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
• • 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
  • C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• • 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
  • C03C17/3639—Multilayers containing at least two functional metal layers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
• • 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
  • C03C17/3652—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 coating stack containing at least one sacrificial layer to protect the metal from oxidation
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
  • Y10T428/24975—No layer or component greater than 5 mils thick
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/31504—Composite [nonstructural laminate]
  • Y10T428/31678—Of metal

Definitions

• the invention relates to transparent substrates, in particular of mineral rigid material such as glass, said substrates being coated with a stack of thin layers comprising at least one metal-type functional layer that can act on the solar radiation and / or the infrared radiation of long wavelength.
• the invention relates more particularly to the use of such substrates for manufacturing thermal insulation and / or sun protection glazings.
• These windows are intended both to equip buildings and vehicles, in particular to reduce the air conditioning effort and / or reduce excessive overheating (so-called “solar control” glazing) and / or reduce the amount of energy dissipated to the outside (so-called “low emissivity” glazing) caused by the ever increasing importance of glazed surfaces in buildings and vehicle interiors.
• a type of layer stack known to give substrates such properties consists of at least one metallic functional layer, such as a silver-based layer, which is disposed between two coatings of dielectric material of the oxide or nitride type. metallic.
• This stack is generally obtained by a succession of deposits made by a technique using the vacuum such as sputtering possibly assisted by magnetic field.
• Two very thin coatings arranged one on each side of the silver layer, can also be provided, the underlying coating being a primer, nucleation and / or protection layer in the event of a heat treatment subsequent to the deposit, and the overlying coating as a protective or "sacrificial" coating to avoid silver spoilage if the oxide layer overlying it is sputtered in the presence of oxygen and / or or if the stack undergoes heat treatment after the deposition.
• European patents EP-0 611 213, EP-0 678 484 and EP-0 638 528 stacks of this type, with one or two functional metal layers based on silver.
• these low-emission or sun protection glazings also have characteristics inherent to the substrates themselves, in particular aesthetic (whether they can be curved), mechanical (whether they are more resistant), or safety (they do not hurt in case of breakage). This requires the glass substrates undergo thermal treatments known in themselves bending type, annealing, quenching and / or processing related to the production of a laminated glazing.
• a first solution is to significantly increase the thickness of the thin metal layers mentioned above and which surround the functional layers: this ensures that all the oxygen that can diffuse from the ambient atmosphere and / or migrate from high temperature glass substrate is "captured” by these metal layers by oxidizing them, without reaching the (the) layer (s) functional (s).
• blocking layers are sometimes called “blocking layers” or “blocking layers”.
• the functional layer (s) a layer of a material capable of acting as a barrier to the diffusion of oxygen at high temperature, a material which itself does not does not undergo a chemical or structural change at high temperature that would result in a change in its optical properties; It can thus be silicon nitride Si 3 N 4 or aluminum nitride AlN,
• the functional layer (s) is (are) directly in contact with the underlying dielectric coating, in particular with zinc oxide ZnO.
• a single blocking layer (or monolayer blocking coating) is preferably further provided on the functional layer (s).
• This blocking layer is based on a metal chosen from niobium Nb, tantalum Ta, titanium Ti, chromium Cr or nickel Ni or an alloy from at least two of these metals, especially from an alloy of niobium and tantalum (Nb / Ta), niobium and chromium (Nb / Cr) or tantalum and chromium (Ta / Cr) or nickel and chromium (Ni / Cr).
• the search for a better resistivity, that is to say a lower resistivity, of the stack is a constant search.
• the state of the functional layer has been the subject of many studies because it is, of course, a major factor in the resistivity of the functional layer.
• the inventors have chosen to explore another way in improving the resistivity: the nature of the interface between the functional layer and the immediately adjacent blocking layer.
• the over-blocking coating is a monolayer of NiCrO x and may have an oxidation gradient.
• the part of the blocking layer in contact with the functional layer is less oxidized than the part of this layer furthest from the functional layer by using a particular deposition atmosphere.
• the object of the invention is to overcome the drawbacks of the prior art, by developing a new type of stack with functional layer (s) of the type of those described above, which stack can undergo high temperature heat treatments of the bending, quenching or annealing type, while preserving its optical quality and its mechanical strength and having an improved resistivity.
• the invention is in particular a solution adequate to the usual problem of the intended application and which is to develop a compromise between the thermal qualities and optical qualities of the thin film stack.
• the object of the invention is therefore, in its broadest sense, a substrate, in particular a transparent glass substrate, provided with a stack of thin layers comprising an alternation of "n" functional layers with reflectance properties in the infrared and / or solar radiation, including metallic silver-based or silver-containing metal-based functional layers, and "(n + 1)" dielectric coatings, with > 1 (n being obviously an integer), said coatings being composed of one or a plurality of layers, at least one of dielectric material, so that each functional layer is disposed between at least two dielectric coatings , characterized in that at least one functional layer comprises a blocking coating consisting of at least one interface layer immediately in contact with said functional layer, this interface layer being based on titanium oxide TiO x .
• the invention thus consisted in providing a blocking coating for the functional layer with at least one layer, this blocking coating being located under ("underblocking” coating) and / or on (“overblocking” coating) the functional layer.
• This blocking coating being located under (“underblocking” coating) and / or on (“overblocking” coating) the functional layer.
• the inventors have thus realized that the state, and even the degree of oxidation of the layer immediately in contact with the functional layer, could have a major influence on the resistivity of the layer.
• the invention does not apply only to stacks having only one "functional" layer, arranged between two coatings. It also applies to stacks comprising a plurality of functional layers, in particular two functional layers alternating with three coatings, or three functional layers alternating with four coatings or even four functional layers alternating with five coatings.
• each, functional layer is provided with a sub-blocking and / or over-blocking coating according to the invention, that is to say a blocking coating comprising at least two distinct layers.
• the interface layer is partially oxidized. It is therefore not deposited in stoichiometric form, but in non-stoichiometric and preferably substoichiometric form, of the MO x type, where M represents the material and x is a number different from the stoichiometry of titanium oxide TiO 2 , that is to say different from 2 and preferably less than 2, in particular between 0.75 times and 0.99 times the normal stoichiometry of the oxide.
• TiO x may be in particular such that 1, 5 ⁇ x ⁇ 1, 98 or 1, 5 ⁇ x ⁇ 1, 7 or even 1, 7 ⁇ x ⁇ 1, 95.
• the interface layer preferably has a geometric thickness less than 5 nm and preferably between 0.5 and 2 nm and the blocking coating thus preferably has a geometric thickness of less than 5 nm and preferably between 0.5 and 2 nm. This thickness may however be greater and in particular be twice the thickness of the interface layer if another layer is provided in the blocking coating.
• the effect underlying the invention can be confirmed by local chemical analysis in contact with the functional layer and the blocking coating using transmission electron microscopy (TEM) combined with energy loss spectroscopy of electron (EELS).
• TEM transmission electron microscopy
• EELS energy loss spectroscopy of electron
• the interface layer according to the invention may comprise one (or more) other chemical element (s) chosen from at least one of the following materials Ti, V, Mn, Co, Cu, Zn, Zr, Hf, Al, Nb, Ni, Cr, Mo, Ta, or an alloy based on at least one of these materials.
• the blocking coating according to the invention may further comprise one (or more) other layer (s), further away from the functional layer than the TiO x interface layer, such as by example a metal layer, and in particular a layer of titanium metal Ti.
• the glazing according to the invention incorporates at least the carrier substrate of the stack according to the invention, optionally associated with at least one other substrate. Each substrate can be clear or colored. At least one of the substrates may be colored glass in the mass. The choice of the type of coloration will depend on the level of light transmission and / or colorimetric appearance sought (s) for the glazing once its manufacture completed.
• tinted glasses which can be retained are those which, for a thickness of 4 mm, have a T L of 65% to 95%, an energy transmission T E of 40% to 80%, a wavelength transmission dominant from 470 nm to 525 nm associated with a transmission purity of 0.4% to 6% according to Illuminant D 65 , which can be "translated" into the colorimetry system (L, a *, b *) by transmission values of a * and b * respectively between -9 and 0 and between -8 and +2.
• the glazing preferably has a light transmission T L of at least 75% or more for "low-emissive” applications, and a light transmission T L of at least 40% even more for "solar control" applications.
• the glazing according to the invention may have a laminated structure, in particular associating at least two rigid substrates of the glass type with at least one thermoplastic polymer sheet, in order to present a glass-like structure / thin-film stack / sheet (s) / glass.
• the polymer may especially be based on polyvinyl butyral PVB, ethylene vinyl acetate EVA, PET polyethylene terephthalate, PVC polyvinyl chloride.
• the glazing may also have a so-called asymmetrical laminated glazing structure, combining a rigid glass-type substrate with at least one sheet of polyurethane polymer with energy absorber properties, optionally combined with another layer of polymers with "self-healing" properties.
• asymmetrical laminated glazing structure combining a rigid glass-type substrate with at least one sheet of polyurethane polymer with energy absorber properties, optionally combined with another layer of polymers with "self-healing" properties.
• the glazing may then have a glass-like structure / stack of thin layers. polymer sheet (s).
• the carrier substrate of the stack is preferably in contact with a polymer sheet.
• the glazings according to the invention are capable of undergoing heat treatment without damage for the stack of thin layers. They are therefore optionally curved and / or tempered.
• the glazing may be curved and / or tempered by being constituted by a single substrate, the one provided with the stack. This is called glazing
• the stack of thin layers is preferably on an at least partially non-flat face.
• the glazing may also be a multiple glazing, in particular a double glazing, at least the carrier substrate of the stack being curved and / or quenched. It is preferable in a multiple glazing configuration that the stack is disposed so as to be turned towards the interleaved gas blade side.
• the carrier substrate of the stack can be curved or tempered glass, the substrate can be curved or tempered before or after the deposit of the stack.
• the invention also relates to the method of manufacturing the substrates according to the invention, which consists in depositing the stack of thin layers on its substrate, in particular glass, by a vacuum technique of the cathode sputtering type possibly assisted by magnetic field. he It is then possible to perform on the coated substrate a bending / quenching heat treatment or annealing without degradation of its optical and / or mechanical quality.
• the first layer or the first layers may be deposited by another technique, for example by a pyrolysis type thermal decomposition technique.
• the interface layer is deposited from a ceramic target, in a non-oxidizing atmosphere (i.e. without voluntary oxygen introduction) preferably consisting of noble gas (s) (He, Ne, Xe, Ar, Kr).
• a non-oxidizing atmosphere i.e. without voluntary oxygen introduction
• noble gas s
• He, Ne, Xe, Ar, Kr noble gas
• FIG. 1 illustrates a functional monolayer stack whose functional layer is coated with a blocking coating according to the invention
• FIG. 2 illustrates a functional monolayer stack whose functional layer is deposited on a blocking coating according to the invention
• FIG. 3 illustrates a functional monolayer stack whose functional layer is deposited on an overblocking coating according to the invention and under a subblocking coating according to the invention
• FIG. 4 illustrates the resistivity in ohms per square of a stack according to example 5 as a function of the thickness in angstroms of the interface layer according to the invention.
• FIG. 5 illustrates a functional bilayer stack of which each functional layer is deposited on a subblocking coating according to the invention
• FIG. 6 illustrates a functional four-layer stack of which each functional layer is deposited on a sub-blocking coating according to the invention.
• Stacking figures do not respect the proportions between the thicknesses of the different layers so that their reading is facilitated.
• Figures 1 and 2 illustrate functional monolayer stacking schemes, respectively when the functional layer is provided with an over-blocking coating and when the functional layer is provided with a sub-blocking coating.
• the stack is deposited on the substrate 10, which is a 2.1 mm thick clear silico-soda-lime glass substrate.
• the stack comprises a single functional layer based on silver 40.
• a dielectric coating 20 consisting of a plurality of superimposed layers of dielectric material referenced 22, (23), 24 and on the functional layer 40 is a dielectric coating 60 consisting of a plurality of superposed layers based on dielectric material referenced 62, 64.
• the layers 22 are based on Si 3 N 4 and have a physical thickness of 20 nm;
• the layers 24 are based on ZnO and have a physical thickness of 8 nm;
• the layers 62 are based on ZnO and have a physical thickness of 8 nm;
• the layers 64 are based on Si 3 N 4 and have a physical thickness of 20 nm;
• the layers 40 are silver-based and have a physical thickness of 10 nm.
• the blocking coating respectively 50, 30 comprises a single layer respectively of metal, here of metal titanium neither oxidized nor nitrided, this layer being deposited in an argon atmosphere pure.
• the blocking coating respectively 50, 30 comprises an oxide interface layer, respectively 52, 32, in this case titanium oxide under -stoichiometric TiOx, with a thickness of 1 nm, deposited in a pure argon atmosphere using a ceramic cathode.
• the blocking coating 50 comprises an interface layer, 52, 32 in oxide, here substoichiometric titanium oxide. TiOx, 2 nm thick, deposited in a pure argon atmosphere using a ceramic cathode.
• the successive depositions of the layers of the stack are carried out by magnetic field assisted sputtering, but any other deposition technique can be envisaged as long as it allows good control and good control of the thicknesses. layers to deposit.
• the deposition installation comprises at least one sputtering chamber provided with cathodes equipped with targets of suitable materials under which the substrate 1 passes successively.
• These deposition conditions for each of the layers are as follows: • the silver-based layers 40 are deposited using a silver target, under a pressure of 0.8 Pa in a pure argon atmosphere,
• the ZnO-based layers 24 and 62 are deposited by reactive sputtering using a zinc target at a pressure of 0.3 Pa and in an argon / oxygen atmosphere
• the S1 3 N 4 layers 22 and 64 are deposited by reactive sputtering using an aluminum-doped silicon target at a pressure of 0.8 Pa in an argon / nitrogen atmosphere.
• the power densities and running speeds of the substrate 10 are adjusted in a known manner to obtain the desired layer thicknesses.
• the resistance of each stack was measured before a heat treatment (BHT) and after this heat treatment (AHT).
• the heat treatment applied was in each case a warming at 620 0 C for 5 minutes, then rapid cooling in ambient air (about 25 0 C).
• the comparison of the resistivity values before heat treatment of Example 1 with the resistivity values before heat treatment of Examples 2 and 3 clearly shows an improvement in the resistivity of Examples 2 and 3 with resistivity values much lower than those of Example 1.
• the presence of the TiOx layer deposited on the metallic silver-based functional layer in place of the metallic titanium layer thus improves the resistivity before or without heat treatment.
• an oxidized state of titanium at this interface with the silver-based layer improves the resistivity while a metallic state is detrimental to the resistivity.
• the case of the subblocking coating is more complex than that of overblocking because this coating influences the heteroepitaxy of silver on the underlying layer of oxide, in this case based on zinc.
• the underblocking coating In contrast to the overblocking coating, the underblocking coating is generally not exposed to an oxygen-containing plasma atmosphere. This implies that when the underblocking coating is made of unoxidized and / or non-nitrided metal titanium, it will of course not be oxidized or nitrided at the interface with the silver-based functional layer.
• the presence of the TiOx interface layer 32 improves the light transmission both before the heat treatment and after this treatment.
• examples 4 and 5 a configuration similar to that of FIG. 1 was used, with in order, on the substrate: a layer 22 based on SnO 2 ; An intermediate layer 23 (not shown in FIG. 1) based on TiO 2 ;
• a functional metal layer 40 based on silver An interface layer 52 made of TiOx substoichiometric titanium oxide, with a physical thickness of 2 nm;
• the blocking coating 50 respectively comprises an interface layer.
• the oxide material is TiO x , a sub-stoichiometric titanium oxide with a thickness of 2 nm deposited in a pure argon atmosphere using a ceramic cathode.
• Layers 24, 40, 52, 62 and 64 are deposited as before.
• the SnO 2 -based layer 22 is deposited by reactive sputtering using a metal tin target at a pressure of 0.3 Pa and in an argon / oxygen atmosphere and the TiO 2 -based layer 23. is deposited by reactive sputtering using a metal target of tin, at a pressure of 0.3 Pa and in an argon / oxygen atmosphere.
• Table 3 summarizes the physical thicknesses in nanometers of the layers of the two examples 4 and 5 according to the invention and Table 4 the essential characteristics of these examples.
• Example 5 a counterexample of Example 5 was carried out by depositing a stack identical to that of Example 5 except that the layer 52 was not deposited in the form of titanium oxide of a thickness of 2 nm, but in the form of metallic titanium with a thickness of 0.5 nm, deposited under a neutral atmosphere (argon).
• FIG. 3 illustrates a variant of the invention corresponding to a functional monolayer stack, whose functional layer 40 is provided with a subblocking coating 30 and an overblocking coating.
• the stack is covered with a protective layer 200 based on mixed oxide, such as a mixed oxide of tin and zinc.
• mixed oxide such as a mixed oxide of tin and zinc.
• FIG. 5 thus illustrates a variant with two functional metal layers based on silver 40; 80; and three dielectric coatings 20; 60; 100; said coatings being composed of a plurality of layers, respectively 22, 24; 62, 64, 66; 102, 104, so that each functional layer is disposed between at least two dielectric coatings.
• the layers 40; 80; based on silver are deposited using a silver target, under a pressure of 0.8 Pa in an atmosphere of pure argon
• the layers 24; 62, 66; 102 are based on ZnO and are deposited by reactive sputtering using a zinc target, at a pressure of 0.3 Pa and in an argon / oxygen atmosphere
• the layers 22, 64 and 104 are based on Si 3 N 4 and are deposited by reactive sputtering using an aluminum-doped silicon target at a pressure of 0.8 Pa in a argon / nitrogen atmosphere.
• the stack is covered with a protective layer 200 based on mixed oxide, such as a mixed oxide of tin and zinc.
• mixed oxide such as a mixed oxide of tin and zinc.
• Each functional layer 40, 80 is deposited on a sub-blocking coating 30, 70 constituted respectively of an interface layer 32, 72 of titanium oxide TiO x immediately in contact with said functional layer.
• FIG. 6 also illustrates a variant with four functional metal layers based on silver 40; 80; 120; 160; and five dielectric coatings 20; 60; 100; 140; 180; said coatings being composed of a plurality of layers, respectively 22, 24; 62, 64, 66; 102, 104, 106; 142, 144, 146; 182, 184; so that each functional layer is disposed between at least two dielectric coatings.
• the layers 40; 80; 120; 160 silver are deposited using a silver target, under a pressure of 0.8 Pa in an atmosphere of pure argon,
• the layers 24; 62, 66; 102, 106; 142, 146; 182 are based on ZnO and are deposited by reactive sputtering using a zinc target, at a pressure of 0.3 Pa and in an argon / oxygen atmosphere,
• the layers 22, 64, 104, 144 and 184 are based on Si 3 N 4 and are deposited by reactive sputtering using a target doped with boron or aluminum, under a pressure of 0 , 8 Pa in an argon / nitrogen atmosphere.
• the stack is also covered with a protective layer 200 based on mixed oxide, such as a mixed oxide of tin and zinc.
• a protective layer 200 based on mixed oxide such as a mixed oxide of tin and zinc.
• Each functional layer 40; 80; 120; 160 is deposited on a subblocking coating 30; 70; 110; 150 constituted respectively of an interface layer 32; 72; 112; TiO 2 x titanium oxide x immediately in contact with said functional layer.

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