Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
  • C03C17/366—Low-emissivity or solar control coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3694—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer having a composition gradient through its thickness
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/90—Other aspects of coatings
  • C03C2217/91—Coatings containing at least one layer having a composition gradient through its thickness
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/32—After-treatment
  • C03C2218/322—Oxidation

Definitions

• the invention relates to solar protection glazing.
• Known high-performance solar protection glazings are multiple glazings comprising at least two substrates separated by at least one spacer layer of gas.
• the substrate constituting the outer wall of the glazing comprises on its face facing the interior a stack of layers comprising at least one functional layer based on silver.
• the silver-based functional metal layers have advantageous properties of electrical conduction and reflection of infrared radiation (IR), hence their use in these so-called “solar control" glazing aimed at reducing the amount of solar energy entering a building or vehicle.
• IR infrared radiation
• dielectric coatings are deposited between coatings based on dielectric materials generally comprising several dielectric layers (hereinafter “dielectric coatings”) making it possible to adjust the optical properties of the stack. These dielectric layers also make it possible to protect the silver layer from chemical or mechanical attack.
• the solar factor of the glazing "FS or g" corresponds to the ratio in % between the total energy entering the room through the glazing and the incident solar energy.
• the solar factor therefore measures the contribution of glazing to warming the “room”.
• the heat loss coefficient also called “Ug value” expresses the heat flow per square meter of glazing caused by a temperature difference between the external environment and the interior separated by the glazing. The lower this value, the lower the losses and the better the insulation.
• the invention is limited to stacks comprising a single functional layer based on silver because they are likely to exhibit lower light absorption values in the visible and therefore higher light transmissions. Obtaining such high light transmissions, a low solar factor and low heat losses in combination is tricky because very few modifications of the stack are possible. To obtain such low heat loss at these levels of light transmission, in particular with stacks with a single functional layer based on silver, it is necessary to reduce the emissivity of the stack without increasing the absorption or the reflection. There is therefore no great flexibility of action.
• the emissivity depends directly on the quality of the silver layers such as their crystalline state, their homogeneity and their environment. “Environment” means the nature of the layers close to the silver layer and the surface roughness of the interfaces with these layers. Another way to reduce the emissivity therefore consists in improving the quality of the silver layer by choosing a favorable environment. Emissivity and resistivity (or resistance) per square vary proportionately. Therefore, it is often possible to assess the emissivity of a material by evaluating its resistance per square.
• dielectric coatings comprising dielectric layers with stabilizing function intended to promote wetting, nucleation and crystallization of the layer.
• dielectric layers based on crystallized zinc oxide are notably used for this purpose. Indeed, the zinc oxide deposited by the sputtering process crystallizes without requiring additional heat treatment. The layer based on zinc oxide can therefore serve as an epitaxial growth layer for the silver layer.
• Another avenue for preventing the degradation of the silver layers resides in the choice of the layer located above and in contact with the silver layer.
• the known proposals is the use of so-called blocking layers or dielectric layers based on crystallized zinc oxide.
• the objective is to protect the functional layers from a possible degradation during the deposition of the upper dielectric coating and/or during a heat treatment.
• the blocking layers are generally based on a metal chosen from nickel, chromium, titanium, niobium, or an alloy of these various metals.
• the various metals or alloys mentioned can also be partially oxidized, in particular have an oxygen sub-stoichiometry (for example TiOx OR NiCrOx).
• blocking layers are very thin, normally less than 2 nm thick, and are susceptible at these thicknesses to being partially oxidized during heat treatment or during deposition of an overlying layer.
• these blocking layers are sacrificial layers, capable of capturing oxygen coming from the atmosphere or from the substrate, thus avoiding the oxidation of the silver layer.
• each dielectric coating comprises at least one layer comprising silicon.
• the silver layer is located in contact with two layers of crystallized zinc oxide located respectively above and below the silver layer. Materials of this type comprising the sequence ZnO/Ag/ZnO are qualified as reference material in the present application.
• the applicant has surprisingly discovered that the use of a coating comprising an oxidation gradient based on titanium oxide located above and in contact with the functional layer based on silver, in a particular stack , overcomes these disadvantages.
• the solution of the invention makes it possible to achieve the required properties, namely to obtain a solar protection glazing having a high light transmission, in particular of the order of 78.5% and a low emissivity.
• the emissivity can be low enough to allow the lowest possible heat transfer coefficients (Ug values) to be obtained.
• the invention therefore relates to a multiple glazing unit comprising at least two substrates separated by at least one spacer layer of gas, the substrate constituting the outer wall of the glazing unit comprises, on its face facing inwards, a stack of layers comprising a functional metal layer silver base and at least two dielectric coatings, each dielectric coating including at least one dielectric layer, such that each functional metal layer is disposed between two dielectric coatings, characterized in that the stack comprises a coating based on titanium oxide comprising, as deposited, an oxidation gradient, located above and in contact with the functional metallic layer based on silver , the part of the oxidation gradient coating in contact with the functional layer is less oxidized than the part of this coating further from the functional layer.
• the stack comprises a coating comprising an oxidation gradient as deposited. This means that a coating with an oxidation gradient is directly deposited. The gradient is present from the deposition. The gradient is not obtained following a possible heat treatment, the deposition of an overlying layer or a possible long storage.
• a coating based on titanium oxide comprising an oxidation gradient is based on titanium oxide over its entire thickness. This coating is in contact with the silver layer. This means that the invention excludes the depositing in contact with the silver layer of a metallic titanium layer.
• the solution of the invention makes it possible to obtain an improvement in the resistivity with the obtaining of a gain in square resistance of at least 10%, or even 15%, even in the absence of thermal treatment.
• the improvement in resistivity is obtained without an increase in absorption. This gain in resistivity makes it possible to achieve emissivity values sufficiently low to reach the required Ug values without increasing the thicknesses of the silver layer and therefore without lowering the light transmission.
• the dielectric coating located below the silver layer comprises a layer with a high refractive index.
• the joint presence of the coating based on titanium oxide which has a high refractive index above the functional layer based on silver and of a high index layer below the functional layer contributes to obtaining high light transmission.
• the coating comprising an oxidation gradient based on titanium oxide associated with a layer based on zinc oxide and particular tin contributes to obtaining the properties advantages of the invention. It seems that this layer makes it possible to reduce the residual absorption in the event of incomplete oxidation of the part farthest from the silver layer of the titanium oxide-based oxidation gradient coating.
• the invention combining a coating based on titanium oxide in contact with a layer of zinc and tin oxide makes it possible to obtain:
• the present invention is particularly suitable in the case of stacks with a single functional layer based on silver.
• the solution of the invention is also suitable in the case of stacks with several functional layers based on silver, in particular stacks with two or three functional layers.
• the oxidation gradient coating comprises at least two layers of titanium oxide each comprising different proportions of oxygen
• the oxidation gradient coating comprises a first layer deposited from a ceramic target, in particular sub-stoichiometric, in an atmosphere whose percentage by volume flow of oxygen represents between 0 and 4%, preferably 0%,
• the first layer has a thickness between 0.2 and 2 nm
• the oxidation gradient coating comprises a second layer based on titanium oxide deposited from a ceramic target, in particular sub-stoichiometric, in an atmosphere comprising higher proportions of oxygen than that used for the first layer ,
• the second layer has a thickness between 0.2 and 30 nm
• the stack further comprises a layer based on zinc oxide and tin comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact the layer based on titanium oxide,
• the layer based on zinc oxide and tin has a thickness:
• the dielectric coating located above the functional layer comprises a layer comprising silicon chosen from among the layers of silicon nitride,
• the dielectric coating located below the functional layer comprises a layer based on zinc oxide located in contact with the functional layer, - the dielectric coating located below the functional layer further comprises a layer with a refractive index greater than 2.20,
• the layer with a refractive index greater than 2.20 is chosen from layers based on titanium oxide and layers based on silicon nitride and zirconium,
• the thickness of all the layers with a refractive index greater than 2.20 in the dielectric coating located below the functional layer is greater than 10 nm, greater than 15 nm, greater than 20 nm,
• the dielectric coating located above the functional layer comprises a layer based on silicon nitride and zirconium
• the dielectric coating located below the functional layer comprises a layer based on silicon nitride and zirconium
• the stack comprises a single functional metallic layer based on silver
• the stack and the substrate have been subjected to a heat treatment at a high temperature above 500°C such as quenching, annealing or bending.
• the invention also relates to:
• the substrate according to the invention is considered laid horizontally.
• the stack of thin layers is deposited above the substrate.
• the meaning of the expressions “above” and “below” and “lower” and “higher” should be considered in relation to this orientation.
• the expressions “above” and “below” do not necessarily mean that two layers and/or coatings are arranged in contact with one another. When it is specified that a layer is deposited "in contact” with another layer or a coating, this means that there cannot be one (or more) interposed layer(s) between these two layers (or layer and coating).
• the luminous characteristics are measured according to the D65 illuminant at 2° perpendicular to the material mounted in a double glazing:
• Rint corresponds to the interior light reflection in the visible in %, observer on the interior space side
• the properties must be obtained even when the stack or the substrate carrying the stack has not undergone heat treatment at high temperature.
• the substrate and the stack undergo heat treatment at high temperature.
• the present invention therefore relates to the non-heat-treated coated substrate.
• the stack may not have undergone heat treatment at a temperature above 500°C, preferably 300°C.
• the present invention also relates to the substrate coated with the heat-treated stack.
• the heat treatments are chosen from:
• the material that is to say the transparent substrate coated with the stack, may have undergone a heat treatment at high temperature.
• the stack and the substrate may have been subjected to a heat treatment at a high temperature such as quenching, annealing or bending. It is also possible to heat treat only the stack. In this case, the stack only may have undergone heat treatment.
• the stack may have undergone a heat treatment at a temperature above 300°C, preferably 500°C.
• the heat treatment temperature (at the level of the stack) is greater than 300°C, preferably greater than 400°C, and better still greater than 500°C.
• Rapid Thermal annealing such as laser annealing or flash lamp annealing.
• Rapid thermal annealing is for example described in applications WO2008/096089 and WO2015/185848.
• each point of the stack is brought to a temperature of at least 300° C. while maintaining a temperature less than or equal to 150° C. at any point on the face of the substrate opposite to that on which locate the stack.
• This process has the advantage of only heating the stack, without significant heating of the entire substrate.
• the coated materials can be treated using a laser line formed from laser sources such as InGaAs diode lasers or Yb:YAG disc lasers. These continuous sources emit at a wavelength between 900 and 1100 nm.
• the laser line has a length of the order of 3.3 m, equal to the width 1 of the substrate, and an average FWHM half-width between 45 and 100 ⁇ m.
• the materials are arranged on a roller conveyor so as to scroll along an X direction, parallel to its length.
• the laser line is fixed and positioned above the coated surface of the substrate with its longitudinal direction Y extending perpendicularly to the running direction X of the substrate, i.e. along the width of the substrate, in extending across that width.
• the position of the focal plane of the laser line is adjusted to be within the thickness of the functional coating when the substrate is positioned on the conveyor.
• the surface power of the laser line at the focal plane is less than 100kW/cm2.
• the substrate was moved under the laser line at a speed of about 8 m/min.
• the stack may therefore have been subjected to rapid thermal annealing in which each point of the stack is brought to a temperature of at least 300°C while maintaining a temperature less than or equal to 150°C at any point on the face. of the substrate opposite to that on which the stack is located.
• the stack and the substrate may have been subjected to a heat treatment at a high temperature above 500°C such as quenching, annealing or bending.
• the coated substrate of the stack can be bent or tempered glass.
• the stack is deposited by cathode sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by cathodic sputtering assisted by a magnetic field.
• the expressions “above” and “below” do not necessarily mean that two layers and/or coatings are arranged in contact with one another. When it is specified that a layer is deposited "in contact” with another layer or a coating, this means that there cannot be one (or more) interposed layer(s) between these two layers (or layer and coating).
• the thicknesses referred to in this document are physical thicknesses and the layers are thin layers.
• thin layer is meant a layer having a thickness of between 0.1 nm and 100 micrometers.
• the expression "based on”, used to qualify a material or a layer as to what it or it contains, means that the mass fraction of the constituent which it or it comprises is at least 50%, in particular at least 70%, preferably at least 90%.
• the stack may comprise a single functional metal layer based on silver.
• the silver-based metallic functional layers comprise at least 95.0%, preferably at least 96.5% and better still at least 98.0% by weight of silver relative to the weight of the functional layer.
• a silver-based functional metallic layer comprises less than 1.0% by mass of metals other than silver relative to the mass of the silver-based functional metallic layer.
• the silver-based metallic functional layers have a thickness:
• Dielectric coatings include dielectric layers.
• dielectric layer within the meaning of the present invention, it should be understood that from the point of view of its nature, the material is “non-metallic", that is to say is not a metal. In the context of the invention, this term designates a material having an n/k ratio over the entire visible wavelength range (from 380 nm to 780 nm) equal to or greater than 5.
• n designates the index of real refraction of the material at a given wavelength and k represents the imaginary part of the refractive index at a given wavelength; the ratio n/k being calculated at a given wavelength identical for n and for k.
• the thickness of a dielectric coating corresponds to the sum of the thicknesses of the layers constituting it.
• the dielectric coatings have a thickness greater than 10 nm, greater than 15 nm, between 15 and 200 nm, between 15 and 100 nm or between 15 and 70 nm.
• the dielectric layers in addition to their optical function, can have various other functions.
• the dielectric layers are conventionally chosen from layers based on oxide, based on nitride or based on oxynitride.
• the oxide-based layers of one or more elements consist mainly of oxygen and very little nitrogen.
• the oxide-based layers include in particular at least 90% in atomic percentage of oxygen relative to the oxygen and nitrogen in said layer.
• the nitride-based layers consist mainly of nitrogen and very little oxygen.
• Nitride-based layers include at least 90% atomic percent nitrogen relative to the oxygen and nitrogen in said layer.
• Oxynitride layers include a mixture of oxygen and nitrogen. Layers based on silicon oxynitride comprise 10 to 90% (limits excluded) in atomic percentage of nitrogen relative to the oxygen and nitrogen in said layer.
• the amounts of oxygen and nitrogen in a layer are determined in atomic percentages relative to the total amounts of oxygen and nitrogen in the layer under consideration.
• the dielectric layers are conventionally chosen from:
• the stack comprises a coating comprising a titanium oxide-based oxidation gradient located above and in contact with a silver-based functional metal layer, the part of the oxidation gradient coating in contact with the functional layer is less oxidized than the part of this coating furthest from the functional layer.
• the titanium oxide coating is described as it is deposited, that is to say before any heat treatment or before any long storage.
• a heat treatment at high temperature or a long storage can generate modifications within layers or coating. These changes may include correspond to a rearrangement of the oxygen atoms within the coating making it more difficult to observe the gradient.
• the oxidation gradient coating has a thickness:
• nm less than or equal to 30 nm, less than or equal to 25 nm, less than or equal to 20 nm, less than or equal to 15 nm, less than or equal to 10 nm, less than or equal to 8 nm.
• the oxidation gradient coating may include:
• the layers based on titanium oxide comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 95.0%, at least 96.5% and better still at least 98.0 % by mass of titanium relative to the mass of all the elements constituting the layer based on titanium oxide other than oxygen.
• the layers based on titanium oxide can include or consist of elements other than titanium and oxygen. These elements can be chosen from silicon, chromium and zirconium. Preferably, the elements are chosen from zirconium.
• the layer based on titanium oxide comprises at most 35%, at most 20% or at most 10% by mass of elements other than titanium relative to the mass of all the elements constituting the layer based on titanium oxide other than oxygen.
• the layers based on titanium oxide can have a thickness:
• nm less than or equal to 30 nm, less than or equal to 25 nm, less than or equal to 20 nm, less than or equal to 15 nm, less than or equal to 10 nm, less than or equal to 8 nm, less than or equal to 4 nm.
• the layers based on titanium oxide can be obtained:
• the deposition atmosphere includes significant proportions of oxygen.
• the layers based on titanium oxide are preferably obtained from a ceramic target of titanium oxide, preferably under stoichiometric in oxygen, in an atmosphere comprising oxygen or without oxygen.
• the amount of oxygen in the deposition atmosphere can be adapted according to the desired properties.
• a layer based on titanium oxide is deposited from a ceramic target, in particular substoichiometric.
• the layer based on titanium oxide can be deposited from a ceramic target of TiO x under stoichiometric, where x is a number different from the stoichiometry of the titanium oxide TiO2, that is to say different of 2 and preferably less than 2, in particular between 0.75 times and 0.99 times the normal stoichiometry of the oxide.
• TiOx may in particular be such that 1.5 ⁇ x ⁇ 1.98 or 1.5 ⁇ x ⁇ 1.7, or even 1.7 ⁇ x ⁇ 1.95.
• Titanium oxide-based layers can be deposited in an atmosphere that does not contain oxygen or in a controlled atmosphere that includes oxygen.
• controlled atmosphere comprising oxygen means an atmosphere comprising an optimized quantity of oxygen to obtain the desired properties.
• the deposition atmosphere comprises a mixture of noble gases (He, Ne, Xe, Ar, Kr) and oxygen.
• the noble gas is preferably argon.
• the pressure in the deposition chamber is between 1 and 15 pbar, preferably 2 and 10 pbar or 2 and 8 pbar,
• the deposition atmosphere comprises a mixture of argon and oxygen.
• the controlled atmosphere making it possible to obtain the advantageous effects of the invention was obtained with a percentage by volume flow of oxygen comprised between 0 and 20%.
• the maximum oxygen threshold may vary to some extent depending on, for example:
• the configuration of the cathode sputtering deposition chamber (geometry, places of gas inlets, etc.
• the volume flow quantities of oxygen that can be used during the deposition will be lower because the TiOx is deposited more slowly and is therefore more likely to oxidize.
• a person skilled in the art is able to define a satisfactory controlled atmosphere by varying these parameters to some extent.
• the person skilled in the art is in particular perfectly able to determine the power to be applied to the target and the volume flows of oxygen and noble gases.
• the oxidation gradient coating may comprise at least one layer based on titanium oxide deposited from a ceramic target, in particular substoichiometric, in a controlled atmosphere comprising oxygen, preferably in a controlled atmosphere comprising oxygen.
• the layer based on titanium oxide can be deposited with an oxygen percentage in volume flow between 0 and 20%.
• the oxidation gradient coating may comprise at least two layers of titanium oxide each comprising different proportions of oxygen, that is to say different degrees of oxidation.
• the coating is obtained by depositing at least two consecutive layers based on titanium oxide. This deposition in several stages makes it possible to obtain mainly in the coating a layer of titanium oxide with a large quantity of oxygen, while protecting the functional layer based on silver from a first layer of titanium oxide weakly oxidized. The absorption of the stack before heat treatment is then greatly reduced.
• the oxidation gradient coating can therefore comprise a first layer deposited from a ceramic target, in particular sub-stoichiometric, in an oxygen-free atmosphere.
• the oxidation gradient coating may comprise a first layer based on titanium oxide deposited from a ceramic target, in particular sub-stoichiometric, in a non-oxidizing or oxidizing atmosphere whose percentage by volume flow rate of oxygen represents between 0 and 5%, between 0 and 4%, between 0 and 3%, between 0 and 2%.
• This first layer based on titanium oxide is in contact with the functional layer based on silver.
• the amount of oxygen in the first layer based on titanium oxide must be relatively low so as not to degrade the functional layer based on silver.
• using a little oxygen contributes to a better resistance to the brush test without inducing too great a penalty in absorption, especially before heat treatment.
• the thickness of the first layer based on titanium oxide can be as thin as that of a standard blocking layer ( ⁇ 1 nm), as long as the functional layer based on silver does not prove to be degraded by the oxygen present during the deposition of the next layer based on titanium oxide, deposited with more oxygen than the first.
• the first layer has a thickness between 0.2 and 4 nm.
• the first layer can have a thickness of less than 3 nm, less than 2 nm or less than 1 nm or less than 0.5 nm.
• the oxidation gradient coating comprises a second layer based on titanium oxide deposited from a ceramic target, in particular sub-stoichiometric, in an atmosphere comprising higher proportions of oxygen than that used for the first layer.
• the second layer based on titanium oxide can be deposited from a metal target or a ceramic target.
• the second layer based on titanium oxide can be deposited from a ceramic target, in particular under stoichiometric conditions, in an oxidizing atmosphere whose percentage of oxygen in volume flow rate represents between 1 and 15%.
• the second layer based on titanium oxide has a thickness between 0.2 and 30 nm, between 2 and 20 nm or between 5 and 15 nm.
• the second layer based on titanium oxide can have a thickness:
• the oxidation gradient coating can also comprise a single layer of titanium oxide comprising an oxygen gradient.
• a coating based on titanium oxide comprising a single layer with an oxygen gradient can be obtained:
• the volume flow rate of oxygen in the deposition atmosphere is gradually increased as the layer based on titanium oxide is deposited.
• the part of the oxidation gradient coating in contact with the functional layer is less oxidized than the part of this coating further from the functional layer.
• the proportions of oxygen in the deposition atmosphere can vary from 0% to 15%.
• the layers based on titanium oxide of the gradient coating form part of a dielectric coating. This means that when determining the thickness of a dielectric coating, the thickness of these layers is taken into consideration.
• the gradient coating is below and in contact with a dielectric layer.
• the dielectric layer can be based on oxide, nitride or oxynitride of one or more elements chosen from silicon, zirconium, titanium, aluminium, tin and/or zinc.
• this dielectric layer has a thickness greater than 5 nm, 8 nm, 10 nm or 15 nm.
• the stack may comprise at least one layer comprising silicon.
• the dielectric coating located above the silver-based functional layer may comprise a layer comprising silicon.
• Each dielectric coating may also include at least one layer comprising silicon.
• Layers comprising silicon are extremely stable to heat treatments. For example, no migration of the constituent elements is observed. Therefore, these elements are not likely to alter the silver layer.
• the layers comprising silicon therefore also contribute to the non-alteration of the silver layers and therefore to obtaining a low emissivity after heat treatment.
• the layers comprising silicon comprise at least 50% by mass of silicon relative to the mass of all the elements constituting the layer comprising silicon other than nitrogen and oxygen.
• the layers comprising silicon can be chosen from layers based on oxide, based on nitride or based on oxynitride such as layers based on silicon oxide, layers based on silicon nitride and layers based on silicon oxynitride.
• Silicon oxide based layers include at least 90% atomic percent oxygen relative to the oxygen and nitrogen in the silicon oxide based layer.
• the silicon nitride based layers include at least 90% atomic percent nitrogen relative to the oxygen and nitrogen in the silicon nitride based layer.
• the layers based on silicon oxynitride include 10 to 90% (limits excluded) in atomic percentage of nitrogen relative to the oxygen and nitrogen in the layer based on silicon oxide.
• the layers based on silicon oxide are characterized by a refractive index at 550 nm, less than or equal to 1.55.
• the layers based on silicon nitride are characterized by a refractive index at 550 nm, greater than or equal to 1.95.
• the layers comprising silicon can comprise or consist of elements other than silicon, oxygen and nitrogen. These elements can be chosen from aluminum, boron, titanium, and zirconium.
• the layers comprising silicon may comprise at least 2%, at least 5% or at least 8% by mass of aluminum relative to the mass of all the elements constituting the layer comprising silicon other than oxygen and nitrogen.
• the layers comprising aluminum can be chosen from layers based on oxide, based on nitride or based on oxynitride such as layers based on aluminum oxide such as Al2O3, layers based on of aluminum nitride such as AIN and layers based on aluminum oxynitride such as AlOxNy.
• the layers based on silicon nitride and on zirconium Si x Zr y N z form part of the layers comprising silicon, in particular layers based on silicon nitride.
• the refractive index of layers based on silicon nitride and zirconium increases with the increase in the proportions of zirconium in said layer.
• the layers based on silicon nitride can comprise aluminum and/or zirconium. Such layers may include, in atomic proportion to the atomic proportion of Si, Zr and Al:
• the dielectric coating located above the silver layer comprises a layer comprising silicon.
• These layers comprising silicon have, in increasing order of preference, a thickness:
• At least one dielectric coating comprises a layer comprising silicon chosen from layers based on silicon nitride.
• the dielectric coating located above the silver-based functional layer comprises a layer comprising silicon chosen from among the layers based on silicon nitride.
• Each dielectric coating may comprise a layer comprising silicon chosen from layers based on silicon nitride.
• the sum of the thicknesses of all the layers comprising silicon in the dielectric coating located above the first silver-based functional metal layer can be greater than 35%, greater than 50%, of the total thickness dielectric coating.
• the sum of the thicknesses of all the layers comprising silicon based on silicon nitride in each dielectric coating located above the first functional metal layer based on silver can be greater than 35%, greater than 50% , the total thickness of the dielectric coating.
• the stack may comprise a layer based on zinc oxide and tin comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide.
• the layer based on zinc oxide and tin comprises by mass of tin relative to the total mass of zinc and tin:
• the layer based on zinc oxide and tin located in the dielectric coating above the functional layer based on silver has a thickness:
• the dielectric coating above the silver layer may include:
• the dielectric coating above the silver layer may include:
• a layer based on zinc oxide and tin comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide,
• a layer comprising silicon possibly located above and in contact with the layer based on zinc oxide and tin, preferably a layer based on silicon nitride or a layer based on silicon nitride and zirconium or a combination of these two layers.
• the dielectric coating located below the silver layer may include a so-called stabilizing layer which reinforces the adhesion of the functional layer to the layers which surround it.
• the stabilizing layers are preferably layers based on zinc oxide optionally doped, for example, with aluminum.
• the zinc oxide is crystallized.
• the zinc oxide-based layer comprises, in increasing order of preference, at least 90.0%, at least 92%, at least 95%, at least 98.0% by weight of zinc relative to the weight of elements other than oxygen in the layer based on zinc oxide.
• the dielectric coating located below the functional layer may also comprise a layer based on zinc oxide located directly in contact with it.
• a stabilizing layer below and in contact with a functional layer, because it facilitates the adhesion and the crystallization of the silver-based functional layer and increases its quality and its stability.
• the metallic functional layer is deposited above and in contact with a layer based on zinc oxide.
• the zinc oxide-based layer can be deposited from a ceramic target, with or without oxygen or from a metal target.
• the zinc oxide layers have a thickness:
• the dielectric coating located below the silver layer may also comprise a layer based on zinc oxide and tin comprising at least 20% by mass of tin relative to the total mass of zinc and tin , located below and in contact with the layer based on zinc oxide.
• the stack can therefore comprise one or more layers based on zinc oxide and tin comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and contact with the layer based on titanium oxide.
• the layers based on zinc oxide and tin preferably comprise by mass of tin relative to the total mass of zinc and tin:
• the layers based on zinc and tin oxide have a thickness:
• the dielectric coating located below the silver layer comprises a layer with a high refractive index.
• the presence of high index layers above and below the silver-based functional layer contributes to obtaining high light transmission.
• the layers with low refractive index have a refractive index of less than 1.70.
• Layers with an intermediate refractive index have a refractive index between 1.70 and 2.2.
• High refractive index layers have a refractive index greater than 2.2.
• the high refractive index layers can be chosen from:
• n550 2.30
• the layer with a high refractive index is chosen from layers based on titanium oxide and the layer based on silicon nitride and zirconium.
• the stack does not include a metallic blocking layer or one based on titanium oxide below and in contact with the functional metallic layer based on silver.
• the silver-based functional metallic layer is located above and in contact with a dielectric layer of the dielectric coating.
• this dielectric layer is a stabilizing layer.
• the dielectric coating located below the silver layer may comprise a sequence of layers, defined starting from the substrate, chosen from:
• the stack includes a layer of silicon nitride and a layer of silicon nitride and zirconium, these layers are different, i.e. they are not composed of the same elements in the same proportions.
• the dielectric coating located above the silver layer may comprise a sequence of layers, defined starting from the substrate, chosen from:
• the oxidation gradient coating // layer based on silicon nitride and zirconium // layer based on silicon nitride // layer based on silicon oxide.
• the stack of thin layers can optionally include a protective layer.
• the protective layer is preferably the last layer of the stack, that is to say the layer farthest from the coated substrate of the stack (before heat treatment). These layers generally have a thickness of between 0.5 and 10 nm, between 1 and 5 nm, between 1 and 3 nm or between 1 and 2.5 nm.
• This protective layer can be chosen from a layer of titanium, zirconium, hafnium, silicon, zinc and/or tin, this or these metals being in metallic, oxidized or nitrided form.
• the protective layer is based on zirconium oxide and/or titanium, preferably based zirconium oxide, titanium oxide or titanium oxide and zirconium. When determining the thickness of a dielectric coating, the thickness of the protective layer is taken into account.
• the transparent substrates according to the invention are preferably made of a rigid mineral material, such as glass, or organic based on polymers (or polymer).
• the organic transparent substrates according to the invention can also be made of polymer, rigid or flexible.
• polymers suitable according to the invention include, in particular:
• PET polyethylene terephthalate
• PBT polybutylene terephthalate
• PEN polyethylene naphthalate
• PMMA polymethyl methacrylate
• fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluorethylene (PCTFE), ethylene chlorotrifluorethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
• fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluorethylene (PCTFE), ethylene chlorotrifluorethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
• photocrosslinkable and/or photopolymerizable resins such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate and
• the substrate is preferably a glass or glass-ceramic sheet.
• the substrate is preferably transparent, colorless (it is then a clear or extra-clear glass) or colored, for example blue, gray or bronze.
• the glass is preferably of the soda-lime-silico type, but it can also be of borosilicate or alumino-borosilicate type glass.
• the substrate is made of glass, in particular silico-soda-lime or of polymeric organic material.
• the substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and even 3 m.
• the thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, in particular between 2 and 8 mm, or even between 4 and 6 mm.
• the substrate can be flat or curved, even flexible.
• the invention relates to glazing in the form of multiple glazing, in particular double glazing or triple glazing.
• Double glazing has 4 faces, face 1 is outside the building and therefore constitutes the outer wall of the glazing, face 4 is inside the building and therefore constitutes the inner wall of the glazing, faces 2 and 3 being inside the double glazing.
• Stacking according to the invention is in front 2.
• Triple glazing has 6 faces, face 1 is outside the building and therefore constitutes the outer wall of the glazing, face 6 is inside the building and therefore constitutes the inner wall of the glazing, faces 2 and 3 and 4 and 5 being inside the double glazing.
• the stack according to the invention can be on face 2 and/or face 5.
• These glazings can be mounted on a building or a vehicle.
• Stacks of thin layers defined below are deposited on clear soda-lime glass substrates with a thickness of 4 mm.
• Stacks of thin layers defined below are deposited on clear soda-lime glass substrates with a thickness of 4 mm.
• the functional layers are layers of silver (Ag),
• the dielectric layers are based on silicon nitride doped with aluminum (SisN4: Al), based on silicon nitride and zirconium doped with aluminum (SiZrN: Al), based on zinc oxide and tin, based on zinc oxide (ZnO).
• TiOx titanium oxide layers are deposited from a TiOx ceramic target with or without oxygen in the deposition atmosphere.
• %wt % by weight; at%: atomic.
• the stacks according to the invention comprise coatings based on titanium oxide (coating with oxygen gradient) comprising at least two layers of titanium oxide comprising different proportions of oxygen.
• the first layer is deposited in contact with the silver layer in an oxygen-free atmosphere with a thickness of 1 nanometer. This layer is therefore under-oxidized.
• the second base coat of titanium oxide is deposited in an atmosphere with 10% oxygen by volume flow and has a thickness of at least 5 nm. This layer is therefore more oxidized than the first.
• the square resistance Rsq corresponding to the resistance referred to the surface, is measured by induction with a Nagy SMR-12.
• the “s” selectivity corresponds to the TL/g ratio.
• Glazings each comprising the stacks described above were tested.
• the invention indeed makes it possible to obtain high light transmissions while maintaining sufficiently low resistivity values to achieve a low emissivity and thus a lower value of Ug .
• the obtaining of colors in external reflection that are more neutral, i.e. less red (value of a* closer to 0).
• EBT Erichsen Brush Test
• the Erichsen brush test (EBT) consists in subjecting various coated substrates to a certain number of cycles (1000) during which the stack covered with water is rubbed using a brush. A substrate is considered to pass the test if no mark is visible with the naked eye.
• the EBT test before tempering gives a good indication of the ability of the glazing to be scratched during a washing operation with water using a brush.
• the Erichsen scratch test (EST) consists of applying a force to the sample, in Newtons, using a tip (Van Laar tip, steel ball). Depending on the scratch resistance of the stack, different types of scratches can be obtained: continuous, discontinuous, wide, narrow, etc.
• the following stacks have been developed for use after laser heat treatment. In this case, only the stack undergoes heat treatment at high temperature.
• the coated substrates were processed using a laser line formed from a disc laser. The following conditions were used:
• the glazings according to the invention have the lowest values of solar factor ( ⁇ 0.3%) and of resistance per square (1.76 vs. 2.02 Q/n). In all cases, the solution of the invention makes it possible to obtain the specifications of the glazing more easily.
• this layer aims to reduce the residual absorption that may result from the incomplete oxidation of the TiOx following the laser treatment.
• the following stacks have been developed for use after being subjected to a quench type heat treatment.
• the heat treatments are carried out in a NABER oven at a temperature of 650°C for 10 minutes.
• the glazing of the VI.3a invention has a lower solar factor (-0.5%) and a lower resistance per square (1.82 vs. 2.13Q/n) for the same level of light transmission. Equivalent results were obtained with stacks 3b and 3c comprising respectively:
• examples Emp.0-1 and 0-2 may include after this heat treatment an oxidation gradient in the titanium oxide layer. However, this gradient was not present in the coating as deposited.
• the square resistance Rsq corresponding to the resistance referred to the surface, is measured by induction with a Nagy SMR-12. Square resistance and absorption Abs. were measured before heat treatment (BT) and after heat treatments at a temperature of 650°C for 10 min (AT).
• the brush resistance tests were carried out after TT-EBT heat treatment. Each sample is observed after a certain number of cycles: 50, 100, 200, 300.
• the Ok boxes indicate good resistance to the TT-EBT test after 300 cycles.
• the Nok boxes indicate poor resistance to the EBT or TTEBT test after 300 cycles.
• the number indicated next corresponds to the number of cycles from which the test becomes bad (Nok).
• the stacks according to the invention all make it possible to obtain good results in the brush test, whereas it is not for the stacks without gradient.
• the stacks according to the invention all make it possible to obtain better results in terms of resistivity and absorption after heat treatment.

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• 2022
  • 2022-01-10 FR FR2200149A patent/FR3131741B1/fr active Active
• 2023
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