
• a cyclohexasilane compound may be prepared by a method comprising contacting trichlorosilane with a reagent composition, which comprises (a) tertiary polyamine, e.g., tertiary polyalkylenepolyamme; and (b) tertiary amine having a pKa of at least about 10.5 to produce a compound containing a reagent composition, which comprises (a) tertiary polyamine, e.g., tertiary polyalkylenepolyamme; and (b) tertiary amine having a pKa of at least about 10.5 to produce a compound containing a reagent composition, which comprises (a) tertiary polyamine, e.g., tertiary polyalkylenepolyamme; and (b) tertiary amine having a pKa of at least about 10.5 to produce a compound containing a reagent composition, which comprises
• the reaction mixture typically comprises tertiary polyamine ligand, deprotonating reagent and trichlorosilane in a molar ratio of tertiary polyamine ligand: deprotonating reagent: trichlorosilane from 1 :3:3 to 1 :400:700.
• reaction mixture which comprises tertiary polyalkylenepolyamme, trialkylamine and trichlorosilane in a the mole ratio of tertiary polyalkylenepolyamine: trialkylamine: trichlorosilane from 1 :3:3 to 1 :400:700.
• reaction mixture which comprises the tertiary polyalkylenepolyamine, the trialkylamine and trichlorosilane in a the mole ratio of tertiary polyalkylenepolyamine: trialkylamine: trichlorosilane from 1 :3:5 to 1 :30:50.
• a reagent composition which comprises (a) nucleophilic tertiary polyamine; (b) sterically-hindered, non-nucleophilic amine to produce a compound containing a tetradecachlorocyclohex
• the present method includes contacting trichlorosilane with a reagent composition comprising (a) tertiary polyamine ligand; and (b) high pKa tertiary amine (e.g., a tertiary amine having a pKa of at least 10.5).
• the tertiary polyamine ligand may include tertiary polyalkylenepolyamine.
• the tertiary amine may include sterically-hindered, non-nucleophilic amines such as N,N-diisopropylalkylamine and/or an N,N-diisobutylalkylamine.
• the tertiary polyamine ligand may be a fully alkylated polyamine, such as a pentaalkyldialkylenetriamine, tetraalkylalkylenediamine or
• the tertiary polyamine ligand may include N,N,N',N",N"-penta(n- alkyl)diethylenetriamine and/or N,N,N',N-tetra(/7-alkyl)ethylenediamine.
• pentaalkyldiethylenetriamines and tetraalkylethylenediamines for use in the present method include N,N,N',N-tetraethylethylenediamine (TEED A) and
• PEDETA N,N,N:N",N"-pentaethyl-diethylenetriamine
• the reagent composition may further comprise a quaternary salt, such as a tetraarylphosphonium salt (e.g., a tetraarylphosphonium halide).
• a tetraarylphosphonium salt e.g., a tetraarylphosphonium halide.
• Suitable examples of tetraarylphosphonium salts for use in the present method comprise tetraphenylphosphonium halides (e.g., Ph 4 PCl, Ph 4 PBr and/or Ph 4 PI).
• the tetradecachlorocyclo-hexasilane dianion-containing reaction product may be isolated as a tetraarylphosphonium salt, such as the compound having the formula (Ph 4 P) 2 (Si6Cli 4 ).
• the reaction mixture typically comprises the quaternary salt, tertiary polyamine ligand, deprotonating reagent and trichlorosilane in a molar ratio of quaternary salt: tertiary polyamine ligand: deprotonating reagen trichlorosilane from 1 : 1 :3:5 to 100: 1 :400:600.
• reaction mixture which comprises the quaternary salt, tertiary polyalkylenepolyamine, tertiary amine (e.g., trialkylamine) and trichlorosilane in a molar ratio of quaternary salt: tertiary polyalkylenepolyamine: tertiary amine :trichlorosilane from 1 : 1 :3:5 to 100: 1 :400:600.
• reaction mixture which comprises tetraarylphosphonium chloride, N,N,N',N'-tetraalkylethylenediamine, trialkylamine and trichlorosilane in a molar ratio of tetraarylphosphonium chloride N,N,N',N '- tetraalkylethylenedi amine: trialkylamine: trichlorosilane from 1 : 1 :3:5 to 1 :30:40:60.
• the present method includes contacting trichlorosilane with a reagent composition to form a compound containing a
• tetradecahalocyclohexasilane dianion such as a tetradecachlorocyclohexasilane dianion
• the reagent composition comprises (a) tertiary polyamine ligand; and (b) high pKa tertiary amine.
• the tetradecachlorocyclohexasilane dianion-containing compound may be contacted with a reagent having a formula RMgX (wherein R is alkyl or aryl and X is chloro, bromo, or iodo) to produce dodecaorganocyclohexasilane ( Si 6 Ri2 ) ⁇
• the present method includes contacting trichlorosilane with a reagent composition to form a compound containing a
• tetradecahalocyclohexasilane dianion such as a tetradecachlorocyclohexasilane dianion
• the reagent composition comprises (a) a tertiary polyamine ligand and (b) a high pKa tertiary amine.
• the tetradecahalocyclohexasilane dianion-containing compound may be contacted with a metal hydride reducing agent (e.g., lithium aluminum hydride or diisobutylaluminum hydride) to produce cyclohexasilane ( Si 6 Hi 2 ).
• a metal hydride reducing agent e.g., lithium aluminum hydride or diisobutylaluminum hydride

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)

Priority Applications (5)

Applications Claiming Priority (4)

Publications (1)

Family

ID=44319713

Family Applications (1)

Country Status (6)

Cited By (9)

Families Citing this family (6)

Citations (2)

Family Cites Families (32)

• 2011
  • 2011-01-25 US US13/522,289 patent/US8975429B2/en not_active Expired - Fee Related
  • 2011-01-25 CN CN201180007314.9A patent/CN102762497B/zh not_active Expired - Fee Related
  • 2011-01-25 WO PCT/US2011/022360 patent/WO2011094191A1/en not_active Ceased
  • 2011-01-25 JP JP2012551225A patent/JP5697692B2/ja not_active Expired - Fee Related
  • 2011-01-25 EP EP11737505.5A patent/EP2528864B1/en not_active Not-in-force
  • 2011-01-25 KR KR1020127021848A patent/KR101818272B1/ko not_active Expired - Fee Related

Patent Citations (2)

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events