WO2016149239A1 - Titanium nickel niobium alloy barrier for low-emissivity coatings - Google Patents

Titanium nickel niobium alloy barrier for low-emissivity coatings Download PDF

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Publication number
WO2016149239A1
WO2016149239A1 PCT/US2016/022416 US2016022416W WO2016149239A1 WO 2016149239 A1 WO2016149239 A1 WO 2016149239A1 US 2016022416 W US2016022416 W US 2016022416W WO 2016149239 A1 WO2016149239 A1 WO 2016149239A1
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WO
WIPO (PCT)
Prior art keywords
layer
titanium
nickel
alloy
niobium
Prior art date
Application number
PCT/US2016/022416
Other languages
English (en)
French (fr)
Inventor
Guowen Ding
Brent Boyce
Jeremy Cheng
Muhammad Imran
Jingyu Lao
Mihn Huu LE
Daniel Schweigert
Zhi-wen WEN SUN
Yu Wang
Yongli Xu
Guizhen Zhang
Original Assignee
Intermolecular Inc.
Guardian Industries Corp.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US14/661,958 external-priority patent/US10604834B2/en
Application filed by Intermolecular Inc., Guardian Industries Corp. filed Critical Intermolecular Inc.
Priority to MX2017011943A priority Critical patent/MX2017011943A/es
Priority to EP16716955.6A priority patent/EP3271169A1/en
Priority to CN201680028471.0A priority patent/CN107645988A/zh
Priority to JP2017568006A priority patent/JP6526255B2/ja
Priority to BR112017019742-1A priority patent/BR112017019742A2/pt
Priority to KR1020177029905A priority patent/KR20180021675A/ko
Priority to RU2017135082A priority patent/RU2721607C2/ru
Publication of WO2016149239A1 publication Critical patent/WO2016149239A1/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00Layered products comprising a layer of metal
    • B32B15/04Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/361Coatings of the type glass/metal/inorganic compound/metal/inorganic compound/other
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3613Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3639Multilayers containing at least two functional metal layers
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3642Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3644Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3652Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3657Surface 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
    • C03C17/366Low-emissivity or solar control coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3681Surface 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 being used in glazing, e.g. windows or windscreens
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C27/00Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
    • C22C27/02Alloys based on vanadium, niobium, or tantalum
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021Reactive sputtering or evaporation
    • C23C14/0036Reactive sputtering
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08Oxides
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/18Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/208Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
    • GPHYSICS
    • G02OPTICS
    • G02BOPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00Optical elements other than lenses
    • G02B5/20Filters
    • G02B5/28Interference filters
    • G02B5/285Interference filters comprising deposited thin solid films

Definitions

  • the present invention relates generally to films providing high transmittance and low emissivity, and more particularly to such films deposited on transparent substrates.
  • Sunlight control glasses are commonly used in applications such as building glass windows and vehicle windows, typically offering high visible transmission and low emissivity. High visible transmission can allow more sunlight to pass through the glass windows, thus being desirable in many window applications. Low emissivity can block infrared (IR) radiation to reduce
  • a reflective layer e.g., silver
  • the overall quality of the reflective layer is important for achieving the desired performance, such as high visible light transmission and low emissivity (i.e., high heat reflection).
  • a reflective layer e.g., silver
  • the various layers typically include dielectric layers, such as silicon nitride, tin oxide, and zinc oxide, to provide a barrier between the stack and both the substrate and the environment, as well as to act as optical fillers and function as anti-reflective coating layers to improve the optical characteristics of the panel.
  • One known method to achieve low emissivity is to form a relatively thick silver layer.
  • the visible light transmission of the reflective layer is reduced, as is manufacturing throughput, while overall manufacturing costs are increased. Therefore, is it desirable to form the silver layer as thin as possible, while still providing emissivity that is suitable for low-e applications.
  • barrier structures, and methods for forming the barrier structures, for an infrared reflective layer are provided to be used in low emissivity coatings.
  • the barrier structures can include a ternary alloy of titanium, nickel and niobium.
  • the percentage of titanium can be between 5 and 15 wt%.
  • the percentage of nickel can be between 30 and 50 wt%.
  • the percentage of niobium can be between 40 and 60 wt%.
  • barrier structures, and methods for forming the barrier structures, for an infrared reflective layer are provided to be used in low emissivity coatings.
  • the barrier structures can include a ternary alloy of nickel, titanium, and niobium.
  • the percentage of nickel can be between 5 and 15 wt%.
  • the percentage of titanium can be between 30 and 50 wt%.
  • the percentage of niobium can be between 40 and 60 wt%.
  • the infrared reflective layer is formed on an underlayer, such as an antireflective layer or a seed layer.
  • the underlayer can include metal oxide materials, such as zinc oxide, doped zinc oxide, tin oxide, doped tin oxide, or an oxide alloy of zinc and tin.
  • the barrier structures can be optimized for both optical and mechanical properties, including low visible light absorption, high visible light transmission, high infrared reflection, and high mechanical durability and adhesion performance.
  • the high content of nickel and niobium can improve the durability of the coated layers, such as by strengthening the interface with a silver layer.
  • the ternary alloy can show better overall
  • FIG. 1A illustrates an exemplary thin film coating according to some embodiments.
  • FIG. 1 B illustrates a low emissivity transparent panel 105 according to some embodiments.
  • FIGs. 2A - 2B illustrate physical vapor deposition (PVD) systems according to some embodiments.
  • FIG. 3 illustrates an exemplary in-line deposition system according to some embodiments.
  • FIG. 4 illustrates a sheet resistance response of a low-e stack having different barrier materials according to some embodiments.
  • FIG. 5 illustrates a flow chart for sputtering coated layers according to some embodiments.
  • FIG. 6 illustrates a flow chart for sputtering coated layers according to some embodiments.
  • FIG. 7 illustrates a table of data relating to the performance of various materials as barrier layers.
  • FIG. 8 illustrates a flow chart for sputtering coated layers according to some embodiments.
  • the coated panels can include coated layers formed thereon, such as a low resistivity thin infrared reflective layer having a conductive material such as silver.
  • the infrared reflective layer can include a conductive material, with the percentage of reflectance proportional to the conductivity.
  • a metallic layer for example silver, can be used as infrared reflective layer in low emissivity coatings.
  • a barrier layer can be formed on the silver layer.
  • methods and apparatuses for making low emissivity coated panels which include depositing a barrier layer on a conductive layer such as silver in such conditions so that the resistivity of silver, and consequently the emissivity of the coated panels, is optimum are disclosed.
  • the low resistive silver layer or the low emissivity panel can be achieved by being protected with a barrier layer including an alloy of titanium, niobium and nickel.
  • Titanium can be used as a barrier for silver in low emissivity coatings, partly due to its high oxygen affinity, e.g., attracting oxygen to prevent oxidation of the silver layer.
  • Low emissivity coatings utilizing titanium barrier can exhibit excellent visible light transmission, together with minimal infrared reflectivity.
  • low emissivity coatings utilizing titanium barrier can show poor mechanical durability, probably due to poor adhesion with the silver layer.
  • Nickel can be added to a titanium barrier layer to modify the barrier characteristics.
  • titanium nickel alloys can improve corrosion
  • Nickel-inclusive alloys have been reported to have sufficient adhesion to the IR reflecting layer, leading to improved overall chemical and mechanical durability.
  • various nickel alloys have been evaluated, including binary nickel alloys (e.g., nickel chromium and nickel titanium), and ternary nickel alloys (e.g., nickel titanium niobium), !n general, different binary nickel alloys can show different performance in different requirements.
  • binary nickel alloys e.g., nickel chromium and nickel titanium
  • ternary nickel alloys e.g., nickel titanium niobium
  • different binary nickel alloys can show different performance in different requirements.
  • nickel titanium can provide minor improvement in light transmission, with minima! improvement in mechanical durability.
  • More nickel content in a titanium nickel alloy can slightly improve the adhesion with silver.
  • 80 wt% nickel in titanium nickel alloys can show better adhesion than titanium nickel alloys having 50 wt% nickel.
  • nickel chromium can provide significant improvement in mechanical durability, but with worse performance in optical properties.
  • ternary alloys of nickel, titanium and niobium can show better overall performance, e.g., better mechanical durability as compared to titanium, with improved adhesion to the silver layer.
  • the nickel, titanium and niobium ternary alloys can also provide similar, or slightly
  • optical performance e.g., reducing emissivity and absorption together with increasing light transmittance.
  • resistance e.g., reducing emissivity and absorption together with increasing light transmittance.
  • measurement data indicates that the ternary alloys provide better barrier protection than titanium and binary alloys, e.g., NiTi or NiCr.
  • ternary alloys of titanium, nickel and niobium with various ranges of composition are disclosed, which can provide excellent overall performance, including good optical properties together with good mechanical properties.
  • a high percentage of niobium e.g., between 40 and 60 wt%
  • nickel e.g., higher than titanium but lower than niobium, such as between 30 and 50 wt%
  • the percentage of titanium can be low, e.g., between 5 and 15 wt%, to provide the desired optical properties.
  • a ternary alloy having 50 wt% niobium, 40 wt% nickel, and 10 wt% titanium can show better overall performance as compared with titanium and titanium-nickel alloys.
  • ternary alloys of titanium, nickel and niobium with various ranges of composition are disclosed, which can provide, for example, desirable (i.e., relatively low) absorption, resistance, and emissivity.
  • the alloys may include a high percentage of niobium, e.g., between 40 and 60 wt%, can be used to improve the mechanical durability without affecting the optical or electrical properties.
  • a relatively high percentage of titanium, e.g., higher than nickel but lower than niobium, such as between 30 and 50 wt%, can be used.
  • the percentage of nickel can be low, e.g., between 5 and 15 wt%.
  • a ternary alloy may include 50 wt% niobium, 40 wt% titanium, and 10 wt% nickel.
  • the barrier layer can include ternary oxide alloys of titanium, nickel and niobium.
  • the oxide alloy barrier can be a
  • the oxide alloy barrier can be a sub-oxide alloy, e.g., the amount of oxygen atoms in the oxide alloy is less than the stoichiometric ratio.
  • the barrier layer can improve the low emissivity coated panels, for example, by reducing absorption in the visible range, e.g., allowing high transmission of visible light, minimizing or eliminating reactivity with Ag, which can prevent degradation of the color of the coated system, resulting in color- neutral panels, and improving adhesion between Ag and the top barrier layer.
  • methods and apparatuses for making low emissivity panels which include a low resistivity thin infrared reflective layer including a conductive material such as silver, gold, or copper are disclosed.
  • the thin silver layer can be thinner than 15 nm, such as 7 or 8 nm.
  • the silver layer can have low roughness, and is preferably deposited on a seed layer also having low roughness.
  • the low emissivity panels can have improved overall quality of the infrared reflective layer with respect to conductivity, physical roughness and thickness.
  • the methods allow for improved conductivity of the reflective layer such that the thickness of the reflective layer may be reduced while still providing desirably low emissivity.
  • the reflective layer preferably has low sheet resistance, since low sheet resistance is related to low emissivity.
  • the reflective layer is preferably thin to provide high visible light transmission.
  • methods and apparatuses to deposit a thin and highly conductive reflective layer, providing a coated layer with high visible transmittance and low infrared emissivity are disclosed. The methods can also maximize volume production, throughput, and efficiency of the manufacturing process used to form low emissivity panels.
  • improved coated transparent panels such as a coated glass, that has acceptable visible light transmission and IR reflection are disclosed.
  • Methods of producing the improved, coated, transparent panels, which comprise specific layers in a coating stack are also disclosed.
  • the coated transparent panels can include a glass substrate or any other transparent substrates, such as substrates made of organic polymers.
  • the coated transparent panels can be used in window applications such as vehicle and building windows, skylights, or glass doors, either in monolithic glazings or multiple glazings with or without a plastic interlayer or a gas-filled sealed interspace.
  • FIG. 1A illustrates an exemplary thin film coating according to some embodiments.
  • a barrier layer 1 15 is disposed on an infrared reflective layer 1 13, such as a silver layer, which is disposed on a substrate 1 10 to form a coated transparent panel 100, which has high visible light transmission, and low IR emission.
  • the layer 1 15 can be sputtered deposited using different processes and equipment, for example, the targets can be sputtered under direct current (DC), pulsed DC, alternate current (AC), radio frequency (RF) or any other suitable conditions.
  • DC direct current
  • AC alternate current
  • RF radio frequency
  • physical vapor deposition methods for depositing a layer 1 15 with minimum effect on the infrared reflective layer 1 13 are disclosed.
  • the infrared reflective layer can include a conductive material, with the percentage of reflectance proportional to the conductivity. Metals are typically used as infrared reflective layers, with silver offering between 95 - 99% and gold 98 - 99% reflectivity in the infrared region. Thus a metallic layer, for example silver, can be used as infrared reflective layer in low emissivity coatings. The deposition of the silver layer can be optimized to obtain high conductivity, for example, by minimizing the impurities in the silver layer.
  • the layer immediately on top of the silver layer is very important in protecting the silver from oxidation, such as during oxygen reactive sputtering process in the deposition of subsequent layers.
  • this barrier layer can protect the silver layer against reaction with oxygen diffusion during the glass tempering process, or during long term use where the piece of glass may be exposed to moisture or environment.
  • a barrier layer can be formed on the silver layer.
  • the barrier layer can be an oxygen diffusion barrier, protecting the silver layer from oxygen diffusing through the barrier to the react with the silver layer.
  • the barrier layer In addition to the oxygen diffusion barrier property, there are other desirable properties for the barrier layer. For example, since the barrier layer is placed directly on the silver layer, low or no solubility of the barrier material in silver is desirable to minimize reactivity between the barrier layer and silver at the interface. The reaction between the barrier layer and silver can introduce impurity to the silver layer, potentially reducing the conductivity.
  • high temperature processes can be used, for example, to anneal the deposited films or to tempering the glass substrate.
  • the high temperature processes can have adverse effects on the low emissivity coating, such as changing the structure or the optical properties, e.g., index of refraction n or absorption coefficient k, of the coated films.
  • barrier material might have low extinction coefficient, e.g., low visible absorption, in both metallic form and oxide form.
  • barrier structures, and methods for forming the same, for an infrared reflective layer to be used in low emissivity coatings are disclosed.
  • the barrier structures can be formed on an infrared reflective layer to protect the infrared reflective layer from impurity diffusion, together with exhibiting good adhesion and good optical properties, for example, during the fabrication process.
  • the barrier structure can include a ternary alloy of titanium, nickel and niobium. High percentage of niobium and lower percentage of nickel, e.g., lower than that of niobium, can be used to improve the mechanical durability properties while not affecting the optical properties. Low percentage of nickel, e.g., lower than those of niobium and titanium, can be used to provide an oxygen diffusion barrier to the silver underlayer,
  • a layer 1 15 on a high transmittance, low emissivity coated article having a substrate and a smooth metallic reflective film including one of silver, gold, or copper are disclosed.
  • other layers can be included, such as an oxide layer, a seed layer, a conductive layer, an antireflective layer, or a protective layer.
  • coating stacks comprising multiple layers for different functional purposes are disclosed.
  • the coating stacks can comprise a seed layer to facilitate the deposition of the reflective layer, an oxygen diffusion layer disposed on the reflective layer to prevent oxidation of the reflective layer, a protective layer disposed on the substrate to prevent physical or chemical abrasion, or an antireflective layer to reduce visible light reflection.
  • the coating stacks can comprise multiple layers of reflective layers to improve IR emissivity.
  • FIG. 1 B illustrates a low emissivity transparent panel 105 according to some embodiments.
  • the low emissivity transparent panel can comprise a glass substrate 120 and a low emissivity (low-e) stack 190 formed over the glass substrate 120.
  • the glass substrate 120 in some embodiments is made of a glass, such as borosilicate glass, and has a thickness of, for example, between 1 and 10 millimeters (mm).
  • the substrate 120 may be square or rectangular and about 0.5 - 2 meters (m) across.
  • the substrate 120 may be made of, for example, plastic or polycarbonate.
  • the iow-e stack 190 includes a lower protective layer 130, a lower oxide layer 140, a seed layer 150, a reflective layer 154, a barrier layer 156, an upper oxide 160, an optical filler layer 170, and an upper protective layer 180. Some layers can be optional, and other layers can be added, such as interface layers or adhesion layers. Exemplary details as to the functionality provided by each of the layers 130-180 are provided below.
  • the various layers in the low-e stack 190 may be formed sequentially (i.e., from bottom to top) on the glass substrate 120 using a physical vapor deposition (PVD) and/or reactive (or plasma enhanced) sputtering processing tool.
  • PVD physical vapor deposition
  • the iow-e stack 190 is formed over the entire glass substrate 120.
  • the iow-e stack 190 may only be formed on isolated portions of the glass substrate 120.
  • the lower protective layer 130 is formed on the upper surface of the glass substrate 120.
  • the lower protective layer 130 can comprise silicon nitride, silicon oxynitride, or other nitride material such as SiZrlM, for example, to protect the other layers in the stack 190 from diffusion from the substrate 120 or to improve the haze reduction properties, !n some embodiments, the lower protective layer 130 is made of silicon nitride and has a thickness of, for example, between about 10 nm to 50 nm, such as 25 nm.
  • the lower oxide layer 140 is formed on the lower protective layer 130 and over the glass substrate 120.
  • the lower oxide layer is preferably a metal or metal alloy oxide layer and can serve as an antireflective layer.
  • the lower metal oxide layer 140 may enhance the crystallinity of the reflective layer 154, for example, by enhancing the crystallinity of a seed layer for the reflective layer, as is described in greater detail below.
  • the layer 150 can be used to provide a seed layer for the IR reflective film, for example, a zinc oxide layer deposited before the deposition of a silver reflective layer can provide a silver layer with lower resistivity, which can improve its reflective characteristics.
  • the seed layer can comprise a metal such as titanium, zirconium, and/or hafnium, or a metal alloy such as zinc oxide, nickel oxide, nickel chrome oxide, nickel alloy oxides, chrome oxides, or chrome alloy oxides.
  • the seed layer 150 can be made of a metal, such as titanium, zirconium, and/or hafnium, and has a thickness of, for example, 50 A or less.
  • seed layers are relatively thin layers of materials formed on a surface (e.g., a substrate) to promote a particular characteristic of a subsequent layer formed over the surface (e.g., on the seed layer).
  • seed layers may be used to affect the crystalline structure (or crystallographic orientation) of the subsequent layer, which is sometimes referred to as
  • templating More particularly, the interaction of the material of the subsequent layer with the crystalline structure of the seed layer causes the crystalline structure of the subsequent layer to be formed in a particular orientation.
  • a metal seed layer is used to promote growth of the reflective layer in a particular crystallographic orientation.
  • the metal seed layer is a material with a hexagonal crystal structure and is formed with a (002) crystallographic orientation which promotes growth of the reflective layer in the (1 1 1 ) orientation when the reflective layer has a face centered cubic crystal structure (e.g., silver), which is preferable for iow-e panel applications.
  • the crystallographic orientation can be characterized by X-ray diffraction (XRD) technique, which is based on observing the scattered intensity of an X-ray beam hitting the layer, e.g., silver layer or seed layer, as a function of the X-ray characteristics, such as the incident and scattered angles.
  • XRD X-ray diffraction
  • zinc oxide seed layer can show a pronounced (002) peak and higher orders in a ⁇ - 2 ⁇ diffraction pattern. This suggests that zinc oxide crystallites with the respective planes oriented parallel to the substrate surface are present.
  • crystallographic orientation include a meaning that there is a (1 1 1 )
  • the crystallographic orientation can be determined, for example, by observing pronounced
  • the seed layer 150 can be continuous and covers the entire substrate. Alternatively, the seed layer 150 may not be formed in a completely continuous manner.
  • the seed layer can be distributed across the substrate surface such that each of the seed layer areas is laterally spaced apart from the other seed layer areas across the substrate surface and do not completely cover the substrate surface.
  • the thickness of the seed layer 150 can be a monolayer or less, such as between 2.0 and 4.0 A, and the separation between the layer sections may be the result of forming such a thin seed layer (i.e., such a thin layer may not form a continuous layer).
  • the reflective layer 154 is formed on the seed layer 150.
  • the IR reflective layer can be a metallic, reflective film, such as silver, gold, or copper. In general, the IR reflective film comprises a good electrical conductor, blocking the passage of thermal energy.
  • the reflective layer 154 is made of silver and has a thickness of, for example, 100 A. Because the reflective layer 154 is formed on the seed layer 150, for example, due to the (002) crystallographic orientation of the seed layer 150, growth of the silver reflective layer 154 in a (1 1 1 ) crystalline orientation is promoted, which offers low sheet resistance, leading to low panel emissivity.
  • the conductivity and emissivity of the reflective layer 154 is improved. As a result, a thinner reflective layer 154 may be formed that still provides sufficient reflective properties and visible light transmission. Additionally, the reduced thickness of the reflective layer 154 allows for less material to be used in each panel that is manufactured, thus improving manufacturing throughput and efficiency, increasing the usable life of the target (e.g. , silver) used to form the reflective layer 154, and reducing overall manufacturing costs.
  • the target e.g. , silver
  • the seed layer 150 can provide a barrier between the metal oxide layer 140 and the reflective layer 154 to reduce the likelihood of any reaction of the material of the reflective layer 154 and the oxygen in the lower metal oxide layer 140, especially during subsequent heating processes. As a result, the resistivity of the reflective layer 154 may be reduced, thus increasing performance of the reflective layer 154 by lowering the emissivity.
  • a barrier layer 156 which can protect the reflective layer 154 from being oxidized.
  • the barrier can be a diffusion barrier, stopping oxygen from diffusing into the silver layer from the upper oxide layer 160.
  • the barrier layer 156 can include titanium, nickel, and niobium, !n some embodiments, the barrier layer 156 can include titanium, nickel, niobium, and oxygen.
  • an upper oxide layer which can function as an antireflective film stack, including a single layer or multiple layers for different functional purposes.
  • the antireflective layer 160 serves to reduce the reflection of visible light, selected based on transmitfance, index of refraction, adherence, chemical durability, and thermal stability.
  • the antireflective layer 160 comprises tin oxide, offering high thermal stability properties.
  • the antireflective layer 160 can also include titanium dioxide, silicon nitride, silicon dioxide, silicon oxynitride, niobium oxide, SiZrN, fin oxide, zinc oxide, or any other suitable dielectric material.
  • the optical filler layer 170 can be used to provide a proper thickness to the low-e stack, for example, to provide an antireflective property.
  • the optical filler layer preferably has high visible light transmitfance.
  • the optical filler layer 170 is made of tin oxide and has a thickness of, for example, 100 A.
  • the optical filler layer may be used to tune the optical properties of the low-e panel 105.
  • the thickness and refractive index of the optical filler layer may be used to increase the layer thickness to a multiple of the incoming light wavelengths, effectively reducing the light reflectance and improving the light transmittance.
  • An upper protective layer 180 can be used for protecting the total film stack, for example, to protect the panel from physical or chemical abrasion.
  • the upper protective layer 180 can be an exterior protective layer, such as silicon nitride, silicon oxynitride, titanium oxide, tin oxide, zinc oxide, niobium oxide, or SiZrN.
  • adhesion layers can be used to provide adhesion between layers.
  • the adhesion layers can be made of a metal alloy, such as nickel-titanium, and have a thickness of, for example, 30 A.
  • some of the layers of the low-e stack 190 may have some elements in common.
  • An example of such a stack may use a zinc-based material in the oxide dielectric layers 140 and 160.
  • a relatively low number of different targets can be used for the formation of the low- e stack 190.
  • the coating can comprise a double or triple layer stack, having multiple IR reflective layers, !n some embodiments, the layers can be formed using a plasma enhanced, or reactive sputtering, in which a carrier gas (e.g., argon) is used to eject ions from a target, which then pass through a mixture of the carrier gas and a reactive gas (e.g., oxygen), or plasma, before being deposited.
  • a carrier gas e.g., argon
  • a reactive gas e.g., oxygen
  • the effects of the deposition process of the layers deposited on the silver conductive layer on the quality of the silver conductive layer are disclosed. Since the silver conductive layer is desirably thin, for example, less than 20 nm , to provide high visible light transmission, the quality of the silver conductive layer can be affected by the deposition of the subsequently deposited layer, such as the barrier layer or the antireflective layer.
  • sputter deposition processes which can be applied for a barrier layer deposited on a conductive layer are disclosed.
  • the barrier layer can protect the infrared reflective layer from being oxidized.
  • the oxide layer can function as an antireflective layer.
  • the materials of the barrier layer can reduce reaction for the conductive underiayer such as oxidation, preventing resistivity and emissivity degradation.
  • deposition processes, and coated articles fabricated from the process, using a layer having an alloy of a high oxygen affinity material and a low oxygen affinity material during the sputter deposition, for example, to achieve higher quality coated layers and coated panels are disclosed.
  • the alloy barrier layer can be sputtered from an alloyed target, or co-sputtered from different elemental targets onto the same substrate.
  • the process may be in pure Ar (which will deposit a pure metallic barrier layer), or may include oxygen to make the film slightly oxidized,
  • FIGs. 2A - 2B illustrate physical vapor deposition (PVD) systems according to some embodiments.
  • PVD physical vapor deposition
  • a PVD system also commonly called sputter system or sputter deposition system, 200 includes a housing that defines, or encloses, a processing chamber 240, a substrate 230, a target assembly 210, and reactive species delivered from an outside source 220.
  • the target is bombarded with argon ions, which releases sputtered particles toward the substrate 230.
  • the sputter system 200 can perform blanket deposition on the substrate 230, forming a deposited layer that cover the whole substrate, e.g., the area of the substrate that can be reached by the sputtered particles generated from the target assembly 210.
  • the materials used in the target 210 may, for example, include tin, zinc, magnesium, aluminum, lanthanum, yttrium, titanium, antimony, strontium, bismuth, niobium, silicon, silver, nickel, chromium, copper, gold, or any
  • the materials used in the targets may include oxygen, nitrogen, or a combination of oxygen and nitrogen in order to form the oxides, nitrides, and oxynitrides of the metals described above.
  • additional target assemblies may be used. As such, different combinations of targets may be used to form, for example, the dielectric layers described above. For example, in some
  • the barrier material is titanium-nickei-niobium
  • the titanium, the nickel, and the niobium may be provided by separate titanium, nickel, and niobium targets, or they may be provided by a single titanium-nickei- niobium alloy target.
  • the target assembly 210 can comprise a silver target, and together with argon ions to sputter deposit a layer on substrate 230.
  • the target assembly 210 can include a metal or metal alloy target, such as fin, zinc, or tin-zinc alloy, and together with reactive species of oxygen to sputter deposit a metal or metal alloy oxide layer,
  • the sputter deposition system 200 can include other components, such as a substrate support for supporting the substrate.
  • the substrate support can include a vacuum chuck, electrostatic chuck, or other known mechanisms.
  • the substrate support can be capable of rotating around an axis thereof that is perpendicular to the surface of the substrate.
  • the substrate support may move in a vertical direction or in a planar direction. It should be appreciated that the rotation and movement in the vertical direction or planar direction may be achieved through known drive mechanisms which include magnetic drives, linear drives, worm screws, lead screws, a differentially pumped rotary feed through drive, etc.
  • the substrate support includes an electrode which is connected to a power supply, for example, to provide a RF or DC bias to the substrate, or to provide a plasma environment in the process housing 240.
  • the target assembly 210 can include an electrode which is connected to a power supply to generate a plasma in the process housing.
  • the target assembly 210 is preferably oriented towards the substrate 230.
  • the sputter deposition system 200 can also include a power supply coupled to the target electrode.
  • the power supply provides power to the electrodes, causing material to be, at least in some embodiments, sputtered from the target.
  • inert gases such as argon or krypton
  • reactive gases may also be introduced, such as oxygen and/or nitrogen, which interact with particles ejected from the targets to form oxides, nitrides, and/or oxynitrides on the substrate.
  • the sputter deposition system 200 can also include a control system (not shown) having, for example, a processor and a memory, which is in operable communication with the other components and configured to control the operation thereof in order to perform the methods described herein.
  • a control system (not shown) having, for example, a processor and a memory, which is in operable communication with the other components and configured to control the operation thereof in order to perform the methods described herein.
  • methods and apparatuses for making layers above the thin low resistive silver layer including controlling the ion energy on the substrate, so that the deposition is performed at a low ion energy, which can reduce damage to the silver underlayer are disclosed.
  • FIG. 2B shows a sputter system having co-sputtering targets according to some embodiments.
  • a sputter deposition chamber 205 can include two targets 212 and 214 disposed in a plasma environment 245, containing reactive species delivered from an outside source 225.
  • the targets 212 and 214 can include a first element of the alloy barrier, e.g., Ta, Nb, Zr, Hf, Mn, Y, Si, and Ti and a second element of the alloy barrier, e.g., Pd, Ru, Ni, Co, Mo, and W, together with optional reactive species of oxygen to deposit an alloy of barrier layer on substrate 230,
  • a first element of the alloy barrier e.g., Ta, Nb, Zr, Hf, Mn, Y, Si, and Ti
  • a second element of the alloy barrier e.g., Pd, Ru, Ni, Co, Mo, and W
  • methods and apparatuses for making low emissivity panels including forming an infrared reflective layer formed under or over a barrier structure that includes a ternary alloy of titanium, nickel and niobium are disclosed.
  • the panels can exhibit optimal infrared reflectance, thermal stability and durability, for example, due to the barrier layer protecting the infrared reflective layer while not degrading the low emissivity coating
  • a transport mechanism can be provided to move a substrate under one or more sputter targets, to deposit a conductive layer underlayer before depositing a barrier layer, an antireflecfive layer, together with other layers such as a surface protection layer.
  • in-line deposition systems including a transport mechanism for moving substrates between deposition stations are disclosed.
  • FIG. 3 illustrates an exemplary in-line deposition system according to some embodiments.
  • a transport mechanism 370 such as a conveyor belt or a plurality of rollers, can transfer substrate 330 between different sputter deposition stations.
  • the substrate can be positioned at station #1 , having a target assembly 31 OA, then transferred to station #2, having target assembly 310B, and then transferred to station #3, having target assembly 310C.
  • the station #1 having target 31 OA can be a silver deposition station, sputtering an infrared reflective layer having silver.
  • the station #2 having target 310B can be a barrier deposition station, sputtering a metallic alloy having titanium, nickel and niobium materials.
  • the station #2 includes a single target 310B.
  • other configurations can be used, such as co-sputtering system utilizing two different targets.
  • the station #3 having target 310C can be used to deposit other layers, such as an antireflective layer or a protection layer.
  • composition percentages of titanium, nickel and niobium are provided to achieve excellent performance in all properties, including optical and mechanical properties.
  • High percentage of niobium can be used to improve the mechanical properties, including adhesion, thermal stability, and panel durability.
  • higher than 40 wt% of niobium can be used to obtain a desired mechanical durability, e.g., comparable with NiCr alloy barriers and much better than titanium barriers.
  • Lower than 60 wt% of niobium can be used to not degrading the optical performance, e.g., maintaining similar or better visible light transmission with low reflection or absorption.
  • a low percentage of titanium can be used, e.g., to provide oxygen diffusion barrier properties.
  • the barrier thickness can be between 0.3 and 8 nm, such as between 0.5 and 5 nm.
  • composition percentages of nickel, titanium, and niobium are provided to achieve excellent performance, at least with respect to, absorption, resistance, and emissivity (i.e., relatively low).
  • absorption, resistance, and emissivity i.e., relatively low.
  • higher than 40 wt% of niobium can be used to obtain a desired mechanical durability, e.g., comparable with NiCr alloy barriers and much better than titanium barriers.
  • Lower than 60 wt% of niobium can be used to not degrading the optical performance, e.g., maintaining similar or better visible light transmission with low reflection or absorption.
  • a low percentage of nickel (e.g., between 5 wt% and 15 wt%) can be used with a medium percentage of titanium, (e.g., lower than that of niobium and higher than that of nickel, such as between 30 wt% and 50 wt%).
  • the barrier thickness can be between 0.3 and 8 nm, such as between 0.5 and 5 nm.
  • FIG. 4 illustrates a sheet resistance response of a low ⁇ e stack having different barrier materials according to some embodiments.
  • the sheet resistance can provide an evaluation of optical properties, with lower sheet resistance values, for a same silver layer thickness, correlated to higher transmission and lower reflection.
  • Low-e stacks used on the sheet resistance measurement include a barrier layer on an 8 nm silver layer on a 10 nm ZnO seed layer.
  • the barrier materials include titanium, titanium nickel alloy having 20 wt% titanium and 80 wt% nickel, and titanium nickel niobium alloy with 10 wt% nickel, 40 wt% titanium and 50 wt% niobium.
  • the thicknesses of the barriers range from 0.3 nm to 7 nm, such as from 1.5 nm to 4.5 nm.
  • the ternary alloy of titanium, nickel, and niobium has lower sheet resistance, e.g., better optical performance, for all thicknesses, as compared to titanium and titanium nickel binary alloy.
  • optimum barrier performance can be at around 2 nm, e.g., between 1 .5 and 2.7 nm.
  • FIG. 5 illustrates a flow chart for sputtering coated layers according to some embodiments.
  • a barrier layer can be sputtered deposited on the conductive layer.
  • the barrier layer can include a ternary alloy of titanium, nickel and niobium, including ternary metal alloys, e.g., consisting of the metal components of titanium, nickel, and niobium, and ternary oxide alloys, e.g., comprising titanium, nickel, niobium, and oxygen.
  • a substrate is provided.
  • the substrate can be a transparent substrate, such as a glass substrate or a polymer substrate.
  • a first layer is formed on the substrate.
  • the first layer can be operable as an infrared reflective layer.
  • the first layer can include a conductive material or a metallic material such as silver.
  • the thickness of the first layer can be less than or equal to about 20 nm, or can be less than or equal to about 10 nm.
  • a second layer is sputter deposited on the first layer.
  • the second layer can be operable as a barrier layer.
  • the second layer can include an alloy of titanium, nickel and niobium.
  • the percentage of titanium can be between 5 and 15 wt%
  • the percentage of nickel can be between 30 and 50 wt% (or between 35 and 45 wt%)
  • the percentage of niobium can be between 40 and 60 wt% (or between 45 and 45 wt%).
  • the second layer can include an alloy of nickel, titanium, and niobium.
  • the percentage of nickel can be between 5 and 15 wt%
  • the percentage of titanium can be between 30 and 50 wt% (or between 35 and 45 wt%)
  • the percentage of niobium can be between 40 and 60 wt% (or between 45 and 45 wt%).
  • the second layer can also include oxygen to form an oxide alloy.
  • the second layer can be deposited as a ternary metal alloy or a ternary oxide alloy.
  • the ternary metal alloy can be oxidized, for example, by a subsequent layer deposition, to become a ternary oxide layer.
  • the ternary oxide alloy can also be further oxidized.
  • the second layer can remain a ternary metal alloy, or can become a ternary oxide or a ternary sub-oxide for better emissivity performance.
  • an underiayer can be formed under the first layer, such as a seed layer of ZnO for the silver layer.
  • the seed layer can enhance the crystal orientation of silver, leading to better conductivity.
  • other layers can be formed on the second layer.
  • FIG. 6 illustrates a flow chart for sputtering coated layers according to some embodiments.
  • a barrier layer can be sputtered deposited on the conductive layer.
  • the barrier layer can include a ternary alloy of titanium, nickel and niobium.
  • a substrate is provided.
  • the substrate can be a transparent substrate, such as a glass substrate or a polymer substrate. Other substrates can also be used.
  • a metal oxide layer is formed on the substrate.
  • the metal oxide layer can functioned as a seed layer for the subsequent layer.
  • the metal oxide layer can have a crystal orientation that promotes a crystal orientation of the to-be-deposited first layer,
  • the metal oxide layer can include a seed layer having a crystal orientation that promotes a (1 1 1 ) crystal orientation of a silver layer.
  • the metal oxide layer can include ZnO having (002) crystal orientation, which can served as a template for growing (1 1 1 ) silver layer.
  • the thickness of the metal oxide layer can be less than or equal to about 20 nm, or can be less than or equal to about 10 nm.
  • a first layer is formed on the metal oxide layer.
  • the first layer can be operable as an infrared reflective layer.
  • the first layer can include a conductive material or a metallic material such as silver.
  • the thickness of the first layer can be less than or equal to about 20 nm, or can be less than or equal to about 10 nm.
  • a second layer is sputter deposited on the first layer.
  • the second layer can be operable as a barrier layer.
  • the second layer can include an alloy of titanium, nickel and niobium.
  • the percentage of titanium can be between 5 and 15 wt%
  • the percentage of nickel can be between 30 and 50 wt% (or between 35 and 45 wt%)
  • the percentage of niobium can be between 40 and 60 wt% (or between 45 and 45 wt%).
  • the second layer can include an alloy of nickel, titanium, and niobium.
  • the percentage of nickel can be between 5 and 15 wt%
  • the percentage of titanium can be between 30 and 50 wt% (or between 35 and 45 wt%)
  • the percentage of niobium can be between 40 and 60 wt% (or between 45 and 45 wt%).
  • the second layer can also include oxygen to form an oxide alloy.
  • the second layer can be deposited as a ternary metal alloy or a ternary oxide alloy.
  • the ternary metal alloy can be oxidized, for example, by a subsequent layer deposition, to become a ternary oxide layer.
  • the ternary oxide alloy can also be further oxidized.
  • the second layer can remain a ternary metal alloy, or can become a ternary oxide or a ternary sub-oxide for better emissivity performance, !n some embodiments, other layers can be included.
  • the barrier layer (e.g., barrier layer 1 15 in FIG. 1A and/or barrier layer 156 in FIG. 1 B) includes (e.g., consists of) a ternary alloy that includes less nickel than titanium and niobium (e.g., between 5 and 15 wt% nickel, between 30 and 50 wt% titanium, and between 40 and 60 wt%).
  • the performance of the resulting barrier layer may vary based (at least in part) on, for example, the amount of niobium compared to nickel and/or titanium.
  • FIG. 7 illustrates a data related to the performance of various materials for use in barrier layers.
  • the materials represented include nickel chromium alloy (i.e., 80 wt% nickel and 20 wt% chromium), nickel titanium, and various nickel titanium niobium alloys (i.e., 15:60:25, 10:40:50, and 5:20:75).
  • nickel chromium alloy i.e. 80 wt% nickel and 20 wt% chromium
  • nickel titanium i.e., nickel titanium
  • various nickel titanium niobium alloys i.e., 15:60:25, 10:40:50, and 5:20:75.
  • nickel titanium niobium alloys i.e., 15:60:25, 10:40:50, and 5:20:75.
  • the layer may exhibit relatively poor absorption (i.e., Avis, Abs % at 400 nm, 550 nm, and 1000 nm), but desirable resistance (i.e., Rs) and emissivity (i.e,. ⁇ ), at least compared to nickel chromium and nickel titanium.
  • relatively poor absorption i.e., Avis, Abs % at 400 nm, 550 nm, and 1000 nm
  • desirable resistance i.e., Rs
  • emissivity i.e,. ⁇
  • niobium e.g., 5 wt% nickel, 20 wt% titanium, and 75 wt% niobium
  • the absorption is desirable, but the resistance and emissivity are relatively poor.
  • performance is optimized (at least relatively) by using 50 wt% niobium (e.g., 10 wt% nickel, 40 wt% titanium, and 50 wt% niobium), as absorption, resistance, and emissivity are ail desirable (i.e., relatively low).
  • FIG. 8 illustrates a flow chart for sputtering coated layers according to some embodiments.
  • a barrier layer can be sputtered deposited on the conductive layer.
  • the barrier layer can include a ternary alloy of nickel, titanium, and niobium, including ternary metal alloys, e.g., consisting of the metal components of nickel, titanium, and niobium, and ternary oxide alloys, e.g., comprising nickel, titanium, niobium, and oxygen.
  • a substrate is provided.
  • the substrate can be a transparent substrate, such as a glass substrate or a polymer substrate. Other substrates can also be used.
  • a first layer is formed on the substrate.
  • the first layer can be operable as an infrared reflective layer.
  • the first layer can include a conductive material or a metallic material such as silver.
  • the thickness of the first layer can be less than or equal to about 20 nm, or can be less than or equal to about 10 nm.
  • a second layer is sputter deposited on the first layer.
  • the second layer can be operable as a barrier layer.
  • the second layer can include an alloy of nickel, titanium, and niobium.
  • the percentage of nickel can be between 5 and 15 wt% (e.g., 10 wt%, or about 10 wt%)
  • the percentage of titanium can be between 30 and 50 wt% (e.g., 40 wt%, or about 40 wt%)
  • the percentage of niobium can be between 40 and 60 wt% (e.g., 50 wt%, or about 50 wt%).
  • the second layer can also include oxygen to form an oxide alloy.
  • the second layer can be deposited as a ternary metal alloy or a ternary oxide alloy.
  • the ternary metal alloy can be oxidized, for example, by a subsequent layer deposition, to become a ternary oxide layer.
  • the ternary oxide alloy can also be further oxidized.
  • the second layer can remain a ternary metal alloy, or can become a ternary oxide or a ternary sub-oxide for better emissivity performance.
  • At least some of the other layers shown, and described above with reference to, FIG. 1 B may also be formed over the substrate to form a low emissivity transparent panel.
  • an underiayer can be formed under the first layer, such as a seed layer of ZnO for the silver layer.
  • the seed layer can enhance the crystal orientation of silver, leading to better conductivity.
  • other layers can be formed on the second layer.

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MX2017011943A MX2017011943A (es) 2015-03-18 2016-03-15 Barrera de aleacion de titanio, niquel y niobio para revestimientos de baja emisividad.
EP16716955.6A EP3271169A1 (en) 2015-03-18 2016-03-15 Titanium nickel niobium alloy barrier for low-emissivity coatings
CN201680028471.0A CN107645988A (zh) 2015-03-18 2016-03-15 用于低辐射率涂层的钛镍铌合金阻挡层
JP2017568006A JP6526255B2 (ja) 2015-03-18 2016-03-15 低放射率コーティング用のチタンニッケルニオブ合金バリア
BR112017019742-1A BR112017019742A2 (pt) 2015-03-18 2016-03-15 barreira de liga de titânio, níquel e nióbio para revestimentos de baixa emissividade
KR1020177029905A KR20180021675A (ko) 2015-03-18 2016-03-15 저방사율 코팅용 티타늄 니켈 니오브 합금 배리어
RU2017135082A RU2721607C2 (ru) 2015-03-18 2016-03-15 Барьер из сплава ниобий-никель-титан для покрытий с низкой излучательной способностью

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RU2017135082A (ru) 2019-04-08
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KR20180021675A (ko) 2018-03-05
JP2018514499A (ja) 2018-06-07
BR112017019742A2 (pt) 2018-05-29
RU2017135082A3 (zh) 2019-09-06
RU2721607C2 (ru) 2020-05-21
CN107645988A (zh) 2018-01-30
EP3271169A1 (en) 2018-01-24

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