WO2000037384A1 - Methods and apparatus for producing silver based low emissivity coatings without the use of metal primer layers and articles produced thereby - Google Patents
Methods and apparatus for producing silver based low emissivity coatings without the use of metal primer layers and articles produced thereby Download PDFInfo
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- WO2000037384A1 WO2000037384A1 PCT/US1999/029634 US9929634W WO0037384A1 WO 2000037384 A1 WO2000037384 A1 WO 2000037384A1 US 9929634 W US9929634 W US 9929634W WO 0037384 A1 WO0037384 A1 WO 0037384A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
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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
- C03C17/3605—Coatings of the type glass/metal/inorganic compound
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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
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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
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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
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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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
- C03C17/3639—Multilayers containing at least two functional metal layers
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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
- C03C17/3642—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 containing a metal layer
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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
- C03C17/3644—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
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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
- C03C17/3657—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
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- 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
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
Definitions
- the invention relates generally to the field of magnetron sputtering vacuum deposition and, more particularly, to sputtering a multi-layer coating stack having an infrared reflective metal layer without overlaying metal primer layers and also relates to the article made thereby.
- Sunlight contains light energy which falls generally into three broad regions: ultraviolet, visible and infrared.
- ultraviolet visible
- infrared For many commercial applications, such as the windows of buildings or automobile windows, it is desirable to reduce the amount of energy, i.e., heat, transferred through the window into and/or out of the building or automobile. This heat reduction can be affected by reducing the transmitted light energy from any of these three regions.
- infrared reflective metal layers such as silver, gold, aluminum or copper
- an antireflective layer is usually provided on one or both sides of the infrared reflective layer to produce a substrate which is highly reflective of infrared energy but which is also highly transmissive of visible energy.
- These antireflective layers are usually formed of a dielectric material, e.g., metal oxides, such as Zn 2 Sn0 4 , In 2 Sn0 4 , Ti0 2 , Sn0 2 , ln 2 0 3/ ZnO, Si 3 N or Bi 2 0 3 to name a few.
- the infrared reflective and antireflective layers are typically formed on the glass substrate in a cathode sputtering coater using a technique known in the sputtering art as magnetron sputtering vacuum deposition.
- the antireflective layer is usually deposited over the substrate by sputtering a metal or metal alloy cathode in a reactive atmosphere, e.g., an oxygen rich atmosphere, to deposit a metal oxide dielectric coating over the glass substrate surface.
- a reactive atmosphere e.g., an oxygen rich atmosphere
- a cathode made of an infrared reflective metal, such as silver, is sputtered in a non-reactive, e.g., oxygen-free, inert, atmosphere such as argon to deposit an infrared reflective metal layer over the antireflective layer.
- the oxygen-free atmosphere is used to deposit a metal layer and to prevent oxidation of the infrared reflective metal cathode.
- a protective metal primer layer such as copper, niobium, titanium, tantalum, chromium, tungsten, zinc, indium, nickel-chromium alloys or similar metal, is deposited over the silver layer.
- a protective metal primer layer such as copper, niobium, titanium, tantalum, chromium, tungsten, zinc, indium, nickel-chromium alloys or similar metal.
- the thickness of the metal primer layers is determined based upon the system coating parameters so that most of the metal primer layer is reacted, i.e., oxidized, during the sputtering of the subsequent antireflective layer.
- the protective metal primer layer becomes transparent when completely oxidized so that the oxidized metal primer layer does not adversely impact upon the light transmittance and reflective qualities of the coated substrate.
- this subsequent oxidation of the metal primer layer is not easily controlled and it is not unusual for this oxidation to be less than complete.
- metal atoms from some metal primers tend to alloy with the metal of the infrared reflective metal layer which degrades the interface between the two layers.
- the thickness of the metal primer layer must be increased during processing to leave sufficient unoxidized residual metal primer for protection of the silver layer during such subsequent heat treatment.
- two inventories of the coated substrate must usually be maintained, one having a relatively thin, oxidized primer layer capable of immediate use and one having a relatively thicker primer layer with unoxidized metal primer for use after further heat treatment.
- the coating properties such as color, transmission and haze, to be adversely affected by subsequent heat treatment of conventional low emissivity coated substrates with even thicker primer layers.
- a coated article e.g., an automotive transparency, e.g. windshield or architectural window, made in accordance with the invention has a substrate with an infrared reflective metal layer, for example, a silver layer, deposited over the substrate and a ceramic layer, e.g., an aluminum doped zinc oxide layer, deposited preferably from a ceramic cathode over the silver layer. Additional antireflective or ceramic layers may be deposited below the infrared reflective metal layer or over the ceramic layer.
- the invention provides a method of sputtering a multi-layer coating stack having an infrared reflective metal, e.g., silver, over a substrate by sputtering an infrared reflective metal cathode to deposit an infrared reflective layer over the substrate and then sputtering a ceramic cathode, such as an aluminum doped zinc oxide cathode, to deposit a non-sacrificial, ceramic layer over the silver layer.
- the silver layer and the ceramic layer may each be sputtered in an inert atmosphere containing a low percentage of oxygen, for example, in the same coating chamber of a coater with the oxygen content controlled in a manner to be described to a level to minimize undesired effects on the silver layer.
- the oxygen content can be regulated to be about 0-20 vol.% to prevent the resistivity of the silver layer from increasing to a non-preferred level, e.g., increasing by an amount equal to about 75% or more of the resistivity of a silver layer of similar thickness sputtered in an inert, non-reactive atmosphere.
- Additional ceramic or antireflective layers can be deposited below the silver layer or over the ceramic layer.
- a coater is also provided for sputtering a multi- stack coating having an infrared reflective metal, e.g., silver, onto a substrate.
- the coater includes an infrared reflective metal cathode with at least one ceramic cathode located downstream and preferably spaced from and adjacent to the infrared reflective metal cathode.
- the infrared reflective metal cathode and the ceramic cathode may be located in the. same coating zone.
- Fig. 1 is a side, fragmented view of a coater having the sidewall removed for purposes of clarity and utilizing the principles of the invention
- Fig. 2 is a side view of a substrate having a multilayer coating incorporating features of the invention
- Fig. 3 is a graph of deposition rate versus percent oxygen for the experiments disclosed in Table 1;
- Fig. 4 is a graph of absorptance versus percent oxygen for the experiments disclosed in Table 1;
- Fig. 5 is a graph of sheet resistance and emissivity versus percent oxygen for the experiments disclosed in Table 2 ;
- Fig. 6 is a graph of transmittance versus percent oxygen for the experiments disclosed in Table 2. DESCRIPTION OF THE PREFERRED EMBODIMENTS
- the terms “above”, “below”, “right”, “left”, “top”, “bottom”, and similar spatial indicators shall relate to the invention as it is oriented in the figures. However, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. It is also to be understood that the specific coater and coating processes illustrated in the attached drawings, and described in the following specification, are simply exemplary embodiments of the invention. Hence, specific dimensions and other physical characteristics related to the embodiments disclosed herein are not to be considered as limiting.
- the term “ceramic” used herein refers generally to materials comprising compounds of metallic and non-metallic elements and the term “ceramic layer” refers to a layer deposited from. a “ceramic” cathode. The term “over” means above but not necessarily adjacent to or in contact with.
- the coater is designated 10 in Fig. 1 and includes a first coating zone 12, a second coating zone 14 and a third coating zone 16.
- a conveyor 18 is configured to move a substrate 20 to be coated through the zones 12, 14, and 16 at a selected speed.
- the substrate may be made of any material, for example, but not limiting to the invention, plastic, clear or tinted glass, metal, glass ceramic.
- the zones 12, 14 and 16 are isolated from one another in any usual manner, e.g., by structurally separate stages or interstages having turbo molecular or diffusion pumps to help prevent gasses from one zone diffusing into an adjacent zone as indicated by dashed lines in Fig. 1.
- the first zone 12 includes one or more cathode holders 24 for receiving a cathode target 26 for sputtering.
- the third zone 16 is similar to the first zone 12 and includes one or more cathode holders 28 for receiving one or more cathode targets 30.
- the second zone 14 has two cathode holders 34 and 36, each holding a cathode target 38 and 40, respectively.
- the cathode targets will simply be referred to as "cathodes” hereinafter.
- the cathode 38 is a conventional infrared reflective metal cathode, such as silver, gold, etc.
- the other cathode 40 is a conductive ceramic cathode incorporating features of the invention, for example, a metal oxide which is conductive or is doped to be conductive, e.g., an aluminum doped zinc oxide cathode available from the Cerac Company of Milwaukee, Wisconsin.
- the ceramic cathode 40 is used instead of the metal primer cathode of the prior art.
- the cathodes 26 and 30 in the first and third zones 12 and 16 may be conventional metal cathodes, e.g., zinc cathodes and/or zinc and tin alloy cathodes, of the type discussed in U.S. Patent No. 4,610,771, which disclosure is herein incorporated by reference, or zinc cathodes or silicon cathodes of the type used in the art to deposit an antireflective layer, e.g., as disclosed in United States Patent Application Serial No.
- the first and third zones 12 and 16 will contain conventional reactive, e.g., oxygen rich, atmospheres.
- the infrared reflective cathode 38 may be a silver cathode and the ceramic cathode 40 may be an aluminum doped zinc oxide cathode.
- a zinc stannate layer is deposited over the substrate 20 in a conventional manner.
- the zinc stannate layer preferably has a thickness of about 20-1000 A, preferably 100-400 A, most preferably 200-350 A.
- the zinc stannate coated substrate 20 is moved by the conveyor 18 into the second coating zone 14 and under the energized cathode 38.
- An infrared reflective layer e.g., preferably a silver layer of about 80-150 A, is deposited over the zinc stannate layer from the silver cathode 38 in conventional manner.
- the ceramic, aluminum doped zinc oxide cathode 40 is sputtered to deposit an aluminum doped zinc oxide layer onto the silver layer.
- some or all of the cathodes may be continuously energized during the deposition process or cathodes may be energized prior to deposition and deenergized after the deposition.
- the atmosphere for sputtering the ceramic cathode 40 may contain oxygen, e.g., 0-20 vol.%.
- oxygen e.g., 0-20 vol.%.
- zinc, aluminum and oxygen atoms are ejected from the ceramic cathode 40 either separately or as multi-atom species. These atoms recombine on the substrate 20 to form a ceramic, e.g., aluminum doped zinc oxide, layer over the silver layer.
- the minimum amount of ceramic material applied should be that to give uniform coverage over the silver to prevent breakdown when the subsequent antireflective layer is sputtered and the maximum amount is generally limited by the economics of the coating process and may, for example, be on the order of about 20-100 A, preferably about 30-80 A and more preferably about 40-50 A without adversely impacting the coating properties.
- the method of the invention reduces or eliminates the metal to metal alloying problem associated with the metal primer layers of the prior art as previously discussed.
- the ceramic cathode material may include tin oxide, indium oxide and/or zinc oxide with dopants such as indium, zinc, antimony, cadmium and/or fluorine added to form conductive ceramic cathodes such as zinc stannate, antimony doped tin oxide, cadmium stannate, fluorine doped tin oxide, indium doped tin oxide, tin doped indium oxide and indium doped zinc oxide .
- the infrared reflective metal layer and the metal primer layer are deposited in an oxygen-free atmosphere to prevent breakdown of the silver layer by oxidation.
- an oxygen containing ceramic cathode in an oxygen-free atmosphere may result in the loss of oxygen from the sputtered ceramic material to the gas phase. This oxygen may then be pumped away by the diffusion pumps of the interstages . Additionally, some of the oxygen from the ceramic cathode material may react with coating material deposited on the walls or other free surface areas of the coater to reduce the total amount of oxygen available for forming the ceramic layer.
- the resulting ceramic layer such as an aluminum doped zinc oxide layer, deposited over the silver in an oxygen-free atmosphere may have a higher metal e.g. zinc and aluminum to oxygen ratio than stoichiometric.
- a small amount for example, greater than 0 and less than 20 vol.%, preferably 3-10 vol.%, of oxygen may be used in the sputtering atmosphere in the second zone 14. This small amount of oxygen in the zone atmosphere has a negligible effect on the deposition rate and properties of the silver during sputtering, however, this small amount of oxygen results in a substantially completely oxidized ceramic layer, e.g., having a substantially stoichiometric metal to oxygen ratio, over the silver layer.
- the oxygen content should be regulated to prevent an increase in the resistivity of the silver layer by more than an amount equal to about 75% of the resistivity of a silver layer of similar thickness sputtered in an inert, e.g., argon, atmosphere, preferably by an amount less than about 50%, more preferably by an amount less than about 30% and most preferably 0% i.e. no change.
- an inert e.g., argon
- the resistivity varies from about 10.75 ⁇ ⁇ cm at a thickness of about 60 to a resistivity of about 4.5 ⁇ ⁇ cm at a thickness of about 300 A.
- the amount of oxygen added should preferably not result in an increase in resistivity of the silver layer by an amount of more than 8.1 ⁇ ⁇ cm (0.75 x 10.75 ⁇ ⁇ cm), i.e., a final resistivity of 18.85 ⁇ ⁇ cm, preferably by not more than 5.4 ⁇ ⁇ cm (0.5 x 10.75 ⁇ ⁇ cm) and more preferably by not more than 3.2 ⁇ ⁇ cm (0.30 x 10.75 ⁇ ⁇ cm), and most preferably no change i.e. 0 ⁇ ⁇ cm in the silver layer.
- the aluminum doped zinc oxide layer over the silver layer protects the silver layer during subsequent sputter deposition of the second dielectric layer in the third zone 16. Additionally, while energized the ceramic cathode 40 acts as a scavenger for oxygen which may diffuse into the second zone 14 from the first and third zones 12 and 16, i.e., this diffused oxygen can combine with the sputtered cathode material to help form the ceramic layer. In that regard, another ceramic cathode, cathode 41 shown in phantom in Fig. 1, may be operationally positioned upstream of the silver cathode 38 to scavenge oxygen on the upstream side of the silver cathode 38.
- the conveyor 18 moves the substrate into the third zone 16 where a zinc stannate layer is deposited over the ceramic layer in conventional manner.
- additional cathodes 126 and 130 shown in phantom in the first and third zones 12 and 16, respectively, may be present.
- the cathodes 126 and 130 may be zinc cathodes to deposit a zinc oxide layer, over the adjacent zinc stannate layer and under the adjacent silver layer of the coating.
- the substrate 18 can then be moved into other zones similar to zones 12, 14 and 16 for the application of additional coating layers to produce, for example, a mechanically durable multi-layered coated substrate structure 82 of the type shown in Fig. 2.
- the coated substrate structure 82 has a first antireflective layer 84, which may include one or more different types of antireflective materials or one or more films of different antireflective materials, e.g., a zinc oxide layer over a zinc stannate layer; a first infrared reflective metal, e.g., silver, layer 86; a first ceramic, e.g., aluminum doped zinc oxide, layer 88; a second antireflective layer 90, which may include one or more different types of antireflective materials or one or more films of different antireflective materials, e.g., a -zinc oxide layer over a zinc stannate layer; a second silver layer 92; a second aluminum doped zinc oxide layer 94; a third antireflective layer 96, which may include one or more different types of antireflective materials or one or more films of different antireflective materials, e.g., a zinc oxide layer over a zinc stannate layer; and a protective over
- the aluminum doped zinc oxide layers of the instant invention provide improved physical and optical characteristics and eliminate or reduce the problems associated with presently used metal primer layers. Since the aluminum doped zinc oxide layer is transparent and has a similar refractive index to conventional dielectric materials, such as zinc stannate, the thickness of the aluminum doped zinc oxide layer is generally not critical in forming transparent coatings, i.e., the properties of the coated substrate are not typically adversely affected by the thickness of the aluminum doped zinc oxide layer.
- the transmittance and reflectivity components of the coated glass substrate are not adversely affected, as they would be with the prior art metal protective layer.
- the total thickness of the aluminum doped zinc oxide layer and adjacent antireflective layer will have to be controlled to maintain a desired optical thickness, e.g., if the thickness of the aluminum doped zinc oxide layer is increased, the thickness of the adjacent antireflective layer will have to be decreased to maintain the desired optical thickness for a particular desired color. If the refractive index of the aluminum doped zinc oxide layer is substantially different from that of the adjacent dielectric layer, the thicknesses of these layers may have to be adjusted to maintain a desired optical thickness for a desired color.
- Conventional optical monitors (not shown) may be present in the coater 10 to permit the thickness of the coating layers to be monitored and controlled.
- the aluminum doped zinc oxide layer enhances the physical properties of the coated substrate, such as hardness.
- a substrate utilizing an aluminum doped zinc oxide layer of the invention instead of a conventional primer layer may be subsequently heat treated, e.g., to bend, temper or heat strengthen the coated glass substrate. Since the transmission of the ceramic primer layer of the instant invention does not significantly change upon heating as compared to a coating including a thick metal primer layer, one coated substrate can be used for both heated and non- heated applications, eliminating the requirement of separate inventories of coated substrates necessitated with prior art systems. As can be appreciated, in the instance where the ceramic primer layer is substoichiometric, heating the ceramic primer layer is expected to make the composition more oxidized changing the transmittance of the ceramic primer layer and therefore changing the transmittance of the coated article.
- cathodes 26 and 30 in the first and third zones 12 and 16, respectively were conventional zinc and tin alloy cathodes
- one or both of these cathodes 26 and 30 could be a ceramic, e.g., aluminum doped zinc oxide cathode to replace the conventional antireflective layers 84, 90 with aluminum doped zinc oxide layers.
- Samples were made to study the effects of depositing an aluminum doped zinc oxide layer from a ceramic cathode onto a glass substrate and also onto a multi-stack coated substrate. All of the samples discussed below were made with a conventional Airco ILS 1600 deposition system utilizing a system pressure of about 4 mTorr and power settings between 0.5-1.5 kW. Deposition parameters and results for the deposition of an aluminum doped zinc oxide layer onto a glass substrate and also for the deposition of a silver containing low emissivity coating with aluminum doped zinc oxide primers on a glass substrate are shown in Tables 1 and 2, respectively.
- Fig. 3 shows a plot of deposition rate versus oxygen percentage in the total glass flow for preparation of these samples.
- the two sets of data correspond to different deposition power levels for the Airco ILS 1600 deposition system.
- Fig. 4 shows the absorptance of thin films of the same materials with thicknesses of about 500-1800 Angstroms. In pure argon, the absorptance of the deposited ceramic layer is high, indicating that the layer is a highly reduced material.
- the results reported in Table 2 are for multi-stack coatings deposited on clear float glass substrates twelve inches (30.48 cm) square and 0.09 inch (2.3 mm) thick.
- the coating stack comprised a first zinc stannate layer deposited directly on the clear float glass substrate; a first silver layer deposited on the first zinc stannate layer; a first aluminum doped zinc oxide layer deposited from a ceramic cathode onto the first silver layer; a second zinc stannate layer deposited on the first aluminum doped zinc oxide layer; a first zinc oxide layer deposited on the second zinc stannate layer; a second silver layer deposited on the first zinc oxide layer; a second aluminum doped zinc oxide layer deposited from a ceramic cathode onto the second silver layer; a second zinc oxide layer deposited on the second aluminum doped zinc oxide layer; and a titanium oxide overcoat deposited on the second zinc oxide layer.
- Shear resistance, tape and haze tests were performed on the coated substrates in conventional manner and the results are shown in Table 2.
- the tape test is conducted by applying a piece of Scotch brand tape onto the coating surface, pressing the tape by hand against the coating and then pulling the tape off to visually determine whether the coating has delaminated. If there is no delamination, a passing (P) grade is recorded and if there is delamination, a failing grade (F) is recorded.
- the haze test was also a visual test to qualitatively determine the amount of coating haze from A + (meaning no haze) to a D " (very hazy) .
- the shear resistance test was conducted by stroking the coated substrate twenty times with a damp cloth followed by a visual rating from A + , meaning high shear resistance, to D " , meaning low shear resistance.
- a + meaning high shear resistance
- D meaning low shear resistance
- Sample No. 14 of Table 2 at 30% oxygen the coating layer was highly broken down and therefore no haze result was recorded. Examples of such tests are described in the previously cited U.S. Patent No. 5,821,001. From the above results, for an Airco ILS 1600 chamber utilizing a total working gas pressure of 4 mTorr and a cathode power of 0.5-1.5 kW, the preferred region for sputtering a non-absorbing aluminum doped zinc oxide cathode appears to be between about 3-10 vol.% oxygen, preferably about 3-5 vol.% oxygen.
- this range could differ for other coaters or for other pressures or power settings.
- a minimum emissivity of 0.045 can be obtained with about 3-5 vol.% oxygen. This compares favorably with reproducible emissivity of 0.05 for coatings where conventional titanium primer layers are used.
- maximum coating conductivity and transmittance are observed.
- the above coating characteristics are progressively degraded as the amount of oxygen in the gas is increased.
- the optimum range of oxygen concentration corresponds to the range where the deposition rate of the fully oxidized aluminum doped zinc oxide is highest.
- the optimum oxygen content was found to be between about 3-5 vol.%. This optimal range may vary with other model systems .
- the amount of oxygen should not result in an increase in resistivity of the silver layer.
- Fig. 5 in this system, this corresponds to an oxygen presence of 10 vol.% or lower. However, as also shown in Fig. 5, an oxygen presence of up to 20 vol.% still results in a coating with an acceptable level of emissivity. However, as .discussed above, the maximum amount of oxygen should not be more than that producing about a 30%-75% increase in the resistivity of the silver layer for a given thickness calculated with respect to a silver layer of similar thickness sputtered in an inert, e.g., argon, atmosphere. In the instance that a stable but absorbing primer layer is desired e.g.
- the ceramic cathode may be sputtered in an inert atmosphere or an atmosphere containing less than about 3% reactive gas e.g. oxygen to provide a substoichiometric optically absorbing ceramic primer layer.
- a stable layer is a layer that does not chemically change during normal use of the coated product having the stable layer and is expected to change when the stable layer is heated during manufacture of the final product.
- the cathodes 26 and 30 in the first and third zones 12 and 16 may be replaced with ceramic, for example, aluminum doped zinc oxide, cathodes.
- the cathode holder 36 and cathode 40 in the second zone 14 may be eliminated.
- the amount of oxygen in the first and third zones 12 and 16 may be controlled as described above such that ceramic layers deposited from the cathodes 26 and 30 are substantially completely oxidized.
- a ceramic layer e.g., an aluminum doped zinc oxide layer
- additional silver and ceramic layers may be applied to form a multi-layered stack.
- the ceramic, e.g., aluminum doped zinc oxide is utilized not only as a protective layer for the silver layer but also comprises all of the antireflective layers.
- the principles of the invention are applicable to other coater types, such as batch coaters.
- the antireflective and infrared reflective metals can be of any conventional type, such as those described above.
Abstract
Description
Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000589459A JP4498615B2 (en) | 1998-12-18 | 1999-12-14 | Method and apparatus for producing silver-based low emissivity coatings without the use of a metal primer layer, and articles of manufacture thereby |
DK99966212T DK1140721T3 (en) | 1998-12-18 | 1999-12-14 | Methods and Apparatus for Manufacturing Low-Emission Silver-Based Coatings Without Using a Metal Primer Coat |
AT99966212T ATE260874T1 (en) | 1998-12-18 | 1999-12-14 | METHOD AND DEVICE FOR PRODUCING SILVER-BASED COATINGS WITH LOW RADIANTITY WITHOUT METAL PRIMER |
AU21812/00A AU757917B2 (en) | 1998-12-18 | 1999-12-14 | Methods and apparatus for producing silver based low emissivity coatings without the use of metal primer layers and articles produced thereby |
EP99966212A EP1140721B1 (en) | 1998-12-18 | 1999-12-14 | Methods and apparatus for producing silver based low emissivity coatings without the use of metal primer layers |
DE69915350T DE69915350T2 (en) | 1998-12-18 | 1999-12-14 | METHOD AND DEVICE FOR PRODUCING COATINGS BASED ON SILVER WITH LOW RADIATION CAPACITY WITHOUT A METAL PRIMER |
BR9917073-6A BR9917073A (en) | 1998-12-18 | 1999-12-14 | Methods and apparatus for producing low-emissivity coatings based on silver without using layers of metallic primers and articles thus produced |
KR1020017007712A KR20010086125A (en) | 1998-12-18 | 1999-12-14 | Methods and apparatus for producing silver based low emissitivity coatings without the use of metal primer layers and articles produced thereby |
CA002352845A CA2352845A1 (en) | 1998-12-18 | 1999-12-14 | Methods and apparatus for producing silver based low emissivity coatings without the use of metal primer layers and articles produced thereby |
NO20012974A NO20012974D0 (en) | 1998-12-18 | 2001-06-15 | Method and apparatus for the manufacture of silver-based low-emissive coatings without the use of metal primer layers and products made therefrom |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/215,560 | 1998-12-18 | ||
US09/215,560 US6398925B1 (en) | 1998-12-18 | 1998-12-18 | Methods and apparatus for producing silver based low emissivity coatings without the use of metal primer layers and articles produced thereby |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2000037384A1 true WO2000037384A1 (en) | 2000-06-29 |
Family
ID=22803456
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1999/029634 WO2000037384A1 (en) | 1998-12-18 | 1999-12-14 | Methods and apparatus for producing silver based low emissivity coatings without the use of metal primer layers and articles produced thereby |
Country Status (20)
Country | Link |
---|---|
US (1) | US6398925B1 (en) |
EP (1) | EP1140721B1 (en) |
JP (1) | JP4498615B2 (en) |
KR (1) | KR20010086125A (en) |
CN (1) | CN1250475C (en) |
AR (1) | AR023349A1 (en) |
AT (1) | ATE260874T1 (en) |
AU (1) | AU757917B2 (en) |
BR (1) | BR9917073A (en) |
CA (1) | CA2352845A1 (en) |
CZ (1) | CZ302809B6 (en) |
DE (1) | DE69915350T2 (en) |
DK (1) | DK1140721T3 (en) |
ES (1) | ES2217875T3 (en) |
NO (1) | NO20012974D0 (en) |
PT (1) | PT1140721E (en) |
TR (1) | TR200101723T2 (en) |
TW (1) | TWI249582B (en) |
WO (1) | WO2000037384A1 (en) |
ZA (1) | ZA200104007B (en) |
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0464789A1 (en) * | 1990-07-05 | 1992-01-08 | Asahi Glass Company Ltd. | A low emissivity film |
JPH08171824A (en) * | 1994-03-27 | 1996-07-02 | Gunze Ltd | Manufacture of transparent conductive film |
EP0747330A1 (en) * | 1995-06-08 | 1996-12-11 | Balzers und Leybold Deutschland Holding Aktiengesellschaft | Sheet from transparent material and method for its manufacture |
GB2311540A (en) * | 1996-03-26 | 1997-10-01 | Glaverbel | Coated substrate for tranparent assembly with high selectivity |
EP0803481A2 (en) * | 1996-04-25 | 1997-10-29 | Ppg Industries, Inc. | High transmittance, low emissivity coated articles |
US5942338A (en) * | 1996-04-25 | 1999-08-24 | Ppg Industries Ohio, Inc. | Coated articles |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3386906A (en) * | 1965-11-26 | 1968-06-04 | Philips Corp | Transistor base and method of making the same |
DE3316548C2 (en) * | 1983-03-25 | 1985-01-17 | Flachglas AG, 8510 Fürth | Process for coating a transparent substrate |
US4610771A (en) | 1984-10-29 | 1986-09-09 | Ppg Industries, Inc. | Sputtered films of metal alloy oxides and method of preparation thereof |
US4716086A (en) | 1984-12-19 | 1987-12-29 | Ppg Industries, Inc. | Protective overcoat for low emissivity coated article |
JPS6241740A (en) * | 1985-08-19 | 1987-02-23 | Nippon Sheet Glass Co Ltd | Production of heat-reflection glass |
US4786563A (en) | 1985-12-23 | 1988-11-22 | Ppg Industries, Inc. | Protective coating for low emissivity coated articles |
US5318685A (en) | 1987-08-18 | 1994-06-07 | Cardinal Ig Company | Method of making metal oxide films having barrier properties |
US5480531A (en) * | 1991-07-24 | 1996-01-02 | Degussa Aktiengesellschaft | Target for cathode sputtering and method of its production |
US5229194A (en) * | 1991-12-09 | 1993-07-20 | Guardian Industries Corp. | Heat treatable sputter-coated glass systems |
US5344718A (en) * | 1992-04-30 | 1994-09-06 | Guardian Industries Corp. | High performance, durable, low-E glass |
-
1998
- 1998-12-18 US US09/215,560 patent/US6398925B1/en not_active Expired - Lifetime
-
1999
- 1999-12-14 BR BR9917073-6A patent/BR9917073A/en not_active Application Discontinuation
- 1999-12-14 PT PT99966212T patent/PT1140721E/en unknown
- 1999-12-14 CN CNB998145122A patent/CN1250475C/en not_active Expired - Lifetime
- 1999-12-14 KR KR1020017007712A patent/KR20010086125A/en not_active Application Discontinuation
- 1999-12-14 JP JP2000589459A patent/JP4498615B2/en not_active Expired - Lifetime
- 1999-12-14 DE DE69915350T patent/DE69915350T2/en not_active Expired - Lifetime
- 1999-12-14 AT AT99966212T patent/ATE260874T1/en not_active IP Right Cessation
- 1999-12-14 TR TR2001/01723T patent/TR200101723T2/en unknown
- 1999-12-14 CZ CZ20011943A patent/CZ302809B6/en not_active IP Right Cessation
- 1999-12-14 WO PCT/US1999/029634 patent/WO2000037384A1/en not_active Application Discontinuation
- 1999-12-14 CA CA002352845A patent/CA2352845A1/en not_active Abandoned
- 1999-12-14 DK DK99966212T patent/DK1140721T3/en active
- 1999-12-14 AU AU21812/00A patent/AU757917B2/en not_active Ceased
- 1999-12-14 EP EP99966212A patent/EP1140721B1/en not_active Revoked
- 1999-12-14 ES ES99966212T patent/ES2217875T3/en not_active Expired - Lifetime
- 1999-12-17 AR ARP990106489A patent/AR023349A1/en active IP Right Grant
-
2000
- 2000-01-15 TW TW088122344A patent/TWI249582B/en not_active IP Right Cessation
-
2001
- 2001-05-16 ZA ZA200104007A patent/ZA200104007B/en unknown
- 2001-06-15 NO NO20012974A patent/NO20012974D0/en not_active Application Discontinuation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0464789A1 (en) * | 1990-07-05 | 1992-01-08 | Asahi Glass Company Ltd. | A low emissivity film |
JPH08171824A (en) * | 1994-03-27 | 1996-07-02 | Gunze Ltd | Manufacture of transparent conductive film |
EP0747330A1 (en) * | 1995-06-08 | 1996-12-11 | Balzers und Leybold Deutschland Holding Aktiengesellschaft | Sheet from transparent material and method for its manufacture |
GB2311540A (en) * | 1996-03-26 | 1997-10-01 | Glaverbel | Coated substrate for tranparent assembly with high selectivity |
EP0803481A2 (en) * | 1996-04-25 | 1997-10-29 | Ppg Industries, Inc. | High transmittance, low emissivity coated articles |
US5942338A (en) * | 1996-04-25 | 1999-08-24 | Ppg Industries Ohio, Inc. | Coated articles |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Section Ch Week 199636, Derwent World Patents Index; Class L02, AN 1996-360139, XP002135851 * |
QIU C X ET AL: "Tin- and indium-doped zinc oxide films prepared by RF magnetron sputtering", SOLAR ENERGY MATERIALS,NL,ELSEVIER SCIENCE PUBLISHERS B.V. AMSTERDAM, vol. 13, no. 2, February 1986 (1986-02-01), pages 75 - 84-84, XP002112921 * |
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US8659822B2 (en) | 2010-11-08 | 2014-02-25 | Industrial Technology Research Institute | Multilayered infrared light reflective structure |
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Also Published As
Publication number | Publication date |
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CN1330615A (en) | 2002-01-09 |
CZ302809B6 (en) | 2011-11-23 |
AU757917B2 (en) | 2003-03-13 |
JP2002533565A (en) | 2002-10-08 |
ATE260874T1 (en) | 2004-03-15 |
EP1140721B1 (en) | 2004-03-03 |
BR9917073A (en) | 2001-09-25 |
AU2181200A (en) | 2000-07-12 |
PT1140721E (en) | 2004-06-30 |
KR20010086125A (en) | 2001-09-07 |
AR023349A1 (en) | 2002-09-04 |
DE69915350D1 (en) | 2004-04-08 |
ES2217875T3 (en) | 2004-11-01 |
EP1140721A1 (en) | 2001-10-10 |
US6398925B1 (en) | 2002-06-04 |
TWI249582B (en) | 2006-02-21 |
CZ20011943A3 (en) | 2001-12-12 |
DE69915350T2 (en) | 2005-02-10 |
CA2352845A1 (en) | 2000-06-29 |
TR200101723T2 (en) | 2001-10-22 |
NO20012974L (en) | 2001-06-15 |
NO20012974D0 (en) | 2001-06-15 |
JP4498615B2 (en) | 2010-07-07 |
CN1250475C (en) | 2006-04-12 |
ZA200104007B (en) | 2002-05-16 |
DK1140721T3 (en) | 2004-05-24 |
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