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
  • C03C17/3411—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

Definitions

• TITLE SOLAR CONTROL GLAZING COMPRISING A TITANIUM NITRIDE-BASED LAYER
• the invention relates to a material and a process for preparing a material, such as glazing, comprising a transparent substrate coated with a functional coating acting on infrared and/or thermal radiation.
• the invention also relates to glazing comprising these materials as well as the use of such materials for manufacturing thermal insulation and/or solar protection glazing.
• the invention relates in particular to so-called “low-e” low-emissivity insulating glazing.
• a functional coating generally comprises at least one functional layer.
• the term "functional" layer within the meaning of the present application, is understood to mean the layer(s) which gives the coating most of its thermal properties.
• the functional layer acts on solar and/or thermal radiation essentially by reflection and/or absorption of near infrared (solar) or far (thermal) radiation.
• a functional coating generally comprises a stack of one or more functional layers, each placed between two dielectric coatings generally comprising several dielectric layers (hereinafter dielectric coatings) which make it possible to adjust the optical properties of the stack.
• Functional coatings act on the flow of solar radiation passing through said glazing, as opposed to other dielectric coatings which more often mainly have the function of chemical or mechanical protection of said functional layers.
• Glazing provided with a functional coating is grouped under the designation of solar control glazing. They are mainly marketed and used:
• thermal insulation is meant within the meaning of the present invention a glazing provided with at least one functional layer giving it reduced energy loss, said layer having properties of reflection of IR radiation of between 5 and 50 micrometers.
• the functional layers used in this function have a high reflection coefficient of IR radiation and are called low-emissive (or more often low-e according to the English term).
• a classic parameter for evaluating this capacity is the normal emissivity £ n of the glazing, as calculated in standard EN12898. The lower this value, the more the functional coating reflects thermal IR and the better the thermal insulation provided by the material.
• one way to improve thermal performance is to develop functional coatings with lowered emissivity.
• these materials must frequently undergo heat treatments at high temperature, intended to improve the properties of the substrate and/or of the functional coating.
• heat treatments intended to improve the properties of the substrate and/or of the functional coating.
• it may involve thermal toughening treatments intended to mechanically reinforce the substrate. These treatments can modify certain properties of the stack, in particular the energy and optical properties.
• the materials must be capable of undergoing, once coated with the functional coating, a heat treatment of the quenching, annealing or even bending type, without significant variation, or at least without degradation, of their optical and/or energy properties.
• the materials after the heat treatment, the materials must retain an acceptable light transmission and have an emissivity that is preferably substantially improved, or at least substantially unchanged.
• these glazings may be in the form of monolithic glazing or single glazing, multiple glazing, laminated glazing or multiple and laminated glazing.
• the faces of a glazing are designated starting from the outside of the building and by numbering the faces of the substrates from the outside towards the inside of the passenger compartment or the room it equips. This means that the incident sunlight passes through the faces in increasing order of their number.
• the coatings comprising a functional layer based on titanium nitride are particularly interesting. Indeed, titanium nitride has a high hardness, a high chemical stability and confers a low emissivity.
• layers based on titanium nitride are used as functional layers in high performance coatings intended for aggressive environments where more fragile functional layers such as layers based on silver would be degraded.
• coatings based on titanium nitride are now used in laminated glazing and in single glazing because they are strong enough to be located on one side of a substrate directly in contact with the ambient air.
• Obtaining a low emissivity is an important property, particularly for single glazing applications. The emissivity directly impacts the energy performance of the glazing, by reducing the heat transfer coefficient (“Ug”) as well as the solar factor (g).
• Known functional coatings include a titanium nitride layer located between two dielectric layers which are conventionally silicon nitride layers.
• the objective of the invention is to improve the energy performance conferred by coatings based on titanium nitride. These properties must advantageously be obtained with or without heat treatment of the quenching or bending type.
• the invention therefore consists in the development of new materials, with a view to manufacturing improved solar protection glazing.
• the targeted improvement is in particular a reduction in emissivity while maintaining the other properties, in particular high chemical and mechanical resistance.
• Another object is to provide a material provided with a functional coating capable of withstanding heat treatments without damage. This results in an absence of variation, or even an improvement in its thermal and optical properties before and after heat treatment, in particular of the quenching type.
• the applicant has surprisingly discovered that the choice of the nature of the layers constituting the dielectric coating located below the titanium nitride layer makes it possible to significantly improve the energy performance. This results in particular in an improvement in emissivity and/or conductivity.
• the invention therefore relates to a material comprising a substrate coated with a functional coating comprising at least one functional layer based on titanium nitride and at least two dielectric coatings, each dielectric coating comprising at least one dielectric layer, so that each functional layer is placed between two dielectric coatings, characterized in that: the dielectric coating located directly below a functional layer comprises a dielectric layer located in contact with the functional layer chosen from:
• the dielectric coating located directly below the functional layer comprises: - a first layer comprising silicon, preferably based on silicon nitride,
• the functional layer is located in contact with the layer based on zinc oxide or the layer based on nitride aluminum.
• the dielectric coating located directly below the functional layer does indeed include a dielectric layer located in contact with the functional layer chosen from:
• the layer based on aluminum nitride is deposited by magnetron cathodic sputtering at a deposition pressure of less than 5.0 pbar.
• the use of a layer based on zinc oxide in contact with the functional layer of titanium nitride is particularly advantageous when the material does not undergo heat treatment at high temperature.
• the good energy performances are not preserved when the material undergoes a treatment at high temperature. This can be attributed to various phenomena including oxidation or diffusion reactions such as the oxidation of the functional layer by the zinc oxide layer.
• the use of the sequence zinc oxide layer / layer based on aluminum nitride / functional layer of titanium nitride is particularly advantageous It does not matter whether the material undergoes high temperature heat treatment or not.
• the presence of the zinc oxide layer below and in contact with the aluminum nitride layer promotes the crystallization of said layer.
• the zinc oxide layer then seems to play the role of epitaxial growth layer for the aluminum nitride layer and for the titanium nitride layer.
• Synergy is obtained for this embodiment.
• the decrease in emissivity is greater than that obtained with a zinc oxide layer alone or with an aluminum nitride layer alone.
• the advantageous effect linked to the presence of the zinc oxide layer, before or without heat treatment, is obtained.
• the advantageous effect linked to the presence of the aluminum nitride layer after heat treatment is also obtained.
• the aluminum nitride layer then also acts as a barrier layer preventing degradation of the titanium nitride layer by the zinc oxide layer.
• - a light transmission in ascending order of preference, greater than or equal to 35%, greater than or equal to 40%, greater than or equal to 45%, greater than or equal to 50%, between 50 and 60%,
• the invention also relates to:
• - glazing comprising a material according to the invention mounted on a vehicle or on a building
• a glazing according to the invention as solar control and/or low-emission glazing for the building or vehicles
• the invention therefore relates to glazing comprising at least one material according to the invention in the form of monolithic, laminated and/or multiple glazing, in particular double glazing or triple glazing.
• the application more particularly targeted by the invention is firstly monolithic glazing and laminated glazing.
• the windows of the invention can be used in vehicles, such as side windows, car roofs, rear windows.
• the glazings of the invention can be used in the building sector, as solar control glazing.
• a glazing for the building generally delimits two spaces, a space qualified as “exterior” and a space qualified as “internal”. Sunlight entering a building is considered to flow from the exterior to the interior.
• building applications also include glazing used as a constituent element of balustrades, balconies and/or railings.
• the functional coating is deposited by sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the functional coating are deposited by sputtering assisted by a magnetic field.
• the invention also relates to the process for obtaining a material and a glazing according to the invention, in which the layers of the coatings are deposited by magnetron cathode sputtering.
• the substrate according to the invention is considered laid horizontally.
• the stack of thin layers is deposited above the substrate.
• 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).
• refractive indices are measured at a wavelength of 550 nm.
• the thicknesses referred to in this document without further details are physical, real or geometric thicknesses referred to as Ep and are expressed in nanometers (and not optical thicknesses).
• 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 he or she comprises is at least 50%, in particular at least 70%, preferably at least 90%.
• the stacks according to the invention do not comprise a functional layer based on silver, or else of the gold or platinum or even copper type. More generally, the stacks according to the invention do not contain such precious metals, or else in very negligible quantities, in particular in the form of unavoidable impurities.
• the titanium nitride layers are based on titanium nitride or more preferably consist of titanium nitride.
• Layers based on titanium nitride according to the invention comprise for example more than 50% by weight of titanium nitride, preferably more than 80%, or even more than 90% by weight of titanium nitride.
• the titanium nitride according to the invention is not necessarily stoichiometric (Ti/N atomic ratio of 1) but can be over- or under-stoichiometric. According to an advantageous mode, the N/Ti ratio is between 1 and 1.2. Also, the titanium nitride according to the invention can comprise a minor quantity of oxygen, for example between 1 and 10% molar of oxygen, in particular between 1 and 5% molar of oxygen.
• the titanium nitride layers according to the invention correspond to the general formula TiN x O y , in which 1.00 ⁇ x ⁇ 1.20 and in which 0.01 ⁇ y ⁇ 0.10.
• the functional coating comprises at least one functional layer and at least two dielectric coatings comprising at least one dielectric layer, such that each functional layer is disposed between two dielectric coatings.
• the functional coating may comprise at least two functional layers based on titanium nitride and at least three dielectric coatings comprising at least one dielectric layer, so that each functional layer is placed between two dielectric coatings.
• the functional coating may comprise at least three functional layers based on titanium nitride and at least four dielectric coatings comprising at least one dielectric layer, so that each functional layer is placed between two dielectric coatings.
• a dielectric coating corresponds to a sequence of layers comprising at least one dielectric layer, located between the substrate and the first functional layer, between two functional layers or above the last functional layer. If a dielectric coating is composed of several dielectric layers, the physical thickness of the dielectric coating corresponds to the sum of the physical thicknesses of the various dielectric layers constituting the dielectric coating.
• Dielectric coatings have a thickness between 2 and 200 nm.
• 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.
• the dielectric materials have a resistivity initially greater than 10 10 ohms. meters (Qm) at 25°C.
• the dielectric coating located directly below a functional layer comprises a dielectric layer located in contact with the functional layer chosen from:
• the aluminum nitride-based layers may comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% by mass of aluminum relative to the total mass of all the elements constituting the layer based on aluminum nitride, excluding oxygen and nitrogen.
• the layers based on aluminum nitride can comprise one or more elements chosen from silicon, boron, zirconium, etc.
• the layer based on aluminum nitride is not oxidized, however traces may exist.
• the layer based on aluminum nitride comprises, in increasing order of preference, at least 80%, at least 90%, at least 95%, at least 98%, at least 100%, by mass of nitrogen with respect to the total mass of oxygen and nitrogen.
• the aluminum nitride-based layer is deposited from a metal target in an atmosphere comprising nitrogen.
• the applicant has demonstrated that during the deposition by magnetron sputtering of the layer based on aluminum nitride, the application of a particularly low pressure in the deposition chamber contributes to obtaining coatings having a lower emissivity compared to to the same coating comprising a layer of aluminum nitride deposited at higher pressure. This advantageous effect is obtained with or without heat treatment.
• the layer based on aluminum nitride is deposited by magnetron cathode sputtering at a deposition pressure advantageously lower than 5.0 pbar, in particular 4.0 pbar, or even 3.0 pbar, and even 2.7 pbar.
• deposition pressure is meant the pressure prevailing in the chamber where the deposition of this layer is carried out. Excessively low pressures, which are difficult to achieve on an industrial deposition machine, do not, however, provide any additional advantage in terms of resistance to aging.
• the deposition pressure during the deposition of the oxygen barrier layer is preferably greater than 1.0 pbar, in particular 1.5 pbar.
• the layers based on zinc oxide can comprise, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% by mass of zinc relative to the total mass of all the elements constituting the layer based on zinc oxide excluding oxygen and 'nitrogen.
• the layers based on zinc oxide advantageously comprise at least 80%, even at least 90% by mass of zinc relative to the total mass of all the elements constituting the layer based zinc oxide excluding oxygen and nitrogen.
• the layers based on zinc oxide can comprise one or more elements chosen from among aluminum, titanium, niobium, zirconium, magnesium, copper, silver, gold, silicon, molybdenum, nickel, chromium, platinum, indium, tin and hafnium, preferably aluminum.
• Layers based on zinc oxide can optionally be doped with at least one other element, such as aluminum.
• the layer based on zinc oxide is not nitrided, however traces may exist.
• the layer based on zinc oxide comprises, in increasing order of preference, at least 80%, at least 90%, at least 95%, at least 98%, at least 100%, by mass of oxygen with respect to the total mass of oxygen and nitrogen.
• the zinc oxide-based layer is deposited from a ceramic target, with or without oxygen or from a metal target.
• the zinc oxide layers have, in increasing order of preference, a thickness:
• the stack may comprise at least one layer comprising silicon.
• Each dielectric coating may 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 functional layer.
• the layers comprising silicon therefore also contribute to the non-alteration of the functional layers and therefore to obtaining a low emissivity after heat treatment.
• the layers comprising silicon can be chosen from layers based on oxide, based on nitride or based on silicon oxynitride such as layers based on silicon oxide, layers based on silicon nitride and layers based on silicon oxynitride.
• each coating comprises a layer comprising silicon
• these layers are not necessarily of the same nature.
• the layers comprising silicon can comprise or consist of elements other than silicon, oxygen and nitrogen. These elements can be chosen from among aluminum, boron, titanium, and zirconium.
• the layers comprising silicon may comprise at least 50%, at least 60%, at least 65%, at least 70% at least 75.0%, at least 80% or at least 90% in mass of silicon relative to the mass of all the elements constituting the layer comprising silicon other than nitrogen and oxygen.
• the layer comprising silicon comprises at most 35%, at most 20% or at most 10% by mass of elements other than silicon relative to the mass of all the elements constituting the layer comprising silicon other than oxygen and nitrogen.
• the layers comprising silicon comprise less than 35%, less than 30%, less than 20%, less than 10%, less than 5% or less than 1% by mass of zirconium with respect to the mass of all the elements constituting the layer based on silicon oxide other than oxygen and nitrogen.
• the layers comprising silicon can comprise at least 2.0%, at least 5.0% or at least 8.0% by mass of aluminum with respect to the mass of all the elements constituting the layer based on silicon oxide. silicon other than oxygen and nitrogen.
• 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.
• - layers based on silicon oxynitride include a mixture of oxygen and nitrogen.
• 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.
• Silicon oxynitride layers include 10 to 90% (limits excluded) atomic percent nitrogen to the oxygen and nitrogen in the silicon oxynitride layer.
• 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 based on silicon oxynitride are characterized by a refractive index at 550 nm intermediate between a layer of non-nitrided oxide and a layer of non-oxidized nitride.
• the layers based on silicon oxynitride preferably have a refractive index at 550 nm greater than 1.55, 1.60 or 1.70 or between 1.55 and 1.95, 1.60 and 2.00 , 1.70 and 2.00 or 1.70 and 1.90.
• refractive indices may vary to some extent depending on the deposition conditions. Indeed, by playing on certain parameters such as the pressure or the presence of dopants, it is possible to obtain more or less dense layers and therefore a variation in refractive index.
• the layers comprising silicon can be layers of silicon and aluminum nitride and optionally of zirconium. These layers of silicon nitride and aluminum and/or zirconium may also comprise, by weight relative to the weight of silicon, aluminum and zirconium:
• At least one dielectric coating comprises a layer comprising silicon chosen from layers based on silicon nitride and/or aluminum.
• each dielectric coating comprises a layer comprising silicon chosen from layers based on silicon nitride.
• the sum of the thicknesses of all the layers comprising silicon, preferably based on silicon nitride, in the dielectric coating located below the functional layer is greater than 35%, greater than 50%, greater than 60 % greater than 70%, greater than 75% of the total thickness of the dielectric coating.
• the sum of the thicknesses of all the layers comprising silicon, preferably based on silicon nitride, in the dielectric coating located above the functional layer can be greater than 35%, greater than 50%, greater than 60% greater than 70%, greater than 75%, greater than 80%, greater than 90% of the total thickness of the dielectric coating.
• the sum of the thicknesses of all the layers comprising silicon, preferably based on silicon nitride, in each dielectric coating located above the functional layer can be greater than 35%, greater than 50%, greater than 60% greater than 70% greater than 75% greater than 80% greater than 90% of the total thickness of the dielectric coating.
• first layer based on silicon nitride and a second layer, located above the first layer, based on zinc oxide or based on aluminum nitride,
• first layer comprising silicon, preferably based on silicon nitride
• second layer located above the first layer, based on zinc oxide
• third layer located above the second layer, based on aluminum nitride
• first layer comprising silicon, preferably based on silicon nitride
• second layer located above the first layer, based on zinc oxide
• third layer located above above the second layer, based on aluminum nitride.
• the titanium nitride layer has a thickness greater than or equal to 2 nm, greater than or equal to 5 nm, greater than or equal to 7 nm, greater than or equal to 10 nm or greater than or equal to 15 nm,
• the titanium nitride layer has a thickness less than or equal to 40 nm, less than or equal to 35 nm, less than or equal to 30 nm or less than or equal to 25 nm,
• the dielectric coatings have a thickness between 2 and 200 nm, from 5 to 100 nm,
• the dielectric coating located directly below the functional layer has a thickness of between 2 and 100 nm, between 5 and 70 nm, between 10 and 50 nm; between 20 and 40 nm or between 25 and 35 nm.
• the dielectric coating located directly above the functional layer has a thickness of between 2 and 100 nm, between 5 and 70 nm, between 10 and 50 nm; between 20 and 40 nm or between 25 and 35 nm, - the first layer has a thickness between 2 and 40 nm, between 10 and 30 nm or between 15 and 25 nm,
• the first layer comprises silicon, preferably based on silicon nitride
• the second layer based on zinc oxide has a thickness of between 2 and 15 nm, between 3 and 10 or between 3 and 8 nm
• the second or the third layer based on aluminum nitride has its thickness between 2 and 30 nm, between 2 and 15 nm, between 3 and 10 nm or between 3 and 8 nm.
• a dielectric layer comprising silicon, preferably a layer based on silicon nitride
• the sum of the thicknesses of all the layers comprising silicon in the dielectric coating located above the functional layer is greater than 50% of the total thickness of the dielectric coating.
• the stack of thin layers can optionally include a protective layer.
• the protective layer is preferably the last layer of the coating, that is to say the layer farthest from the substrate coated with the coating (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 among 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 a layer of titanium oxide, a layer of zinc and tin oxide or a layer based on titanium and zirconium oxide.
• the invention relates to single glazing comprising a material according to the invention.
• the coating is preferably placed on face 2 of the single glazing.
• the invention relates to multiple glazing comprising a material according to the invention and at least one additional substrate, the material and the additional substrate are separated by at least one spacer layer of gas.
• the invention relates to a laminated glazing comprising a material according to the invention and at least one additional substrate, the material and the additional substrate are separated by at least minus one lamination insert.
• the coating can be deposited:
• the invention also relates to automobile glazing, in particular a roof for an automobile, comprising a material as described above and comprising a single substrate, in which said substrate is preferentially tinted in its mass, and in which said stack is preferentially positioned towards the side of the glazing exposed towards the interior of the vehicle.
• the invention also relates to an automobile glazing, in particular a roof for an automobile, comprising a first substrate, preferably colored, bonded by lamination insert, in particular PVB, to a material as described above, the substrate of which is preferably clear glass and wherein the coating is preferably disposed on the face exposed to the outside of said glazing.
• 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 on which the coating is deposited 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 silico-sodo-lime type, but it can also be of borosilicate or alumino-borosilicate type glass.
• Ordinary clear glass 2 to 6 mm thick has the following light characteristics:
• colored substrate it is meant that the substrate includes in its glass composition elements aimed at giving it a coloring (i.e. different from that of a so-called “clear” glass), in particular elements such as cobalt, iron, selenium, or even chromium, which can also aim to reduce light transmission.
• elements such as cobalt, iron, selenium, or even chromium, which can also aim to reduce light transmission.
• the substrate is made of glass, in particular silico-sodo-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 substrate coated with the coating or the coating only can be intended to undergo a heat treatment.
• the present invention also relates to the unheat-treated coated substrate.
• the material that is to say the transparent substrate coated with the stack, may be intended to undergo 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.
• the heat treatments are chosen from:
• the materials of the invention can be used in both untempered and tempered versions.
• the stack may not have undergone heat treatment at a temperature above 500°C, preferably 300°C.
• 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.
• 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 substrate coated with the stack can be a curved and/or tempered glass.
• Functional coatings defined below are deposited on clear silica-soda-lime glass substrates with a thickness of 4 mm.
• All the layers are deposited in a known manner by sputtering assisted by magnetic field (often called magnetron).
• the titanium nitride functional layer(s) are deposited from a target of pure metallic titanium in a reactive atmosphere containing nitrogen and argon.
• the deposition conditions of the layers, which were deposited by sputtering (so-called “cathodic magnetron” sputtering), are summarized in Table 1
• At. atomic; hp: high pressure; IP: low pressure.
• Table 2 lists the materials and the physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating which constitutes the coatings according to their position with respect to the carrier substrate of the stack (last line at the bottom of the table ).
• the heat treatments are carried out in a Naber oven at a temperature of 650° C. for 10 minutes.
• the gain is positive when the resistance per sheet is improved and negative when the resistance per sheet is deteriorated following the heat treatment.
• the examples show that at a constant light transmission value, by replacing all or part of the silicon nitride layers in the lower dielectric coating, a gain in emissivity is obtained.
• the optimal configuration depends on the presence or absence of heat treatment.
• a dielectric coating comprising a layer of ZnO is advantageous (lnv-1 vs cp-1). This can be attributed to the crystalline state of ZnO which favors the crystallization of TiN. On the other hand, the emissivity and the resistivity are strongly degraded following a heat treatment. This effect can be attributed to the oxidation of TiN by the oxygen of ZnO.
• the low-pressure deposition of the AIN layers makes it possible to obtain a significant improvement in emissivity and resistivity (lnv-5 and lnv-6 vs cp-1 and lnv.2). This results in a decrease of one emissivity point in all configurations, all other things being equal.
• this layer of zinc oxide which crystallizes at room temperature acts as a growth layer.
• the zinc oxide layer improves crystallization titanium nitride located above. However, better crystallization leads to an improvement in the emissivity.
• this zinc oxide layer also acts as a growth layer for both the layer of aluminum nitride and for the layer of titanium nitride.
• Figure 1.a represents the X-ray diffraction diagrams in Bragg-Brentano geometry of example cp-3 (lower curve) and lnv-7 (upper curve).
• cp-3 lower curve
• lnv-7 upper curve
• Figure 1.b represents the X-ray diffraction diagrams in Bragg-Brentano geometry of example cp-4 (lower curve) and cp-5 (upper curve).
• cp-4 lower curve
• cp-5 upper curve
• the aluminum nitride layer seems to contribute to a better stress distribution within the coating. This effect seems even more marked when the aluminum nitride layer is deposited at reduced pressure.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Laminated Bodies (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=78828098

Family Applications (1)

Country Status (5)

Families Citing this family (2)

Family Cites Families (3)

• 2021
  • 2021-09-27 FR FR2110150A patent/FR3127490B1/fr active Active
• 2022
  • 2022-09-26 WO PCT/FR2022/051806 patent/WO2023047069A1/fr not_active Ceased
  • 2022-09-26 EP EP22790337.4A patent/EP4408809A1/de active Pending
  • 2022-09-26 MX MX2024003762A patent/MX2024003762A/es unknown
• 2024
  • 2024-04-17 CO CONC2024/0004803A patent/CO2024004803A2/es unknown

Also Published As

Similar Documents

Legal Events