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|||||||I|| US005464656A United States Patent (19) 11 Patent Number: 5,464,656 Verkade (45) Date of Patent: Nov. 7, 1995 54 METHOD OF APPLYING SINGLE-SOURCE A. H. Cowley et al., "Organometallic Chemical Vapor MOLECULAR ORGANIC CHEMICAL Deposition of III/V Compound Semiconductors with Novel WAPOR DEPOSITION AGENTS Organometallic Precursors', J. Am. Chem. Soc., 110, 6248-6249 (1988). 75 Inventor: John G. Verkade, Ames, Iowa A. H. Cowley et al., "An Aluminaphosphacubane, a New Aluminum Phosphide Precursor”, Angew. Chem. Int. Ed. 73) Assignee: Iowa State University Research Engl., 29, 1409-1410 (1990). Foundation, Inc., Ames, Iowa A. H. Cowley et al., "Preparation of Indium Antimonide Using a Single-Source Precursor”, Chem. Mater, 2, (21) Appl. No.: 253,106 221-222 (1990). (22 Filed: Jun. 2, 1994 A. H. Cowley et al., “III/V Precursors with P-H or As-H Bonds. A Low-Temperature Route to Gallium Arsenide and Related U.S. Application Data Gallium Phosphide', Organometallics, 10, 652-656 (1991). A. H. Cowley et al., “Isopropylphosphido and Arsenido 60 Division of Ser. No. 911,923, Jul. 10, 1992, Pat. No. Derivatives of Gallium and Indium. Isolation of 5,344,948, which is a continuation-in-part of Ser. No. 841, Gallium-Phosphorous and Indium-Phosphorous Dimers 589, Feb. 25, 1992, abandoned. and Trimers', Organometalics, 10, 1635-1637 (1991). (51) Int. Cl." ...................................... C23C 16/18 C. C. Cummins et al., “Trigonal-Monopyramidal M'Com 52 U.S. Cl ... 427/248.1; 427/250; 427/255.6 plexes of the Type M(NN) (M=Ti, V, Cr, Mn, Fe; 58 Field of Search .............................. 427/248.1, 255.6, NN=(tBuMeSi) NCHCHN)", Angew. Chem. Int. Ed. 427/250 Engl., 31, 1501-1503 (Dec. 1992). (56) References Cited (List continued on next page.) U.S. PATENT DOCUMENTS Primary Examiner-Shrive Beck Assistant Examiner-Bret Chen 3,994,740 11/1976 Morton ...................................... 106/65 4,885,376 12/1989 Verkade. Attorney, Agent, or Firm-Schwegman, Lundberg & Woess 5,051,533 9/1991 Verkade ...................... .............. 564/13 ne OTHER PUBLICATIONS 57 ABSTRACT C. C. Amato et al., "Gas Phase Decomposition of an Neutral single-source molecular organic precursors contain Organometallic Chemical Vapor Deposition Precursor to ing tetradentate tripodal chelating ligands are provided that AlN: Al(CH))NH), Mat. Res. Soc. Symp. Proc., are useful for the preparation of films chemical vapor 119-124 (1990). deposition. These complexes can be generally represented D. A. Atwood et al., "X-ray crystal structure of the dimeth by the formula ylgallium azide polymer and its use as a gallium nitride precursor", J. Organomet. Chem., 394, C6-C8 (1990). D. C. Bradley, "Metallo-organic Compounds containing (R), Metal-Nitrogen bonds. Part I. Some Dialkylamino-derivatives of Titanium and Zirconium', J. l N 2 Chem. Soc., 3857-3861 (1960). (R --- Y. CR 2n D. C. Bradley et al., "Novel Precursors for the Growth of E(R)2C) E-(R'), III-V Semiconductors by MOVPE', J. Cryst. Growth, 75, S / 101-106 (1986). E-IC(R)2) T. A. Brooks et al., “Plasma-Enhanced Chemical Vapor Deposition of Silicon Nitride from 1,1,3,3,5, wherein 'M' is selected from the group consisting of a 5-Hexamethylcyclotrisilazane and Ammonia, Thin Solid lanthanide, an actinide, a Group IIIA metal, a Group IIIA Films, 153, 521-529 (1987). metalloid, a Group IVA metal, a Group IVA metalloid, a D. M.-T. Chan et al., “Trialkoxynitridomolydbenum Com Group VA metal, a Group VA metalloid, a Group IIIB metal, pounds: (RO)MoEN. Preparation, Structures (R=t-Bu a Group IVB metal, a Group VB metal, a Group VIB metal, and i-Pr), and Comparisons with a Tungsten Analogue a Group VIIB metal, and a Group VIIIB metal. The ligand (R=t-Bu)", Inorg. Chem., 25, 4170-4174 (1986). "Z", when present (k=1), is selected from the group con H. L. M. Chang et al., "Preparation, Structure and Properties sisting of hydrogen, halide, and a group bonded to "M" through N, O, P, S, As, Si, or C. "E" is N, P, or As, and of VO, and TiO, Thin Films by MOCVD', Mat. Res. Soc. m=0-1. When “E” is N, P, or As, m=1. When "E" is O, S, Symp. Proc., 168, 343-348 (1990). or Se, m=0. Each "R" is selected from the group consisting H. Cohen, "Mono-and trititanates of cyclic nitrilotriethylene of hydrogen, (C-C2)alkyl, (C-C-o)alkenyl, triorganotin titanate (IV)', J. Organometal. Chem., 9, (C-Co)alkynyl, (C-C)aryl, (C7-Co)aralkyl, a 177-179 (1967). (Cs. Cs)heterocycle, and triorganosilyl. In-ICOR)2)-, H. J. Cohen, "Cyclic Nitrilotriethylene Triorganosilyl Titan n=1-4, and each “R” is selected from the group consisting ate (IV): "Mono-, Di- and “Trititanates', J. Organomet. of hydrogen, alkyl, alkenyl, alkynyl, aryl, aralkyl, and a Chem., 5, 413-419 (1966). heterocycle. F. A. Cotton et al., Advanced Inorganic Chemistry, 4th Ed., Wiley-Interscience, New York; pp. 737, 751, 767, 986, 1010, and 1011 (1980). 18 Claims, No Drawings 5,464,656 Page 2 OTHER PUBLICATIONS J. Mater. Res., 6, 5-7 (1991). D. Gudat et al., “Novel Properties of New Phosphatranes C. C. Cummins et al., "Synthesis of Vanadium and Titanium and Silatranes”, Phosphorus, Sulfur and Silica, 41, 21-29 Complexes of the Type RM (MeSiNCHCH)N) (R=Cl, (1989). Alkyl) and the Structure of CIVICMeSiNCH2CH2)4N]", D. Gudat et al., "New AZasilatranes: Synthesis and Substi Organometallics, 11, 1452-1454 (Apr. 1992). tution Reactions', Organometallics, 8, 2772-2779 (1989). A. G. Davies et al., "The Structure and Reactions of Some D. Gudat et al., "New Azasilatranes: Sterically Induced Mono-Organo-Tin (IV) Compounds', J. Organomet. Transannular Bond Weakening and Cleavage', J. Am. Chem. Chem. 39, 279-288 (1972). Soc., 111, 8520-8522 (1989). B. de Ruiter et al., "Formation of Unexpected Silicon D. Gudat et al., "New AZasilatranes: Bidentate and Triden Alkoxide Isomers in a Rectangular Planar Chelating Frame tate Coordination Modes of the Novel Ligand work”, Inorg. Chem., 29, 1065-1068 (1990). EtOSi(Ph-PNCHCH2)(HNCHCH)N', Organometallics, S. B. Desu et al., "Structure, Composition, and Properties of 9, 1464-1470 (1990). MOCVD ZrO, Thin Films", Mat. Res. Soc. Symp. Proc., D. Gudat et al., “AZasilatrane Methanolysis Pathways: Ste 168, 349-356 (1990). reoelectronic Influences', Organometallics, 9, 2172–2175 D. D. Devore et al., "Complexes of (Arylimido)vanadi (1990). um(V). Synthetic, Structural, Spectroscopic, and Theoretical R. L. Harlow, "Dimer of (2, 2, Studies of V(Ntol)Cl and Derivatives', J. Am. Chem. Soc., 2"-Nitrilotriethanolato)(2-propanolato)titanium(IV), - 109, 7408-7416 (1987). Ti(CHNO)(CHO))', Acta Cryst., C39, 1344-1346 S. Dou et al., "Crystal structure of 2,8.9-trioxa-5-aza-l (1983). bora=tricyclo[3.3.3.0 undecane-3-one", Jiegou Hua D. E. Heaton et al., "Potential Sources of the Electronics xue, 2, 273-276 (1983); Chem. Abstr, 106, Abstract No. Materials GaP and AlAs. Synthesis and X-Ray Structures of 129709z, p. 671 (1987) (Abstract Only). It-BuGaGu-(CH)PH2 and Et2A(u-t-BuAS)2 H. Du et al., "Low-Temperature Metal-Organic Chemical (CH=Cyclopentyl)”, Polyhedron, 7, 1901-1908 (1988). Vapor Deposition of Silicon Nitride', J. Am. Ceram. Soc., K.-L. Ho et al., “MOCVD of Wide Bandgap III-V Semi 73, 764-766 (1990). conductors by Using Novel Precursors', Mat. Res. Soc. C. Eaborn et al., "A Silatrane-Platinum Complex, trans Symp. Proc., 162, 605-610 (1990). -PtCl-Si(OCHCH.)N-(PMePh) with a Planar Nitro K.-L. Ho et al., "MOCVD of AlN by Using Novel Precur gen and No Si-N Bond; X-Ray Crystal Structure', J. Chem. sors', Proc. Electrochem. Soc., 90-12, 388-394 (1990). Soc., Chem. Comm., 317–318 (1976). M. G. Hocking et al., "Chemical Vapour Deposition (CVD)" R. M. Fix et al., “Solution-Phase Reactivity as a Guide to in Metallic and Ceramic Coatings; Longman Scientific and the Low-Temperature Chemical Vapor Deposition of Technical; Essex, England; Ch. 4, pp. 103-172 (1989). Early-Transition-Metal Nitride Thin Films', J. Am. Chem. L. V. Interrante et al., "Preparation and Properties of Alu Soc., 112, 7833-7835 (1990). minum Nitride Films Using an Organometallic Precursor', R. M. Fix et al., “Synthesis of Thin Films by Atmospheric J. Electrochem. Soc., 136, 472-478 (1989). Pressure Chemical Vapor Deposition Using Amido and K. Jones et al., "Amino-derivatives of Metals and Metal Imido Titanium (IV) Compounds as Precursors', Chem. loids. Part I. Preparation of Aminostannanes, Stanny Mater, 2, 235-241 (1990). lamines, and Stannazanes', J. Chem. Soc., 1944-1951 W. H. Follner, "Triathanolaminkomplexe. I. Die Kristall (1965). struktur von ZnCl. CHON”, Acta Cryst., B28, 157-160 V. K. Jurkschat et al., "Assoziationsverhalten von Stan (1972) (English Language Abstract is included on the first natranen”, Z. anorg. allg. Chem., 463, 123-131 (1980) page of the reference). (English Language Abstract is included on the first page of R. J. Garant et al., "Lewis Basicity of Silatranes and the the reference). Molecular Structures of EtOSi(OCHCH)N, MeO" N. Kakimoto et al., "Organogermanium Compound. New Si(OCH2CH2)N, and CFCOHEtOSi(OCHCH)N", J. Simplified Synthesis of Germatranes Substituted with Novel Am. Chem. Soc., 113,5728-5735 (1991). Functional Groups', Heterocycles, 23, 1493–1496 (1985). G. S. Girolami et al., "Organometallic Route to the Chemical L. Korecz et al., "Determination of the Coordination Num Vapor Deposition of Titanium Carbide Films at Exception ber and Geometry of the Coordination Sphere of the Central ally Low Temperatures', J. Am. Chem. Soc., 109, Tin Atom in Stannatrane Complexes by Mössbauer Spec 1579-1580 (1987). troscopy”, Inorg. Chim. Acta. 58,243-249 (1982). G. S. Girolami et al., "Tailored Organometallics as M.
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    DOE/ER-0002 Summaries of FY 1977 Research in the Chemical Sciences February 1978 U.S. Department of Energy Office of Energy Research Division of Chemical Sciences DOE/ER-0002 UC -4 Summaries of FY 1977 Research in the Chemical Sciences February 1978 U.S. Department of Energy Office of Energy Research Division of Chemical Sciences Washington, D. C. 20545 FOREWORD In the Chemical Sciences basic energy research program, scientists at government, university and corporate laboratories conduct research on fundamental interactions, processes and techniques important to the production, use and conservation of energy. The goal is to provide, within the scientific disciplines encompassed by Chemical Sciences, the necessary base of scientific knowledge required to advance the nation's energy technology programs. The research covers a spectrum of scientific and engineering areas and is conducted generally by personnel trained in the disciplines of chemistry, analytical chemistry, chemical engineering, chemical physics, physical chemistry and physics. The research projects documented in this report were conducted under the aegis of the U.S. Energy Research and Development Administration (ERDA). They constituted the program of the Office of Chemical Sciences in the Division of Basic Energy Sciences. During FY 1977 a Department of Energy was proposed by the President and enacted by Congress. The new Department of Energy (DOE) came into existence on October 1, 1977. ERDA was incorporated into DOE along with other agencies and elements of the Federal Government. The Chemical Sciences basic energy research program now constitutes the program of the Division of Chemical Sciences in the Office of Basic Energy Sciences (BES) under the Director of the DOE Office of Energy Research.
  • Group Transfer Polymerization Catalyzed by Mercury Compounds

    Group Transfer Polymerization Catalyzed by Mercury Compounds

    turopaiscnes Patentamt 1� European Patent Office © Publication number: 0 266 062 Office europeen des brevets A1 © EUROPEAN PATENT APPLICATION Q) number: 87308549.2 C08F Application © Int. CI.4: 4/42 , C08F 4/72 © Date of filing: 2&09.87 © Priority: 29.09.86 US 912118 © Applicant: E.I. DU PONT DE NEMOURS AND COMPANY ® Date of publication of application: 1007 Market Street 04.05.88 Bulletin 88/18 Wilmington Delaware 19898(US) © Designated Contracting States: © Inventor: Dicker, Ira Bernard AT BE CH DE ES FR GB GR IT LI LU NL SE 1016 Jeffrey Road Wilmington Delaware 19810(US) © Representative: Jones, Alan John et al CARPMAELS & RANSFORD 43 Bloomsbury Square London, WC1A 2RA(GB) & Group transfer polymerization catalyzed by mercury compounds. Mercury compounds which are useful as co-catalysts in Group Transfer Polymerization are disclosed. IN D a D a. JJ .erox Copy Centre 0 266 062 Group Transfer Polymerization Catalyzed by Mercury Compounds BACKGROUND OF THE INVENTION Field of the Invention 5 This invention relates to Group Transfer Polymerization of acrylates catalyzed by selected mercury compounds. 70 Background United States Patents 4,414,372; 4,417,034; 4,508,880; 4,524,196; 4,581,428; 4,588,795; 4,605,716; 4,656,233; and 4,681,918, and EP-A-0 145 263, EP-A-0 188 539, and EP-A-87305069.4, referred to hereinafter as "the aforesaid patents and patent applications", disclose processes for polymerizing an 75 acrylic or maleimide monomer to a "living" polymer in the presence of an initiator, which is a tetracoor- dinate organosilicon, organotin or organogermanium compound having at least one initiating site, and a co- catalyst which is a source of fluoride, bifluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selection oxyanion.
  • Catalyst for Group Transfer Polymerization

    Catalyst for Group Transfer Polymerization

    Europaisches Patentamt 19 European Patent Office Office europeen des brevets © Publication number: 0 407 414 B1 EUROPEAN PATENT SPECIFICATION @ Date of publication of patent specification © int. ci.5 : C08F 4/42, C08F 20/00, 27.01.93 Bulletin 93/04 C08F 22/40 (2j) Application number : 89903556.2 (22) Date of filing : 15.03.89 (86) International application number : PCT/US89/00972 @ International publication number : WO 89/09236 05.10.89 Gazette 89/24 (54) CATALYST FOR GROUP TRANSFER POLYMERIZATION. (30) Priority: 01.04.88 US 176808 (73) Proprietor : E.I. DU PONT DE NEMOURS AND COMPANY 1007 Market Street (43) Date of publication of application Wilmington Delaware 19898 (US) 16.01.91 Bulletin 91/03 (72) Inventor : DICKER, Ira, Bernard (45) Publication of the grant of the patent : 1016 Jeffrey Road 27.01.93 Bulletin 93/04 Wilmington, DE 19810 (US) @ Designated Contracting States : (74) Representative : Jones, Alan John et al BE DE FR GB IT NL CARPMAELS & RANSFORD 43 Bloomsbury Square London, WC1A 2RA (GB) © References cited : EP-A- 0 083 018 EP-A- 0 145 263 EP-A- 0 190 631 US-A- 4 581 428 US-A- 4 588 795 CO o Note : Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been LU filed until the opposition fee has been paid (Art. 99(1) European patent convention).