EP3262005A1 - Vitrage comprenant un substrat revetu d'un empilement comprenant au moins une couche fonctionnelle a base d'argent - Google Patents
Vitrage comprenant un substrat revetu d'un empilement comprenant au moins une couche fonctionnelle a base d'argentInfo
- Publication number
- EP3262005A1 EP3262005A1 EP16713528.4A EP16713528A EP3262005A1 EP 3262005 A1 EP3262005 A1 EP 3262005A1 EP 16713528 A EP16713528 A EP 16713528A EP 3262005 A1 EP3262005 A1 EP 3262005A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- silver
- material according
- layer
- grains
- dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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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
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B27/00—Tempering or quenching glass products
- C03B27/012—Tempering or quenching glass products by heat treatment, e.g. for crystallisation; Heat treatment of glass products before tempering by cooling
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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
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
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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
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
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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
- C03C17/3647—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 in combination with other metals, silver being more than 50%
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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
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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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
- C03C17/3681—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 being used in glazing, e.g. windows or windscreens
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/216—ZnO
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/24—Doped oxides
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/251—Al, Cu, Mg or noble metals
- C03C2217/254—Noble metals
- C03C2217/256—Ag
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/261—Iron-group metals, i.e. Fe, Co or Ni
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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
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/28—Other inorganic materials
- C03C2217/281—Nitrides
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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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Definitions
- the invention relates to a material such as a glazing unit comprising a transparent substrate coated with a stack of thin layers comprising at least one silver-based functional metal layer.
- Functional metal layers based on silver (or silver layers) have advantageous electrical conduction and reflection properties of infrared (IR) radiation, hence their use in "solar control" glazing aimed at reducing the amount of incoming solar energy and / or in so-called “low emissivity” glazing aimed at reducing the amount of energy dissipated to the outside of a building or a vehicle.
- IR infrared
- These silver layers are deposited between coatings based on dielectric materials which generally comprise several dielectric layers to adjust the optical properties of the stack. These dielectric layers also make it possible to protect the silver layer from chemical or mechanical aggression.
- the optical and electrical properties of the glazings depend directly on the quality of the silver layers such as:
- the silver layers comprise monocrystalline grains based on silver
- dielectric-based coatings comprising dielectric layers with a stabilizing function intended to promote the wetting and nucleation of the silver layer.
- the quality of the silver layer affects not only the visual appearance but also the optical properties including the presence of blur, electrical conductivity and chemical resistance including the corrosion resistance of the stack.
- the applicant has discovered that it is possible to improve the homogeneity of the silver layer both in terms of thickness, surface area and volume by optimizing the crystallization. Homogenization is achieved by controlling the distribution, shape and size of monocrystalline silver grains. Obtaining a better homogenization affects several properties, in particular the mechanical durability of the stacks, the plasticity of the silver layer but also the electrical properties such as square resistance.
- the subject of the invention is a material comprising a transparent substrate coated with a stack of thin layers comprising at least one silver-based functional metal layer, comprising a doping element of thickness E formed of monocrystalline grains having a lateral dimension. D, defined as a grain edge cord characterized in that the D / E ratio is greater than 1.05.
- the invention also relates to a method for preparing a material comprising a transparent substrate coated with a stack of thin layers, according to which:
- At least one silver-based functional layer comprising a doping element over a thickness E is deposited, the functional layer is formed of monocrystalline grains having a lateral dimension d defined as a rope of the edge of grain and then
- DIGM-induced diffusion growth is a phenomenon known in the field of metallurgy.
- this growth technique is particularly advantageous when it is applied to silver-based functional layers which have, by their small thickness, to be formed of columnar monocrystalline grains.
- Columnar means that the monocrystalline silver grains are arranged so that there is essentially a single monocrystalline grain occupying the thickness of the silver layer at any point.
- the doping of silver-based metal layers with other elements allows for increased and controlled growth of monocrystalline silver-based grains during heat treatment.
- the lateral growth of the grains induced by diffusion of the doping elements is carried out by a heat treatment of quenching or annealing type.
- Silver-based metal functional layers in stacks are deposited at thicknesses less than 20 nm.
- the lateral dimension of the grains is generally of the order of thickness.
- a heat treatment equivalent to quenching for example about 10 minutes at 620 ° C., thus produces an increase of about 45% in the average size of the monocrystalline grains in the absence of a doping element.
- the grain growth induced by diffusion of doping elements operates according to the diagram presented in FIG.
- a silver layer 1 comprises several monocrystalline grains 2 separated by grain boundaries 4. These monocrystalline grains 2 comprise doping elements 3 in solution.
- the diffusion rate of the doping elements 3 is a function of the temperature.
- the doping elements 3 diffuse little or no while the grain boundaries 4 can in turn diffuse.
- they "sweep" an area of material represented by the two horizontal arrows.
- the doping elements 3 will then concentrate in the grain boundaries 4 where their presence disturbs less the crystal lattice.
- the doping elements concentrated at the grain boundaries are then in a more favorable energy position. This energy balance will then further promote the movement of grain boundaries and thus the lateral growth of monocrystalline grains.
- a lateral dimension is defined as a rope of the grain edge.
- Chord D or d
- the lateral dimension of the grains can be measured by image processing obtained by any microscopic observation mode, direct or indirect, such as scanning electron microscopy, transmission electron microscopy, backscatter electron diffraction (Electron backscatter diffraction "), Atomic force microscopy and optical microscopy.
- D corresponds to the lateral dimension of the grains before lateral growth of grains induced by diffusion of the doping elements and "D" corresponds to the lateral dimension of the grains after lateral growth of grains induced by diffusion of the doping elements.
- the D / E characteristic greater than 1 is considered to be satisfied when at least 80%, preferably at least 90%, better still at least 95% and even better 100% of the grains have at least one lateral dimension D satisfying this relationship.
- the lateral dimension of 100 to 200 grains is measured manually.
- the monocrystalline grain or grains have, in order of increasing preference, a lateral dimension D, defined as a chord of the grain edge, on all grains, greater than 15 nm, greater than 16 nm, greater than 17 nm, greater at 18 nm, greater than 19 nm, greater than 20 nm and better still greater than 23 nm.
- the lateral dimension D is less than 300 nm, or even less than 200 nm or better still less than 100 nm.
- the ratio D / E is, in order of increasing preference, greater than 1, 10, greater than 1, 20, greater than 1, 30, greater than 1, 40, greater than 1, 50 and better still greater than 1, 60.
- the ratio D / E is less than 10.
- the stack is deposited by sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by sputtering assisted by a magnetic field.
- the thicknesses discussed herein are physical thicknesses and the layers are thin layers.
- thin film is meant a layer having a thickness of between 0.1 nm and 100 micrometers.
- the substrate according to the invention is considered laid horizontally.
- the stack of thin layers is deposited above the substrate.
- the meaning of the terms “above” and “below” and “below” and “above” should be considered in relation to this orientation.
- the terms “above” and “below” do not necessarily mean that two layers and / or coatings are arranged in contact with each other.
- a layer is deposited "in contact” with another layer or a coating, this means that there can not be one or more layers interposed between these two layers.
- a silver-based metal functional layer comprises at least 95.0%, preferably at least 96.5% and most preferably at least 97.0% by weight of silver based on the weight of the functional layer.
- the silver-based functional metal layer comprises less than 3.5 mass% of non-silver metals relative to the weight of the silver-based functional metal layer.
- the functional silver-based metal layer comprises at least 95.0%, preferably at least 96.5% and better still at least 97.0% by weight of silver relative to the weight of the layer functional means that the total mass of doping elements or impurities does not exceed 5.0%, preferably 3.5% and better 3.0% of the mass of the functional layer.
- the silver-based functional metal layers have a thickness E of less than 20 nm.
- the thickness of the silver-based functional layers is in order of increasing preference ranging from 5 to 20 nm, from 8 to 15 nm.
- the silver-based metal functional layers comprise a doping element. These layers can be obtained by sputter deposition either from two targets or from a silver target doped with the element. dopant.
- the doping element is preferably a metal chosen from aluminum, nickel, zinc or chromium.
- the doping element is chosen from aluminum, nickel and zinc, and even more advantageously, it is chosen from aluminum and nickel. Better yet, it is aluminum.
- the silver-based functional metal layer may comprise in particular 0.5 to 5.0% by weight of doping element relative to the mass of doping element and silver in the functional layer.
- the silver-based functional metal layer may be doped with aluminum and possibly only with aluminum. It comprises less than 1.0%, preferably less than 0.5%, or even less than 0.1% by weight of metals other than silver and aluminum relative to the weight of the functional metallic layer. based on money.
- the doping element is aluminum, its weight proportions are from 1.0 to 4.0%, preferably from 1.5 to 3.5% with respect to the mass of doping element and silver in the functional layer.
- the silver-based functional metal layer may be doped with nickel and possibly only with nickel. It comprises less than 1.0%, preferably less than 0.5%, or even less than 0.1% by weight of metals other than silver and nickel relative to the weight of the functional metal layer based on silver.
- the doping element is nickel, its weight proportions are from 1.0 to 3.0%, preferably from 1.0 to 2.0% relative to the mass of doping element and silver in the layer. functional.
- the silver-based functional metal layer may be doped with zinc and optionally only with zinc. It comprises less than 1.0%, preferably less than 0.5%, or even less than 0.1% by weight of metals other than silver and zinc relative to the weight of the functional metal layer based on silver.
- the silver-based functional metal layer can be doped with chromium and optionally only with chromium. It comprises less than 1.0%, preferably less than 0.5%, or even less than 0.1% by weight of metals other than silver and chromium relative to the weight of the functional metal layer based on silver.
- Doping measurement can be performed for example by microprobe analysis of Castaing (ElectroProbe MicroAnalyzer or EPMA in English).
- the thin film stack advantageously comprises at least one silver-based functional metal layer and at least two dielectric material-based coatings, each coating comprising at least one layer dielectric, so that each functional layer is disposed between two dielectric material-based coatings.
- Coatings based on dielectric materials have a thickness greater than 15 nm, between 15 and 50 nm or between 30 and 40 nm.
- barrier dielectric layers means a layer of a material capable of barrier to the diffusion of oxygen and water at high temperature, from the ambient atmosphere or the transparent substrate, to the functional layer.
- the barrier-type dielectric layers may be based on silicon and / or aluminum compounds chosen from oxides such as SiO 2 , nitrides such as silicon nitride Si 3 N 4 and aluminum nitrides AlN, and the oxynitrides SiO x N y optionally doped with at least one other element.
- the barrier-type dielectric layers may also be based on zinc oxide and tin.
- dielectric layers with stabilizing function means a layer made of a material capable of stabilizing the interface between the functional layer and this layer.
- the dielectric layers with a stabilizing function are preferably based on crystalline oxide, in particular based on zinc oxide, optionally doped with at least one other element, such as aluminum.
- the dielectric layer (s) with a stabilizing function are preferably zinc oxide layers.
- the stabilizing function dielectric layer (s) may be above and / or below, preferably below, at least one silver-based functional metal layer or each functional metal-based layer. money, either directly to him or separated by a blocking layer.
- the material according to the invention is characterized in that the stack of thin layers comprises at least one functional metal layer based on silver and at least two coatings based on dielectric materials, each coating with less a dielectric layer, so that each silver-based functional metal layer is disposed between two dielectric material-based coatings, said dielectric layer being selected from the barrier-function or stabilizer-function dielectric layers.
- Said dielectric layer is particularly advantageously a stabilizing function dielectric layer lying beneath said silver-based functional layer. It is preferably based on zinc oxide, optionally doped with at least one other element.
- said element is aluminum.
- the stack comprises a dielectric layer based on silicon nitride and / or aluminum located above at least a portion of the functional layer.
- the dielectric layer based on silicon nitride and / or aluminum has a thickness:
- the stacks may further include blocking layers whose function is to protect the functional layers by avoiding possible degradation related to the deposition of a coating based on dielectric materials or linked to a heat treatment.
- the stack comprises at least one blocking layer located below and in contact with a silver-based functional metal layer and / or at least one blocking layer situated above and -contact of a functional metallic layer based on silver.
- the metal-based blocking layers chosen from among niobium Nb, tantalum Ta, titanium Ti, Cr chromium or nickel Ni or based on an alloy obtained from at least two of these metals, in particular an alloy of nickel and chromium (NiCr).
- each blocking layer is preferably:
- the stack may comprise an upper protective layer deposited as the last layer of the stack, in particular to give anti-scratch properties.
- the upper layers of protection may be chosen from among the layers based on titanium oxide, zirconium oxide and / or zinc oxide. These layers have a thickness of between 2 and 5 nm.
- An example of a stack that is suitable according to the invention comprises: a coating based on dielectric materials located beneath the functional metallic layer based on silver, the coating possibly comprising at least one dielectric layer based on silicon nitride and / or aluminum,
- a coating based on dielectric materials situated above the silver-based functional metal layer possibly comprising at least one dielectric layer based on silicon nitride and / or aluminum, a top layer of protection.
- the transparent substrates according to the invention are preferably made of a mineral rigid material, such as glass, in particular silico-soda-lime or organic based on polymers (or polymer).
- the transparent organic substrates according to the invention can also be made of polymer, rigid or flexible.
- suitable polymers according to the invention include, in particular:
- polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN);
- polyacrylates such as polymethyl methacrylate (PMMA);
- fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- photocurable and / or photopolymerizable resins such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate and
- the thickness of the substrate generally varies between 0.5 mm and 19 mm.
- the thickness of the substrate is preferably less than or equal to 6 mm or even 4 mm.
- the invention also relates to the process for preparing the material according to the invention.
- the stack of thin layers is deposited on the substrate by a vacuum technique of the cathode sputtering type possibly assisted by a magnetic field.
- the lateral grain growth induced by diffusion of the doping elements is preferably carried out by a heat treatment. This heat treatment can be carried out at temperatures between 350 and 800 ° C, preferably between 500 and 700 ° C.
- the heat treatment may in particular be quenching carried out at a temperature of at least 500 ° C., preferably at least 600 ° C.
- the heat treatment may in particular be annealing carried out at a temperature of between 200 ° C. and 550 ° C., or even between 350 ° C. and 500 ° C. for a period of preferably at least 1 hour.
- the material according to the invention may therefore have undergone a heat treatment, said heat treatment being advantageously chosen from annealing, quenching and / or a bending. It is said that it is a heat-treated material. Advantageously, it is an annealed, tempered and / or curved material.
- the material may be monolithic glazing, laminated glazing or multiple glazing including double glazing or triple glazing.
- Stacks of thin layers defined below are deposited on clear soda-lime glass substrates with a thickness of 2 mm.
- Doping of the silver layer can be achieved:
- the two targets When deposition by co-spraying from two targets, the two targets are placed inclined and lit at the same time.
- the desired doping is obtained by adjusting the deposition powers.
- the deposition power of the silver target is fixed and the deposition power of the doping element target is varied.
- Silver layers with different doping elements and proportions of doping elements were tested.
- Silver layers doped with zinc (Zn), chromium (Cr) and nickel (Ni) are obtained by co-spraying from two targets.
- the silver layers doped with aluminum are obtained by sputtering from a single already doped target (3% doped Ag / Al target).
- composition of the layers, and in particular the proportions of doping elements in the doped silver layer were measured by conventional microprobe techniques of Castaing (also known as Electron Probe Microanalyser or EPMA). Concentration as a doping element is expressed as a mass of doping element with respect to the mass of silver and of the doping element.
- Atomic wt weight; * : at 550 nm.
- stacks which differ in the nature of the silver-based functional layer and in particular by the presence and nature of the doping element.
- the stacks comprise the following thin layers, defined starting from the substrate, according to the physical thicknesses in nanometers given:
- FIG. 2 presents a light-field transmission electron microscopy image of a substrate comprising a stack comprising at least one silver-based functional metal layer.
- the grain boundaries are redrawn by white dotted lines.
- the lateral dimension of the monocrystalline grains is determined by measuring this quantity over 100 to 200 grains.
- FIG. 3 is a graph showing the evolution of the mean lateral grain size as a function of temperature and annealing time, for pure silver-based layers and for silver-based layers comprising a doping element .
- the measurement of the evolution of the mean lateral dimension of the grains as a function of the temperature, the annealing time and the doping element confirms that the addition of doping element makes it possible to obtain an increased growth of the monocrystalline grains of money.
- the lateral growth of the grains induced by diffusion of doping elements chosen especially from aluminum and nickel makes it possible to obtain grains having a lateral dimension of about 25 nm.
- a silver-based layer without a doping element comprises grains having a lateral dimension, generally less than 15 nm. This method of doping makes it possible to obtain a layer based on silver with grains almost twice as large.
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- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Physics & Mathematics (AREA)
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- Physical Vapour Deposition (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR1551592A FR3032959A1 (fr) | 2015-02-25 | 2015-02-25 | Vitrage comprenant un substrat revetu d'un empilement comprenant au moins une couche fonctionnelle a base d'argent |
PCT/FR2016/050427 WO2016135420A1 (fr) | 2015-02-25 | 2016-02-24 | Vitrage comprenant un substrat revetu d'un empilement comprenant au moins une couche fonctionnelle a base d'argent |
Publications (1)
Publication Number | Publication Date |
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EP3262005A1 true EP3262005A1 (fr) | 2018-01-03 |
Family
ID=53177628
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16713528.4A Withdrawn EP3262005A1 (fr) | 2015-02-25 | 2016-02-24 | Vitrage comprenant un substrat revetu d'un empilement comprenant au moins une couche fonctionnelle a base d'argent |
Country Status (4)
Country | Link |
---|---|
US (1) | US20180072616A1 (fr) |
EP (1) | EP3262005A1 (fr) |
FR (1) | FR3032959A1 (fr) |
WO (1) | WO2016135420A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10227819B2 (en) * | 2017-02-24 | 2019-03-12 | Guardian Glass, LLC | Coated article with low-E coating having doped silver IR reflecting layer(s) |
SE543408C2 (en) | 2018-10-22 | 2021-01-05 | Mimsi Mat Ab | Glazing and method of its production |
US20240199479A1 (en) * | 2021-06-29 | 2024-06-20 | Agp America S.A. | Improved solar coating method of manufacture and glass laminate comprising such coating |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2798738B1 (fr) * | 1999-09-16 | 2001-10-26 | Saint Gobain Vitrage | Substrat transparent muni d'un empilement de couches reflechissant la chaleur |
US20020037414A1 (en) * | 2000-07-18 | 2002-03-28 | Cunningham James A. | Low emissivity panel assembly |
AU2003248890A1 (en) * | 2002-07-08 | 2004-01-23 | Academy Corporation | Reflective or semi-reflective metal alloy coatings |
DE102009051796A1 (de) * | 2009-11-03 | 2011-05-05 | Kramer & Best Process Engineering Gmbh | Thermisch belastbares Schichtsystem |
FR3013349B1 (fr) * | 2013-11-15 | 2015-11-20 | Saint Gobain | Vitrage comprenant un substrat revetu d'un empilement comprenant au moins une couche fonctionnelle a base d'argent dope par du zinc |
CN103802379B (zh) * | 2014-01-26 | 2015-08-05 | 林嘉佑 | 一种含银合金的可钢化低辐射镀膜玻璃 |
EP3146528A4 (fr) * | 2014-05-23 | 2018-01-03 | The Regents of The University of Michigan | Films ultra-minces de métal noble dopé pour applications optoélectroniques et photoniques |
-
2015
- 2015-02-25 FR FR1551592A patent/FR3032959A1/fr not_active Withdrawn
-
2016
- 2016-02-24 EP EP16713528.4A patent/EP3262005A1/fr not_active Withdrawn
- 2016-02-24 WO PCT/FR2016/050427 patent/WO2016135420A1/fr active Application Filing
- 2016-02-24 US US15/553,369 patent/US20180072616A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
US20180072616A1 (en) | 2018-03-15 |
WO2016135420A1 (fr) | 2016-09-01 |
FR3032959A1 (fr) | 2016-08-26 |
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