US3808035A - Deposition of single or multiple layers on substrates from dilute gas sweep to produce optical components, electro-optical components, and the like - Google Patents

Deposition of single or multiple layers on substrates from dilute gas sweep to produce optical components, electro-optical components, and the like Download PDF

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US3808035A
US3808035A US00096428A US9642870A US3808035A US 3808035 A US3808035 A US 3808035A US 00096428 A US00096428 A US 00096428A US 9642870 A US9642870 A US 9642870A US 3808035 A US3808035 A US 3808035A
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substrate
metal
layer
sweeping
mixture
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M Stelter
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Priority to CH1160971A priority patent/CH558837A/xx
Priority to DE2140092A priority patent/DE2140092C3/de
Priority to GB3816871A priority patent/GB1356040A/en
Priority to NL7113284A priority patent/NL7113284A/xx
Priority to FR7135435A priority patent/FR2117849B1/fr
Priority to JP8682771A priority patent/JPS5318530B1/ja
Priority to BE774932A priority patent/BE774932A/xx
Priority to IT30901/71A priority patent/IT941737B/it
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    • 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
    • C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45512—Premixing before introduction in the reaction chamber
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • 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
    • 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
    • C23C16/401—Oxides containing silicon
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    • 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
    • C23C16/403—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C23C16/404—Oxides of alkaline earth metals
    • 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
    • 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
    • C23C16/406—Oxides of iron group metals
    • 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
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C23C16/408—Oxides of copper or solid solutions thereof
    • 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
    • C23C16/455—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 introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45593—Recirculation of reactive gases
    • 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
    • C23C16/56—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/229—Non-specific enumeration
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802—Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2956—Glass or silicic fiber or filament with metal coating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2933—Coated or with bond, impregnation or core
    • Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
    • Y10T428/2958—Metal or metal compound in coating

Definitions

  • a very thin layer is deposited from a dilute gas sweep onto suitable substrates including glass, metal, plastic, etc., in an atmospheric pressure process.
  • Moderate temperatures i.e., between 100C and 300C, can be used, although higher temperatures are sometimes US.
  • This invention relates to a method and apparatus for producing optically or electro-optically active layers, and the like, e.g., dichroic filters of the type comprising an optical substrate having multiple micro-thin layers of optical filter material thereon.
  • Some heretofore suggested methods involved vapor deposition from atmosphere rich in the deposited material, or rich in a precursor, or reactant which results in or yields a material constituting the resulting layer. These methods are considered to be deficient because of the difficulty in depositing a large number of high quality substantially equal coatings simultaneously. The deficiency is believed to be the result of localized differences in availability of reactants and, at least in part, because of chemical interference at the substrate which is occasioned by what I now believe to be excessive quantity of reactants.
  • Another shortcoming of many heretofore available methods of manufacturing such optical filters and electro-optical layers relates to layer quality, and is believed to result from the so-called line of sight nature of deposition transfer achieved in many high vacuum methods.
  • one difficulty associated with such coating methods is the tendency for the coating to be incomplete due to the presence of voids. These voids are believed to be caused by the shadow of minute surface irregularities. Since irregularities shade the regions immediately behind themselves from coating material traveling in a straight line from the source, minute projecting irregularities are found to build up and the shadows behind them are found to be deficient in, if not devoid of, layer material.
  • FIG. 1 illustrates a dichroic filter coated optical lens shown in side elevational view
  • FIG. 2 is a greatly enlarged elevational cross sectional view taken approximately along the line 22 of FIG. 1;
  • FIG. 3 is a graph showing percent transmission versus wavelength, which graph illustrates the optical property of the dichroic filter shown in FIGS. 1 and 2;
  • FIG. 4 is a schematicdiagram of a preferred apparatus for use in accordance with the invention.
  • the numeral 10 refers to an optical lens having multiple layers generally 12 of dichroic filter deposited on the convex surface 14 thereof.
  • the layers 12 were deposited in accordance with the method of this invention, and specifically, in accordance with the preferred embodiment described hereinafter in the example.
  • the filter segment illustrated in FIG. 2 includes a glass substrate 16 which is provided with a first coating 18 of iron oxide, a second layer 20 comprising chromium oxide, a third layer 22 comprising iron oxide, a fourth layer 24 comprising chromium oxide and an outer layer 26 comprising iron oxide.
  • a rather sharp interface 28 is shown between glass substrate 16 and layer 18.
  • transition zone 30 occurs between layer 18 and 20, and transition zones 32, 34, 36 occur respectively between layers 20, and 22, 22 and 24, and 24 and 26. These transition zones represent relatively narrow transition in which the zone has decreasing concentration of the inner layer material and increasing concentration of the nextouter material at points increasing in distance from the substrate.
  • the coated lens of FIG. 1 and FIG. 2 has optical properties illustrated in the graph of FIG. 3. It is noted that the percent transmission of light having wavelengths greater than 0.7 is virtually constant at about 8 percent. However, percent transmission of light at wavelengths less than 0.4 is substantially zero.
  • Vaporizers 40, 42 in this embodiment, have an internal volume of about one pint. Vaporizers 40, 42 are heated by heating means 44, 46 respectively, which are diagrammatically illustrated by resistance coils. Any convenient, compatible method of, and apparatus for, heating vaporizers 40, 42 can be used. It is most desirable that heating means 44, 46 include means for automatically temperature-regulating vaporizers 40, 42. Either or both vaporizers 40, 42 can be supplied with a stream of helium or other inert gas through manifold 50 and conduits 52, 54, respectively.
  • Elements 53, 55, respectively, indicate supply and metering system by which respective volatile (or gaseous) reactant meterial is charged to vaporizer mixers 40, and 42, respectively.
  • vaporizer mixers 40, and 42 For extremely precise control of vaporizer output rate, it is preferred to operate vaporizers practically dry, with sweep passing through, with the volatile liquid, being continuously added by means of a conventional constant advance piston, preferably one driven by a geared-down variable speed electric motor in a conventional manner.
  • Elements 56, 58 schematically represent gas flow measuring and control devices.
  • vaporizer flow is shown passing through submerged porous plates 59, 59', any conventional means for intimately contacting vaporizer sweep gas with vaporizing material can be used, e.g., a submerged inlet, fritted plate, etc.
  • Conduits 60, 62 carry effluent gas mixture from vaporizers 40, 42 respectively, to a second manifold 64.
  • Valves 66, 68 provide on-off flow control from respective vaporizers 40, 42 to manifold 64.
  • Devices 69, 69 are intended schematically to illustrate vented pressure-relief safety valves.
  • Manifold 64 receives conduits 70, 72, and 74 for supplying reactant or sweep gases, e.g., CO 0 and N respectively.
  • Elements designated as 76, 78, and 80 are intended schematically to indicate flow measuring and control devices for measuring and controlling respective gas flow in conduits 70, 72 and 74, respectively.
  • Conduit 74 receives a gas stream from manifold 82.
  • Manifold 82 also supplies conduit 84 which is equipped with on-off valve 86.
  • Manifold 64 empties into mix chamber which has a relatively large volume, about 1 gallon, and preferably includes a number of baffles 92.
  • Mix chamber 90 is equipped with temperature regulating heating means 94, which temperature regulating device is diagrammatically illustrated.
  • Mix chamber effluent is carried by way of conduit 96 from chamber 90, past on-off valve 98 into conduit 99 which is hermetically joined to coating chamber 100.
  • the temperature of the dilute gas stream being conveyed to chamber 100 is maintained below the deposition temperature, and below a temperature at which chemical reaction in the vapor phase is significant.
  • Coating chamber 100 is of relatively large volume, about four cubic feet including the volume of contents, and includes supports 102, 104 for supporting a plurality of lenses 10.
  • supports 102, 104 are shown highly perforated to facilitate gas movement around lenses 10.
  • Elements 102, 104 are intended to schematically illustrate either supports or separators each of which is carrying a layer of lenses 10. It is noted that'a first layer of lenses 10 is supported on element 102 and a separate layer of lenses is supported on element 104. It is also noted that lenses 10 are separated from one another horizontally, as well, to provide ready access of the gas phase in chamber 100 to the faces of lenses 10.
  • Chamber 100 vents through vented exit conduit 106 and the flow through exit 106 can be regulated by valve 108.
  • Lenses 10 in chamber 100 are maintained at substantially constant temperature, e.g., 200C, by heater 110.
  • the heater can be a high resistance type heater, microwave or similar heater.
  • Mechanical pump 112 can be used to facilitate flow through coating chamber 100, and to provide the necessary pressure increase to recycle a portion or substantially all of the gas stream through recycle line 116 back through the system.
  • Element 114 represents a conventional liquid nitrogen trap for freezing substantially all of the condensibles out of the recycled stream.
  • Cooling means 120 schematically indicated as a coiled water-cooled tubing is provided to keep conduit 99 from being excessively heated due to conduction from chamber 100. Appearance of smoke emitting from conduit 99 indicates temperature of the gas stream is too high, and heat input must be reduced upstream.
  • the lens is cleaned in strong acid, e.g., concentrated sulfuric, nitric, or the like, to remove all possible organic and inorganic contaminants.
  • This acid treatment is followed by a water rinse and a neutralizing step.
  • the glass is immersed in a solution of ammonium hydroxide and hydrogen peroxide.
  • a second water rinse follows, and the glass is dried in a solvent mixture that absorbs water clinging to the glass and allows flash drying Without residue.
  • a preferred drying mixture is a mixture of ethanol, methanol, isoamyl acetate, and isobutanol in the ratio of 5:l:0.5:0.4. After drying the glass is ready for deposition.
  • the thus cleaned glass is transferred to supports 102, 104 in chamber 100 using care not to re-contaminate the surface to be coated, and is then heated to 200C.
  • the process is started by flushing the system comprising manifold 82, conduit 80, 84, manifold 86, mix chamber 90, conduit 99, chamber 100 and vent 106 with a nitrogen sweep.
  • any other inert gas such as helium, neon, or other noble gases can be used for the sweep.
  • lines leading to and coming from vaporizers 40, 42 likewise be swept with an inert gas at the initial stage of the method. After the initial sweep is completed valves 86, 80 are closed, thus interrupting the flow of nitrogen.
  • Valve 76 is opened and adjusted to provide a flow rate of 5,000 ml/min of carbon dioxide.
  • Valve 78 is regulated to provide a flow rate of oxygen of 5 ml/min into manifold 64.
  • Vaporizer 40 is charged with iron amyl-acetonate and is heated to elevated temperature somewhat below the atmospheric pressure boiling point of iron-amyl-acetonate. Vaporizer 40 is then swept with helium admitted from manifold 50 through conduit 52 at a flow of 5,000 ml/min regulated by adjustment of flow measuring and controlling device 56. Hence, the carbon dioxide, oxygen, and the helium carrying gaseous iron amyl-acetonate are thoroughly mixed in manifold 64 and in mix chamber 90.
  • valves 56, 66 are closed and valves 68, 58 are opened.
  • Valve 58 is adjusted to regulate the sweep flow through vaporizer 42 at about 5,000 ml/min. Vaporizer 42 had been previously charged .with chromium carbonyl and is maintained at a temperature somewhat below the boiling point of chromium carbonyl. Because of the high volume sweep rate, vaporizers 40, 42 are maintained at a temperature below the atmospheric pressure boiling point of the material being vaporized.
  • the primary chromium carbonyl-containing helium stream now entering manifold 64 through conduit 62 is likewise mixed with the secondary carbon dioxide-oxygen stream which is maintained at the constant flow levels defined above, and the primary and secondary streams are thoroughly mixed and the temperature is equilibrated in mixing chamber 90.
  • the mixture resulting from the primary and secondary streams may be considered to be a tertiary stream containing chromium carbonyl and oxygen in low level.
  • the concentration of the iron amyl-acetonate in the gas in manifold 64 and mix chamber 70 abruptly drops and the concentration of chromium carbonyl in manifold 64 and mix chamber 90 abruptly increases to its equilibrium level.
  • the chromium carbonyl-containing tertiary gas stream is conveyed through conduit 99 into largevolume deposition chamber 100.
  • concentration of iron amyl-acetonate in the reaction chamber 100 will decline gradually, relatively speaking, as the concentration of chromium carbonyl in the reaction chamber 100 gradually increases to its equilibrium level, i.e., about the concentration in the tertiary stream.
  • the deposition of the respective films on respective substrates 10 during this relatively short period of time in which a mixture of iron amylacetonate and chromium carbonyl is available results in the presence of transition zones 30, 32, 34 and 36.
  • the period of time during which iron amylacetonate concentration in chamber 100 is decreasing and in which the concentration of chromium carbonyl in chamber 100 is increasing depends primarily on gas flow rates, since the volume of chamber 100 is constant. This reliably results in the formation of a uniform zone 30 between layers 18-20 in separate runs, provided gas flow rates and temperatures are the same in each separate run.
  • a layer which is substantially chromium oxide is deposited. After lapse of another predetermined period of time, during which a high quality chromium oxide layer is deposited,-
  • valves 68, 58 are closed. Valves 56, 66 are immediately reopened and the flow of helium through vaporizer 40 is regulated to again provide 5,000 m./min.
  • the concentration of chromium carbonyl in manifold 64 and mixer very abruptly drops to substantially zero, and the concentration of iron amyl-acetonate very abruptly increases to substantially its equilibrium level.
  • the primary gas stream again contains iron acetyl acetonate
  • the secondary gas stream still contains a low level of oxygen
  • the tertiary stream leaving mixer 90 is a homogeneous mixture of the two streams.
  • Example I The procedure described in Example I hereinbefore includes a high velocity sweeps passing through the vaporizers. It is not essential that such a sweep pass through the vaporizer in accordance with this invention. It is essential however that the volatile reactant be thoroughly admixed and diluted with the inert carrier stream prior to contacting the substrate. Thus, for example, introduction of pure volatile reactant directly into a large volume gas stream passing through manifold 64 is within the concept of this invention, although such operation is not most preferred. Also, it is apparent to one skilled in the art, that heat is not essential in the vaporizer, in all instances.
  • the vaporizer be operated at sufficiently high temperature for it to be maintained in a substantially dry condition with a relatively high velocity gas through-put while liquid volatile reactant is being continuously charged thereto at the required constant, although relatively slow, rate of addition.
  • the total concentration of the reactants in the inert carrier gas stream be below percent volume/- volume. It is more preferred that the concentration of the reactants in the carrier gas stream be less than 1 percent v/v, and use of concentrations of individual reactants at less than 0.1 percent v/v is most preferred. Though it may appear to be inefficient to provide the coating material at these low concentrations in the gas phase, at least in terms of mass-transfer, I now appreciate that use of the low concentration reactant streams in accordance with this invention provides layer uniformity and quality which was heretofore unattainable.
  • Any metal-eontaining vaporizable material can be charged to vaporizers 40, 42, providing that material decomposes or deposits on the hot substrate surface a desired layer composition.
  • the number of vaporizers used and the number of kinds of layers can be greater than the two which are illustrated in the example.
  • a larger number of compositions can be conveniently deposited as an optical filter. in accordance with this invention.
  • volatile material which can be used to provide an iron oxide layer include any of the volatile iron organo-metallic compounds, for example, iron pentacarbonyl, when used in conjunction with oxygen in the second sweep stream.
  • any volatile chromium compound can be used in vaporizer 42, for example, chromyl chloride.
  • the metallic compounds employed in this invention are those which exhibit a substantial vapor pressure, preferably in excess of about 40 mm Hg. at
  • the secondary carrier gas need not be limited to the carbon dioxide disclosed in the example but can be nitrogen, oxygen, H 0 or similar gases. Oxygen is used only in very low levels and only when an oxide coating is desired.
  • the primary metal-containing gas sweep stream is mixed with a secondary gas stream, in accordance with this invention, which secondary stream includes a low concentration level of a second reactant.
  • the second reactant which was selected to provide an oxide layer in the illustrated embodiment set forth above is oxygen.
  • the deposited layer be a sulfide, selenide, telluride, nitride, arsenide, phosphide, or other desired compound, it is only necessary to substitute for the low level of oxygen in the secondary stream a relatively low level of hydrogen sulfide, hydrogen selenide, hydrogen telluride, ammonia, arsine or phosphine, respectively, and the like.
  • the identity of the material being laid down to provide the optical layer can be changed by varying the makeup of the gas stream entering the deposition chamber either by varying the identity of the material being vaporized in vaporizers 40, 42 and the like, or alternatively, in accordance with this invention, the material entering the manifold from the vaporizers, e.g., from vaporizer 40, can remain constant. in the latter instance the second reactant, e.g., 0 being mixed with the CO can be eliminated and can be replaced by similar amounts of a third reactant, e.g., H S, for mixing with the CO to provide an H S-CO secondary stream. Alternating the makeup of the secondary stream in this manner would provide alternating layers of iron oxide and iron sulfide, for example.
  • a doped layer can be deposited using the method of this invention by adding very low levels of volatile activator-metallic compounds to either the compound in vaporizer, or into the secondary reactant gas stream.
  • volatile activator-metallic compounds for example, tetraethyl lead can be vaporized in a N stream at 5,000 ml/min sweep at 25C vaporizer temperature.
  • the secondary reactant could be H S, at 5 m./min instead of O Argon would be used instead of CO ln second vaporizer, silver or copper activator precursor, e.g., copper formate is vaporized in argon or helium at 100C temperature or silver chloride is vaporized at 400C.
  • the metal itself, can be vaporized and diluted in accordance with the present invention for incorporation into a layer, especially as a dopant. It is also contemplated that an optical component such as a filter comprising a single deposited optical filter layer can be deposited in accordance with this invention.
  • An example of an application of the method of this invention to the deposition of a layer coating which exhibits a continuous and continual transition from one density to another density is the use of this invention to provide a coating on glass fiber optic fibers.
  • a layer of material having a relatively low index of refraction is initially deposited on the glass fiber, and the concentration of thelayer precursor in the sweep gas phase is gradually decreased over a relatively long period of time, e.g., a half hour.
  • the concentration of a second layer precursor -i.e., one which provides a layer which exhibits a relatively high index of refraction, is gradually increased during the same period of time.
  • This provides a transition zone layer or coating on the glass fiber which exhibits a low index of refraction of the coating gradually increasing with increased distance from the fiber through the coating layer.
  • a mirror layer can be deposited at the outer surface of the thus coated fiber as described herein, also in accordancewith this invention. Such coatings improve reflection characteristics and absorbance to prevent interfere'nce from neighboring fibers.
  • the method of this invention is also highly useful for depositing opaque, or mirror layers, as well as for depositing transparent layers.
  • an exterior oxide layer of a desired metal is deposited as disclosed herein.
  • the oxide is then reduced in an oxygen-free atmosphere, e.g., with hydrogen, ammonia, carbon monoxide, or the like, most preferably by introducing the reducing gas into a high velocity stream in low concentration, e.g., at the ml/min rate in a 10,000 ml/min sweep.
  • osmium or rhodium mirrors do not need an oxide shielding layer deposited on the top thereof.
  • these layers i.e., osmium or rhodium, are preferably laid down on a foundation layer of an oxide of tin, titanium, chromium, or iron.
  • a preferred over-layer for use on a mirror film layer is silicon dioxide.
  • an iron mirror flushing with carbon dioxide prior to exposure to atmospheric oxygen passivates the mirror metal for at least temporary corrosion protection. In the latter case it is not necessary to deposit an oxide layer before exposing the metal to atmospheric oxygen.
  • a thin film of photo-sensitive resist can be applied to a glass substrate cleaned as in Example I.
  • a photoresist relief pattern (either positive or negative) is generated and developed on the substrate, e.g., see Photo Fabrication pamphlets numbered P. 7 and P. 91 respectively published by Eastman Kodak Company, the contents of which are incorporated herein by reference thereto.
  • Substrates so patterned, are transferred to coating chamber and the flush and layer forming procedure of Example I is repeated to produce a desired layer. After a layer is deposited, the stencil is removed by a conventional procedure.
  • the preferred layer or layers which are deposited is a metal oxide, e.g., an oxide of iron, chromium, cobalt, nickel, uranium, copper, manganese, vanadium, rare earths, lead, etc.
  • a metal oxide e.g., an oxide of iron, chromium, cobalt, nickel, uranium, copper, manganese, vanadium, rare earths, lead, etc.
  • a single layer can suffice.
  • lf reflection or dichroic characteristics are desired, multiple layers are used, e.g., as illustrated in Example I.
  • a reactant composition is selected to produce an oxide which is then reduced by dilute reducing gas to a metallic mirror deposit.
  • any reducing gas sufficiently reductive to reduce the specific metallic oxide to the metal can be used.
  • an exterior iron oxide layer is reduced, in accordance with this invention, using hydrogen, carbon monoxide, methane, or the like.
  • the sweep atmosphere in which the reducing gas is transported be nitrogen.
  • lf passivation is required, e.g., with an iron mirror, carbon dioxide sweep over the coating or deposition is adequate for at least temporary protection.
  • a silicon dioxide layer or other protective oxide layer is also eminently satisfactory.
  • a preferred method for providing a silicon dioxide overcoat for a mirror layer includes vaporizing tetraethoxysilanol in a vaporizer with an inert gas sweep, and in a second dilute sweep, adding oxygen, and admixing these streams under the conditions described in Example I herein.
  • tetraethyl lead can be vaporized in a high velocity inert gas sweep through vaporizer and low concentrations of hydrogen sulfide provided in the second sweep gas.
  • Silver chloride or copper formate can be vaporized at an extremely low rate, in a second vaporizer, as described hereinbefore, to deposit minute levels of silver or copper dopant in the lead sulfide layer.
  • the resulting silver or copper doped lead sulfide can function as an optical sensor providing electrical readout.
  • the table is presented herein to illustrate the farreaching applicability of the method of this invention, with respect to elemental constitutents of the layer compound.
  • illustrative volatile compounds or elements are set forth, and arranged in alphabetical order according to the chemical symbol for the element involved. All temperatures are suggested temperatures and are provided only for the purpose of illustration, and not for limitation.
  • Dop. is an abbreviation for Dopant, Min, for Mirror, and Trans. for transparent layer.
  • a Yes under the respective column heading indicates the material set forth is readily used in accordance with this invention to provide a dopant, opaque layer (mirror) or transparent layer, respectively.
  • the entire process of this invention is preferably carried on at substantially atmospheric pressure. However, it is not essential that all portions of the system be maintained at precisely atmospheric pressure. In fact, it is highly desirable to provide the input gases at a pressure somewhat above atmospheric pressure, e.g., 5-l 5 psig, so that the flow rates through the system can be maintained at constant value. Also, to provide a higher TABLE Metal Material Being Vap. Deposit Formula Metal Name Vaporized Temp. Temp. Dop. Mir Trans.
  • Ag Silver Silver Chloride 400 300 Yes Yes Al Aluminum Al l 50 200 Yes Yes As Arsenic Arsine (AsH gas 200 Yes Yes Chloridc(AsCl 30 200 Yes Yes Av Gold (C H P-AuCl 30 I Yes Yes Be Beryllium diethyl beryllium, 30 200 Yes Yes dimethyl, I00 200 Yes Yes ditert butyl 30 200 Yes Yes Bi Bismuth BiH gas 200 Yes Yes BiCl; 200 200 Yes Yes 8 Boron lhH gas 300 Yes Yes Cd Cadmium Metal 400 Cond Yes Co Cobalt Co(CO) 30 200 Yes Yes Yes acetylacetonate 30 200 Yes Yes Yes Cr Chromium dicumene chromium 50 200 Yes Yes Yes Yes Yes acetyl acetonate 100 250 Yes Yes Yes ehromyl chloride 30 300 Yes Yes Yes Cr(CO), 30 300 Yes Yes Yes Yes Cs Cesium metal 400 Cond Yes 300 Cu Copper Formate I00 300 Yes Yes Yes Yes Yes acetyl acetonate
  • Rh Rhodium RhCl 03 CO 50 200 Yes Yes S Sulfur Sulfur 300 Cond.
  • Sb Antimony SbCl 100 500 Yes Yes Yes Yes SbH gas lOO Yes Yes Yes Se Selenium Sell gas 300 Yes Yes Yes Si Silicon metal 500 Cond.
  • pressures higher than atmospheric pressure can be employed, providing the essential concentration limitations are observed though elevated pressure is not necessary.
  • pressures in the range 0.1 to 4 atmospheres are eminently satisfactory.
  • the deposition temperatures useful in accordance with this invention are preferably in the range 40 to 400C.
  • the more preferred temperatures range from about 100 to 280C inclusive. Higher deposition temperatures are sometimes useful. It is important that the dilute gas stream moving towards chamber 100 be maintained at temperatures below deposition temperatures when a chemical reaction is involved in the deposition mechanism.
  • Those embodiments in which the primary and secondary streams carry first and second reactants which result in a third material in the layer, e.g., as in the detailed illustrated example herein, are of this type.
  • condensation when elemental metal is vaporized and condensed, it is imat least at a reduced rate if it is intended to change over from one deposition layer to another, in order to reduce the time in which the transition zones, e.g., 30, 32, 34, 36, are being laid down.
  • the detailed example set forth above is a preferred embodiment in which relatively narrow transition zones are automatically laid down, it is not essential that in all instances such transition zones be laid down.
  • the entire system could be flushed with an inert sweep gas, e.g., C0,, or N (or operated with valves 66, 68 closed when trap 114 is operating and recycle mode prevails) and the second deposition material, e.g., chromium carbonyl, with low level of oxygen, can be introduced into chamber 100 in a dilute sweep flow with the result that no iron amyl acetate is present during deposition of the second layer, e.g., chromium oxide.
  • an inert sweep gas e.g., C0,, or N
  • the second deposition material e.g., chromium carbonyl, with low level of oxygen
  • Such an embodiment provides sharp demarcation between the respective iron oxide and chromium oxide layers.
  • the operation of the apparatus. of this invention be as described since this provides the relatively narrow transition zones 30, 32, 34, 36 which, for some purposes, are believed to be highly desirable.
  • the magnitude of zones 30, 32, 34, 36 can be increased by providing a longer period of time in which several deposition materials are being admitted simultaneously to manifold 64, e.g., through both conduits 60, 62, inthe example.
  • manifold 64 e.g., through both conduits 60, 62, inthe example.
  • Such an embodiment in which several materials are being vaporized simultaneously requires careful'control of vaporizer input rates in order to assure a high degree of reproductivity from batch to batch, however. Since the flow rates set forth in the detailed example herein are constant, and since a given apparatus will be constant with respect to its gas-occupied volume and other structural dimensions, controlling the other parameters, i.e., time, and temperature, provides for highly reproducible dimensions of layers and transition zones. Controlling the period of time in which the deposition material is admitted to manifold 64 effectively and reproducibly controls the magnitude of the corresponding layer being laid down on lenseslO, given constant temperature of substrate from layerto layer.
  • the substrates which can be used in accordance with this invention include glass, ceramic, and metal, e.g., stainless steel, as well as plastics, e.g., teflon, phenolics, etc., and the like.
  • plastic substrates it is preferred that they be selected from the class of plastics known as thermosets.
  • the method of this invention provides uniform layers regardlessof contour, shape, or line-of-sight accessibility of the substrate surface and regardless of number of substrates being processed.
  • the method of this invention is likewise singularly beneficial in depositing minute microscopic patterns, e.g., microminiature patterns, on a substrate.
  • this invention is not directed to any particular method of masking or shielding the substrate whereby a particular pattern can be laid down. It is preferred, however, that photographyrelated techniques be employed to develop masks or shields on the substrate.
  • the combination of the conventional photo-developed pattern generation technique with the dilute sweep layer deposition method of this invention produces a new dimension in manufacture of microminiature patterned layers involving no manual manipulations relating to the production of the layer design on the substrate, only those manipulations involving handling of the substrate itself. Hence the resulting layers are deposited in patterns which are extremely clean-edged even under high magnification.
  • this invention provides a substantial advance in the art of simultaneously manufacturing large numbers of layered products, e.g., selectively deposited patterns, optical filters, such as di- 14 chroic' filters, and for simultaneously depositing such layers on all surfaces of the products unless those surfaces are appropriately shielded.
  • a method of depositing a micro-thin opaque or transparent layer on a substrate comprising: maintaining said substrate at a deposition temperature between [00C and 300C; forming a dilute gaseous mixture of vapor of a first metal-containing reactant in an inert gas stream, forming a second gaseous mixture comprising vapor of a second reactant in an inert gas stream, admixing said first and second mixtures, and contacting the resulting admixture in a high velocity stream with said substrate while it is at said deposition temperature at a pressure in the range 0.1 to 4 atmospheres, the total concentration of the reactants in the resulting admixture being less than 5 percent v/v and continuing said contacting until said layer is formed on said substrate.
  • a method of depositing micro-thin oxide layer on a substrate comprising: sweeping a substrate which is maintained at a temperature between l00280C with a sweep gas containing an organo-metallic compound at a concentration less than 5 percent v/v in an inert carrier gas therein, said gas sweep containing oxygen at a concentration less than 0.1 percent v/v, and continuing said sweeping for a period of time sufficient to form said layer on said substrate.
  • a method of making an opaque film on a substrate comprising: forming a micro-thin oxide layer on the substrate, by a method comprising maintaining the substrate at a deposition temperature between C to 300C, sweeping said substrate with a dilute gaseous mixture of a metal-containing vaporizable material, and oxygen in an inert carrier gas stream, said material and oxygen being present in the inert carrier gas stream in a total concentration not exceeding 5 percent v/v, said sweeping phase taking place at a pressure between 0.1 and 4 atmospheres; and continuing said sweeping for a period of time until said micro-thin oxide layer is formed on said substrate; heating the resulting substrate to a temperature in the range l280C and sweeping the thus heated substrate with an inert gas carrier containing a reducing reactant in an amount less than percent v/v therein.
  • a method of manufacturing an optical filter which includes a multiple layer light filtering coating on the surface of an optical substrate comprises the steps of:
  • a first dilute gaseous coating mixture including at least one gaseous metal-containing material and a second reactant in an inert carrier gas, said mixture being capable of depositing at said elevated temperature on said substrate a film containing a first metal compound while continuously venting gas from said chamber, and continuing the continuous introducing and venting of step 4 for a period of time sufficient for a first layer to form on said substrate;
  • introducing into the chamber a second gaseous coating mixture including at least one gaseous metal-containing material and a third reactant in an inert carrier gas, said second mixture being capable of depositing at said elevated temperature a film containing a second metal compound, thereby gradually reducing the concentration of said first coating mixture, while increasing the concentration of said second coating mixture, wherein the total concentration of said metal-containing materials and said second reactants in said coating mixture in steps 4 and 5 is less than 5 percent v/v while continuously venting gas from said chamber; and continuing the continuous introducing and venting of step 5 for a period of time sufficient for a second layer to form on the first layer.
  • a method of manufacturing multiple layer optical filters comprising the steps of:
  • a gaseous member selected from the group H 5, Asl-l PH NH;,, and H Te, to provide a coating-gas stream;
  • said first metallic compound being reactive with said gaseous member to develop a layer on said substrate
  • a method of manufacturing dichroic filters comprising the steps of:
  • heating filter substrates in a coating chamber to a temperature in the range l00-280C;
  • said chamber being maintained at substantially atmospheric pressure
  • first dilute gaseous admixture of a first reactive metallic compound and chemically inert sweep gas admixing with said first admixture a relatively small amount of a second reactive compound, which second reactive compound is characterized as coacting with said first admixture to deposit a first filter layer material on said heated substrate, the mixture resulting being a second gaseous mixture;
  • a third gaseous admixture of a vaporizable metallic compound and inert carrier gas admixing the third mixture thoroughly with a relatively small amount of fourth reactive gaseous compound characterized by its ability to co-act with said third mixture to form a second filter layer material, on said first filter layer material, the admixing of said fourth compound with said third mixture resulting in a fifth gaseous mixture; and sweeping the fifth gaseous mixture over the substrate by discharging the fifth gaseous mixture into the coating chamber and continuously venting the chamber, wherein the total concentration of reactants in any substratecontacting gas stream is 5 percent v/v or less, said sweeping continuing in each instance, until a respective filter layer is deposited.
  • a method of selectively depositing a micro-thin layer on a substrate comprising: maintaining the substrate at an elevated temperature between C and 300C; contacting said substrate with a dilute gaseous mixture containing a deposit precursor consisting of a metal-containing material in vapor form and a second reactive compound characterized as co-acting with said material to form a first filter layer on the heated substrate in a concentration not exceeding 5 percent v/v, and continuing the contacting for a period of time sufficient for a layer to be deposited on said substrate, said depositing taking place through stencil means for preventing deposition in nonselected areas, and for depositing said layers in selected areas.
  • a method of depositing a micro-thin optical layer on a substrate comprising: maintaining said substrate at a deposition temperature between 100C and 300C; sweeping said substrate with a sweep of a dilute gaseous mixture containing a depositprecursor comprising a metal-containing vaporizable material in vapor form and a second reactant capable of reacting with the precursor to produce an optically active layer on said substrate, said reactants being in an inert carrier gas stream in which the total concentration of deposit precursor and second reactant does not exceed 5 percent v/v; and continuing said sweeping for a period of time sufficient to form an optically active layer on said substrate.
  • a gaseous mixture includes a plurality of reactants which produce a layer having a composition which is different from any of the reactants, and in which gaseous mixtures a concentration of no one reactant is in excess of l percent v/v.
  • a method of forming a uniform oxide coating on a substrate comprising: maintaining said substrate at a deposition temperature between 100C and 300C; sweeping said substrate with a dilute gaseous mixture of a metal-containing vaporizable material, and oxygen in an inert carrier gas stream, said material and oxygen being present in said inert carrier gas stream in a total concentration not exceeding percent v/v, said sweeping taking place at a pressure between 0.1 and 4 atmospheres; and continuing said sweeping for a period of time until a metal oxide layer is formed on said substrate.
  • the metal containing material is selected from the group consisting of silver chloride, Al l arsenic chloride, arsine (C H P-AuCl, dimethyl beryllium, ditert butyl beryllium, Bil-l BiCl B H cadmium metal, cobalt acetylacetonate, Co(CO) dicumene chromium, chromium acetyl acetonate, chromyl chloride, Cr(CO) cesium metal, copper formate,copper acetyl acetonate, Fe( CO) iron acetylacetonate, iron amyl-acetonate, GeH,,, Gel mercury metal, diethyl mercury, iodine (l potassium metal, magnesium metal, manganese dicyclopentadienyl, Mo(CO) Ni(CO) nickel acetylacetonate, Os(CO) Cl phosphorous, Pl-l tetraethy
  • a method of depositing an optically active layer on a substrate comprising: maintaining substrate at a deposition temperature between C and 300C; sweeping said substrate with a sweep of dilute gaseous mixture containing a primary and secondary reactant in an inert carrier gas stream wherein said primary reactant is a metal-containing vaporizable material, and wherein said secondary reactant is a member selected from the group consisting of oxygen, hydrogen sulfide, hydrogen selenide, hydrogen telluride, ammonia, arsine, and phosphine, and wherein said reactants are present in a concentration not exceeding 5 percent v/v, and continuing said sweeping for a period of time sufficient to form an optically active coating on said substrate.
  • said primary reactant is a member selected from the group consisting of silver chloride, A1 1 arsenic chloride, arsine, (C H P'AuCl, dimethyl beryllium, diethyl beryllium, ditert butyl beryllium, BiH BiCl B H cadmium metal, cobalt acetylacetonate, Co(CO) dicumene chromium, chromium acetyl acetonate, chromyl chloride, Cr(CO) cesium metal, copper formate, copper acetyl acetonate, Fe(CO) iron acetylacetonate, iron amyl-acetonate, GeH Gel mercury metal, diethyl mercury, iodine (l potassium metal, magnesium metal, manganese dicyclopentadienyl, Mo(CO) Ni(- CO) nickel acetylacetonate, Os(CO) Cl phosphorous, PH
  • W(CO) zinc metal and diethyl zinc.

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US00096428A 1970-12-09 1970-12-09 Deposition of single or multiple layers on substrates from dilute gas sweep to produce optical components, electro-optical components, and the like Expired - Lifetime US3808035A (en)

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Application Number Priority Date Filing Date Title
US00096428A US3808035A (en) 1970-12-09 1970-12-09 Deposition of single or multiple layers on substrates from dilute gas sweep to produce optical components, electro-optical components, and the like
CH1160971A CH558837A (de) 1970-12-09 1971-08-06 Verfahren zum aufbringen duenner schichten auf substrate sowie vorrichtung zur durchfuehrung des verfahrens.
DE2140092A DE2140092C3 (de) 1970-12-09 1971-08-10 Verfahren zur Herstellung dünner Schichten auf Substraten
GB3816871A GB1356040A (en) 1970-12-09 1971-08-13 Methods of producing thin uniform optical layers on substrates
NL7113284A NL7113284A (sk) 1970-12-09 1971-09-28
FR7135435A FR2117849B1 (sk) 1970-12-09 1971-10-01
JP8682771A JPS5318530B1 (sk) 1970-12-09 1971-11-02
BE774932A BE774932A (fr) 1970-12-09 1971-11-04 Depot de couches minces en phase vapeur sur des
IT30901/71A IT941737B (it) 1970-12-09 1971-11-10 Metodo per l applicazione di stra ti sottili su substrati ed apparec chiatura per l attuazione del metodo

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Cited By (27)

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US4140814A (en) * 1977-12-01 1979-02-20 Texas Instruments Incorporated Plasma deposition of transparent conductive layers
EP0066288A1 (en) * 1981-06-01 1982-12-08 Kabushiki Kaisha Toshiba Method for ion-implanting metal elements
EP0097819A1 (en) * 1982-06-30 1984-01-11 International Business Machines Corporation Photo deposition of metals onto substrates
EP0103470A1 (en) * 1982-09-13 1984-03-21 Hitachi, Ltd. Titanium disulfide thin film and process for fabricating the same
EP0112989A1 (en) * 1982-12-30 1984-07-11 International Business Machines Corporation Copper texturing process
EP0127373A2 (en) * 1983-05-26 1984-12-05 Hitachi, Ltd. Cathode structure for a thin film battery, and a battery having such a cathode structure
DE3438437A1 (de) * 1983-10-20 1985-05-02 Ricoh Co., Ltd., Tokio/Tokyo Transparenter, elektrisch leitender film
EP0140625A1 (en) * 1983-10-19 1985-05-08 The Marconi Company Limited Tellurides
WO1985003460A1 (en) * 1984-02-13 1985-08-15 Schmitt Jerome J Iii Method and apparatus for the gas jet deposition of conducting and dielectric thin solid films and products produced thereby
US4545646A (en) * 1983-09-02 1985-10-08 Hughes Aircraft Company Process for forming a graded index optical material and structures formed thereby
US4676992A (en) * 1984-09-19 1987-06-30 D.M.E. Process for the deposition, on optical substrates, of antireflection coatings capable of being engraved
US4717596A (en) * 1985-10-30 1988-01-05 International Business Machines Corporation Method for vacuum vapor deposition with improved mass flow control
US4859492A (en) * 1986-02-24 1989-08-22 Hughes Aircraft Company Process for forming an environmentally stable optical coating thereby
EP0353461A1 (en) * 1988-07-05 1990-02-07 Ppg Industries, Inc. Chemical vapor deposition of bismuth oxide
US5431800A (en) * 1993-11-05 1995-07-11 The University Of Toledo Layered electrodes with inorganic thin films and method for producing the same
US5534314A (en) * 1994-08-31 1996-07-09 University Of Virginia Patent Foundation Directed vapor deposition of electron beam evaporant
US5571332A (en) * 1995-02-10 1996-11-05 Jet Process Corporation Electron jet vapor deposition system
FR2758318A1 (fr) * 1997-01-15 1998-07-17 Air Liquide Procede et installation d'elaboration d'un melange gazeux comportant un gaz porteur, un gaz oxydant et un silane
US5789086A (en) * 1990-03-05 1998-08-04 Ohmi; Tadahiro Stainless steel surface having passivation film
US6613385B2 (en) * 2001-04-23 2003-09-02 The United States Of America As Represented By The Secretary Of The Navy Highly spin-polarized chromium dioxide thin films prepared by CVD using chromyl chloride precursor
US6656373B1 (en) * 1999-07-09 2003-12-02 Wavefront Sciences, Inc. Apodized micro-lenses for Hartmann wavefront sensing and method for fabricating desired profiles
US20040045889A1 (en) * 2002-09-11 2004-03-11 Planar Systems, Inc. High conductivity particle filter
US20050092244A1 (en) * 2003-10-29 2005-05-05 Samsung Electronics Co., Ltd. Diffusion system
US20050147749A1 (en) * 2004-01-05 2005-07-07 Msp Corporation High-performance vaporizer for liquid-precursor and multi-liquid-precursor vaporization in semiconductor thin film deposition
US20090304918A1 (en) * 2005-04-25 2009-12-10 Georg Mayer Method and apparatus for coating objects
US20150225845A1 (en) * 2014-02-12 2015-08-13 Electronics And Telecommunications Research Institute Method for forming metal oxide thin film and device for printing metal oxide thin film
US10308541B2 (en) 2014-11-13 2019-06-04 Gerresheimer Glas Gmbh Glass forming machine particle filter, a plunger unit, a blow head, a blow head support and a glass forming machine adapted to or comprising said filter

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ZA735383B (en) * 1972-12-15 1975-03-26 Ppg Industries Inc Coating composition vaporizer
CA1134214A (en) * 1978-03-08 1982-10-26 Roy G. Gordon Deposition method
JPS5772318A (en) * 1980-10-24 1982-05-06 Seiko Epson Corp Vapor growth method
DE102010000479A1 (de) * 2010-02-19 2011-08-25 Aixtron Ag, 52134 Vorrichtung zur Homogenisierung eines verdampften Aerosols sowie Vorrichtung zum Abscheiden einer organischen Schicht auf einem Substrat mit einer derartigen Homogenisierungseinrichtung

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US2847330A (en) * 1954-07-28 1958-08-12 Ohio Commw Eng Co Method and apparatus for gas plating printing circuits
US3014815A (en) * 1957-11-04 1961-12-26 Philips Corp Method of providing articles with metal oxide layers
US3032397A (en) * 1957-01-25 1962-05-01 Du Pont Preparation of metal nitride pigment flakes
US3081200A (en) * 1959-04-10 1963-03-12 Armour Res Found Method of applying an oxide coating onto a non-porous refractory substrate
US3142586A (en) * 1961-12-11 1964-07-28 Clairex Corp Method for the manufacture of photosensitive elements
US3306768A (en) * 1964-01-08 1967-02-28 Motorola Inc Method of forming thin oxide films

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DE1812455C3 (de) * 1968-12-03 1980-03-13 Siemens Ag, 1000 Berlin Und 8000 Muenchen Verfahren zum Herstellen einer aus einem Metalloxyd bestehenden isolierenden Schutzschicht an der Oberfläche eines Halbleiterkristalls

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US2847330A (en) * 1954-07-28 1958-08-12 Ohio Commw Eng Co Method and apparatus for gas plating printing circuits
US2831780A (en) * 1955-04-21 1958-04-22 Du Pont Method for improving the scratch resistance and strength of glass articles
US3032397A (en) * 1957-01-25 1962-05-01 Du Pont Preparation of metal nitride pigment flakes
US3014815A (en) * 1957-11-04 1961-12-26 Philips Corp Method of providing articles with metal oxide layers
US3081200A (en) * 1959-04-10 1963-03-12 Armour Res Found Method of applying an oxide coating onto a non-porous refractory substrate
US3142586A (en) * 1961-12-11 1964-07-28 Clairex Corp Method for the manufacture of photosensitive elements
US3306768A (en) * 1964-01-08 1967-02-28 Motorola Inc Method of forming thin oxide films

Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4140814A (en) * 1977-12-01 1979-02-20 Texas Instruments Incorporated Plasma deposition of transparent conductive layers
EP0066288A1 (en) * 1981-06-01 1982-12-08 Kabushiki Kaisha Toshiba Method for ion-implanting metal elements
EP0097819A1 (en) * 1982-06-30 1984-01-11 International Business Machines Corporation Photo deposition of metals onto substrates
EP0103470A1 (en) * 1982-09-13 1984-03-21 Hitachi, Ltd. Titanium disulfide thin film and process for fabricating the same
EP0112989A1 (en) * 1982-12-30 1984-07-11 International Business Machines Corporation Copper texturing process
EP0127373A3 (en) * 1983-05-26 1986-12-10 Hitachi, Ltd. Cathode structure for a thin film battery, and a battery having such a cathode structure
EP0127373A2 (en) * 1983-05-26 1984-12-05 Hitachi, Ltd. Cathode structure for a thin film battery, and a battery having such a cathode structure
US4545646A (en) * 1983-09-02 1985-10-08 Hughes Aircraft Company Process for forming a graded index optical material and structures formed thereby
EP0140625A1 (en) * 1983-10-19 1985-05-08 The Marconi Company Limited Tellurides
DE3438437A1 (de) * 1983-10-20 1985-05-02 Ricoh Co., Ltd., Tokio/Tokyo Transparenter, elektrisch leitender film
US4788082A (en) * 1984-02-13 1988-11-29 Schmitt Jerome J Method and apparatus for the deposition of solid films of a material from a jet stream entraining the gaseous phase of said material
WO1985003460A1 (en) * 1984-02-13 1985-08-15 Schmitt Jerome J Iii Method and apparatus for the gas jet deposition of conducting and dielectric thin solid films and products produced thereby
US4676992A (en) * 1984-09-19 1987-06-30 D.M.E. Process for the deposition, on optical substrates, of antireflection coatings capable of being engraved
US4717596A (en) * 1985-10-30 1988-01-05 International Business Machines Corporation Method for vacuum vapor deposition with improved mass flow control
US4859492A (en) * 1986-02-24 1989-08-22 Hughes Aircraft Company Process for forming an environmentally stable optical coating thereby
EP0353461A1 (en) * 1988-07-05 1990-02-07 Ppg Industries, Inc. Chemical vapor deposition of bismuth oxide
US5789086A (en) * 1990-03-05 1998-08-04 Ohmi; Tadahiro Stainless steel surface having passivation film
US5431800A (en) * 1993-11-05 1995-07-11 The University Of Toledo Layered electrodes with inorganic thin films and method for producing the same
US5534314A (en) * 1994-08-31 1996-07-09 University Of Virginia Patent Foundation Directed vapor deposition of electron beam evaporant
US5571332A (en) * 1995-02-10 1996-11-05 Jet Process Corporation Electron jet vapor deposition system
EP0854204A1 (fr) * 1997-01-15 1998-07-22 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Procédé et installation d'élaboration d'un mélange gazeux comportant un gaz porteur, un gaz oxydant et un silane
US6177134B1 (en) 1997-01-15 2001-01-23 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Goerges Claude Process and plant for the production of a gaseous mixture containing a carrier gas an oxidizing gas and a silane
FR2758318A1 (fr) * 1997-01-15 1998-07-17 Air Liquide Procede et installation d'elaboration d'un melange gazeux comportant un gaz porteur, un gaz oxydant et un silane
US6864043B2 (en) 1999-07-09 2005-03-08 Wavefront Sciences, Inc. Apodized micro-lenses for Hartmann wavefront sensing and method for fabricating desired profiles
US6656373B1 (en) * 1999-07-09 2003-12-02 Wavefront Sciences, Inc. Apodized micro-lenses for Hartmann wavefront sensing and method for fabricating desired profiles
US20040060903A1 (en) * 1999-07-09 2004-04-01 Neal Daniel R. Apodized micro-lenses for hartmann wavefront sensing and method for fabricating desired profiles
US6613385B2 (en) * 2001-04-23 2003-09-02 The United States Of America As Represented By The Secretary Of The Navy Highly spin-polarized chromium dioxide thin films prepared by CVD using chromyl chloride precursor
US6936086B2 (en) 2002-09-11 2005-08-30 Planar Systems, Inc. High conductivity particle filter
US20040124131A1 (en) * 2002-09-11 2004-07-01 Aitchison Bradley J. Precursor material delivery system for atomic layer deposition
US20040045889A1 (en) * 2002-09-11 2004-03-11 Planar Systems, Inc. High conductivity particle filter
US7141095B2 (en) 2002-09-11 2006-11-28 Planar Systems, Inc. Precursor material delivery system for atomic layer deposition
US20050092244A1 (en) * 2003-10-29 2005-05-05 Samsung Electronics Co., Ltd. Diffusion system
EP1529855A2 (en) * 2003-10-29 2005-05-11 Samsung Electronics Co., Ltd. Diffusion system
EP1529855A3 (en) * 2003-10-29 2005-06-22 Samsung Electronics Co., Ltd. Diffusion system
CN100372067C (zh) * 2003-10-29 2008-02-27 三星电子株式会社 扩散系统
US7452423B2 (en) 2003-10-29 2008-11-18 Samsung Electronics Co., Ltd. Diffusion system
US20050147749A1 (en) * 2004-01-05 2005-07-07 Msp Corporation High-performance vaporizer for liquid-precursor and multi-liquid-precursor vaporization in semiconductor thin film deposition
US20090304918A1 (en) * 2005-04-25 2009-12-10 Georg Mayer Method and apparatus for coating objects
US20150225845A1 (en) * 2014-02-12 2015-08-13 Electronics And Telecommunications Research Institute Method for forming metal oxide thin film and device for printing metal oxide thin film
US10308541B2 (en) 2014-11-13 2019-06-04 Gerresheimer Glas Gmbh Glass forming machine particle filter, a plunger unit, a blow head, a blow head support and a glass forming machine adapted to or comprising said filter

Also Published As

Publication number Publication date
FR2117849B1 (sk) 1976-02-13
BE774932A (fr) 1972-03-01
NL7113284A (sk) 1972-06-13
DE2140092B2 (de) 1977-12-15
IT941737B (it) 1973-03-10
CH558837A (de) 1975-02-14
GB1356040A (en) 1974-06-12
JPS5318530B1 (sk) 1978-06-15
FR2117849A1 (sk) 1972-07-28
DE2140092C3 (de) 1978-08-24
DE2140092A1 (de) 1972-06-22

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