EP0417253A1 - Procede a basse temperature de formation de materiaux en utilisant un ou plusieurs agents de reaction metalliques et un agent de reaction contenant de l'halogene pour former un ou plusieurs intermediaires reactifs - Google Patents

Procede a basse temperature de formation de materiaux en utilisant un ou plusieurs agents de reaction metalliques et un agent de reaction contenant de l'halogene pour former un ou plusieurs intermediaires reactifs

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Publication number
EP0417253A1
EP0417253A1 EP90905897A EP90905897A EP0417253A1 EP 0417253 A1 EP0417253 A1 EP 0417253A1 EP 90905897 A EP90905897 A EP 90905897A EP 90905897 A EP90905897 A EP 90905897A EP 0417253 A1 EP0417253 A1 EP 0417253A1
Authority
EP
European Patent Office
Prior art keywords
metal
reactant
metals
containing reactant
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP90905897A
Other languages
German (de)
English (en)
Inventor
Angel Sanjurjo
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SRI International Inc
Original Assignee
SRI International Inc
Stanford Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SRI International Inc, Stanford Research Institute filed Critical SRI International Inc
Publication of EP0417253A1 publication Critical patent/EP0417253A1/fr
Withdrawn legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/20—Methods for preparing oxides or hydroxides in general by oxidation of elements in the gaseous state; by oxidation or hydrolysis of compounds in the gaseous state
    • C01B13/22—Methods for preparing oxides or hydroxides in general by oxidation of elements in the gaseous state; by oxidation or hydrolysis of compounds in the gaseous state of halides or oxyhalides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/064—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with boron
    • C01B21/0643—Preparation from boron halides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/068—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with silicon
    • C01B21/0682—Preparation by direct nitridation of silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • 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
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/03—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of silicon halides or halosilanes or reduction thereof with hydrogen as the only reducing agent
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/442—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using fluidised bed process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/121—Halogen, halogenic acids or their salts
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/123—Oxides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/124—Boron, borides, boron nitrides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/126—Carbides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/12—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with inorganic substances ; Intercalation
    • D01F11/128—Nitrides, nitrogen carbides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/0617—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
    • C01B21/062—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with chromium, molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
    • C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases

Definitions

  • This invention relates to the production of mater ⁇ ials in the form of coatings or powders using a 5 halogen-containing reactant which will react with a second reactant to form one or more reactive inter ⁇ mediates from which the powder or coating may be formed by disproportionation, decomposition, or reaction.
  • the powder or coating 10 is formed directly from the one or more reactive intermediates.
  • the one or more reactive intermediates react with a gaseous third reactant resulting in the formation of a powder or coating.
  • Metallic and ceramic powders and coatings can be formed by a variety of techniques including vapor deposition, chemical vapor deposition (CVD) , sput ⁇ tering, dip coating, slurry painting, pack cementa-
  • CVD chemical vapor deposition
  • sput ⁇ tering dip coating
  • slurry painting pack cementa-
  • the material may be milled or
  • the material may be applied as a vapor by first volatilizing the material, which may in some cases require very high temperatures, e.g. as high as 2000"C or higher for materials such as silicon and titanium, or the coating may be applied by other means mentioned above such as sputtering, coating, painting, or spraying which, while not requiring as high a temperature as the vaporization techniques, may not form a bond which is as satisfactory.
  • CVD is particularly well suited for many applications including deposition of semiconductor and metallic interconnects, deposition of hard coatings for tools and gears, and deposition of corrosion resis ⁇ tant coatings for aqueous and high temperature environments.
  • a gas mix such as, for example, TiCl 4 and NH 3 are passed over a substrate heated to high temperature, (>1000'C) so that a film of TiN, which is formed in situ, deposits on the substrate.
  • CVD chemical vapor deposition
  • a coating compris ⁇ ing a compound, e.g., of silicon nitride or titanium carbide, it is necessary to both form the compound as well as provide a means for depositing or forming the coating on a substrate.
  • a compound e.g., of silicon nitride or titanium carbide
  • an object of this invention to provide a low temperature process for forming a coating or powder comprising one or more metals or metal compounds by reacting the one or more metals with a halide-containing reactant in a moving bed reactor to form one or more reactive intermediates capable of forming a coating or powder with or without reaction with another material.
  • Figure 1 is a flow sheet illustrating a first embodiment of the process of the invention.
  • Figure 2 is a flow sheet illustrating a second embodiment of the process of the invention.
  • Figure 3 is a flow sheet illustrating a third embodiment of the process of the invention.
  • Figure 4 is a flow sheet illustrating a fourth embodiment of the process of the invention.
  • Figure 5 is a vertical cross section view of a moving bed reactor showing the production of metal powder from the decomposition of one or more reac ⁇ tive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
  • Figure 6 is a vertical cross section view of a moving bed reactor showing the formation of a metal coating on a substrate by the decomposition of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-contain ⁇ ing reactant.
  • Figure 7 is a vertical cross section view of a moving bed reactor showing the formation of a pow ⁇ der comprising one or more metal compounds by reac- tion with a third reactant, in a second zone, of one or more reactive intermediates formed by react ⁇ ing one or more metal reactants with a halogen- containing reactant.
  • Figure 8 is a vertical cross section view of a moving bed reactor showing the formation of a coat ⁇ ing on graphite fibers of one or more metal com ⁇ pounds by reaction with a third reactant, in a second zone, of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
  • Figure 9 is a vertical cross section view of a moving bed reactor showing the formation of a coat ⁇ ing on steel plates of one or more metal compounds by reaction with a third reactant, in a second zone, of one or more reactive intermediates formed by reacting one or more metal reactants with a halogen-containing reactant.
  • Figure 12 is a graph showing the mass spectrum of species in the Si-H-Br system obtained when HBr is passed through silicon powder.
  • the invention provides a novel low temperature process for forming a powder or a coating compris ⁇ ing one or more metals or metal compounds by reacting the one or more metals with a halide- containing reactant in a moving bed reactor to form one or more reactive intermediates capable of form- ing a coating or powder.
  • the coating or powder may comprise one or more decomposition products of the one or more reactive intermediates comprising the one or more metals initially reacted with the halide-containing reactant.
  • the coating or powder may comprise the reaction product of the one or more reactive intermediates reacted with another reactant intro ⁇ quizzed into a second reaction zone of the reactor and selected from the class consisting of a boron- containing reactant, a carbon-containing reactant, a nitrogen-containing reactant, an oxygen-contain ⁇ ing reactant, and mixtures thereof to form the powder or coating which comprises, respectively, one or more metal borides, metal carbides, metal nitrides, metal oxides, or a mixture thereof, of the one or more metal reactants depending upon the other reactant.
  • the gravamen of the invention is the initial reaction of the one or more metal reactants with the halide-containing reactant at atmospheric pressure and at a low temperature to form one or more reactive intermediates. This low temperature formation of the reactive intermediates makes possible the subsequent low temperature for ⁇ mation of the powders or coatings.
  • low temperature herein to describe the initial reaction between the one or more metal reactants with the halide-containing reactant is meant a temperature ranging from about 200-C, but no higher than about 1000"C.
  • a prefer ⁇ able range for this reaction is from about 400 ⁇ C to about 800 ' C, but the term "low temperature", when used herein without further definition of the tem ⁇ perature, will be understood to mean the broader range of from about 200*C to about 1000*C.
  • low temperature to describe the reaction in a second zone of the reactor used in forming either the powder or coating comprising the boride, nitride, carbide, oxide, or mixture of the one or more metal reactants is intended to define a temperature range of from about room tem ⁇ perature, i.e., 20-25'C to about 1300'C.
  • the tem ⁇ perature in this second zone preferably ranges from about 600 to about 900-C.
  • This temperature range may be maintained within the one or more reaction zones within the reactor by any convenient heating means such as resistance heating, RF heating, microwave heating, radiation heating ⁇ laser heating, arc heating, or gas heating.
  • the one or more metal reactants which are reacted with the halide-containing reactant may comprise any metal or metals capable of reacting with a halide-containing reactant to form one or more metal halide intermediates, regardless of the in ⁇ stability of the reaction intermediate.
  • metals include the transition metals Ti, V, Cr, Zr, Nb, Mo-, Hf, Ta, and W, as well as Al, Si and B. WJjile it is recognized that silicon and boron are not technically considered to be metals, the use of the terms "metaj. reactant” and/or "metal reactants” herein ill be understood to include Si and B as well as those elements traditionally recognized as metals.
  • the metal reactant is preferably provided in particulate form comprising particles having a size of from about 100 to about 1000 microns.
  • the metal reactant may also be provided in other forms such as foils and fibers and other shapes which provide dispersions with large surface to volume ratios.
  • the metal reactant is reacted with the halide-containing reactant by placing the metal reactant powder in a moving bed reactor such as a fluidized bed reactor.
  • An inert gas may be used to fluidize the bed or the powder may be rotated, moved by gravity, vibration, or any other suitable means which will move or agitate the particle bed.
  • the particle bed itself comprising the moving bed in the reactor comprises the metal reactant in particulate form, not an inert material.
  • the reactor may comprise any suitable non-reactive containment vessel capable of containing a moving bed such as, for example, a fluidized bed.
  • a suit- able containment vessel for example, would be a quartz cylinder.
  • the walls of the reactor are kept hotter than the bed to inhibit deposition on the walls.
  • a fluidized bed reactor 10 may comprise a cylindrical vessel 14 having an exit port 18 and a tapered lower portion 16 into which an inert fluidizing gas enters through a first port 20 and is mixed with the halogen-containing reactant in gaseous form which enters tapered portion 16 through a second port 24.
  • first reaction zone 34 The gaseous mixture then enters a first reaction zone 34 through a distribution plate 30 located just above tapered portion 16 in reactor 10. Above distribution plate 30 is located, in first reaction zone 34, the bed of particles comprising the one or more metal reactants, e.g., titanium particles.
  • a heating means 40 which may, for example, comprise a tubular resistance furnace which cooperates with thermocouple temperature sensor 42 to maintain first reaction zone 34 in reactor 10 within the temperature range of from about 200 ⁇ C to about
  • the metal reactant particles are both fluidized and brought into intimate contact with the one or more metal reactants to thereby form the one or more reactive intermediates.
  • these reactive intermediates then either form the powder or a coating deposited on a substrate; or pass on into a second reaction zone to react with a third reactant to form the powders or coatings of metal nitrides, metal carbides, or metal borides, or mixtures thereof as will also be described below.
  • reaction time, or residence time needed in the first reaction zone for the one or more metal reactants to react with the halogen-containing reactant to form the reactive intermediate varies from about 0.1 seconds up to 100 minutes, preferab- ly about 1 second to about 100 seconds.
  • the substrate may comprise any material capable of withstanding the temperatures which will be used in the reactor to form the coating.
  • most metals or ceramic materials for example, will be suitable substrate materials on which the coating may be deposited.
  • suitable substrate materials include metals such as Cu, Ni, Fe, alloys such as steels, super alloys, monolithic ceramics such as A1 2 0 3 , Zr0 2 , Si0 2 , SiC, Si 3 N 4 , TiN, etc., or fibers, whiskers, or powders of any of the above, or composites thereof.
  • the halide-containing reactant is a gaseous reac- tant which comprises one or more reactants contain ⁇ ing one or more of the halides selected from the class consisting of F, CI, Br, and I. Included in the definition of halide-containing reactants are compounds having the formula X 2 , HX, MX & , or MX a _ b ) H b where X is F, CI, Br, or I; M is one or more metals selected from the class consisting of any of the metal reactants and Pb; a is the maximum oxida ⁇ tion state or valence of the metal M; and b has a value of from 1 to a-1.
  • gaseous By use of the term “gaseous” is meant that the halogen-containing reactant is introduced into the first reaction zone as a gas or a vapor at the temperature of operation.
  • the halogen-containing reactant is a vapor, for example, it may be introduced into the first reaction zone with a carrier gas.
  • all of the metal reactants may be present as particles or one or more of the metal reactants may be introduced into the reaction zone in the form of the fluidized particles, while one or more other metal reactants may form a part of the gaseous halogen-containing reactant, if de- sired.
  • the additional reactant may comprise a nitrogen, carbon, oxygen, or boron source, respec ⁇ tively, (or mixture of same when a mixed nitride, carbide, oxide, or boride is desired) which is in the gaseous state at the reaction pressure and temperature.
  • the reaction time in the second reaction zone needed for the one or more reactive intermediates to react with the third reactant to form a nitride, carbide, oxide, or boride of the one or more metal reactants or a mixture of such compounds, in the form of a powder deposit or a deposit of a coating on a suitable substrate varies from about 10 "16 seconds to about 100 seconds, preferably about 10 ⁇ 6 seconds to about 10 seconds.
  • the additional reactant may be any 1-20 carbon hydrocarbon containing hy ⁇ drogen and carbon such as, for example, methane, ethane, ethene, ethyne, propane, propene, propyne, butane, 1-butene, and 1-butyne, which will be gas ⁇ eous at the reaction temperature.
  • the additional reactant may be any boron-containing material which contains only boron and hydrogen or other materials already present in the first reaction zone such as a hal- ide.
  • the source of boron will be a borane such as diborane (B 2 H 6 ) .
  • the nitrogen, carbon, oxygen, and boron sources which may be used as the additional reactant may be greatly expanded, subject to the provisions discussed above with regard to the gaseous state of the reactant.
  • any organic material containing only carbon, hydrogen, and nitrogen may be used as the additional reactant when it is desired to form a mixture of at least one carbide and at least one nitride; while organic sources containing carbon, hydrogen and boron may be used to form mixtures containing at least one carbide and at least one boride.
  • mixtures of more than one additional reactant may be used, either to form solely a nitride, carbide, oxide, or boride, or, as will more likely be the case, to form various mixtures of nitrides, carbides, oxides, and borides.
  • the initial formation of one or more reactive in ⁇ termediates from the reaction between the metal reactant and the halogen-containing reactant is believed to form unstable intermediates which may then, in turn, either react with another reactant such as the nitrogen, carbon, oxygen, or boron- containing reactants discussed above to respective- ly form a nitride, carbide, oxide, or boride; or decompose to permit formation of a coating or pow ⁇ der consisting essentially of the initial metal reactant or reactants.
  • the metal reactant is silicon and the halide-containing reactant is bromine
  • the silicon may react with the silicon according to the following equation:
  • Si + 2 Br 2 > SiBr 4 may, in turn, then further react with the silicon present in the reactor to form equilibriums of the following species:
  • subhalide and halosilane species are very reactive and it is believed that they either decompose to form a powder deposit or a coating, if a coatable substrate is present, of the metal reac ⁇ tant, e.g., silicon; or, if another reactant is then introduced into the reactor, these unstable subhalide species react with the additional reac ⁇ tant, e.g., NH 3 to form a powder or coating com ⁇ prising the reaction product of the metal reactant and the other reactant, e.g., the formation of S ---3 N 4 -°y reaction of one or more of the reactive silicon-containing intermediate subhalide species with NH 3 .
  • the halogen-containing reactant is merely passed through the bed of metal reactant particles in the first reaction zone while main ⁇ taining this reaction zone at from about 200 ⁇ C to about 1000-C, preferably from about 400"C to about 800-C, for a period of from about 0.01 to about 100 minutes as shown in the apparatus in Figure 5.
  • the one or more metal reactants react with the halogen-containing reactant to form the one or more reactive intermediates, as discussed above, which then react or disproportionate to form a powder of the one or more metal reactants.
  • This step may take place in a cooler zone 58 which may be pro ⁇ vided by a cold solid or a liquid substrate or, as shown in Figure 5, by a stream of cold gas flowing into cool zone 58 of reactor 10 through a plenum. 6.
  • the average temperature in cool zone 58 may J_>e 50 ⁇ C or more below that of first reaction z@ne 34.
  • the two zones may be part of the same chamber as
  • the resulting metal powder will be an alloy of the metal reac ⁇ tants with the ratio of the constituents of the alloy proportional to the ratio of the metal reac- tants in the reaction zone.
  • the resultant powder is a pure and ultrafine metal powder, typically having a particle size of from about 100 Angstroms to about 10 microns. This powder is light enough to pass out of the reactor entrained with the gas used to form the moving bed.
  • a titanium/aluminum alloy powder may be formed when titanium and alumi- num are both used as metal reactants. It should be noted that, in contrast to the prior art, the present process operates at atmospheric pressure, i.e., vacuum conditions are not needed.
  • the substrate to be coated may be placed in the reaction zone and, as the reaction between the one or more metal reactants and the halogen- containing reactant proceeds, the one or more reac ⁇ tive intermediates formed in this reaction will decompose and the resulting metal or metals will form a coating on the substrate.
  • Coatings are obtained on substrates placed inside the particle bed and immediately above it, i.e., less than 5 cm. above the bed.
  • the substrate temperature may be 50 ⁇ C higher than the bed with the rate of deposition increasing with temperature differences reaching a maximum for temperature differences of about 200'C.
  • This val ⁇ ue may change with the chemical system and reactor design, and is, therefore, given only for illustration purposes.
  • Coatings can also be obtained on substrates located immediately above the bed and maintained at temper ⁇ atures below that of the bed, typically 50 ⁇ C, but as much as 200 ⁇ C lower than the bed temperature.
  • coatings can be obtained in some cases even when the bed and the substrate are kept at the same temperature, for example, silicon can be coated on copper when both the bed and the sub ⁇ strate are kept at about 600'C. Silicon deposits and diffuses in the copper thus decreasing the silicon activity.
  • the gas phase in the bed acts as a transport agent for silicon from the bed with silicon activity of 1. In this mode, the driving force is the partial chemical gradient due to ac- tivity differences rather than temperature differ ⁇ ences.
  • copper tubes 50 are shown suspended in first reac ⁇ tion zone 34 where they are coated with the one or more metal reactants.
  • copper, steel, and silica substrates were coated respectively with silicon (copper substrate) , titanium (copper, steel, and silica substrates) and zirconium (steel substrate) as shown in the table below.
  • the one or more reactive intermediates formed in first reaction zone 34 may pass upward in the reactor into a second reaction zone 60 above the particle bed comprising first reactive zone 34 where a third reactant, comprising a material as previously described, which is intro ⁇ quizd therein through an inlet port 70, contacts the one or more reactive intermediates to form, respectively, one or more metal nitrides, carbides, oxides, borides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, " oxygen, boron, or a mixture of same, as powders which are then passed out of the reactor through exit port 18 with the gases leaving reactor 10.
  • a third reactant comprising a material as previously described, which is intro ⁇ quizd therein through an inlet port 70
  • silicon nitride (Si 3 N 4 ) powder was produced by fluidizing 325 mesh silicon particles in a 5 cm ID 50 cm long fluidized bed reactor by an argon flow of 4 liters/min having a bed height (in repose) of 10 cm.
  • the fluidized bed was heated externally to 600 ⁇ C for 1 hour, after which a flow of HBr gas was mixed with the argon fluidizing gas and coijijected into the bed as shown in Figure 7.
  • a flow of ammonia gas at a rate of 30-100 cm 3 /min was fed through the top of.
  • Figures 8 and 9 show, respectively, formation of coatings of metal compounds on a substrate in the second reaction zone in the reactor.
  • a first plug 80 of graphite fibers is inserted into reactor 10 just above first reaction zone 34 and a second plug 82 of graphite fibers is also inserted into reactor 10 a spaced distance from first plug 80 forming a second reaction zone 60' commencing with the bottom of first plug 80 and extending upward through second plug 82.
  • a coating is formed on at least the first plug 80 of graphite fibers comprising, respectively, one or more metal ni ⁇ trides, carbides, borides, oxides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, oxygen, boron, or a mixture of same.
  • a fluidized bed of 325 mesh silicon particles was formed in the reactor of Figure 8 by fluidizing the bed with nitrogen gas after preheat ⁇ ing the reactor bed to about 600'C.
  • HBr was mixed with the fluidizing gas as the halogen-containing reactant.
  • NH 3 was then injected through the upper graphite plug into the second reaction zone com ⁇ prising the space above the fluidized bed.
  • the resulting bromosilanes and subbromides formed in the first reaction zone (the fluidized bed) reacted with the NH 3 in the second reaction zone which was maintained at about 1200*C.
  • the process was al ⁇ lowed to proceed for 2.5 hours after which the process was stopped and the lower graphite plug removed for analysis.
  • the hard grayish brittle coating on the carbon fibers was studied using both scanning electron microscopy (SEM) and energy dis ⁇ persive x-ray analysis (EDAX) which confirmed the presence of a Si 3 N coating on the carbon fibers.
  • substrates 50 are shown suspended in second reaction zone 60 above reaction zone 34 and a third reactant is injected into this second zone, similarly to that shown in Figures 7 and 8, where it contacts the one or more reactive intermediates rising from first reaction zone 34 to form a coat- ing on the suspended substrate comprising, respectively, one or more metal nitrides, carbides, oxides, borides, or mixtures of same, depending upon whether the third reactant contains nitrogen, carbon, oxygen, boron, or a mixture of same.
  • a bed of 325 mesh titanium particles was formed and preheated to 750"C prior to being fluid ⁇ ized by a flow of argon gas at atmospheric press- ure.
  • HBr gas was then mixed with the argon fluid ⁇ izing gas to obtain a partial pressure of 7 torr.
  • Steel and silica substrates were suspended in the second reaction zone above the bed and a flow of NH 3 gas was injected into this zone from the top of the reactor while maintaining this second reaction zone at a temperature of 800'C.
  • Gold colored coatings were formed on the substrates and these coatings were confirmed by subsequent x- ray diffraction, SEM, and EDAX to be TiN.
  • the coated steel substrate was tested for corrosion resistance in aqueous chloride solutions and found to have an increase in corrosion resistance of approximately 30 times that of uncoated steel.
  • the invention provides a novel process for the formation of powders or coatings of either one or more metal reactants powders in a moving bed reactor initially reacted with a halogen-containing reactant to form reactive intermediates which dis ⁇ proportionate or decompose to form the metal powder or coating; or which reactive intermediates may react further with another reactant introduced into a second reaction zone to form one or more metal compounds in the form of either a powder or a coating.

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Abstract

Un procédé à basse température permet de former un revêtement ou poudre comprenant un ou plusieurs métaux ou composés métalliques en faisant réagir d'abord un ou plusieurs agents de réaction métalliques avec un agent de réaction contenant un halogénure pour former un ou plusieurs intermédiaires réactifs capables d'une réaction, disproportion ou décomposition pour former un revêtement ou poudre comprenant le ou les agents de réaction métalliques. Lorsqu'un ou plusieurs composés métalliques sont formés, soit sous forme de poudre soit sous forme de revêtement, un troisième agent de réaction peut être injecté dans une seconde zone de réaction à l'intérieur du réacteur pour entrer en contact avec le ou les intermédiaires réactifs formés dans la première zone de réaction dans le but de former un ou plusieurs composés métalliques tels que des nitrures, carbures, oxydes ou borures métalliques ou des mélanges de ceux-ci.
EP90905897A 1989-04-04 1990-04-02 Procede a basse temperature de formation de materiaux en utilisant un ou plusieurs agents de reaction metalliques et un agent de reaction contenant de l'halogene pour former un ou plusieurs intermediaires reactifs Withdrawn EP0417253A1 (fr)

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DE3934351A1 (de) * 1989-10-14 1991-04-18 Studiengesellschaft Kohle Mbh Verfahren zur herstellung von mikrokristallinen bis amorphen metall- bzw. legierungspulvern und ohne schutzkolloid in organischen solventien geloesten metallen bzw. legierungen
AU4321493A (en) * 1992-05-26 1993-12-30 Lonza A.G. Fluidized bed reaction pipe with gas distributor, and its use
CN1047807C (zh) * 1993-06-01 1999-12-29 高级陶瓷有限公司 形成金属碳化物层的流化床反应器装置
JP3814841B2 (ja) * 1995-07-06 2006-08-30 住友化学株式会社 金属酸化物粉末の製造方法
FR2745299B1 (fr) * 1996-02-27 1998-06-19 Centre Nat Rech Scient Procede de formation de revetements de ti1-xalxn
FR2767841B1 (fr) * 1997-08-29 1999-10-01 Commissariat Energie Atomique PROCEDE DE PREPARATION PAR DEPOT CHIMIQUE EN PHASE VAPEUR (CVD) D'UN REVETEMENT MULTICOUCHE A BASE DE Ti-Al-N
KR20010032764A (ko) 1997-12-02 2001-04-25 베리 아이클스 아이오도사일렌 전구체로부터 형성된 실리콘계 필름과 그제조방법
FR2784694B1 (fr) * 1998-10-15 2000-11-10 Commissariat Energie Atomique Procede de preparation par depot chimique en phase vapeur assiste par plasma (pacvd) de revetements a base de titane
JP2004071970A (ja) * 2002-08-08 2004-03-04 Shin Etsu Chem Co Ltd 太陽電池用シリコン基板の製造方法およびその製造システム
KR101282544B1 (ko) 2008-12-12 2013-07-04 도쿄엘렉트론가부시키가이샤 성막 방법 및 성막 장치
JP5908476B2 (ja) * 2010-08-30 2016-04-26 インテグリス・インコーポレーテッド 固体材料から化合物又はその中間体を調製するための装置及び方法並びにそのような化合物及び中間体の使用
EP2890635B1 (fr) 2012-08-29 2021-04-28 Hemlock Semiconductor Operations LLC Réacteur à lit fluidisé effilé et un procédé pour son utilisation
CN103521774A (zh) * 2013-10-22 2014-01-22 吴海勇 一种自蔓延制备金刚石节块工具的方法

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FR2309648A1 (fr) * 1975-04-30 1976-11-26 Anvar Procede et dispositif pour l'obtention d'un depot de metal de transition
FR2508063A1 (fr) * 1981-06-18 1982-12-24 Snecma Procede, en phase vapeur, pour le depot d'un revetement protecteur sur une piece metallique, dispositif pour sa mise en oeuvre et pieces obtenues selon ledit procede
DE3610713A1 (de) * 1985-09-07 1987-03-19 Hoechst Ag Verfahren zur herstellung von silicium und dessen verbindungen in feinstteiliger form

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