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US20040241490A1 - Substrates coated with mixtures of titanium and aluminum materials, methods for making the substrates, and cathode targets of titanium and aluminum metal - Google Patents

Substrates coated with mixtures of titanium and aluminum materials, methods for making the substrates, and cathode targets of titanium and aluminum metal Download PDF

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Publication number
US20040241490A1
US20040241490A1 US10/809,770 US80977004A US2004241490A1 US 20040241490 A1 US20040241490 A1 US 20040241490A1 US 80977004 A US80977004 A US 80977004A US 2004241490 A1 US2004241490 A1 US 2004241490A1
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Prior art keywords
aluminum
titanium
coating
layer
target
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US10/809,770
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English (en)
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James Finley
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Vitro SAB de CV
Vitro Flat Glass LLC
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Individual
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Priority to US10/809,770 priority Critical patent/US20040241490A1/en
Assigned to PPG INDUSTRIES OHIO, INC. reassignment PPG INDUSTRIES OHIO, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FINLEY, JAMES J.
Publication of US20040241490A1 publication Critical patent/US20040241490A1/en
Priority to US11/706,454 priority patent/US8597474B2/en
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: PPG INDUSTRIES OHIO, INC.
Assigned to VITRO, S.A.B. DE C.V. reassignment VITRO, S.A.B. DE C.V. CORRECTIVE ASSIGNMENT TO CORRECT THE ASSIGNEE ADDRESS PREVIOUSLY RECORDED AT REEL: 040473 FRAME: 0455. ASSIGNOR(S) HEREBY CONFIRMS THE ASSIGNMENT. Assignors: PPG INDUSTRIES OHIO, INC.
Assigned to VITRO FLAT GLASS LLC reassignment VITRO FLAT GLASS LLC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: VITRO, S.A.B. DE C.V.
Abandoned legal-status Critical Current

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    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3615—Coatings of the type glass/metal/other inorganic layers, at least one layer being non-metallic
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
    • 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
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3694—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer having a composition gradient through its thickness
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/027—Graded interfaces
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • 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
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/34—Gas-filled discharge tubes operating with cathodic sputtering
    • H01J37/3411—Constructional aspects of the reactor
    • H01J37/3414—Targets
    • H01J37/3426—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
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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
    • C03C2217/29—Mixtures
    • 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
    • C03C2217/70—Properties of coatings
    • C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
    • 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
    • C03C2217/90—Other aspects of coatings
    • C03C2217/91—Coatings containing at least one layer having a composition gradient through its thickness
    • 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
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • 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
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component

Definitions

  • the present invention relates generally to coatings comprising titanium and aluminum on substrates, methods for coating such mixtures, and titanium and aluminum-containing materials as sputtering targets.
  • Technology for depositing specific types of metallic or metal oxide-containing coatings on larger area substrates includes various methods, such as vapor deposition, like chemical vapor deposition; spray pyrolysis; sol-gel; and sputtering, such as magnetic sputtering vapor deposition (“MSVD”).
  • vapor deposition like chemical vapor deposition
  • spray pyrolysis sol-gel
  • sputtering such as magnetic sputtering vapor deposition (“MSVD”).
  • MSVD magnetic sputtering vapor deposition
  • Larger area substrates of around 1 square foot (30 square centimeters) and larger provide challenges in economically consistent production of quality coated substrates by virtue of the size of the substrate that is coated.
  • Consistency in coating uniformity and reduction of defects in the coating of larger areas require equipment that is able to handle the larger substrates and the volumes of coating material and the fabrication of the coated substrate. Such equipment is generally more expensive to purchase and operate; thus making efficient operation of the equipment imperative for cost-effective production.
  • Specific metallic (metals and/or metal oxide) containing coatings on substrates can exist as multi-layered coatings in which each layer is comprised of the same or different materials from one or more applications of the coating materials or precursors. Also, a layer of the coating can have one or more films from more than one application of the same or different materials. Examples of multi-layered coatings on a substrate are conventional silver-based low emissivity coatings that are deposited on both glass and plastic substrates, generally by sputtering.
  • cathode targets In sputtering to deposit metals and metal oxides on larger surface area substrates, like sheets or panels of light transmitting materials, like plastic or glass, cathode targets have been used of the specific metal for deposition as the metal or metal oxide on the substrate.
  • elongated cathode targets For larger area substrates of plastic and glass, such as float glass with a surface area of at least 1 square foot (30 square centimeters), elongated cathode targets have been used. The targets are elongated to a length substantially the length or width of the substrate to be coated.
  • U.S. Pat. Nos. 4,990,234 and 5,170,291 to Szczyrbowski et al. and 5,417,827 to Finley disclose sputtering silica and silicides, such as transition metal silicide (NiSi 2 ), in an oxidizing atmosphere to deposit dielectric oxide films.
  • U.S. Pat. No. 5,320,729 to Narizuka et al. discloses a sputtering target with which a high resistivity thin film consisting of silicon, titanium and aluminum, and oxygen can be produced.
  • the target is formed by selecting the grain size of silicon powder and titanium and aluminum dioxide powder drying the powders by heating and mixing the dried powders to obtain a mixed powder containing from 20 to 80 percent by weight of silicon, for example 50 to 80 percent, the remainder being titanium and aluminum dioxide, packing the mixed powder in a die, and sintering the packed powder by hot pressing to produce a target which has a two-phase mixed structure.
  • the sputtering target is used to manufacture thin film resistors and electrical circuits.
  • Sputtering cathode targets of various metallic materials are useful in vacuum deposited low emissivity (“Low-E”) coating stacks which usually have the following general layer sequence: S/(D 1 /M/P/D 2 ) R where:
  • S is a substrate, such as a transparent substrate like glass
  • D 1 is a first transparent dielectric layer, usually a metal oxide, and can include one or more transparent dielectric films;
  • M is an infrared reflective layer, usually silver or other noble metal
  • P is a primer layer to protect the underlying infrared reflective layer
  • D 2 is a second transparent dielectric film similar to D 1 ;
  • R is an integer equal to or greater than one and is the number of repetitions of the above layers.
  • the dielectric layers, D 1 and D 2 adjust the optical properties of the coating stack. These layers also provide some physical and chemical protection to the fragile infrared reflective layer(s).
  • dielectric materials are often susceptible to abrasion and corrosion as well.
  • zinc oxide e.g., as disclosed in U.S. Pat. No. 5,296,302 which usually forms a crystalline film, is susceptible to attack by acids and bases; bismuth oxide, which usually forms an amorphous film, is soluble in certain acids; tin oxide, which usually forms an amorphous film, is susceptible to attack in certain basic environments.
  • the P primer or blocker layers are incorporated into such low emissivity coatings to protect the M layer or film from oxidation during the sputtering process.
  • the M layer like silver, is susceptible to breakdown during deposition of the overlying dielectric layer or film if the oxygen to reactive gas ratio is high, e.g., greater than 20 percent of the gas volume.
  • the primer layers which can be composed of pure metal layers or ceramic layers, act as sacrificial layers by preferentially oxidizing to protect the underlying silver layer or film. Generally thicker primer layers are necessary if the low emissivity coating is to survive the high temperature of a glass fabrication process (up to 650° C. or 1202° F.), e.g., bending and tempering of soda-lime glass.
  • Low-E coating stacks have an overlaying protective overcoat of a chemically-resistant dielectric layer.
  • This layer has desirable optical properties, manageable sputter deposition characteristics, and is compatible with other materials of the coating stack.
  • the titanium dioxide films disclosed in U.S. Pat. Nos. 4,716,086 and 4,786,563 are protective films having the above qualities.
  • the primer layer continues to oxidize during high temperature processing, and it is desirable for the oxidation to continue to completion in order to reduce visible light absorption from the primer layer.
  • This effect is better utilized for metals that form metal oxides with low absorption coefficients, e.g., titanium and aluminum. For performance glazing applications, this leads to a higher visible light transmission to infrared transmittance ratio. If the oxidation continues beyond consumption of the primer layer to full oxidation, the coating can degrade and performance can suffer. Metal ions in the dielectric layers can inter-diffuse with the silver layer, and the well-defined interface can become fuzzy. This can lead to a loss of the antireflective behavior and loss of a continuous silver layer.
  • the degree of oxidation of the primer is related to several factors, including the reactivity of the metal (Gibbs free energy), the density of the oxide formed during heating, and the diffusion or dissolution of oxygen in the oxide or metal.
  • a metal such as titanium
  • Titanium in a thin film of less than around 20 Angstroms will pass through several oxidation states before reaching the thermally stable phase of TiO 2 .
  • Titanium has been a preferred choice of material for primer layers in low emissivity multi-layered coatings.
  • the present invention involves coatings of at least mixtures of titanium and aluminum-containing materials on flat and/or curved substrates that can be larger than at least 1 square foot (30 square centimeters).
  • the titanium and aluminum-containing coatings (“Ti—Al coating”) have a weight ratio of titanium-containing materials to aluminum-containing materials, respectively, in the range of around 99:1 to 1:99 for the mixture of titanium and aluminum-containing materials (“Ti—Al containing materials”), such as 40 to 80 titanium to 20 to 60 aluminum, such as 50 to 80 titanium to 20 to 50 aluminum, such as 50 to 70 titanium to 30 to 50 aluminum, such as 60 to 70 titanium to 30 to 40 aluminum.
  • Ti—Al containing materials can be via several coating techniques well know in the art, such as but not limited to vapor deposition, spray pyrolysis, sol gel and/or sputtering methods.
  • the flat or curved substrates can be, but are not limited to, non-metallic uncoated base substrates, plastics, PET, glass, light-transmitting substrates, and already coated variations of these substrates and the like in the form of flat, curved or contoured substrates.
  • the Ti—Al coating is deposited by sputtering Ti—Al containing materials from cathode targets.
  • These targets can be elongated planar or cylindrical targets comprised of at least titanium and aluminum mixtures or alloys.
  • the targets can also have other materials, such as transition metals, like silicon, silicon-transition metal, or transition metal and/or silicon.
  • the targets can also have other materials to affect the conductivity of the cathode target.
  • Targets of titanium and aluminum mixtures can be sputtered in an atmosphere comprising inert gas, nitrogen, oxygen, and/or mixtures thereof to produce titanium and aluminum metal-containing coatings including oxides, nitrides and oxynitrides, as well as metallic films on substrates.
  • the titanium and aluminum metal cathode target compositions of the present invention comprise sufficient metal to provide target stability and a desirable sputtering rate.
  • the titanium and aluminum-containing targets which as oxides, nitrides and/or oxynitrides materials are very hard and chemically resistant, produce sputtered mechanically and/or chemically durable titanium and aluminum mixture or alloy compound coatings.
  • the Ti—Al mixtures are sputtered in pure argon, or in an oxygen and argon gas mixture, the resultant titanium and aluminum mixture coating is more chemically resistant than titanium and aluminum alone and harder than titanium oxide alone.
  • a purpose of these titanium and aluminum mixtures is to provide target materials that sputter readily in inert gas, reactive gas or gas mixtures, to produce extremely durable coatings with variable optical properties.
  • Each target material combination can produce coatings with different optical constants, i.e., refractive index and absorption coefficient.
  • each target material combination can also produce coatings with a range of optical constants, which generally increase as the reactive gas mixture, with or without inert gas, such as argon, is varied from oxygen, to combinations of oxygen and nitrogen with increasing proportions of nitrogen, to nitrogen.
  • the coatings with Ti—Al mixtures permit a widening of the range of the oxidation of the primer layers and better control of the thermal processing of the low emissivity coatings.
  • FIG. 1 is a sectional view (not to scale) of a coated article incorporating features of the invention
  • FIG. 2 is a graph of coating composition versus position for a coated glass plate
  • FIG. 3 is a graph of sheet resistance versus weight percent titania for a coated article incorporating features of the invention
  • FIGS. 4 and 5 are graphs of reflectance versus time for coated articles of the invention.
  • FIG. 6 is a graph of reflectance versus time for a coated article of the invention.
  • FIG. 7 is a graph of reflectance versus time for a coated article of the invention.
  • FIG. 8 is a graph of thickness versus atomic percent aluminum for a coating of the invention.
  • FIG. 9 is a graph of sheet resistance versus position for a coated glass plate
  • FIG. 10 is a graph of sheet resistance versus weight percent aluminum for a coated article of the invention.
  • FIG. 11 is a graph of sheet resistance versus atomic percent titanium for a coating of the invention.
  • FIG. 12 is a graph of sheet resistance versus atomic percent aluminum for a coating of the invention.
  • FIGS. 13 and 14 are graphs of sheet resistance versus thickness for coatings of the invention before and after heating;
  • FIGS. 15 and 16 are graphs of transmittance versus thickness for coatings of the invention before and after heating
  • FIG. 17 is a graph of percent coating removed versus time for various coatings of the invention.
  • FIG. 18 is a graph of time until 80 percent coating removal versus atomic percent aluminum for a coating of the invention.
  • FIG. 19 is a graph of percent coating removed versus time for various coatings of the invention.
  • FIG. 20 is a graph of refractive index and extinction coefficient versus atomic percent aluminum and weight percent aluminum for coatings of the invention.
  • coating film refers to a region of a desired or selected coating composition.
  • a “coating layer” or “layer” can include one or more coating films.
  • a “coating stack” or “stack” includes one or more coating layers.
  • spatial or directional terms such as “left”, “right”, “inner”, “outer”, “above”, “below”, “top”, “bottom”, and the like, relate to the invention as it is shown in the drawing figures. However, it is to be understood that the invention can assume various alternative orientations and, accordingly, such terms are not to be considered as limiting.
  • a stated range of “1 to 10” should be considered to include any and all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, all subranges beginning with a minimum value of 1 or more and ending with a maximum value of 10 or less, e.g., 1 to 7.2, or 3.5 to 6.1, or 5.5 to 10, just to illustrate a few.
  • the terms “flat” or “substantially flat” substrate refer to a substrate that is substantially planar in form; that is, a substrate lying primarily in a single geometric plane, which substrate, as would be understood by one skilled in the art, can include slight bends, projections, or depressions therein.
  • the terms “deposited over”, “applied over”, or “provided over” mean deposited, applied, or provided on but not necessarily in contact with the surface.
  • a coating “deposited over” a substrate does not preclude the presence of one or more other coating films of the same or different composition located between the deposited coating and the substrate.
  • the substrate itself can include a coating such as those known in the art for coating substrates, such as glass and ceramics. All references referred to herein are to be understood to be incorporated by reference in their entirety.
  • the instant invention relates to titanium and aluminum-containing films or layers that can be used as dielectric, primer, and/or protective layers or films that can protect all or selected ones of the underlying coating layers or films of a coating stack from mechanical wear and/or chemical attack.
  • the embodiments of the invention can protect underlying infrared reflective metal layers or films as part of a functional film or layer and metal oxide layers of the type present in any conventional type of coating stack.
  • the titanium and aluminum-containing films or layers of the present invention can be formed or deposited over substrates by various methods, such as but not limited to sol gel, vapor deposition, and sputtering.
  • the temperature of the substrate during formation of the coating thereon should be within the range that will cause the metal containing precursor to decompose and form a coating.
  • the lower limit of this temperature range is largely affected by the decomposition temperature of the selected metal-containing precursor.
  • the minimum temperature of the substrate which will provide sufficient decomposition of the precursor is typically within the temperature range of 400° C. (752° F.) to 500° C. (932° F.).
  • the upper limit of this temperature range can be affected by the substrate being coated.
  • the substrate is a glass float ribbon and the coating is applied to the float ribbon during manufacture of the float ribbon
  • the float glass can reach temperatures in excess of 1000° C. (1832° F.).
  • the float glass ribbon is usually attenuated or sized (e.g., stretched or compressed) at temperatures above 800° C. (1472° F.). If the coating is applied to the float glass before or during attenuation, the coating can crack or crinkle as the float ribbon is stretched or compressed, respectively. Therefore, in one practice of the invention, the coating is applied when the float ribbon is dimensionally stable, e.g., below 800° C.
  • a glass float ribbon is manufactured by melting glass batch materials in a furnace and delivering the refined molten glass onto a bath of molten tin. The molten glass on the bath is pulled across the tin bath as a continuous glass ribbon while it is sized and controllably cooled to form a dimensionally stable glass float ribbon.
  • the float ribbon is removed from the tin bath and moved by conveying rolls through a lehr to anneal the float ribbon.
  • the annealed float ribbon is then moved through cutting stations on conveyor rolls where the ribbon is cut into glass sheets of desired length and width.
  • U.S. Pat. Nos. 4,466,562 and 4,671,155 provide a discussion of the float glass process.
  • Temperatures of the float ribbon on the tin bath generally range from 1093° C. (2000° F.) at the delivery end of the bath to 538° C. (1000° F.) at the exit end of the bath.
  • the temperature of the float ribbon between the tin bath and the annealing lehr is generally in the range of 480° C. (896° F.) to 580° C. (1076° F.); the temperatures of the float ribbon in the annealing lehr generally range from 204° C. (400° F.) to 557° C. (1035° F.) peak.
  • U.S. Pat. Nos. 4,853,257; 4,971,843; 5,464,657; and 5,599,387 describe CVD coating apparatus and methods that can be used in the practice of the invention to coat the float ribbon during manufacture thereof. Because the CVD method can coat a moving float ribbon yet withstand the harsh environments associated with manufacturing the float ribbon, the CVD method is well suited to provide the coating on the float ribbon.
  • the CVD coating apparatus can be employed at several points in the float ribbon manufacturing process.
  • CVD coating apparatus can be employed as the float ribbon travels through the tin bath after it exits the tin bath, before it enters the annealing lehr, as it travels through the annealing lehr, or after it exits the annealing lehr.
  • concentration of the metal-containing precursor in the carrier gas, the rate of flow of the carrier gas, the speed of the float ribbon (the “line speed”), the surface area of the CVD coating apparatus relative to the surface area of the float ribbon, the surface areas and rate of flow of exhausted carrier gas through exhaust vents of the CVD coating apparatus, more particularly, the ratio of exhaust rate through the exhaust vents versus the carrier gas input rate through the CVD coating unit, known as the “exhaust matching ratio”, and the temperature of the float ribbon are among the parameters which will affect the final thickness and morphology of the coating formed on float ribbon by the CVD process.
  • U.S. Pat. Nos. 4,719,126; 4,719,127; 4,111,150; and 3,660,061 describe spray pyrolysis apparatus and methods that can be used with the float ribbon manufacturing process. While the spray pyrolysis method, like the CVD method, is well suited for coating a moving float glass ribbon, the spray pyrolysis has more complex equipment than the CVD equipment and is usually employed between the exit end of the tin bath and the entrance end of the annealing lehr.
  • the constituents and concentration of the pyrolytically-sprayed aqueous suspension, the line speed of the float ribbon, the number of pyrolytic spray guns, the spray pressure or volume, the spray pattern, and the temperature of the float ribbon at the time of deposition are among the parameters which will affect the final thickness and morphology of the coating formed on the float ribbon by spray pyrolysis.
  • the surface of the glass float ribbon on the molten tin (commonly referred to as the “tin side”) has diffused tin in the surface which provides the tin side with a pattern of tin absorption that is different from the opposing surface not in contact with the molten tin (commonly referred to as “the air side”).
  • the air side This characteristic is discussed in Chemical Characteristics of Float Glass Surfaces, Seiger, J., JOURNAL OF NON-CRYSTALLINE SOLIDS, Vol. 19, pp. 213-220 (1975); Penetration of Tin in The Bottom Surface of Float Glass: A Synthesis, Columbin L.
  • a coating can be formed on the air side of the float ribbon while it is supported on the tin bath (by the CVD method); on the air side of the float ribbon after it leaves the tin bath by either the CVD or spray pyrolysis methods, and on the tin side of the float ribbon after it exits the tin bath by the CVD method.
  • U.S. Pat. Nos. 4,379,040; 4,861,669; 4,900,633; 4,920,006; 4,938,857; 5,328,768; and 5,492,750 describe MSVD apparatus and methods to sputter coat metal oxide films on a substrate, including a glass substrate.
  • the MSVD process is not generally compatible with providing a coating over a glass float ribbon during its manufacture because, among other things, the MSVD process requires negative pressure during the sputtering operation, which is difficult to form over a continuous moving float ribbon.
  • the MSVD method is acceptable to deposit the coating over the substrate, e.g., a glass sheet.
  • the substrate can be heated to temperatures in the range of 400° C. (750° F.) to 500° C. (932° F.) so that the MSVD sputtered coating on the substrate crystallizes during deposition process, thereby eliminating a subsequent heating operation.
  • the coated substrate can be heated during the sputtering operation.
  • the sputter coating can be crystallized within the MSVD coating apparatus directly and without post heat treatment by using high energy plasma and/or ion bombardment.
  • One method to provide a coating using the MSVD method is to sputter a coating on the substrate, remove the coated substrate from the MSVD coater and thereafter heat treat or treat by using atmospheric plasmas on the coated substrate to crystallize the sputter coating.
  • a target of titanium metal and aluminum metal sputtered in an argon/oxygen atmosphere having 40 to 100% oxygen, the remainder argon gas mixture, for example 50 to 80 percent oxygen, the remainder argon gas mixture, at a pressure of 5-10 millitorr to sputter deposit a coating of titanium aluminum oxide at the desired thickness on the substrate.
  • the coating as deposited may not be crystallized.
  • the coated substrate can be removed from the coater and heated to a temperature in the range of 400° C. (752° F.) to 600° C. (1112° F.) for a time period sufficient to promote formation of the crystalline forms of titanium aluminum oxide and mixtures and oxide compounds of titanium and aluminum.
  • the coating can be sputter deposited on the air side and/or the tin side.
  • oxides, nitrides, and oxynitrides comprising titanium and aluminum, titanium and aluminum-silicon, titanium and aluminum-silicon-transition metal can be sputtered using dc magnetron sputtering.
  • titanium and aluminum with or without other materials such as silicon or transition metals, can be used for the sputtering targets.
  • Coating transmittance and reflectance are measured as an indicator of the optical properties of refractive index and absorption coefficient.
  • Electrical sheet resistance in ohms per square is measured as an indicator of the emissivity and the solar performance, i.e., the solar energy transmitted and reflected. A decrease in sheet resistance indicates an enhancement in these properties.
  • titanium and aluminum and titanium aluminum-silicon mixture or alloy cathode targets can have a weight ratio of titanium-containing materials to aluminum-containing materials ranging between 1 to 99 weight percent aluminum and 99 to 1 weight percent titanium, for example 10 to 95 weight percent aluminum, or 20 to 80 weight percent aluminum, or 20 to 60 weight percent aluminum, such as 20 to 50 weight percent aluminum, such as 20 to 40 weight percent aluminum, such as 30 to 40 weight percent aluminum.
  • the metals of titanium, aluminum with or without silicon can be sputtered in argon, nitrogen, and/or oxygen; for example in an argon-oxygen gas mixture with up to 100 percent oxygen, or in a nitrogen-oxygen gas mixture containing up to 95 percent oxygen.
  • Titanium-aluminum-silicon alloy cathode targets can have some of the silicon substituted with transition metal.
  • the amount of transition metal is below 15 percent by weight based on the combined weight of titanium and aluminum, silicon and transition metal, for example in the range of 5 to 15 percent, with at least 5 percent silicon based on the total weight of titanium and aluminum, silicon and transition metal.
  • Titanium and aluminum-silicon-transition metal alloy cathode targets with 5 to 15 weight percent transition metal and 5 to 65 weight percent silicon, for example 5 to 10 weight percent transition metal, and 5 to 40 weight percent silicon can be sputtered, for example, in inert gas such as argon, in 100% oxygen, in argon-oxygen gas mixtures, or in nitrogen-oxygen gas mixtures containing up to 95 percent oxygen.
  • titanium and aluminum-transition metal alloy cathode targets can contain up to 20 weight percent transition metal based on the combined weight of titanium and aluminum, but can contain more transition metal or other transition metal subject to the limitation that the alloy remain nonmagnetic for magnetron sputtering.
  • the titanium and aluminum, titanium aluminum-silicon, titanium-aluminum-silicon-transition metal, and titanium and aluminum-transition metal cathode target compositions of the present invention can be determined by chemical analysis from pieces of target material to determine weight percent of silicon, or transition metal.
  • the coating compositions can be measured using X-ray fluorescence to determine the weight percent titanium, aluminum, silicon, or transition metal.
  • the targets can be generally elongated having a length larger than their width and ranging from 30 up to 100 centimeters or more.
  • coatings can be produced on a large-scale magnetron sputtering device capable of coating glass up to 100 ⁇ 144 inches (2.54 ⁇ 3.66 meters).
  • the article having at least one film or layer of titanium and aluminum materials of the present invention in a coating can be an article having a sputtered Low-E coating stack on a substrate.
  • the titanium and aluminum material containing coating can be a protective layer over the coating stack.
  • the substrate can be made of any material, e.g., plastic, glass, metal or ceramic.
  • the substrate is transparent, e.g., nylon, glass or Mylar® plastic sheet.
  • the substrate is glass.
  • the glass can be of any composition having any optical properties, e.g., any value of visible transmittance, ultraviolet transmission, infrared transmission and/or total solar energy transmission. Types of glasses that can be used in the practice of the invention, but not limited thereto, are disclosed in U.S. Pat. Nos. 4,746,347; 4,792,536; 5,240,886; 5,385,872; and 5,393,593.
  • the sputtered coating stack can have any arrangement including, but is not limited to, a base layer also referred to as a dielectric layer, a phase matching layer or an antireflective layer; an infrared reflecting metal layer, such as a silver film or any noble metal; a primer or protective layer, which can be, but is not limited to, a deposited stainless steel film, a niobium film, a deposited copper film or a deposited titanium film, and a-second dielectric layer or antireflective layer.
  • Coating stacks that are single silver film coating stacks that can be used in the practice of the invention, but not limiting to the invention, are disclosed in U.S. Pat. Nos. 4,320,155; 4,512,863; 4,594,137; and 4,610,771.
  • the dielectric layers can have zinc stannate; the primer layer can be deposited as metallic copper, and the IR layer can be silver.
  • the base layer can be deposited on the air surface of a glass sheet cut from a float glass ribbon. The air surface is the surface opposite the surface of the float ribbon supported on the molten pool of metal, e.g., as disclosed in U.S. Pat. No. 4,055,407.
  • An exemplary coating stack as described above is disclosed in the above-mentioned U.S. Pat. Nos. 4,610,771 and 4,786,563.
  • titanium and aluminum-containing layer e.g., protective layer
  • the protective layer can be used with many different types of functional coatings known to those skilled in the art.
  • the coating stack 42 includes a base layer 44 that can include one or more films of different dielectric materials or antireflective materials or phase matching materials, a first infrared reflective metal layer 46 , a primer layer 48 to prevent degradation of the metal layer 46 during sputtering of a dielectric layer or anti-reflective layer or phase matching layer 50 .
  • the layer 50 can have one or more films.
  • a second infrared reflective metal layer 52 is deposited over the layer 50 .
  • a second primer layer 54 is deposited on the second infrared metal reflective layer 52 and a dielectric layer or anti-reflective layer 56 is deposited over the second primer layer 54 .
  • a double metal layer reflective coating stack 42 that can be used in the practice of the invention includes a base layer 44 comprising a zinc-stannate film 58 on the air surface of a glass substrate 14 cut from a float glass ribbon, and a zinc-oxide film 60 on the zinc-stannate film 58 ; a first infrared-reflective metal layer 46 comprising a silver film on the zinc oxide film 60 ; a first primer layer 48 comprising a sputtered titanium metal film on the silver film 46 , wherein the titanium metal oxidizes to titanium dioxide film 48 during sputtering of the next dielectric film; a dielectric layer 50 comprising a zinc-oxide film 62 on the primer layer 48 , a zinc-stannate film 64 on the zinc-oxide film 62 , and a zinc-oxide film 66 on the zinc-stannate film 64 ; a second infrared-reflective layer 52
  • the coating stack 42 is of the type disclosed in published EPO Application No. 0 803 381 based on U.S. patent application Ser. No. 08/807,352 filed on Feb. 27, 1997, in the names of Mehran Arbab, Russell C. Criss, and Larry A. Miller for “Coated Articles”, and in products sold by PPG Industries, Inc., under its trademark SUNGATE® 1000 coated glass and SOLARBAN® 60 coated glass.
  • the protective layer or film 16 of the instant invention discussed in more detail below is deposited over the coating stack 42 .
  • the deposition of the functional coating 42 is not limiting to the invention and can be deposited by any method, e.g., by sputter deposition, electroless metal deposition, and/or pyrolytic deposition.
  • the functional coating can comprise one or more conductive metal nitrides, e.g., titanium nitride, and alloys of nickel and chrome.
  • the invention is not limited to the embodiment shown in FIG. 1.
  • the titanium and aluminum-containing layer (e.g., protective layer) of the invention can be utilized as an overcoat layer 16 as shown in FIG. 1.
  • the titanium and aluminum-containing layer of the invention could also be used as one or both of the primer layers 48 and/or 54 , or as an additional layer, or in place of one or more of the dielectric layers 44 , 50 , 56 .
  • the protective layer 16 of the instant invention can be the last deposited layer on the coating stack or can be an underlying layer for outermost layer.
  • the Ti—Al protective layer 16 of the instant invention can be deposited as the last film of the functional coating to provide protection against mechanical and chemical attack at least equal to presently known and used protective films.
  • the Ti—Al layer 16 can be utilized as one or more of the layers, e.g., primer layers or dielectric layers, of the coating stack.
  • the protective coating 16 further comprises silicon. This can be accomplished by adding silicon to the titanium-aluminum target.
  • the deposited material can include titanium, aluminum, silicon, titanium-aluminum, titanium-silicon, aluminum-silicon, titanium-aluminum-silicon, and combinations thereof.
  • the deposited material can include titanium oxide, aluminum oxide, silicon oxide, (titanium-aluminum)oxide, (titanium-silicon)oxide, (aluminum-silicon)oxide, (titanium-aluminum-silicon)oxide, and combinations thereof.
  • the deposited material can include titanium nitride, aluminum nitride, silicon nitride, (titanium-aluminum)nitride, (titanium-silicon)nitride, (aluminum-silicon)nitride, (titanium-aluminum-silicon)nitride, and combinations thereof.
  • the deposited material can include titanium oxide, aluminum oxide, silicon oxide, (titanium-aluminum)oxide, (titanium-silicon)oxide, (aluminum-silicon)oxide, (titanium-aluminum-silicon)oxide, titanium nitride, aluminum nitride, silicon nitride, (titanium-aluminum)nitride, (titanium-silicon)nitride, (aluminum-silicon)nitride, (titanium-aluminum-silicon)nitride, titanium oxynitride, aluminum oxynitride, silicon oxynitride, (titanium-aluminum)oxynitride, (titanium-silicon)oxynitride, (aluminum-silicon)oxynitride,
  • silicon with combinations of oxides, nitrides, and oxynitrides can be used to provide the film of the instant invention.
  • titanium, aluminum oxide, nitride or combinations of oxide, nitride or oxynitride as dielectric and/or protective layers offer durable coatings with increased flexibility in the choice of color and reflectance.
  • the dielectric and/or protective layer of the instant invention can be “homogeneous”, “graded” or “non-homogeneous”.
  • the coatings were deposited on a smaller scale, using planar magnetron cathodes having 5 ⁇ 17 inch (12.7 ⁇ 43.2 centimeters) titanium-aluminum and titanium-aluminum-silicon targets.
  • Base pressure was in the low 10 ⁇ 5 to 10 ⁇ 6 torr range.
  • the coatings were made by first admitting the sputtering gas to a pressure ranging from 3 to 4 millitorr and then setting the cathode at a constant power.
  • clear float glass substrates were passed under the target on a conveyor roll at a speed of 120 inches (3.05 meters) per minute.
  • the transmittance was monitored during the sputtering process at a wavelength of 550 nanometers using a Dyn-Optics 580D optical monitor.
  • the transmittance and reflectance from both the glass and coated surface were measured in the wavelength range from 380 to 720 nanometers using a TCS spectrophotometer manufactured by BYK Gardner in Columbia, Md. This data was used with a commercially available software program to calculate the coating refractive index (n) and absorption coefficient (k), the integrated transmittance and reflectance. The thicknesses of the coatings were measured using a Tencor P-1 Long Scan Profiler.
  • films containing a combination of Ti and Al produced several surprising features. Ranges of the metal mixture showed preferential oxidation, relative to either of the pure metals of titanium or aluminum films. Independently of this, an enhancement of the low emissivity coating was realized when the metal mixture was incorporated as a primer layer. A dramatic improvement in the long-term exposure to the environment of a thermally processed coating was observed. A range of the mixed metal primer showed no breakdown, compared to the pure metal primers after more than 1.5 years of exposure in the lab environment. In addition, the sheet resistance of the low emissivity coating was lower for a range of the metal mixture than either of the pure metal primers. Both of these benefits clearly indicate an improvement over the pure metal primers in the art.
  • Titanium-aluminum oxide and nitride coatings showed greatly enhanced chemical durability compared to a titanium dioxide coating, as indicated by exposure to condensing humidity testing.
  • a planar cathode target i.e., a solid 5′′ ⁇ 14′′ (12.5 cm ⁇ 35 cm) pure metal plate, was either a solid target composed of the specific metal mixture or alloy, or a split target divided into two, side-by-side 5′′ ⁇ 7′′ (2.5 cm ⁇ 17.5 cm) plates of the two metals.
  • Specific Ti—Al alloys were used for the solid targets and were fabricated by Hot Isostatic Pressing (HIP) powders of the alloy, or Vacuum planar Induction skull Melting (VIM) and casting an ingot target from the metal powders, or plasma sprayed. Chemical analysis of the target alloy was used to determine the weight percent of the individual metals. Both the split and the specific alloy targets were bolted to a backing plate and then to the cathode assembly.
  • Examples 1-4 describe the Ti—Al sputtered coatings on glass
  • Examples 5-7 describe Ti—Al layers as part of a low emissivity coating stack.
  • the split target produced coatings composed of a mixture of Al—Ti in a single run. This mixture had a (non-linear) gradient composition across the width of the glass sheet, and constant composition in the direction of travel.
  • the gradient samples (G1) (G2) were produced on 12′′ ⁇ 12′′ (30 cm ⁇ 30 cm) ⁇ 2.3 mm clear float glass in an Airco ILS chamber. The base pressure in the chamber before sputtering was 1.0 ⁇ 10-5 torr.
  • the Al—Ti target was sputtered at a pressure of 3 microns in a 100% argon gas atmosphere.
  • the power to the cathode target for sample G1 was 1 kilowatt resulting in a voltage of 395 volts and a current of 2.52 amps.
  • the target was passed under the target 3 times at a speed of 120 inches per minute until the transmission was reduced to 20.9%.
  • Sample G2 was deposited at a power of 5 kilowatts, resulting in a voltage of 509 volts and a current of 9.72 amps. After 5 passes under the target, the transmission was reduced to 0.1%.
  • the transmission in the ILS coater is read in the center of the plate, therefore, the transmission reading is approximately that for the center of the gradient layer.
  • Table A The values of the operating parameters for each sample are shown in Table A below.
  • a 1.375 inch strip was cut perpendicular to the direction of travel (along the gradient) into eight ⁇ 1.375 inch (3.5 cm) squares for X-ray fluorescence (XRF) analysis.
  • the average amount of titanium and aluminum in each individual sample in terms of micrograms/cm 2 ( ⁇ g/cm 2 ) was calculated from these measurements.
  • the weight percentage of Al and Ti was then calculated from the amount of ⁇ g/cm 2 for each sample.
  • the center of XRF sample G1 located 3.438 inches (8.7 cm) from the edge of the first sample, contains an average weight of 90.1% titanium.
  • G1 has the value 3 units on the template with a 90.1wt % of titanium.
  • the positions between the centers of each sample are located at a fractional part of the distance between positions on the template.
  • the average composition of the mixed metals was determined by averaging the weight percent of both samples (G1 and G2) for each position along the width of the plate.
  • the micrograms/cm 2 and the weight percent for Al and Ti at each position for each sample are shown in Table B, along with the average of the samples at each position.
  • a Sigmoid 5 parameter fit was used to fit the data.
  • the percent of Ti and Al for each position along the width of the plate, and the calculated fit to the data is shown in FIG. 2.
  • Weight % y 0 +a /(1+exp((1+exp( ⁇ ( x ⁇ x 0 )/ b )) c
  • the oxidation of the metal mixture makes it possible to apply thicker compositions of Ti—Al metal, e.g., as a metal overcoat layer for subsequent oxidation during thermal processing.
  • the metal mixture layer could also be oxidized by other methods that drive the temperature of the coating to the point of oxidation.
  • the metal mixture may segregate after heating, producing a layer with one metal richer than the other.
  • the metal mixture can also be sputtered in a gas mixture with a small percentage of a reactive gas (O 2 or N 2 ), below the switch point.
  • a reactive gas O 2 or N 2
  • the target composed of the metal mixture, a compound or alloy of the metals can be sputtered in an inert, reactive or inert-reactive gas mix, such as argon, O 2 , N 2 or combinations.
  • an inert, reactive or inert-reactive gas mix such as argon, O 2 , N 2 or combinations.
  • the coatings were deposited in an Airco ILS 1600 coater on 12′′ ⁇ 12′′ (30 cm ⁇ 30 cm) square by 2.3 mm thick clear float glass substrates at ambient temperature.
  • the substrate was conveyed at a line speed of the 120 inches per minute.
  • the base pressure was in the low 10-5torr range and the operating pressure was 4 microns (m torr).
  • the substrate was at ambient temperature during deposition.
  • Planar targets of Ti-30Al and Ti-50Al, where the amount of aluminum is expressed in atomic percent, were manufactured (except where noted) by Hot Isostatic Pressing (HIP) powders of the alloy.
  • the alloy oxide films were deposited in an atmosphere of 50% argon and 50% oxygen.
  • a Ti-50Al oxide sample was run at a power setting of 3.0 kilowatts, with a voltage of 432 volts and a current of 6.98 amps. After 10 passes, the transmission was 91.2% and the thickness was 114 Angstroms.
  • a second Ti-50Al oxide sample was run at a power setting of 4.0 kilowatts with a voltage of 494 volts and current 8.14 amps. The transmission was 87.5% after 10 passes and the thickness was 274 Angstroms.
  • a Ti-30Al oxide sample was run a power setting of 3.0 kilowatts with a voltage 490 volts, and the current of 6.14 amps. The transmission was 91.3% after 10 passes and the thickness was 89 Angstroms.
  • a Ti-50Al nitride sample was run in an atmosphere of 100% nitrogen at a power setting of 3.0 kilowatts with a voltage of 640 volts and a current of 4.72 amps. The transmission was 30.5% after 15 passes and the thickness was 713 Angstroms.
  • the titanium dioxide sample shown for comparison, was run at a power setting of 4.0 kilowatts with a voltage 451 volts, and a current of 8.86 amps. The transmission was 88.2% after 10 passes and the thickness was 92 Angstroms.
  • Table C summarizes the target material, coater setting and resulting coating.
  • the Ti-30Al and 50Al oxide thin films showed no deterioration after weeks of exposure in the CCC test chamber. This was an unexpected result for these alloy oxides, considering the poor behavior of aluminum oxide in the CCC test; it would be expected that the addition of aluminum oxide would decrease the corrosion resistance of the alloy. Rather, the presence of aluminum enhances the corrosion resistance over that of titanium oxide. Longer term testing of the alloy oxides shows that the Ti-50Al oxide is even more corrosion resistant than the Ti-30Al oxide. This is an even more surprising result given the higher concentration of aluminum in the coating.
  • FIG. 4 (which is the same as FIG. 5 but with an expanded scale) shows the change in integrated reflectance (Y(R1)) of the coated surface as a function of exposure time in hours in the CCC.
  • the TiO 2 film is shown for comparison. After at least 350 hours of exposure there is no significant change in the coating reflectance.
  • the TiO 2 shows a small change after 28 hours followed by a rapid decrease in reflectance indicating rapid coating degradation. After 200 hours, the coating is around 8%, which is the reflectance of the uncoated glass substrate. This indicates that the coating has been completely removed.
  • FIGS. 4 and 5 show long-term behavior of the Ti—Al oxide coatings in the CCC test chamber.
  • the Ti-50Al oxide coating shows a slower decrease in reflectance than the Ti-30Al oxide coating indicating slower degradation of the coating. As noted earlier, this is surprising considering the higher amount of aluminum in the coating.
  • FIG. 6 shows the 274 Angstrom Ti-50Al oxide coating. The behavior is similar to the thinner film with a slow, rather than rapid decrease in reflectance, as shown by TiO 2 film.
  • FIG. 7 shows the Integrated Reflectance (Y(R1)) from the coated surface as a function of the exposure time in hours in the CCC chamber. There is less than a 1% change in reflectance after almost 2000 hours of exposure. Visual inspection of the Ti-50Al nitride film showed no noticeable degradation as compared to the unexposed section of the coating.
  • Ti—Al metal films were deposited in an Airco ILS 1600 coater on 12′′ ⁇ 12′′ (30 cm ⁇ 30 cm) square by 2.3 mm thick clear float glass substrates at ambient temperature. The substrate was conveyed at a line speed of 120 inches (300 cm) per minute. The base pressure was in the low 10 6 torr range and the operating pressure was 4 microns. Planar targets of Ti-10Al and Ti-90Al, where the amount of aluminum is expressed in atomic percent, were used to deposit the coatings. The Ti-10Al target was manufactured by Hot Isostatic Pressing (HIP) the alloy powder. Analysis of the target material indicated 5.85 weight percent aluminum with the balance titanium.
  • HIP Hot Isostatic Pressing
  • the Ti-90Al target was manufactured by vacuum induction skull melting and casting an ingot target from the metal powders. Analysis of the target material indicated 16.3 weight percent titanium with the balance aluminum.
  • the alloy films were deposited in an atmosphere of 80% argon and 20% oxygen gas mixture.
  • a Ti-90Al metal film sample was run at a power setting of 4 kilowatts, with a voltage of 419 volts and a current of 9.5 amps. The transmission was 90.1% after 10 passes under the target and the thickness was measured at 166 Angstroms.
  • a Ti-90Al metal film sample was run at a power setting of 4.0 kilowatts, with a voltage of 404 volts and a current of 9.5 amps. The transmission was 88.7% after 20 passes under the target and the thickness was measured at 365 Angstroms.
  • a Ti-90Al metal film sample was run at a power setting of 4 kilowatts, with a voltage of 400 volts and a current of 9.95 amps. The transmission was 87.1% after 30 passes under the target and the thickness was measured at 583 Angstroms.
  • a Ti-10Al metal film sample was run at a power setting of 4 kilowatts, with a voltage of 534 volts and a current of 7.45 amps. The transmission was 88.0% after 10 passes under the target and the thickness was measured at 135 Angstroms.
  • a Ti-10Al metal film sample was run at a power setting of 4.0 kilowatts, with a voltage of 536 volts and a current of 7.4 amps. The transmission was 81.5% after 20 passes under the target and the thickness was measured at 278 Angstroms.
  • a Ti-10Al metal film sample was run at a power setting of 4.0 kilowatts, with a voltage of 532 volts and a current of 7.45 amps. The transmission was 75.2% after 30 passes under the target and the thickness was measured at 407 Angstroms.
  • Table D summarizes the target material, coater settings, and resulting coating.
  • Table E illustrates the sputtering rate for various combinations of target material (based on the atomic percentage of each component) in terms of Angstroms per kilowatt-pass.
  • FIG. 8 plots the sputtering rate for the different targets shown in Table E. TABLE D Sample Target ILS Coater Settings ILS Thickness XRF (ug/cm ⁇ circumflex over ( ) ⁇ 2) Wt % No.
  • Ti—Al metal films were deposited in an Airco ILS 1600 coater on 12′′ ⁇ 12′′ (30 cm ⁇ 30 cm) square by 2.3 mm thick clear float glass substrates at ambient temperature. The substrate was conveyed at a line speed of 120 inches per minute. The base pressure was in the low 10 ⁇ 5 torr range and the operating pressure was 4 microns.
  • Planar targets of Ti-30Al and Ti-50Al, where the amount of aluminum is expressed in atomic percent were manufactured by Hot Isostatic Pressing (HIP) powers of the alloy powder.
  • a planar target of Ti-90Al, where the amount of aluminum is expressed in atomic percent was made by Vacuum Induction skull Melting (VIM) and casting an ingot target from the metal powders. The alloy films were deposited in an atmosphere of 100% argon gas.
  • a Ti-30Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 529 volts and a current of 5.72 amps. The transmission was 21.3% after 1 pass under the target and the thickness was measured at 161 Angstroms.
  • a Ti-30Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 529 volts and a current of 5.7 amps. The transmission was 8.5% after 2 passes under the target and the thickness was measured at 270 Angstroms.
  • a Ti-30Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 529 volts and a current of 5.72 amps. The transmission was 0% after 5 passes under the target and the thickness was measured at 704 Angstroms.
  • a Ti-30Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 528 volts and a current of 5.70 amps. The transmission was 0% after 10 passes under the target and the thickness was measured at 1306 Angstroms.
  • a Ti-50Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 610 volts and a current of 4.94 amps. The transmission was 19.1% after 1 pass under the target and the thickness was measured at 169 Angstroms.
  • a Ti-50Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 609 volts and a current of 4.96 amps. The transmission was 7.4% after 2 passes under the target and the thickness was measured at 312 Angstroms.
  • a Ti-50Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 605 volts and a current of 5.0 amps. The transmission was 0% after 5 passes under the target and the thickness was measured at 756 Angstroms.
  • a Ti-50Al metal film sample was run at a power setting of 3.0 kilowatts, with a voltage of 603 volts and a current of 5.0 amps. The transmission was 0% after 10 passes under the target and the thickness was measured at 1500 Angstroms.
  • a Ti-90Al metal film was deposited at a power setting of 3.0 kilowatts, with a voltage of 827 volts and a current of 3.18 amps. The transmission was 8.8% after 1 pass under the target and the thickness was measured at 162 Angstroms.
  • a Ti-90Al metal film was deposited at a power setting of 3.0 kilowatts, with a voltage of 827 volts and a current of 3.13 amps. The transmission was 2.1% after 1 pass under the target and the thickness was measured at 311 Angstroms.
  • a Ti-90Al metal film was deposited at a power setting of 3.0 kilowatts, with a voltage of 827 volts and a current of 3.15 amps. The transmission was 0.0% after 1 pass under the target and the thickness was measured at 756 Angstroms.
  • a Ti-90Al metal film was deposited at a power setting of 3.0 kilowatts, with a voltage of 827 volts and a current of 1.13 amps. The transmission was 0.0% after 1 pass under the target and the thickness was measured at 1505 Angstroms.
  • Table F summarizes the target material, coater settings, and resulting coating.
  • TABLE F Sample Target ILS Coater Settings ILS Thickness Microgm/cm 2 Wt % No. Alloy KW Pass Voltage Current % T Gas ( ⁇ ) Al Ti Al Ti D1 Ti30Al 3.0 1 529 5.72 21.3 Ar 161 0.88 4.13 17.3 82.7 D2 Ti30Al 3.0 2 529 5.70 8.5 Ar 270 1.76 8.48 17.1 82.9 D3 Ti30Al 3.0 5 529 5.72 0.0 Ar 704 4.31 21.31 16.8 83.2 D4 Ti30Al 3.0 10 528 5.70 0.0 Ar 1306 8.24 42.29 16.3 83.7 D5 Ti50Ai 3.0 1 610 4.94 19.1 Ar 169 1.81 3.56 33.6 66.4 D6 Ti50Al 3.0 2 609 4.96 7.4 Ar 312 3.49 6.83 33.8 66.2 D7 Ti50Al 3.0 5 605 5.00 0.0 Ar 756 8.66 17.80 32.7 67.3 D
  • a 12 ⁇ 12 inch (30 cm ⁇ 30 cm) soda-lime glass substrate was placed in an Airco ILS coater with a base pressure of 1.1 ⁇ 10-5 torr.
  • the layer sequence for the low emissivity coating was:
  • the first layer of an alloy of zinc and tin of 48% tin and 52% zinc by weight was deposited at 4 microns pressure in an atmosphere of 50%/50% mix by flow of argon and oxygen.
  • the power to the cathode target was set at 1.7 kilowatts resulting in a voltage of 395 volts and a current of 4.30 amps.
  • the glass was passed under the cathode 4 times until the transmission reached 81.9%.
  • the second layer was deposited using the gradient cathode described earlier.
  • the pressure in the chamber was 3 microns in a 100% argon gas atmosphere.
  • the power to the cathode was set at 0.4 kilowatts, resulting in a voltage of 348 volts and a current of 1.14 amps.
  • the glass was passed under the cathode 1 time, resulting in a transmission of 66.7%.
  • the third layer was deposited using a silver cathode. The pressure in the chamber was 3 microns in a 100% argon gas atmosphere.
  • the power to the cathode was set at 0.6 kilowatts, resulting in a voltage of 394 volts and a current of 1.52 amps.
  • the glass was passed under the cathode 1 time, which resulted in a transmission of 50.9%.
  • the fourth layer was deposited under the same conditions as the second layer.
  • the transmission after this layer was 41.0%.
  • the fifth and final layer was deposited under the same conditions as the first layer.
  • the final transmission was 72.0%.
  • the conveyor-speed was 120 inches per minute. The coating was then heated to
  • the sample was kept in the open environment of the lab for more than 1.5 years and then reevaluated. It was found that a coating had broken down in a pattern that followed the Ti/Al gradient as shown in Table B and FIG. 3.
  • the aluminum end of the sample showed large areas of coating that had completely broken down; the titanium end showed spotty areas of coating breakdown, typical of coating that has been in a unprotected environment for an extended period of time. Surprisingly, there was an area of the coating that clearly showed no breakdown in the region where aluminum and titanium were mixed. Since the sheet resistance of the coating tends to increase as the coating degrades, measurements were made along the gradient of the coating. Although the resistance values were not made initially, the lower values of the sheet resistance corresponded to the section of the coating that showed no breakdown over the time period.
  • FIGS. 3 and 10 show the sheet resistance as a function of the weight percentage of titanium and aluminum, respectively, in the primer layers of the low emissivity coating.
  • the graph shows that for values of wt% titanium greater than 10% and less than 80% the resistance of the coating is lower than the pure metal or low percentage mixture. There is a steep rise in resistance for coatings less than 10% aluminum indicating that the aluminum primer, even after heating, is unstable after exposure in an unprotected environment. For values of titanium greater than 80% there is a leveling off in the value of the resistance, indicating that typical behavior of coatings common in the art today.
  • the coating in the range of 10 to 80 weight percent titanium, with the balance of aluminum, not only has lower sheet resistance but also has increased stability when left unprotected.
  • the corresponding atomic weights are shown in FIGS. 11 and 12.
  • Primer layers using Ti—Al alloy targets were used to make samples of low emissivity coatings with the coating the layer sequence:
  • the coating configuration differs from the gradient target configuration (sample G3) with the omission of the alloy layer below the silver layer.
  • the following examples illustrate the functionality of the alloy layer compared to a titanium layer, which is used in the art. (U.S. Pat. Nos. 4,898,789 and 4,898,790)
  • planar targets used for the primer layer above the silver were Ti-30Al and Ti-50Al, where the amount of aluminum is expressed in atomic percent, were manufactured by Hot Isostatic Pressing (HIP) powders of the alloy. Analysis of the Ti-30Al target material indicated 19.19 weight percent aluminum with the balance titanium. Analysis of the Ti-50% target material indicated 36.48 weight percent aluminum with the balance titanium. A pure titanium target was used to produce primer samples for comparison with the alloy primers.
  • HIP Hot Isostatic Pressing
  • a 12 inch ⁇ 12 inch (30 cm ⁇ 30 xm) by 2.3 mm thick clear float glass substrate was placed in an Airco ILS coater with a base pressure in the low 10 ⁇ 5 Torr.
  • the first layer of an alloy of zinc and tin of 48% tin and 52% zinc by weight was deposited at 4.0 microns pressure in an atmosphere of 80% argon gas and 20% oxygen gas mixture as set on the flow controller.
  • the power to the cathode target was set at 2.2 kilowatts resulting in a voltage of 360 volts and a current of 6.12 amps.
  • the glass was passed under the cathode 5 times at a conveyor speed of 120 inches per minute (3.05 meters per minute) until the transmission reached 81.2%.
  • the thickness of the first layer was 312 Angstroms.
  • the second layer was deposited using a silver cathode. The pressure in the chamber was 4.0 microns in a 100% argon gas atmosphere. The power to the cathode was set at 0.6 kilowatts, resulting in a voltage of 458 volts and a current of 1.32 amps. The glass was passed under the cathode 1 time, which resulted in a transmission of 64.2%. The thickness of the second layer was 111 Angstroms.
  • the third layer was deposited using the Ti-30Al target at a power setting of 0.3 kilowatts, with a voltage of 354 volts and a current of 0.86 amps.
  • the thickness of the Ti—Al primer layer was calculated to be 13 Angstroms after 1 pass the transmission was 55.60%.
  • the fourth and final layer was deposited under the same conditions as the first layer, resulting in a final transmission of the coating of 87.0%.
  • the sheet resistance after coating was 5.96 ohms per square.
  • the coated glass substrate was then heated for 5 minutes at 704° C. (1300° F.) resulting in a substrate temperature of 649° C. (1200° F.).
  • the electrical sheet resistance was infinite and the transmittance was 77.4% after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti-30Al target at a power setting of 0.6 kilowatts, with a voltage of 390 volts and a current of 1.56 amps.
  • the transmission was 47.1% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 79.6%.
  • the sheet resistance after coating was 7.85 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 82.9% and the electrical sheet resistance was 9.1 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti-30Al target at a power setting of 0.9 kilowatts, with a voltage of 410 volts and a current of 2.20 amps. The transmission was 40.3% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 68.5%.
  • the sheet resistance after coating was 7.15 ohms per square.
  • the coating was then heated by the method described above for Sample B1.
  • the transmittance was 83.5% and the electrical sheet resistance was 6.6 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti-30Al target at a power setting of 1.2 kilowatts, with a voltage of 423 volts and a current of 2.84 amps. The transmission was 35.2% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 60.7%.
  • the sheet resistance after coating was 7.66 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 74.8% and the electrical sheet resistance was 8.40 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of example B1.
  • the third layer was deposited by passing the glass one time under the Ti-50Al target at a power setting of 0.3 kilowatts, with a voltage of 380 volts and a current of 0.82 amps. The transmission was 52.4% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 86.2%.
  • the sheet resistance after coating was 6.97 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 84.7% and the electrical sheet resistance was 13.6 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti-50Al target at a power setting of 0.6 kilowatts, with a voltage of 426 volts and a current of 1.42 amps.
  • the transmission was 44.1% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 74.3%.
  • the sheet resistance after coating was 8.46 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 85.1% and the electrical sheet resistance was 6.9 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti-50Al target at a power setting of 0.9 kilowatts, with a voltage of 458 volts and a current of 1.98 amps.
  • the transmission was 37.6 after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 63.7%.
  • the sheet resistance after coating was 8.20 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 80.6% and the electrical sheet resistance was 8.9 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti-50Al target at a power setting of 1.2 kilowatts, with a voltage of 482 volts and a current of 2.52 amps.
  • the transmission was 32.6% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 55.5%.
  • the sheet resistance after coating was 8.08 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 72.9% and the electrical sheet resistance was 13.1 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti target at a power setting of 0.3 kilowatts, with a voltage of 317 volts and a current of 0.96 amps. The transmission was 54.6 after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 87.3%.
  • the sheet resistance after coating was 6.36 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 74.6% and the electrical sheet resistance was infinite after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti target at a power setting of 0.6 kilowatts, with a voltage of 340 volts and a current of 1.78 amps. The transmission was 46.6 after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 80.1%.
  • the sheet resistance after coating was 7.42 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 82.3% and the electrical sheet resistance was 7.90 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti target at a power setting of 0.9 kilowatts, with a voltage of 354 volts and a current of 2.56 amps. The transmission was 39.5% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 68.8%.
  • the sheet resistance after coating was 7.85 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 79.7% and the electrical sheet resistance was 6.50 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, and the second layer of was deposited from the silver target by the same method of Sample B1.
  • the third layer was deposited by passing the glass one time under the Ti target at a power setting of 1.2 kilowatts, with a voltage of 364 volts and a current of 3.32 amps. The transmission was 33.9% after deposition of the third layer.
  • the final transmittance of the coating after the deposition of the fourth layer was 59.6%.
  • the sheet resistance after coating was 7.78 ohms per square.
  • the coating was then heated by the method described for Sample B1.
  • the transmittance was 74.0% and the electrical sheet resistance was 8.2 ohms per square after heating.
  • Table G summarized the target material, coater settings, and resulting coatings. TABLE G Ti—Al Primer Layers Sheet Resistance % Transmittance ILS Coater Settings (ohms/square) ILS TCS Sample Target Power Voltage Current Thickness before after before after No.
  • FIG. 13 shows the behavior of the sheet resistance with primer thickness of the Ti-30Al and the Ti-50Al primers before heating.
  • the Ti primer is shown as a comparison to the alloy primers.
  • the primers behave similarly with the Ti-50Al primer having a slightly higher resistance than the Ti and Ti-30Al primers.
  • FIG. 14 shows the behavior of the sheet resistance with primer thickness of the Ti-30Al and the Ti-50Al primers after heating.
  • the Ti primer is shown as a comparison to the alloy primers.
  • the Ti-50 primer is still electrically conductive with a primer layer less than 20 Angstroms, indicating a continuous silver layer after heating.
  • the Ti and Ti-30Al primers are not conductive after heating with a primer layer less than 25 Angstroms, and consequently the silver layer is not continuous.
  • the primer layers attain a minimum sheet resistance of 6.5 ohms per square, but the Ti-50Al primer attains the minimum resistance at a lower thickness. All the primer layers sharply increase in electrical resistance beyond the minimum resistance.
  • FIG. 15 shows the behavior of the transmittance of the coating in the ILS coater with primer thickness of the Ti-30Al and the Ti-50Al primers before heating.
  • the Ti primer is shown as a comparison to the alloy primers.
  • the transmittance of the coating decreases with increasing thickness for the primers. All primers show about the same behavior. This is due to the increasing absorption of the primer layers with increasing thickness.
  • FIG. 16 shows the behavior of the transmittance of the coating, as measured on the TCS spectrophotometer, with primer thickness of the Ti-30Al and the Ti-50Al primers after heating.
  • the Ti primer is shown as a comparison to the alloy primers.
  • the Ti-50Al primer layer has higher transmittance than the Ti and Ti-30Al primer layers.
  • the chart indicates a constant high transmittance from 15 to 30 Angstroms. This is highly desirable, particularly when minimum light transmittance requirements impose limitations on coating performance, e.g., the 70% and 75% light transmittance requirements (Illuminant A) for windshields in the U.S. and Europe, respectively.
  • [0203] were deposited in an Airco ILS 1600 coater on 12′′ ⁇ 12′′ (30.5 cm ⁇ 30.5 cm) square, by 2.3 mm thick clear float glass substrates at ambient temperature.
  • the substrate was conveyed at a line speed of the 120 inches per minute (3.05 m per minute).
  • the base pressure was in the low 10 ⁇ 6 Torr range and the operating pressure was microns (m Torr).
  • the substrate was at ambient temperature during deposition.
  • Planar targets of Ti—Al alloy where the amount of aluminum is expressed in atomic percent, were used to deposit metal oxide or metal films over the low emissivity coatings, as indicated in the above layer sequence.
  • Ti-30 and Ti-50Al alloy targets were fabricated by Hot Isostatic Pressing (HIP) powders of the alloy.
  • the Ti-90Al alloy target was made by Vacuum Induction skull Melting (VIM) and casting an ingot target from the metal powders. Chemical analysis of the alloy was used to determine the weight percent of the individual metals.
  • the alloy oxide films were deposited in an atmosphere of a mixture of 20% argon and 80% oxygen gas. The alloy films were deposited in 100% argon gas.
  • the coatings with Ti—Al overcoats on the low emissivity were compared with titanium oxide overcoats and no overcoats on the low emissivity coating.
  • the target compositions are shown in Table H below.
  • the first layer of an alloy of zinc and tin of 48% tin and 52% zinc by weight was deposited in an atmosphere of 20% argon gas and 80% oxygen gas mixture as set on the flow controller.
  • the power to the cathode target was set at 2.14 kilowatts resulting in a voltage of 385 volts and a current of 5.56 amps.
  • the glass was passed under the cathode 6 times at a conveyor speed of 120 inches per minute (3.05 meters per minute) until the transmission reached 80.3%.
  • the thickness of the first layer was 426 Angstroms.
  • the second layer was deposited using a silver cathode in a 100% argon gas atmosphere.
  • the power to the cathode was set at 0.40 kilowatts, resulting in a voltage of 437 volts and a current of 0.91 amps.
  • the glass was passed under the cathode 1 time, which resulted in a transmission of 65.7%.
  • the thickness of the second layer was 95 Angstroms.
  • the third layer was deposited using a titanium target at a power setting of 0.42 kilowatts, with a voltage of 322 volts and a current of 1.30 amps.
  • the thickness of the titanium primer layer was calculated to be 20 Angstroms after 1 pass the transmission was 51.2%.
  • the fourth layer was deposited under the same conditions as the first layer, resulting in a transmission of 83.5%.
  • the overcoat layer was deposited by passing the glass 3 times under the Ti-90Al target, in an atmosphere of 20% argon gas and 80% oxygen gas mixture, at a power setting of 3.10 kilowatts, with a voltage of 373 volts and a current of 8.28 amps.
  • the final transmittance of the coating after the deposition of the overcoat layer was 82.1% and after heating was 85.9%.
  • the overcoat thickness is 50 Angstroms.
  • the sheet resistance after coating was 9.07 ohms per square after deposition and 7.88 ohms per square after heating.
  • the first and fourth layer were deposited from the alloy target of zinc and tin, the second layer was deposited from the silver target, and the third layer was deposited from the titanium target in a similar manner to Sample F13.
  • the silver and ZnSn oxide thicknesses are shown in the Table I: Ti—Al Overcoat Layers on Low Emissivity Coating.
  • the oxide overcoat layer (F1-F14) was deposited by passing the glass with the low emissivity coating under the Ti—Al target or Ti target (FC1), set at a constant power on the power supply, in an atmosphere of 20% argon and 80% oxygen.
  • the metal overcoat layer (F15-F22) was deposited by sputtering in a gas of 100% argon.
  • the voltage and currents for each power setting for the overcoats are shown in Table I.
  • the overcoat thickness, the final transmittance of the coating after the deposition and after heating, and the sheet resistance after deposition and after heating, along with the percent change in sheet resistance are shown in Table I. Samples with no overcoat layer (FC3-5) are indicated by 0 thickness in the Overcoat Layer section of the Table I.
  • Table J shows the deposition parameters for oxides, nitrides, and metal coatings for a target having an alloy composition of titanium with 75 atomic weight aluminum. The results of Table J are shown in FIGS. 17 and 18 discussed below. TABLE J Measured Wt % Sample Target ILS Coater Settings ILS Thickness XRF (ug/cm 2 ) Al No.
  • the target compositions of Table H above were applied to a 2.3 mm thick float glass samples and then the removal time of the coating was measured using a conventional Cleveland Condensation Test (CCC) procedure. Multiple sample coupons were cut out of a coated glass sheet. For each sample tested, using the CCC procedure, a neighboring sample (control) was first measured using XRF to determine the number of micrograms per square centimeter of the coating. The samples to be tested were then placed in the CCC device and removed after set periods of time (see FIG. 17). A section of the test sample was then measured using XRF to determine the amount of coating remaining, which was calculated by dividing the measured XRF of the sample versus the XRF of the control.
  • CCC Cleveland Condensation Test
  • FIG. 17 shows the percent coating removed versus time for pure titanium and aluminum coatings as well as titanium and aluminum coatings having 10, 30, 50, 75, and 90 atomic percent aluminum.
  • the samples were sputtered in the manner described in Tables C. D, and J.
  • the coating thicknesses are shown in Table K below. TABLE K Calculated Wt % Sample Target ILS Coater Settings ILS Thickness XRF (ug/cm 2 ) Al No.
  • FIG. 18 shows the time until about 80% of the coating was removed versus the atomic percent aluminum in the coating.
  • the left of the graph represents pure titanium and the right of the graph represents pure aluminum.
  • One would anticipate adding aluminum to titanium would severely degrade the ability of the coating to resist mechanical and/or chemical attack.
  • FIG. 18 surprisingly shows that rather than degrading the titanium, the presence of aluminum in the range of about 10 to 75 atomic percent actually improves the coating performance, i.e., it takes longer to remove the coating. It would appear that this effect is most pronounced in the range of about 40 to 60 atomic percent aluminum, with a peak at about 50 atomic percent aluminum.
  • FIG. 19 is similar to FIG. 17 but shows the results for the nitride coatings of Table K. Again, a titanium and aluminum nitride coating with 50 atomic percent aluminum shows surprisingly unexpected results.
  • FIG. 20 shows the reactive index (n) and extinction coefficient (k) for titanium and aluminum-containing coatings deposited in atmospheres of pure nitrogen or 80% oxygen with the balance argon.
  • an oxide coating of titanium and aluminum provides a lower refractive index than a nitride coating in the range of about 0 to 60 atomic percent aluminum.
  • the use of titanium and aluminum-containing coatings, e.g., oxides, oxynitrides, nitrides, or metals, in a coating stack provide a layer that can provide a range of indices of refraction and/or extinction coefficients. By varying the extinction coefficient, one can vary absorption in the coating.
  • the coating of the invention provides a range of refractive indices. As shown in FIG. 19, above 75 atomic percent Al there is little or no absorption for titanium nitride and this material has a high refractive index. At 50 atomic percent Al, there is a mid-range extinction coefficient and a high index of refraction.
  • a lower index of refraction permits a thicker optical layer and at the same time provides enhanced corrosion resistance.
  • Higher absorption layers provide lower transmittance with functionality, e.g., a lower shading coefficient.
  • the higher absorbing materials contain amounts of titanium nitride, which are shown in the corrosion data above to be very durable. Such coatings could be used as first or second surface coatings on window, automotive, or decorative glazings, just to name a few.
  • the above examples illustrate the present invention which relates to using titanium and aluminum-silicon, titanium and aluminum-silicon-transition metal and titanium and aluminum-transition metal cathode targets sputtered in pure nitrogen, in nitrogen-oxygen mixtures ranging up to 40 percent oxygen, and in argon-oxygen mixtures comprising up to 50 percent oxygen.
  • a single titanium and aluminum-alloy cathode target containing a given weight percentage of silicon, silicon-transition metal or transition metal can be used for stable sputtering of a range of film compositions including oxides, nitrides and oxynitrides with varying absorption at high sputtering rates.
  • the protective coatings discussed above can be used within a low emissivity coating, such as but not limited to those discussed earlier and illustrated in FIG. 1. More particularly, the Ti—Al and Ti—Al—Si oxides, nitrides and oxynitrides and combinations thereof, can be used as dielectric layers like the layers of ZnSn Oxide or Zn Oxide (layers 44 , 50 and 56 ), and the protective overcoat in FIG. 1 (layer 16 ).
  • Ti—Al and Ti—Al—Si metal or alloy coatings can be used as primer layers as shown in FIG. 1 (layers 54 and 48 ) over the silver layers.
  • the coatings of Ti—Al and Ti—Al—Si metal or alloy coatings can also be used as the protective overcoat layer as described above and shown in FIG. 1 (layer 16 ).
  • the metal or alloy coating can be subsequently oxidized to form a metal or alloy oxide coating during high temperature processing of glass, such as tempering or bending.

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CN1777690B (zh) 2010-11-03
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RU2005133184A (ru) 2006-02-27
US8597474B2 (en) 2013-12-03
WO2004087985A2 (fr) 2004-10-14
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