Solar control glazing

Abstract

The invention relates to a multiple glazing unit comprising at least two substrates separated by at least one interposed gas layer, the substrate constituting the outer wall of the glazing unit comprises on its inward-facing face a stack of layers comprising at least one silver-based functional metal layer and at least two dielectric coatings, each dielectric coating comprising at least one dielectric layer, so that each functional metal layer is arranged between two dielectric coatings, characterized in that the dielectric coating located above the functional layer comprises: - a titanium oxide-based layer located above and in contact with the silver-based functional metal layer, having a thickness greater than or equal to 3 nm, and - at least one layer comprising silicon and / or aluminum.

Description

Title of the invention: Solar control glazing

[0001] The invention relates to a solar protection glazing. Known high-performance solar protection glazings are multiple glazings comprising at least two substrates separated by at least one interlayer gas layer. The substrate constituting the outer wall of the glazing comprises on its inward-facing face a stack of layers comprising at least one silver-based functional layer.

[0002] Silver-based functional metal layers (or silver layers) have advantageous electrical conduction and infrared radiation (IR) reflection properties, hence their use in so-called "solar control" glazing aimed at reducing the amount of solar energy entering a building or vehicle.

[0003] These silver layers are deposited between coatings based on dielectric materials generally comprising several dielectric layers (hereinafter "dielectric coatings") making it possible to adjust the optical properties of the stack. These dielectric layers also make it possible to protect the silver layer from chemical or mechanical attacks.

[0004] There is a strong demand for solar protection glazing combining the following properties: - high light transmission, in particular at least 70%, 75% or even 78%, - a low or moderate solar factor, - low heat loss resulting in low Ug coefficients, notably 1.15 W / m2.K, 1.10 W / m2.K, or even 1.00 W / m2.K.

[0005] The solar factor of the glazing "FS or g" corresponds to the ratio in % between the total energy entering the room through the glazing and the incident solar energy. The solar factor therefore measures the contribution of a glazing to heating the "room". The smaller the solar factor, the lower the solar gains.

[0006] The heat loss coefficient, also called the "Ug value", expresses the heat flow per square meter of glazing caused by a temperature difference between the external environment and the interior separated by the glazing. The lower this value, the lower the losses and the better the insulation.

[0007] It is very difficult to obtain sufficiently low absorption with stacks with several silver-based functional layers. This is notably due to the presence of at least four “metal / dielectric” interfaces which each necessarily generate absorption. Preferably, the invention is limited to stacks comprising a single silver-based functional layer because they are likely to have lower light absorption values ​​in the visible range and therefore higher light transmissions.

[0008] Obtaining such high light transmissions, a low solar factor and low heat losses in combination is delicate because very few modifications of the stack are possible. To obtain such low heat losses at these levels of light transmission, in particular with stacks with a single functional layer based on silver, it is necessary to reduce the emissivity of the stack without increasing the absorption or the reflection. There is therefore not much flexibility of action.

[0009] Furthermore, these properties must be obtained even when the stack or the substrate carrying the stack has not undergone high temperature heat treatment. This represents a significant additional constraint in the case of glazing with high light transmission. Generally, high temperature heat treatments such as annealing, bending and / or tempering cause changes within the silver layer leading to a reduction in emissivity. In the present case, an improvement attributable to heat treatment cannot be relied upon.

[0010] However, it is very difficult to reduce the emissivity without reducing the light transmission. Indeed, increasing the thickness of the silver layers makes it possible to lower the emissivity but to the detriment of the light transmission.

[0011] The emissivity depends directly on the quality of the silver layers such as their crystalline state, their homogeneity as well as their environment. By "environment" we mean the nature of the layers close to the silver layer and the surface roughness of the interfaces with these layers. Another way to reduce the emissivity is therefore to improve the quality of the silver layer by choosing a favorable environment. The emissivity and the resistivity (or resistance) per square vary proportionally. Consequently, it is often possible to evaluate the emissivity of a material by evaluating its resistance per square.

[0012] To improve the quality of silver-based functional metal layers, it is known to use dielectric coatings under the silver layers comprising dielectric layers with a stabilizing function intended to promote the wetting, nucleation and crystallization of the silver layer. Dielectric layers based on crystallized zinc oxide are used in particular for this purpose. Indeed, the zinc oxide deposited by the cathode sputtering process crystallizes without requiring additional heat treatment. The zinc oxide-based layer can therefore serve as an epitaxial growth layer for the silver layer.

[0013] Another way to prevent the degradation of silver layers lies in the choice of the layer located above and in contact with the silver layer. Among the known proposals are the use of so-called blocking layers or dielectric layers based on crystallized zinc oxide. The objective is to protect the layers functional of possible degradation during the deposition of the upper dielectric coating and / or during heat treatment.

[0014] The blocking layers are generally based on a metal chosen from nickel, chromium, titanium, niobium, or an alloy of these different metals. The different metals or alloys mentioned may also be partially oxidized, in particular have a sub-stoichiometry in oxygen (for example TiOx or NiCrOx).

[0015] These blocking layers are very thin, normally less than 2 nm thick, and at these thicknesses are susceptible to being partially oxidized during heat treatment or during deposition of an overlying layer. Generally speaking, these blocking layers are sacrificial layers, capable of capturing oxygen from the atmosphere or the substrate, thus preventing oxidation of the silver layer.

[0016] The use of these thin blocking layers does not make it possible to obtain sufficiently high-performance glazing, in particular having a sufficiently low emissivity to obtain, in combination, high light transmission and sufficiently low heat losses.

[0017] Good results in terms of resistivity have been obtained until now with a material not comprising a blocking layer and each dielectric coating of which comprises at least one layer comprising silicon. The silver layer is located in contact with the two layers of crystallized zinc oxide located respectively above and below the silver layer. Materials of this type comprising the ZnO / Ag / ZnO sequence are referred to as reference material in the present application.

[0018] This solution of using only layers based on crystallized zinc oxide below and above the silver is also not entirely satisfactory.

[0019] The applicant has surprisingly discovered that the use of a thick titanium oxide layer located above and in contact with the silver-based functional layer, in a particular stack, makes it possible to overcome these drawbacks. The solution of the invention makes it possible to achieve the required properties, namely to obtain solar protection glazing having a high light transmission, in particular of the order of 78.5% and a low emissivity. The emissivity can in particular be sufficiently low to make it possible to obtain the lowest possible heat transfer coefficients (Ug values).

[0020] The invention therefore relates to a multiple glazing unit comprising at least two substrates separated by at least one interposed gas layer, the substrate constituting the outer wall of the glazing unit comprises on its inward-facing face a stack of layers comprising a silver-based functional metal layer and at least two dielectric coatings, each dielectric coating comprising at least one dielectric layer, such that the functional metal layer is arranged between two dielectric coatings, characterized in that the dielectric coating located above the functional layer comprises: - a titanium oxide-based layer located above and in contact with the silver-based functional metal layer having a thickness greater than or equal to 3 nm, and - at least one layer comprising silicon and / or aluminum.

[0021] The titanium oxide-based layer having a thickness greater than or equal to 3 nm is located above and in contact with the silver-based functional layer. The applicant has surprisingly discovered that the use of this thick titanium oxide-based layer above the silver allows a resistivity gain of the order of 10% even in the absence of heat treatment. In certain embodiments, the improvement in resistivity is obtained without increasing absorption. This resistivity gain makes it possible to achieve emissivity values ​​that are sufficiently low to achieve the required Ug values ​​without increasing the thicknesses of the silver layer and therefore without reducing the light transmission.

[0022] This solution therefore makes it possible to achieve high levels of light transmission, even in the case of stacks used as deposited, i.e. without being subjected to subsequent treatment at high temperature. For these stacks, the quality of the silver layers does not make it possible to obtain resistances per square as low as in the case of toughened or laser-treated stacks. Obtaining low Ug values ​​requires the use of thicker silver layers which prevent the obtaining of sufficiently high levels of light transmission. The gain in resistance per square obtained thanks to the solution of the invention makes it possible to overcome this difficulty.

[0023] Preferably, the dielectric coating located below the silver layer comprises a high refractive index layer. The joint presence of a high index layer above and below the silver-based functional layer contributes to obtaining high light transmission.

[0024] The applicant has also surprisingly discovered that the use of a thick titanium oxide-based layer combined with a particular zinc and tin oxide-based layer contributes to obtaining the advantageous properties of the invention. It appears that this layer makes it possible to reduce residual absorption in the event of incomplete oxidation of the titanium oxide-based layer. The invention combining a thick titanium oxide layer in contact with a zinc and tin oxide layer makes it possible to obtain: - an improvement in resistivity with the achievement of a gain in square resistance of at least 5%, or even 10% or more, for certain structures of the invention, both before and after heat treatment, - an improvement in the mechanical properties of brush resistance before and after heat treatment.

[0025] The present invention is particularly suitable in the case of stacks with a single silver-based functional layer. The solution of the invention is also suitable in the case of stacks with several silver-based functional layers, in particular stacks with two or three functional layers.

[0026] The glazing according to the invention may have the following characteristics alone or in combination: - the titanium oxide-based layer is deposited from a ceramic target, in particular under stoichiometric, - the titanium oxide-based layer has a thickness of at least 10 nm, - the dielectric coating located above the functional layer comprises a layer comprising silicon chosen from silicon nitride layers, - the layer comprising silicon and / or aluminum has a thickness greater than 5 nm, - the dielectric coating located above the functional layer further comprises a layer based on zinc and tin oxide comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide, - the zinc and tin oxide based layer has a thickness: - greater than 5 nm, - less than 40 nm, - the dielectric coating located below the functional layer comprises a zinc oxide-based layer located in contact with the functional layer, - the dielectric coating located below the functional layer comprises a layer with a refractive index greater than 2.20, - the layer with a refractive index greater than 2.20 is chosen from layers based on titanium oxide and layers based on silicon and zirconium nitride, - the thickness of all layers with a refractive index greater than 2.20 in the dielectric coating located below the functional layer is greater than 10 nm, greater than 15 nm, greater than 20 nm, - it has a light transmission greater than 70%, greater than 75%, greater than 76% or greater than 78%, - it has a Ug value of less than 1.15 W / m2.K, less than 1.10 W / m2.K or less than 1.00 W / m2.K, - the stack comprises a single silver-based functional metal layer, - the stack has been subjected to rapid thermal annealing, - the stack and the substrate have been subjected to a heat treatment at a high temperature above 500°C such as quenching, annealing or bending.

[0027] The invention also relates to: - glazing according to the invention mounted on a vehicle or on a building, and - the use of glazing according to the invention as solar control glazing for buildings or vehicles, - a building, a vehicle or a device comprising glazing according to the invention.

[0028] Throughout the description, the substrate according to the invention is considered to be laid horizontally. The stack of thin layers is deposited above the substrate. The meaning of the expressions “above” and “below” and “lower” and “upper” is to be considered in relation to this orientation. In the absence of a specific stipulation, the expressions “above” and “below” do not necessarily mean that two layers and / or coatings are arranged in contact with each other. 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) layer(s) interposed between these two layers (or layer and coating).

[0029] All the luminous characteristics described are obtained according to the principles and methods of the European standards EN 410 relating to the determination of the luminous and solar characteristics of glazing used in glass for construction. The method for calculating the Ug coefficient of insulating glazing is described in the standard NF EN 673. It is considered that the sunlight entering a building goes from the outside to the inside.

[0030] According to the invention, the luminous characteristics are measured according to the illuminant D65 at 2° perpendicular to the material mounted in double glazing: - TL corresponds to the luminous transmission in the visible in %, - Rext corresponds to the external light reflection in the visible in %, observer on the external space side, - Rint corresponds to the interior light reflection in the visible in %, observer side interior space, - a*T and b*T correspond to the transmission colors a* and b* in the L*a*b* system, - a*Rext and b*Rext correspond to the colors in reflection a* and b* in the L*a*b* system, observer on the exterior space side, - a*Rint and b*Rint correspond to the reflected colors a* and b* in the L*a*b* system, observer side interior space.

[0031] As explained previously, according to the invention the properties must be obtained even when the stack or the substrate carrying the stack has not undergone heat treatment at high temperature.

[0032] The stacks according to the invention can be used indifferently: - as deposited, that is to say without having been subjected to any heat treatment at high temperature, in this case neither the substrate coated with the stack, nor the stack alone, has undergone heat treatment at high temperature, - treated by laser radiation, in this case, only the stack undergoes heat treatment at high temperature, - treated by annealing or quenching, in this case the substrate and the stack undergo heat treatment at high temperature.

[0033] The present invention therefore relates to the non-heat-treated coated substrate. The stack may not have undergone heat treatment at a temperature above 500°C, preferably 300°C.

[0034] The present invention also relates to the substrate coated with the heat-treated stack. The heat treatments are chosen from: - annealing, for example rapid annealing, - quenching and / or bending.

[0035] The substrate coated with the stack may have undergone a high temperature heat treatment. The stack and the substrate may have been subjected to a high temperature heat treatment such as quenching, annealing or bending.

[0036] It is also possible to heat treat only the stack. In this case, only the stack may have undergone heat treatment.

[0037] In both cases, the stack may have undergone heat treatment at a temperature above 300°C, preferably 500°C. The heat treatment temperature (at the stack) is above 300°C, preferably above 400°C, and better still above 500°C.

[0038] According to the invention, it is also possible to carry out a rapid thermal annealing process such as laser or flash lamp annealing. Rapid thermal annealing is for example described in applications WO2008 / 096089 and WO2015 / 185848. In these cases, only the stack is subjected to a heat treatment. During this type of treatment, each point of the stack is brought to a temperature of at least 300°C while maintaining a temperature less than or equal to 150°C at any point on the face of the substrate opposite that on which the stack is located. This process has the advantage of heating only the stack, without significant heating of the entire substrate.

[0039] In the case of laser treatment, the coated materials can be treated using a laser line formed from laser sources of the InGaAs laser diode or Yb:YAG disk laser type. These continuous sources emit at a wavelength between 900 and 1100 nm. The laser line has a length of the order of 3.3 m, equal to the width 1 of the substrate, and an average half-maximum width FWHM between 45 and 100 pm.

[0040] The materials are arranged on a roller conveyor so as to travel in a direction X, parallel to its length. The laser line is fixed and positioned above the coated surface of the substrate with its longitudinal direction Y extending perpendicular to the direction X of travel of the substrate, i.e. along the width of the substrate, extending over this entire width.

[0041] The position of the focal plane of the laser line is adjusted to be within the thickness of the functional coating when the substrate is positioned on the conveyor. The surface power of the laser line at the focal plane is less than 100kW / cm2. The substrate was passed under the laser line at a speed of approximately 8 m / min.

[0042] The stack may therefore have been subjected to rapid thermal annealing in which each point of the stack is brought to a temperature of at least 300°C while maintaining a temperature less than or equal to 150°C at any point on the face of the substrate opposite that on which the stack is located.

[0043] It is also possible to combine heat treatments. For example, it is possible to carry out rapid thermal annealing followed by quenching.

[0044] The stack and the substrate may have been subjected to a heat treatment at an elevated temperature above 500°C such as tempering, annealing or bending. The coated substrate of the stack may be a curved or tempered glass.

[0045] The stack is deposited by magnetic field-assisted sputtering (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by magnetic field-assisted sputtering.

[0046] In the absence of a specific stipulation, the expressions "above" and "below" do not necessarily mean that two layers and / or coatings are arranged in contact with each other. 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) layer(s) interposed between these two layers (or layer and coating).

[0047] Unless otherwise stated, the thicknesses referred to in this document are physical thicknesses and the layers are thin layers. A thin layer is understood to mean a layer having a thickness between 0.1 nm and 100 micrometers.

[0048] In the present description, unless otherwise indicated, the expression "based on", used to qualify a material or a layer as to what it contains, means that the mass fraction of the constituent that it comprises is at least 50%, in particular at least 70%, preferably at least 90%.

[0049] The stack may comprise a single silver-based functional metal layer.

[0050] The silver-based metal functional layers comprise at least 95.0%, preferably at least 96.5% and more preferably at least 98.0% by mass of silver relative to the mass of the functional layer. Preferably, a silver-based metal functional layer comprises less than 1.0% by mass of metals other than silver relative to the mass of the silver-based metal functional layer.

[0051] The silver-based metallic functional layers have a thickness: - greater than 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm or 16 nm, and / or - less than 25 nm, 22 nm, 20 nm, 18 nm.

[0052] Dielectric coatings comprise dielectric layers. By "dielectric layer" within the meaning of the present invention, it is to be understood that from the point of view of its nature, the material is "non-metallic", i.e. is not a metal. In the context of the invention, this term designates a material having an n / k ratio over the entire visible wavelength range (from 380 nm to 780 nm) equal to or greater than 5. n designates the real refractive index of the material at a given wavelength and k represents the imaginary part of the refractive index at a given wavelength; the n / k ratio being calculated at a given wavelength identical for n and for k.

[0053] The thickness of a dielectric coating corresponds to the sum of the thicknesses of the layers constituting it. Preferably, the dielectric coatings have a thickness greater than 10 nm, greater than 15 nm, between 15 and 200 nm, between 15 and 100 nm or between 15 and 70 nm.

[0054] The dielectric layers of the coatings have the following characteristics alone or in combination: - they are deposited by magnetic field-assisted sputtering, - they have a thickness greater than 2 nm, preferably between 4 and 200 nm.

[0055] Dielectric layers, in addition to their optical function, can have various other functions. For example, stabilizing layers, smoothing layers, and barrier layers can be mentioned.

[0056] The dielectric layers are conventionally chosen from oxide-based, nitride-based or oxynitride-based layers. The oxide-based layers of one or more elements essentially comprise oxygen and very little nitrogen. The oxide-based layers comprise, in particular, at least 90% by atomic percentage of oxygen relative to the oxygen and nitrogen in said layer. The nitride-based layers comprise essentially nitrogen and very little oxygen. The nitride-based layers comprise at least 90% by atomic percentage of nitrogen relative to the oxygen and nitrogen in said layer. The oxynitride-based layers comprise a mixture of oxygen and nitrogen. The silicon oxynitride-based layers comprise 10 to 90% (limits excluded) by atomic percentage of nitrogen relative to the oxygen and nitrogen in said layer. The amounts of oxygen and nitrogen in a layer are determined as atomic percentages relative to the total amounts of oxygen and nitrogen in the layer in question.

[0057] The dielectric layers are conventionally chosen from: - layers comprising silicon, aluminum and / or zirconium, optionally doped with at least one other element, - layers based on zinc and tin oxide, - layers based on titanium oxide, - layers based on zinc oxide.

[0058] The stack comprises at least one titanium oxide-based layer located above and in contact with a silver-based functional metal layer having a thickness greater than or equal to 3 nm. This means that the layer is a titanium oxide-based layer over this entire thickness. According to the invention, this titanium oxide-based layer is part of a dielectric coating located above the silver layer. This means that when determining the thickness of this dielectric coating, the thickness of this layer is taken into consideration.

[0059] The thick titanium oxide-based layer in contact with the silver contributes to obtaining the advantageous properties of the invention. This oxide layer is non-absorbent, especially when it is mainly deposited from a ceramic target in an oxidizing atmosphere.

[0060] The titanium oxide-based layer is advantageously deposited from a ceramic target, in particular under stoichiometric conditions, in a controlled atmosphere comprising oxygen. Preferably, a first thin thickness of titanium oxide-based layer is deposited in contact with the silver layer, from a ceramic target, in a non-oxidizing atmosphere. Then, a thicker thickness of titanium oxide-based layer is deposited from a ceramic target in an oxidizing atmosphere. The thick titanium oxide-based layer according to the invention is made up of these two thicknesses. The part of the titanium oxide-based layer in contact with the functional layer is less oxidized than the part furthest from the functional layer.

[0061] This multi-step deposition makes it possible to obtain mainly in the coating a layer of titanium oxide with a large quantity of oxygen, while protecting the silver-based functional layer from a first layer of weakly oxidized titanium oxide. The absorption of the stack before heat treatment is then greatly reduced.

[0062] The amount of oxygen in the first part of the titanium oxide-based layer must be relatively low so as not to degrade the silver-based functional layer. For this, a first layer deposited from a ceramic target can be used, in particular under stoichiometric conditions, in an atmosphere without oxygen or with very little oxygen. The thickness of the first part of the titanium oxide-based layer can be as thin as that of a standard blocking layer ( <lnm), tant que la couche fonctionnelle à base d’argent ne s’avère pas dégradée par l’oxygène présent pendant le dépôt de la partie suivante de la couche à base d’oxyde de titane, déposée avec plus d’oxygène que la première.

[0063] The titanium oxide-based layer has a thickness: - greater than 3 nm, greater than 4 nm, greater than or equal to 5 nm, greater than or equal to 8 nm, greater than or equal to 10 nm, greater than or equal to 12 nm and / or - less than or equal to 30 nm, less than or equal to 25 nm, less than or equal to 20 nm, less than or equal to 15 nm.

[0064] The titanium oxide-based layers comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 95.0%, at least 96.5% and better still at least 98.0% by mass of titanium relative to the mass of all the elements constituting the titanium oxide-based layer other than oxygen.

[0065] The titanium oxide-based layers may comprise or consist of elements other than titanium and oxygen. These elements may be chosen from silicon, chromium and zirconium. Preferably, the elements are chosen from zirconium.

[0066] Preferably, the titanium oxide-based layer comprises at most 35%, at most 20% or at most 10% by mass of elements other than titanium relative to the mass of all the elements constituting the titanium oxide-based layer other than oxygen.

[0067] The layers based on titanium oxide can be obtained: - by cathode sputtering, - from a titanium metal target or a ceramic target based on titanium oxide, preferably sub-stoichiometric.

[0068] When the titanium oxide-based layer is obtained from a metal target, the deposition atmosphere comprises significant proportions of oxygen.

[0069] The titanium oxide-based layers are preferably obtained from a titanium oxide ceramic target, preferably under stoichiometric oxygen, in an atmosphere comprising oxygen or without oxygen. The quantity of oxygen in the deposition atmosphere can be adapted according to the desired properties.

[0070] Preferably, the entire titanium oxide-based layer is deposited from a ceramic target, in particular under stoichiometric. The titanium oxide-based layer may be deposited from a ceramic target of TiOx under stoichiometric, where x is a number different from the stoichiometry of titanium oxide TiO2, i.e. different from 2 and preferably less than 2, in particular between 0.75 times and 0.99 times the normal stoichiometry of the oxide. TiOx may in particular be such that 1.5 < x < 1.98 or 1.5 < x < 1.7, or even 1.7 < x < 1.95.

[0071] The deposition atmosphere may comprise a mixture of noble gas (He, Ne, Xe, Ar, Kr) and oxygen. The noble gas is preferably argon. The maximum oxygen threshold may vary to a certain extent depending, for example: - on the nature of the TiOx target, in particular its oxygen substoichiometry or - on the power, - on the configuration of the cathode sputtering deposition chamber (geometry, locations of gas inlets, etc.)

[0072] The titanium oxide-based layer having a thickness greater than or equal to 3 nm is located below and in contact with a dielectric layer. The dielectric layer may be based on oxide, nitride or oxynitride of one or more elements chosen from silicon, zirconium, titanium, aluminum, tin and / or zinc. Preferably, this dielectric layer has a thickness greater than 5 nm, 8 nm, 10 nm or 15 nm.

[0073] The stack may comprise at least one layer comprising silicon. Preferably, the dielectric coating located above the silver-based functional layer may comprise a layer comprising silicon. Each dielectric coating may also comprise at least one layer comprising silicon.

[0074] The layers comprising silicon are extremely stable to heat treatments. For example, no migration of the elements constituting them is observed. Consequently, these elements are not likely to alter the silver layer. The layers comprising silicon therefore also contribute to the non-alteration of the silver layers and therefore to obtaining low emissivity after heat treatment.

[0075] The layers comprising silicon comprise at least 50% by mass of silicon relative to the mass of all the elements constituting the layer comprising silicon other than nitrogen and oxygen.

[0076] The layers comprising silicon may be chosen from oxide-based, nitride-based or oxynitride-based layers such as silicon oxide-based layers, silicon nitride-based layers and silicon oxynitride-based layers.

[0077] The silicon oxide-based layers comprise at least 90 atomic percent oxygen relative to the oxygen and nitrogen in the silicon oxide-based layer. The silicon nitride-based layers comprise at least 90 atomic percent nitrogen relative to the oxygen and nitrogen in the silicon nitride-based layer. The silicon oxynitride-based layers comprise 10 to 90 atomic percent nitrogen relative to the oxygen and nitrogen in the silicon oxide-based layer. Preferably, the silicon oxide-based layers are characterized by a refractive index at 550 nm of less than or equal to 1.55. Preferably, the silicon nitride-based layers are characterized by a refractive index at 550 nm of greater than or equal to 1.95.

[0078] The layers comprising silicon may comprise or consist of elements other than silicon, oxygen and nitrogen. These elements may be chosen from aluminum, boron, titanium, and zirconium. The layers comprising silicon may comprise at least 2%, at least 5% or at least 8% by mass of aluminum relative to the mass of all the elements constituting the layer comprising silicon other than oxygen and nitrogen.

[0079] The layers comprising aluminum may be chosen from oxide-based, nitride-based or oxynitride-based layers such as aluminum oxide-based layers such as Al2O3, aluminum nitride-based layers such as AlN and aluminum oxynitride-based layers such as AlOxNy.

[0080] The layers based on silicon nitride and zirconium SixZryNz are part of the layers comprising silicon, in particular layers based on silicon nitride.

[0081] The refractive index of the layers based on silicon nitride and zirconium increases with increasing proportions of zirconium in said layer.

[0082] The silicon nitride-based layers may comprise aluminum and / or zirconium. Such layers may comprise, in atomic proportion relative to the atomic proportion of Si, Zr and Al: - 50 to 98%, 60 to 90%, 60 to 70% atomic silicon, - 0 to 10%, 2 to 10% atomic aluminum, -0 to 30%, 10 to 40% or 5 to 30% atomic zirconium.

[0083] Preferably, the dielectric coating located above the silver layer comprises a layer comprising silicon. These layers comprising silicon have, in increasing order of preference, a thickness: - less than or equal to 40 nm and / or - greater than or equal to 5 nm, greater than or equal to 10 nm or greater than or equal to 15 nm.

[0084] Preferably, at least one dielectric coating comprises a layer comprising silicon selected from silicon nitride-based layers. Preferably, the dielectric coating located above the silver-based functional layer comprises a layer comprising silicon selected from silicon nitride-based layers. Each dielectric coating may comprise a layer comprising silicon selected from silicon nitride-based layers.

[0085] Preferably, the sum of the thicknesses of all the layers comprising silicon in the dielectric coating located above the first silver-based functional metal layer may be greater than 35%, greater than 50%, of the total thickness of the dielectric coating.

[0086] Preferably, the sum of the thicknesses of all layers comprising silicon nitride-based silicon in each dielectric coating located above the first silver-based functional metal layer may be greater than 35%, greater than 50%, of the total thickness of the dielectric coating.

[0087] The stack may comprise a layer based on zinc and tin oxide comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide. The zinc and tin oxide based layer comprises in mass of tin relative to the total mass of zinc and tin: - at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 45%, at least 50% or at least 55%, - at most 90%, at most 80%, at most 70%, at most 65% or at most 60% by mass of zinc. The zinc tin oxide layer located in the dielectric coating above the silver functional layer has a thickness: - greater than 5 nm, greater than 10 nm, greater than 15 nm, greater than 18 nm, - less than 40 nm, less than 30 nm, less than 25 nm.

[0088] The dielectric coating located above the silver layer may comprise: - the titanium oxide-based layer, - a layer comprising silicon, preferably a layer based on silicon nitride or a layer based on silicon nitride and zirconium or a combination of these two layers.

[0089] The dielectric coating located above the silver layer may comprise: - the titanium oxide-based layer, - a layer based on zinc and tin oxide comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide, - a layer comprising silicon, located above and in contact with the layer based on zinc and tin oxide, preferably a layer based on silicon nitride or a layer based on silicon and zirconium nitride or a combination of these two layers.

[0090] The dielectric coating located below the silver layer may comprise a so-called stabilizing layer which reinforces the adhesion of the functional layer to the layers which surround it. The stabilizing layers are preferably layers based on zinc oxide optionally doped, for example, with aluminum. The zinc oxide is crystallized. The zinc oxide-based layer comprises, in increasing order of preference, at least 90.0%, at least 92%, at least 95%, at least 98.0% by mass of zinc relative to the mass of elements other than oxygen in the zinc oxide-based layer.

[0091] According to this embodiment, the dielectric coating located below the functional layer may further comprise a zinc oxide-based layer located directly in contact with it. Indeed, it is advantageous to have a stabilizing layer, below and in contact with a functional layer, because it facilitates the adhesion and crystallization of the silver-based functional layer and increases its quality and stability. The metallic functional layer is deposited above and in contact with a zinc oxide-based layer. The zinc oxide-based layer may be deposited from a ceramic target, with or without oxygen, or from a metallic target. The zinc oxide layers have a thickness: - at least 1.0 nm, at least 2.0 nm, at least 3.0 nm, at least 4.0 nm, at least 5.0 nm, at least 6.0 nm and / or - not more than 25 nm, not more than 10 nm, not more than 8.0 nm.

[0092] The dielectric coating located below the silver layer may also comprise a zinc and tin oxide-based layer comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located below and in contact with the zinc oxide-based layer.

[0093] The stack may therefore comprise one or more layers based on zinc and tin oxide comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide. The layers based on zinc and tin oxide preferably comprise by mass of tin relative to the total mass of zinc and tin: - at least 10%, at least 15%, at least 20%, at least 30%, at least 40%, at least 45%, at least 50% or at least 55%, - not more than 90%, not more than 80%, not more than 70%, not more than 65% or not more than 60% by mass of zinc. The zinc and tin oxide-based layers have a thickness: - greater than 5 nm, and / or - less than 40 nm, less than 30 nm, less than 25 nm.

[0094] Preferably, the dielectric coating located below the silver layer comprises a high refractive index layer. The presence of high index layers above and below the silver-based functional layer contributes to obtaining high light transmission.

[0095] Among the dielectric layers, a distinction is made, depending on their refractive index at 550 nm, between low refractive index layers, intermediate refractive index layers and high refractive index layers. The low refractive index layers have a refractive index of less than 1.70. The intermediate refractive index layers have a refractive index of between 1.70 and 2.2. The high refractive index layers have a refractive index of greater than 2.2.

[0096] The high refractive index layers can be chosen from: - layers based on titanium oxide (n550 = 2.4), - layers based on mixed titanium oxide and another component chosen from the group consisting of Zn, Zr and Sn, - layers based on a layer of zirconium nitride (n 550 = 2.55), - layers based on silicon and zirconium nitride (n550 nm = 2.20 - 2.40), - layers based on a layer of zirconium oxide, - layers based on manganese oxide MnO (n550 = 2.16), - layers based on a layer of tungsten oxide (n550 = 2.15), - layers based on a layer of niobium oxide (n550 = 2.30), - layers based on a layer of bismuth oxide (n 550 = 2.60). Preferably, the high refractive index layer is chosen from titanium oxide-based layers and silicon and zirconium nitride-based layers.

[0097] Preferably, the stack does not comprise a metal or titanium oxide-based blocking layer below and in contact with the silver-based functional metal layer. In this case, the silver-based functional metal layer is located above and in contact with a dielectric layer of the dielectric coating. Preferably, this dielectric layer is a stabilizing layer.

[0098] The dielectric coating located below the functional layer may comprise a layer sequence, defined starting from the substrate, chosen from: - layer based on titanium oxide (high index layer) / / layer based on zinc oxide, - silicon nitride-based layer / / zinc oxide-based layer, - layer based on silicon and zirconium nitride (high index layer) / / layer based on zinc oxide, - silicon nitride-based layer / / silicon nitride and zirconium layer (high index layer) / / zinc oxide-based layer, - silicon nitride-based layer / / titanium oxide-based layer (high index layer) / / zinc oxide-based layer, - layer based on silicon nitride and zirconium (high index layer) / / layer based on titanium oxide (high index layer) / / layer based on zinc oxide, - layer based on silicon nitride / / layer based on silicon nitride and zirconium / / layer based on titanium oxide (high index layer) / / layer based on zinc oxide, - titanium oxide-based layer (high index layer) / / zinc and tin oxide-based layer / / zinc oxide-based layer, - silicon nitride-based layer / / zinc and tin oxide-based layer / / zinc oxide-based layer, - layer based on silicon and zirconium nitride (high index layer) / / layer based on zinc and tin oxide / / layer based on zinc oxide, - silicon nitride-based layer / / silicon nitride and zirconium layer (high index layer) / / zinc oxide and tin oxide-based layer / / zinc oxide-based layer, - silicon nitride-based layer / / titanium oxide-based layer (high index layer) / / zinc and tin oxide-based layer / / zinc oxide-based layer? - layer based on silicon and zirconium nitride / / layer based on titanium oxide (high index layer) / / layer based on zinc and tin oxide / / layer based on zinc oxide, - silicon nitride-based layer / / silicon nitride and zirconium layer / / titanium oxide-based layer (high index layer) / / zinc oxide and tin layer / / zinc oxide-based layer.

[0099] When the stack comprises a layer of silicon nitride and a layer of silicon and zirconium nitride, these layers are different, that is to say that they are not composed of the same elements in the same proportions.

[0100] The dielectric coating located above the silver layer may comprise a sequence of layers, defined starting from the substrate, chosen from: - the titanium oxide-based layer / / silicon nitride-based layer, - the titanium oxide-based layer / / silicon nitride and zirconium-based layer, - the titanium oxide-based layer / / silicon and zirconium nitride-based layer / / silicon nitride-based layer, - the titanium oxide-based layer / / zinc and tin oxide-based layer / / silicon nitride-based layer, - the titanium oxide-based layer / / zinc and tin oxide-based layer / / silicon oxide-based layer, - the layer based on titanium oxide / / layer based on zinc and tin oxide / / layer based on silicon and zirconium nitride, - the titanium oxide-based layer / / zinc and tin oxide-based layer / / silicon and zirconium nitride-based layer / / silicon nitride-based layer, - the titanium oxide-based layer / / zinc and tin oxide-based layer / / silicon nitride-based layer / / zinc and tin oxide-based layer, - the titanium oxide-based layer / / silicon nitride-based layer / / silicon oxide-based layer, - the layer based on titanium oxide / / layer based on zinc and tin oxide / / layer based on silicon nitride / / layer based on silicon oxide, - the layer based on titanium oxide / / layer based on silicon and zirconium nitride / / layer based on silicon nitride / / layer based on silicon oxide.

[0101] The stack of thin layers may optionally comprise a protective layer. The protective layer is preferably the last layer of the stack, i.e. the layer furthest from the coated substrate of the stack (before heat treatment). These layers generally have a thickness of between 0.5 and 10 nm, between 1 and 5 nm, between 1 and 3 nm or between 1 and 2.5 nm. This protective layer may be chosen from a layer of titanium, zirconium, hafnium, silicon, zinc and / or tin, this or these metals being in metallic, oxidized or nitrided form. According to one embodiment, the protective layer is based on zirconium oxide and / or titanium oxide, preferably based on zirconium oxide, titanium oxide or titanium and zirconium oxide. When determining the thickness of a dielectric coating, the thickness of the protective layer is taken into account.

[0102] The transparent substrates according to the invention are preferably made of a rigid mineral material, such as glass, or organic polymer-based (or polymer).

[0103] The transparent organic substrates according to the invention may also be made of polymer, rigid or flexible. Examples of polymers suitable according to the invention include, in particular: - polyethylene, - polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN); - polyacrylates such as polymethyl methacrylate (PMMA); - polycarbonates; - polyurethanes; - polyamides; - polyimides; - fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP); - photocrosslinkable and / or photopolymerizable resins, such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate resins and - polythiourethanes.

[0104] The substrate is preferably a sheet of glass or glass-ceramic.

[0105] The substrate is preferably transparent, colorless (in which case it is a clear glass or extra-clear) or colored, for example blue, gray or bronze. The glass is preferably of the soda-lime-silica type, but it can also be of borosilicate or alumino-borosilicate type glass. According to a preferred embodiment, the substrate is made of glass, in particular soda-lime-silica or of polymeric organic material.

[0106] 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 may be flat or curved, or even flexible.

[0107] The invention relates to glazing in the form of multiple glazing, in particular double glazing or triple glazing. Double glazing has 4 faces, face 1 is on the outside of the building and therefore constitutes the outer wall of the glazing, face 4 is on the inside of the building and therefore constitutes the inner wall of the glazing, faces 2 and 3 being on the inside of the double glazing. The stack according to the invention is on face 2. Triple glazing has 6 faces, face 1 is on the outside of the building and therefore constitutes the outer wall of the glazing, face 6 is on the inside of the building and therefore constitutes the inner wall of the glazing, faces 2 and 3 and 4 and 5 being on the inside of the double glazing. The stack according to the invention can be on face 2 and / or face 5. These windows can be mounted on a building or a vehicle.

[0108] The following examples illustrate the invention. Examples

[0109] I. Preparation of substrates: Stacking, deposition conditions Thin film stacks defined below are deposited on clear soda-lime glass substrates with a thickness of 4 mm. In the examples of the invention: - the functional layers are silver (Ag) layers, - the dielectric layers are based on aluminum-doped silicon nitride (Si3N4:Al), based on aluminum-doped silicon and zirconium nitride (SiZrN:Al), based on zinc and tin oxide, based on zinc oxide (ZnO). Titanium oxide TiOx layers are deposited from a TiOx ceramic target with or without oxygen in the deposition atmosphere. The deposition conditions of the layers, which were deposited by sputtering (so-called “magnetron cathode sputtering”), are summarized in Table 1.

[0110] [Tables 1] Materials Target composition Pressure Power Gas sccm Ar o2 n2 Ar / O2(90 / 1 0) ZnO ZnO:Al 2% wt ceramic 2 pbar 1300 W 40 2 - - TiOx_0 % TiOx ceramic 2 pbar 2000 W 30 0 - - TiOx_10 % TiOx ceramic 2 pbar 2000 W 30 03 - SnZnO Sn:Zn 60 / 40 %wt metallic 2 pbar 1000 W 7 44 Ag Ag metallic 8 pbar 210 W 80 - - - Si3N4 Si:Al 8%wt metallic 2 pbar 2000 W 18 - 24 - SiZrN Si:Zr 27% wt metallic 2 pbar 1000 W 15 - 15 -

[0111] %wt: % by weight; at%: atomic.

[0112] 1.1. Glazing with non-heat-treated stack

[0113] The following stacks were developed to be used as deposited, i.e., without having been subjected to any high temperature heat treatment. Neither the substrate coated with the stack, nor the stack alone, underwent any high temperature heat treatment. For this first series of examples, we are looking to obtain a light transmission of 78.5% and a resistance per square of 2.3 QO The table below lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that makes up the stacks according to their positions relative to the substrate carrying the stack.

[0114] [T ables 2] Materials Layers Ref.l Lia I.lb Lie Rev. dielectric TiOx 1 1 1 1 Si3N4 25 22 20 14 SiZrN - - 8 - SnZnO - - - 10 TiOx 10% 02 13 19 13 18 ZnO 5 - - - TiOx : 0% 02 1 1 1 1 Functional layer Ag 17.4 16.2 16.2 16.2 Rev. dielectric ZnO 5 5 5 5 TiOx 22 22 15 22 SiZrN - - 8 - Substrate (mm) glass 4 4 4 4

[0115] In all the tables setting out the optical characteristics and performances, the characteristics were measured on a double glazing having a 4 / 16 / 4 structure: 4 mm glass / 16 mm interlayer space filled with 90% argon and 10% air / 4 mm glass, the stack being positioned on face 2 (face 1 of the glazing being the outermost face of the glazing, as usual). The square resistance Rsq, corresponding to the resistance referred to the surface, is measured by induction with a Nagy SMR-12. The selectivity “s” corresponds to the Tl / g ratio. Glazing units each comprising the stacks described above were tested.

[0116] [Tables3] Glazing gs TL a*T b*T RLe xt a* b* RLi nt a* b* Rsq Ug V.Ref .1 49.6 1.53 76.1 -3.9 3.8 16.0 3.5 -6.8 14.8 5.4 -8 .5 2.30 1.11 VI. 52.8 1.49 78.5 -3.0 3.5 14.0 1.5 -7.5 13.1 3.3 -8.4 2.30 1.11 VI. 1b 53.0 1.48 78.5 -3.0 3.5 14.1 1.5 -7.6 13.2 3.2 -8 .4 2.30 1.11 VI. 52.8 1.49 78.5 -3.1 3.5 14.0 1.9 -7.5 13.1 3.6 -8.3 2.30 1.11

[0117] In the case of the reference stack not comprising a thick titanium oxide-based layer, a light transmission of 78.5% cannot be obtained when imposing the constraint on the resistivity of at least 2.3 QO. To achieve this value of 2.3 Q / D, a 17 nm layer of silver is necessary. However, it is not possible to achieve a light transmission greater than 76% with such thicknesses.

[0118] The stacks Lia, I.lb and Lie comprise titanium oxide-based coatings (oxygen gradient coating) comprising at least two layers of titanium oxide comprising different proportions of oxygen. The first layer is deposited in contact with the silver layer and in an oxygen-free atmosphere with a thickness of 1 nanometer. This layer is therefore under-oxidized. The second layer based on titanium oxide is deposited in an atmosphere with 10% oxygen in volume flow and has a thickness of at least 5 nm. This layer is therefore more oxidized than the first.

[0119] In the case of the glazings of the invention VI. la, VI. 1b and VI. le, comprising on face 2, a stack comprising a thick titanium oxide-based layer, a light transmission of 78.5% can be achieved and resistance values ​​per square of 2.3 QO. The gain in resistivity provided by the use of this thick titanium oxide-based layer makes it possible to obtain the value of 2.3 Q / D, with a thinner layer of silver. These thinner thicknesses of silver make it possible to obtain high light transmission values, in particular 78.5%.

[0120] In conclusion, in the case of stacking used “as deposited”, the invention makes it possible to obtain high light transmission while maintaining resistivity values ​​sufficiently low to achieve low emissivity and thus low Ug values. We also note the obtaining of more neutral colors in external reflection, that is to say less red (value of a* closer to 0). It is noted that the substitution of a part of the TiOx layer by silicon and zirconium nitride in each dielectric coating leads to similar results (comparison VI.1a and VI.1b).

[0121] Finally, the use of a layer of zinc and tin oxide in contact with the thick layer based on titanium oxide (VI. le) also leads to similar results in terms of solar factor, light transmission and resistivity. This layer has however to reduce residual absorption that may result from incomplete oxidation of TiOx. In addition, the introduction of this zinc and tin oxide-based layer improves mechanical resistance. This is reflected in particular by satisfactory results in the following tests: - Erichsen Scratch Test (EST), - Erichsen Brush Test (EBT) before and after quenching to 1000 cycles.

[0122] The Erichsen Brush Test (EBT) consists of subjecting different coated substrates to a certain number of cycles (1000) during which the water-covered stack is rubbed using a brush. A substrate is considered to pass the test if no marks are visible to the naked eye. The pre-tempering test gives a good indication of the glazing's ability to be scratched during a washing operation.

[0123] The Erichsen scratch test (EST) consists of applying a force to the sample, in Newtons, using a point (Van Laar point, steel ball). Depending on the scratch resistance of the stack, different types of scratches can be obtained: continuous, discontinuous, wide, narrow, etc.

[0124] 1.2. Glazing with stack treated by laser radiation

[0125] The following stacks were developed for use after being subjected to laser heat treatment. In this case, only the stack undergoes high temperature heat treatment. The coated substrates were treated using a laser line formed from a disk laser. The following conditions were used: - disk laser source: Yb:YAG, - wavelength: 1030nm, - width: 60pm, - power density: 70kW / cm2.

[0126] The table below lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating which constitutes the stacks according to their positions with respect to the substrate carrying the stack.

[0127] [Tables4] Materials Layers Ref.2 I.2a I.2b I.2c Rev. dielectric TiOx 1 1 1 1 Si3N4 18 22 19 13 SiZrN - - 13 - SnZnO - - - 11 TiOx X% 17 18 8 17 ZnO 5 - - - TiOx: 0% 02 1 1 1 1 Functional layer Ag 15.7 16.1 16.1 16.1 Dielectric rev. ZnO 5 5 5 5 TiOx 21 21 15 21 SiZrN - - 6 - Substrate (mm) glass 4 4 4 4

[0128] For this example series, we are seeking to obtain a light transmission of 78.5% and the lowest possible resistance per square.

[0129] [Tables5] Glazing gs TL a*T b*T RLe xt a* b* RLi nt a* b* Rsq Ug VRef.2 53.2 1.477 78.5 -2.9 3.5 14.4 1.4 -7.3 13.4 3.0 -8 .1 2.02 1.09 VI.2a 52.9 1.484 78.5 -2.9 3.5 14.4 1.4 -7.1 13.5 3.0 -7.9 1.76 1.08 VI.2b 53.0 1.482 78.5 -2.9 3.5 14.5 1.5 -7.2 13.5 3.0 -7.9 1.76 1.08 VI. 2c 52.9 1.483 78.5 -2.9 3.5 14.5 1.4 -6.9 13.5 3.0 -7 .7 1.77 1.08

[0130] For a given light transmission value, the glazings according to the invention have the lowest values ​​of solar factor (-0.3%) and resistance per square (1.76 vs. 2.02 Q / D). In all cases, the solution of the invention makes it easier to obtain the glazing specifications. Substitution of a portion of the thickness of the TiOx layer by silicon and zirconium nitride in each dielectric coating leads to similar results (comparison VI.2a and VI.2b). Finally, the use of a layer of zinc and tin oxide in contact with the thick layer based on titanium oxide VI.2c) also leads to similar results in terms of solar factor, light transmission and resistivity. This layer, however, aims to reduce residual absorption which may result from incomplete oxidation of the TiOx following laser treatment.

[0131] I. 3 . Glazing with stack treated by toughening type heat treatment The following stacks have been developed for use after being subjected to toughening type heat treatment. The heat treatments are carried out in a NABER furnace at a temperature of 650°C for 10 minutes.

[0132] [Tableauxô] Materials Layers Ref.3 I.3a I.3b I.3c Dielectric rev. TiOx 1 1 1 1 Si3N4 19 27 24 19 SiZrN 17 - 11 SnZnO - - - 10 TiOx 10% - 15 8 15 ZnO 5 - - - TiOx : 0% O 2 - 1 1 1 NiCr 0.7 Functional layer Ag 15.1 15.7 15.7 15.7 Dielectric rev. ZnO SiZrN 5 22 5 22 5 22 5 22 Substrate (mm) glass 4 4 4 4

[0133] For this example series, we are seeking to obtain a light transmission of 78.5% and the lowest possible resistance per square 2.3 QO

[0134] [Tables?] gs TL a*T b*T RL 1 a* b* RL2 a* b* Rsq Ug V Ref .3 54.1 1.45 78.5 -2.9 3.5 14.1 1.6 -7.8 13.2 3.0 -7 .9 2.13 1.09 VI.3 53.6 1.46 78.5 -2.8 3.5 14.5 1.6 -7.4 13.5 3.0 -7.8 1.82 1.10

[0135] The glazing of the invention VI.3a has a lower solar factor (-0.5%) and a lower resistance per square (1.82 vs. 2.13Q / D) for the same level of light transmission. Equivalent results were obtained with stacks 3b and 3c comprising respectively: - a high index layer based on silicon and zirconium nitride in the upper dielectric coating (3b), - a layer based on zinc and tin oxide in the upper dielectric coating (3c). For these examples according to the invention undergoing a quenching type treatment, we observe: - a decrease in resistivity, - improved scratch resistance with: - less visible scratches, - if present, an absence of hot corrosion of existing scratches.

[0136] The examples concerning the embodiment in which the TiOx layer is in contact with a layer of zinc and tin oxide show that the combination of the invention allows:

[0137] - not to increase absorption after heat treatment, - to obtain a gain in square resistance, - to obtain good corrosion resistance and the absence of blurring, - to obtain good resistance to the brush test after heat treatment. Thanks to the solution of the invention combining a thin under-oxidized layer and a thicker oxidized layer, absorption is limited and therefore contributes to obtaining high light transmission.

Claims

Claims

1. Multiple glazing comprising at least two substrates separated by at least one interposed gas layer, the substrate constituting the outer wall of the glazing comprises on its inward-facing face a stack of layers comprising a silver-based functional metal layer and at least two dielectric coatings, each dielectric coating comprising at least one dielectric layer, so that the functional metal layer is arranged between two dielectric coatings, characterized in that the dielectric coating located above the functional layer comprises: - a titanium oxide-based layer located above and in contact with the silver-based functional metal layer having a thickness greater than or equal to 5 nm and less than or equal to 30 nm, and - at least one layer comprising silicon and / or aluminum, the glazing has a light transmission greater than 70%.

2. Glazing according to the preceding claim, characterized in that the titanium oxide-based layer is deposited from a ceramic target, in particular under stoichiometric.

3. Glazing according to any one of the preceding claims, characterized in that the titanium oxide-based layer has a thickness of at least 10 nm.

4. Glazing according to any one of the preceding claims, characterized in that the dielectric coating located above the functional layer comprises a layer comprising silicon chosen from silicon nitride layers.

5. Glazing according to any one of the preceding claims, characterized in that the layer comprising silicon and / or aluminum has a thickness greater than 5 nm.

6. 6. Glazing according to any one of the preceding claims, characterized in that the dielectric coating located above the functional layer further comprises a layer based on zinc and tin oxide comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide.

7. Glazing according to the preceding claim, characterized in that the layer based on zinc and tin oxide has a thickness: - greater than 5 nm, - less than 40 nm.

8. Glazing according to any one of the preceding claims, characterized in that the dielectric coating located below the functional layer comprises a zinc oxide-based layer located in contact with the functional layer.

9. Glazing according to any one of the preceding claims, characterized in that the dielectric coating located below the functional layer comprises a layer with a refractive index at 550 greater than 2.

20.

10. Glazing according to the preceding claim, characterized in that the layer with a refractive index greater than 2.20 is chosen from layers based on titanium oxide and layers based on silicon and zirconium nitride.

11. Glazing according to claim 9 or 10 characterized in that the thickness of all the layers with a refractive index greater than 2.20 in the dielectric coating located below the functional layer is greater than 10 nm.

12. Glazing according to any one of the preceding claims, characterized in that it has a light transmission greater than 75%, greater than 76% or greater than 78%.

13. Glazing according to any one of the preceding claims, characterized in that it has a Ug value of less than 1.15 W / m2.K, less than 1.10 W / m2.K or less than 1.00 W / m2.K.

14. Glazing according to any one of the preceding claims, characterized in that the stack comprises a single functional metallic layer based on silver.

15. 15. Glazing according to any one of the preceding claims, characterized in that the stack has been subjected to rapid thermal annealing.

16. 16. Glazing according to any one of the preceding claims, characterized in that the stack and the substrate have been subjected to a heat treatment at a high temperature above 500°C such as tempering, annealing or bending.