Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/10165—Functional features of the laminated safety glass or glazing
  • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
  • B32B17/10201—Dielectric coatings
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
  • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
  • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
  • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
  • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
  • B32B17/10165—Functional features of the laminated safety glass or glazing
  • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
  • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
  • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a nitride, oxynitride, boronitride or carbonitride
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/0641—Nitrides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
  • C23C14/083—Oxides of refractory metals or yttrium
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
  • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
  • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
  • C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
  • C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2250/00—Layers arrangement
  • B32B2250/03—3 layers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/20—Inorganic coating
  • B32B2255/205—Metallic coating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2255/00—Coating on the layer surface
  • B32B2255/28—Multiple coating on one surface
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
  • B32B2307/204—Di-electric
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/30—Properties of the layers or laminate having particular thermal properties
  • B32B2307/304—Insulating
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/40—Properties of the layers or laminate having particular optical properties
  • B32B2307/418—Refractive
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2307/00—Properties of the layers or laminate
  • B32B2307/70—Other properties
  • B32B2307/732—Dimensional properties
  • B32B2307/737—Dimensions, e.g. volume or area
  • B32B2307/7375—Linear, e.g. length, distance or width
  • B32B2307/7376—Thickness
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B2315/00—Other materials containing non-metallic inorganic compounds not provided for in groups B32B2311/00 - B32B2313/04
  • B32B2315/08—Glass
• • 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
  • C03C2217/219—CrOx, MoOx, WOx
• • 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 to a transparent substrate provided with a stack of thin layers conferring properties of "solar control".
• Solar control functions are sought for glazing likely to be exposed to high levels of sunlight.
• the ability of a glazing to limit the amount of light energy transmitted is defined by the solar factor, g, which is the ratio of the total energy transmitted through the glazing surface or glazing inwards to the incident solar energy.
• the layer has a “solar control” function thanks to its strong absorption of near infrared radiation.
• EP 3686312 A1 [SUMITOMO METAL MINING CO [JP]] 29.07.2020 describes a layer based on cesium-doped tungsten oxide, and a method for depositing such a layer by sputtering.
• the layer has transparency to radio waves and a "solar control" function thanks, in particular, to its strong absorption of infrared radiation.
• a functional stack is qualified as a suitable functional stack for building applications when it satisfies a double requirement: a high light transmission and a low solar factor value.
• a functional stack is therefore suitable when it has a high selectivity value, s, defined as the ratio of light transmission to solar factor.
• a high selectivity is in particular above 1.2 for monolithic glazing having a light transmission of approximately 70%, or at least 1.3 for laminated glazing having a light transmission of approximately 70%.
• a functional stack has a certain chemical and mechanical durability for certain applications, in particular in single glazing, when it is directly exposed to the exterior or interior environment of a building.
• Transparency at radio frequencies may additionally be desired.
• a first aspect of the invention relates to a transparent substrate as described in claim 1, the dependent claims being advantageous embodiments.
• the transparent substrate according to the invention is provided on one of its main surfaces with a stack of thin layers, said stack of layers consists of the following layers starting from the substrate: - a first dielectric module of several thin layers; - an absorbent layer of tungsten oxide; - a second dielectric module of one or more thin layers; wherein the tungsten oxide comprises at least one doping element selected from the group 1 chemical elements according to the IUPAC nomenclature.
• said stack comprises no metal layer.
• Said second dielectric module preferably comprises at least a succession of two layers (i.e. two layers, one after the other) with a low index layer (i.e. i.e. in a low refractive index material) having a refractive index at 550 nm of between 1.50 and less than 1.90 and a high index layer (i.e. in a material high refractive index) having a refractive index at 550 nm between more than 2.10 and 2.70.
• a mid-index layer i.e. of a mid-refractive index material
• the refractive index of a material is generally evaluated to the hundredth.
• one, or even several, succession(s) of two layers can make it possible to achieve high selectivity while retaining the benefits of the transparency to the electromagnetic waves used in telecommunications and the absence of a metallic layer.
• This advantage is greater when, for a succession of two layers, or even for each succession of two layers, said low index layer is preferably closer to said absorbent layer of tungsten oxide than said high index layer.
• one, or even several, succession(s) of two layers one of which has a low index and the other a high index in the second dielectric module, can make it possible to obtain a high stability of the color in reflection by depending on the viewing angle.
• This advantage is greater when, for a succession of two layers, or even for each succession of two layers, said low index layer is preferably closer to said absorbent layer of tungsten oxide than said high index layer.
• the difference in index between two layers one after the other in a succession of two layers, and more preferably in each succession of two layers, is at least 0.4, and preferably at least 0.5, even at least 0.7; thus, the effect of the succession is more substantial.
• Said second dielectric module preferably comprises two successions of two layers, or even three successions of two layers, with, for each succession, a low index layer and a high index layer, said successions being preferably each with said low index layer of the succession closer to said absorbing layer of tungsten oxide than said high index layer of the succession.
• Said low index layer is preferably chosen from a material based on silicon dioxide SiO 2
• said high index layer is preferably chosen from a material based on zirconium-zirconium silicon nitride Si x N y Zr z , or titanium dioxide TiO 2 .
• a second aspect of the invention relates to a glazing comprising a transparent substrate according to the first aspect of the invention.
• a third aspect of the invention relates to a method of manufacturing a transparent substrate according to the first aspect of the invention.
• a remarkable advantage of a glazing comprising a transparent substrate according to the invention is a gain of up to more than 10% in selectivity while maintaining a sufficient level of light transmission, greater than 65% in single glazing application, and a factor thermal transmission, Ug, of 5 W/m2.K, or even lower.
• the functional stack has better mechanical and chemical durability, as well as preservation of its optical and energy performance after heat treatment, in particular thanks to the encapsulation of the tungsten oxide layer. by layers based on nitrides, as detailed in certain embodiments.
• exterior and interior reflections can be very weak; they may be less than 12%.
• FIG. 1 is a schematic representation of a first embodiment of double glazing according to the second aspect of the invention.
• FIG. 1 is a schematic representation of a second embodiment of double glazing according to the second aspect of the invention.
• FIG. 1 is a schematic representation of a laminated glazing according to the second aspect of the invention.
• FIG. 1 is a schematic representation of exemplary embodiments of transparent substrates provided with a stack.
• the term “thickness” used for a layer corresponds to the physical, real or geometric thickness, e, of said layer. It is expressed in nanometers.
• dielectric module designates one or more layers in contact with each other forming a set of globally dielectric layers, that is to say that it does not have the functions of a metallic functional layer. If the dielectric module comprises several layers, these may themselves be dielectric.
• the physical thickness, real or geometric, of a dielectric module of layers corresponds to the sum of the physical thicknesses, real or geometric, of each of the layers which constitute it.
• a layer of or "a layer based on”, used to qualify a material or a layer as to what it or it contains, are used in an equivalent manner. They mean that the mass fraction of the constituent that he or she comprises is at least 50%, in particular at least 70%, preferably at least 90%. In particular, the presence of minority or doping elements is not excluded.
• transparent used to qualify a substrate, means that the substrate is preferably colorless, non-opaque and non-translucent in order to minimize light absorption and thus maintain maximum light transmission in the visible electromagnetic spectrum.
• the light transmission, TL, in the visible spectrum, the solar factor, g, and the selectivity, s, the internal reflection, Rint, and the external reflection, Rext, in the visible spectrum, as well as their measurement modes and/or calculation are defined in the EN 410, ISO 9050 and ISO 10292 standards.
• thermo transmittance factor Ug
• Ug thermal transmittance factor
• group 1 of chemical elements includes hydrogen and alkali elements i.e. lithium, sodium, potassium, rubidium, cesium and francium.
• optical refractive index and “optical extinction coefficient” it is meant the optical refractive index, n, and optical extinction coefficient, k, as defined in the technical field, in particular according to the model of Forouhi & Bloomer described in the work Forouhi & Bloomer, Handbook of Optical Constants of Solids II, Palik, E.D. (ed.), Academic Press, 1991, Chapter 7.
• a transparent substrate 1000 is provided provided on one of its main surfaces with a stack 1001 of thin layers, said stack 1001 of layers consists of the following layers starting from the substrate 1000: - A first dielectric module 1002 of one or more thin layers; - an absorbent layer 1003 of tungsten oxide; - A second dielectric module 1004 of several thin layers;
• Tungsten oxide comprises at least one doping element selected from the group 1 chemical elements according to the IUPAC nomenclature.
• the absorbing layer 1003 of tungsten oxide is an absorbing layer of infrared radiation, preferably absorbing infrared radiation whose wavelength is greater than 780 nm.
• an absorbent layer 1003 of tungsten oxide comprising a doping element chosen from the elements of group 1 according to the IUPAC nomenclature encapsulated between two dielectric modules makes it possible to increase the selectivity.
• the stack 1001 of the transparent substrate 1000 according to the first aspect of the invention does not include metallic functional layers.
• the absorbent layer 1003 of tungsten oxide can comprise the doping element X or the doping elements X1, X2, etc. in proportions such as the molar ratio, X/W of said element to tungsten, W, or the sum of the molar ratios of each element on tungsten (X1+X2+...)/W is between 0.01 and 1, preferably between 0.01 and 0.6, or even between 0.02 and 0, 3.
• the absorbent layer 1003 of tungsten oxide can comprise at least one doping element selected from hydrogen, lithium, sodium, potassium and cesium.
• the absorbent layer 1003 of tungsten oxide may comprise cesium as a doping element, and the molar ratio of cesium to tungsten is between 0.01 and 1, preferably between 0.05 and 0, 4.
• the thickness of the absorbent layer 1003 of tungsten oxide can be between 6 and 450 nm, preferably between 20 and 250 nm, or even between 40 and 200 nm.
• the transparent substrate 1000 can preferably be planar. It can be organic or inorganic, rigid or flexible. In particular, it may be a mineral glass, for example a silico-sodo-lime glass.
• organic substrates that can be advantageously used for the implementation of the invention can be polymer materials such as polyethylenes, polyesters, polyacrylates, polycarbonates, polyurethanes, polyamides. These polymers can be fluorinated polymers.
• Examples of mineral substrates that can be advantageously implemented in the invention may be sheets of mineral glass or glass-ceramic.
• the glass can preferably be a glass of the silico-sodo-lime, borosilicate, aluminosilicate or even alumino-boro-silicate type.
• the transparent substrate 1000 is a sheet of silico-sodo-lime mineral glass.
• the first dielectric module 1002 and/or the second dielectric module 1004 can comprise one or more layers based on nitride and/or oxide, preferably based on zinc oxide and tin, zinc oxide, titanium oxide, zirconium oxide, aluminum nitride, silicon nitride and zirconium or silicon nitride optionally doped with aluminium, zirconium and/or boron.
• the first dielectric module 1002 and/or the second dielectric module 1004 consist of one or more nitride-based layers.
• the nitride-based layer or layers of the first dielectric module 1002 and/or the second dielectric module 1004 are chosen from among aluminum nitride, silicon nitride, titanium nitride, nitride niobium, silicon nitride and zirconium, silicon nitride doped with aluminium, zirconium and/or boron.
• the layer(s) of the first dielectric module 1002 and of the second dielectric mode 1004 are nitride-based, they make it possible to encapsulate the absorbent layer based on tungsten oxide.
• This encapsulation allows double protection of the absorbent layer 1003 based on tungsten oxide. On the one hand, it warns of possible contamination by elements likely to diffuse into the stack 1001 from the substrate 1000, such as in particular alkaline ions or oxygen in the case of a lord mineral glass substrate. On the other hand, it makes it possible to limit, in particular during an annealing-type heat treatment step, the diffusion of oxygen in the stack 1001 towards the absorbent layer 1003 based on tungsten oxide from the atmosphere and /or the substrate.
• the encapsulation makes it possible to ensure a correct level of selectivity.
• the substrate 1000 according to the first aspect of the invention is more durable, in particular its performance is preserved over the long term.
• a second aspect of the invention relates to glazing, in particular single, double or triple glazing, and laminated glazing, comprising a transparent substrate according to the first aspect of the invention.
• a single or double glazing comprising a substrate according to the first aspect of the invention.
• Single glazing, or monolithic glazing comprises a single substrate, in particular a sheet of mineral glass.
• the substrate according to the invention is used as monolithic glazing, the functional stack of thin layers is preferably deposited on the face of the substrate facing the interior of the room of the building on the walls of which the glazing is installed. In such a configuration, it may be advantageous to protect the first layer and possibly the stack of thin layers against physical or chemical degradation using an appropriate means.
• a multiple glazing unit comprises at least two parallel substrates, in particular mineral glass sheets, separated by a layer of insulating gas. Most multiple glazing is double or triple glazing, i.e. it comprises two or three glazing units respectively.
• the substrate according to the invention is used as an element of multiple glazing, the functional stack of thin layers is preferably deposited on the face of the glass sheet facing inwards in contact with the insulating gas. This arrangement has the advantage of protecting the stack from chemical or physical degradation in the external environment.
• the glazing is a double glazing 2000, 3000 comprising a transparent substrate 1000 according to any of the embodiments described previously so that the functional stack 1001 of layers is located face two and/or face three of said glazing 9000, 10000.
• (E) corresponds to the outside of the room where the glazing is installed, and (I) to the inside of the room.
• the glazing 2000 comprises a first sheet of transparent glass 1000 with an internal surface 1000a and an external surface 1000b, a second sheet of transparent glass 2001 with an internal surface and an external surface, an insulating gas layer 2002, a spacer 2003 and a seal 2004.
• the glass sheet 1000 comprises, on and in contact with its inner surface 1000b in contact with the gas of the layer of insulating gas 9002, a functional stack 1001 according to the first aspect of the invention.
• the functional assembly 1001 is preferably arranged so that its external surface which is opposite to that 1000b of the transparent glass sheet 1000 is oriented towards the interior (I) of the room, for example a building, in which the glazing is used.
• the functional stack 1001 is arranged on face 2 of the glazing starting from the outside (E).
• the glazing is double glazing 3000 comprising a first sheet of transparent glass 1000 with an internal surface 1000a and an external surface 1001b, a second sheet of transparent glass 3001 with an internal surface and an external surface, an insulating gas layer 3004, a spacer 3003 and a seal 3004.
• the glass sheet 1000 comprises, on and in contact with its inner surface 1000a in contact with the gas of the layer of insulating gas 9004, a functional stack 1001 according to the first aspect of the invention.
• the functional assembly 1001 is preferably arranged so that its external surface which is opposite to that 1000a of the transparent glass sheet 1000 is oriented towards the outside (E) of the room.
• the functional stack (1001) is arranged on face 3 of the glazing starting from the outside (E).
• a laminated glazing 4000 comprising a first transparent substrate 1000 according to the first aspect of the invention, a lamination insert 4001 and a second transparent substrate 4002, such that the first transparent substrate 1000 and the second transparent substrate 4002 are in adhesive contact with the lamination insert 4001 and the stack 1001 of thin layers of the first transparent substrate 1000 is in contact with the lamination insert 4001.
• the 4001 lamination insert can be made up of one or more layers of thermoplastic material.
• thermoplastic material are polyurethane, polycarbonate, polyvinyl butyral (PVB), polymethyl methacrylate (PMMA), ethylene vinyl acetate (EA) or an ionomer resin.
• the lamination insert 4001 can be in the form of a multilayer film. It may also have special functionalities such as, for example, acoustic or even anti-UV properties.
• the lamination insert 4001 comprises at least one layer of PVB. Its thickness is between 50 ⁇ m and 4 mm. In general, it is less than 1mm.
• the processes for depositing thin layers on substrates are processes that are well known in industry.
• the deposition of a stack of thin layers on a glass substrate is carried out by the successive depositions of each thin layer of said stack by causing the glass substrate to pass through a succession of deposition cells suitable for depositing a given thin layer.
• Deposition cells can use deposition methods such as magnetic field assisted sputtering (also called magnetron sputtering), ion beam assisted deposition (IBAD), evaporation, chemical vapor deposition (CVD) , plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), etc.
• deposition methods such as magnetic field assisted sputtering (also called magnetron sputtering), ion beam assisted deposition (IBAD), evaporation, chemical vapor deposition (CVD) , plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), etc.
• the magnetic field-assisted sputter deposition process is particularly used.
• the layer deposition conditions are widely documented in the literature, for example in patent applications WO2012/093238 A1 and WO2017/00602 A1.
• a method of manufacturing a transparent substrate according to the first aspect of the invention such that the absorbent layer of tungsten oxide is deposited by a magnetron sputtering method at using a tungsten oxide target doped with a chemical element chosen from the chemical elements of group 1 according to the IUPAC nomenclature.
• the tungsten oxide target may in particular contain one or more doping elements in the proportions as described for the layer of doped tungsten oxide in certain embodiments of the first aspect of the invention.
• the tungsten oxide absorber layer can be deposited by sputtering using the aforementioned target under a deposition atmosphere of 60-100% argon and 0-40% oxygen, preferably 70-85 % argon and 15 to 30% oxygen.
• the absorbent layer of tungsten oxide can be deposited under a pressure of between 1 to 15 mTorr, preferably from 3 to 10 mTorr.
• the deposition can be carried out cold, that is to say at a temperature below 100° C., in particular between 20° C. and 60° C., for the substrate.
• the deposition can also be carried out hot, in particular at a temperature between 100° C. and 400° C.
• the substrate 1000 after deposition of the stack 1001, can undergo an annealing heat treatment.
• the annealing temperature may be between 450°C and 800°C, in particular between 550°C and 750°C, or even between 600°C and 700°C.
• the annealing time can be between 5min and 30min, in particular between 5min and 20min, or even between 5min and 10min.
• Tables 2, 4 and 6 indicate the composition and the thickness expressed in nanometers of the different layers.
• the numbers in the first two columns correspond to the references of the .
• the layer denoted CWO, of tungsten oxide doped with cesium.
• the molar ratio of cesium to tungsten in the layer is about 0.05-0.06.
• the stacks of thin layers of the examples and counter-examples were deposited by cathode sputtering assisted by a magnetic field (magnetron process), the characteristics of which are widely documented in the literature, for example in patent applications WO2012/093238 and WO2017/ 00602.
• the 1000 substrate is a silico-sodo-lime mineral glass 6 mm or 4 mm thick. After deposition and before the optical measurements, the 6 mm substrates were heat treated at 650°C for 10 min in air.
• the layers of silicon nitride, Si 3 N 4 are deposited using an Si:Al 8 wt% target at 5 ⁇ bar under an atmosphere devoid of oxygen and under a nitrogen flow at 14 sccm; in general, layers based on zinc oxide ZnO, or tin dioxide SnO 2 , or silicon nitride Si 3 N 4 , are medium index layers.
• the layers of silicon dioxide, SiO 2 are layers with a low refractive index; it is 1.53 at the wavelength of 550 nm. They are deposited using an 8 wt% Si:Al target at 4 ⁇ bar under an atmosphere devoid of nitrogen and under a flow of oxygen at 10 sccm.
• Silicon-zirconium nitride layers, SiZr27N, are high refractive index layers; it is 2.40 at the wavelength of 550 nm. They are deposited using a target at 27 wt% (by weight) on the total of Si+Zr, at 5 ⁇ bar under an atmosphere devoid of oxygen and under a nitrogen flow at 15 sccm.
• the solar factor, g, the selectivity, s, the light transmission, TL, the light reflection on the inside face, Rint, and on the outside face, Rext, as well as the color in transmission, on the inside face and on the outside face, have been measured for each substrate of examples E1a, E1b, E3 and counter-examples CE1a, CE1b, CE3A, CE3b and CE3c assembled in a single glazing, the stack being on the inside face, called "face 2".
• color used to qualify a transparent substrate equipped with a stack, it is understood the color as defined in the L*a*b* CIE 1976 chromatic space according to the ISO 11664 standard, in particular with a illuminant D65 and a visual field of 2° or 10° for the reference observer. It is measured in accordance with said standard.
• the luminous transmission in the visible spectrum, TL, the solar factor, g, and the selectivity, s, and the internal reflection, Rint, and the external reflection, Rext, in the visible spectrum are defined, measured and calculated in accordance with the standards EN 410, ISO 9050 and/or ISO 10292.
• the thermal transmittance, Ug is defined, measured and calculated in accordance with the EN 673 standard.
• the transparent substrate is a silico-soda-lime glass with a thickness of 6 mm marketed under the brand name Planiclear®.
• Light transmittance, TL, "direct solar transmittance”, TE, “solar factor”, TTS (or T TS ) and selectivity, SEL, were measured and/or calculated according to ISO 13837:2021 for each example and counter-example.
• the colorimetric parameters a* and b* were measured and/or calculated in transmission (a*T, b*T) and in external reflection (a*Rext, b*Rext) in the CIE 1976 L*a*b* color space according to ISO 11664-4:2019 with illuminant D65 and a visual field of 2° or 10° for the reference observer.
• Characteristic a* is the chromatic position on a green-red axis (between -500 and 500)
• b* is the chromatic position on a blue-yellow axis (between -200 and 200).
• Table 3 shows that the two examples E1a and E1b according to the invention have a light transmission TL similar to that of the counter-examples CE1a and CE1b and an energy transmission, TE better (lower) than that of the counter-examples CE1a and CE1b .
• Table 3 shows that the two examples E1a and E1b according to the invention allow a gain (decrease) in solar factor TTS, compared to the counter-examples CE1a and CE1b.
• This gain illustrates the synergistic effect of the combination of the absorbent layer based on tungsten oxide with the two adjacent dielectric modules and with the second module which comprises one, two or three succession(s).
• the selectivity achieved is high; it is greater than 1.2 in the monolithic glazing configuration and for a light transmission of approximately 70%.
• the last six lines of Table 3 show the stability of the color according to a* and b*, in external reflection, at 30°, 45° and 60° compared to the values a* and b* at 0° of the eighth and ninth lines .
• the absorbent layer of tungsten oxide (CWO) and the layers of silicon nitride, Si 3 N 4 , of silicon dioxide, SiO 2 , and of silicon-zirconium nitride, SiZr27N, are deposited as for the examples and against -examples of the first series of examples of tables 2 and 3.
• the lamination interlayer 4001 is a PVB interlayer with a thickness of 0.76mm.
• the second substrate 4002 of the counter-examples CEV2a, CEV2b, and of the examples EV2a and EV2b is a silico-soda-lime mineral glass with a thickness of 4 mm marketed under the Planiclear® brand.
• the stack is positioned on face 3.
• Table 5 shows that the two examples EV2a and EV2b according to the second aspect of the invention have a light transmission TL identical to that of the counter-examples CEV2a and CEV2b and an energy transmission, TE better (lower) than that of the counter-examples. examples CEV2a and CEV2b.
• Table 5 shows that two examples EV2a and EV2b according to the second aspect of the invention allow a gain in solar factor TTS, compared to the counter-examples CEV2a and CEV2b. This gain illustrates the synergistic effect of the combination of the absorbent layer based on tungsten oxide with the two adjacent dielectric modules and with the second module which comprises one, two or three succession(s).
• the selectivity achieved is high; it is equal to or greater than 1.3 in the laminated glazing configuration.
• the last six lines of table 5 show the stability of the color according to a* and b*, in external reflection, at 30°, 45° and 60° compared to the values a* and b* at 0° of the eighth and ninth lines .
• a third series of substrate examples according to the first aspect of the invention are described in table 6 which indicates the composition and the thickness expressed in nanometers of the different layers.
• the absorbent layer of tungsten oxide (CWO) and the layers of silicon nitride, Si 3 N 4 , of silicon dioxide, SiO 2 , and of silicon-zirconium nitride, SiZr27N, are deposited as for the examples and against -examples of the first series of examples of tables 2 and 3.
• Table 7 shows that example E3 has a light transmission TL identical to that of counter-examples CE3a, CE3b and CE3c and an energy transmission, TE better (lower) than that of counter-examples CE3a, CE3b and CE3c.
• Example E3 The selectivity achieved by Example E3 is high; higher than that of counterexamples CE3a to CE3c.
• Table 7 shows that the two examples EV30a and EV30b according to the second aspect of the invention allow a gain in solar factor TTS, compared to the counter-examples CE3a to CE3c. This gain illustrates the synergistic effect of the combination of the absorbent layer based on tungsten oxide with the two adjacent dielectric modules and with the second module which comprises one, two or three succession(s).
• Example 3 The exterior and interior reflections of Example 3 are also very low; they are less than 12%.
• the last six lines of table 7 show the stability of the color according to a* and b*, in external reflection, at 30°, 45° and 60° compared to the values a* and b* at 0° of the eighth and ninth lines .
• the examples according to the invention have levels of reflection on the internal face and on the external face that are lower, if not equivalent, lower than those of the counter-examples for comparable light transmission values.
• the invention also makes it possible to reduce light reflection, in particular on the internal face, while preserving and maintaining the same level of light transmission.
• the examples according to the invention have a lower color parameter b* than the counter-example.
• the examples according to the invention have a lower b*Rext color parameter than the counter-example.
• the examples according to the invention have lower color parameters a*Rint and b*Rint than the counter-example.

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