SOLAR CONTROL GLAZING COMPRISING A TITANIUM NITRIDE LAYER

Abstract

A glass article having anti-solar properties comprising at least one glass substrate provided with a stack of layers where the stack successively comprises from the substrate: - a first module M1 consisting of a layer based on a dielectric material with a thickness e1 or by an assembly of layers based on materials, - a TN1 layer comprising titanium nitride and preferably titanium nitride based with a thickness between 2 nanometers and 80 nanometers, - a second module M2 consisting of a layer based on a dielectric material with a thickness e2 or of an assembly of layers based on dielectric materials with a cumulative thickness e2, - an intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements deposited between the TN1 layer and the first module M1 and / or between the TN1 layer and the second module M2, the intermediate layers having a thickness between 0.2 nm and 6 nm.

Description

SOLAR CONTROL GLAZING UNIT COMPRISING A TITANIUM NITRIDE LAYER FIELD OF INVENTION The invention relates to so-called solar control glazing units, which are provided with stacks of functional thin films. These films act on solar and / or thermal radiation essentially by reflecting and / or absorbing near-infrared (solar) or far-infrared (thermal) radiation. The invention is primarily intended for use in the building industry as a solar control glazing unit. Within the scope of the invention, this glazing unit can also be used in automotive glazing units, such as side windows, roofs, and rear windows. BACKGROUND OF THE INVENTION In the context of the present invention, the term “glazing unit” means any glass product composed of one or more glass substrates, in particular single glazing units, double glazing units, triple glazing units, etc. In the context of this application, the term “functional” or “active” layer refers to the layers of the stack that provide the thermal insulation properties. Most often, the stacks of thin layers used in the glazing unit significantly enhance its insulation properties, primarily due to the intrinsic properties of the active layers. These active layers, when positioned opposite the other layers, act upon the flow of thermal infrared radiation passing through the glazing unit. They are generally made of dielectric material and typically serve the primary function of providing chemical or mechanical protection to the functional layers. The term “dielectric material” means a material whose solid form, free from impurities or dopants, has a high resistivity, specifically a resistivity greater than 10¹⁰ ohm-meters (Ωm) at room temperature 26.85°C (300 K). Glazing units provided with stacks of thin layers that act on incident IR radiation, either substantially by absorption of the radiation by the functional layers or substantially by reflection from these layers. These are called solar control glazing units. They are sold and used primarily in: - whether primarily to provide protection for a dwelling or passenger compartment (vehicle) against solar radiation and to prevent overheating, such glazing units are qualified in the art as anti-solar glazing units; - or primarily to thermally insulate a home and prevent heat loss, then these glazing units are classified as insulating glazing units. Therefore, in the context of the present invention, the expression “anti-solar” shall be understood to mean the ability of a glazing unit to limit the flow of energy and in particular solar infrared radiation (SIR) that passes through it from the outside to the inside of the dwelling or passenger compartment. The term “thermally insulated” shall be understood to mean a glazing unit equipped with at least one functional layer that reduces energy loss through the unit. This layer has reflective properties that allow it to reflect thermal IR radiation between 5 and 50 microns. The functional layers used for this purpose have a high IR reflection coefficient and are referred to as low-emissivity (or low-e) coatings. In certain countries, standards require that glazing units have both anti-solar properties and be thermally insulating for glazing units in buildings. The term “low emissivity” shall be understood to mean a glazing unit provided with at least one functional layer giving it a normal emissivity εη (or total emissivity at normal incidence) of less than 50%, preferably less than 45% or even less than 40%; emissivity is defined by the equation: £n = 1 Rn, where Rn is the normal reflection factor (according to Annex A of the international standard ISO 10292 (1994) of the glazing unit. The concept of a low-e glazing unit is described in the Techniques De l'lngénieur reference article: “Vitrages á isolation thermique renforcée”, C3635 (1999). In general, all the energy characteristics presented in this description were obtained in accordance with the principles and methods described in the international standard ISO 10292 (1994), related to the determination of the energy insulation characteristics of glazing units used in glass for the building industry. These coatings are conventionally deposited using CVD-type deposition techniques for the simplest cases, or more frequently nowadays using vacuum sputtering deposition techniques, often referred to in the field as magnetron sputtering techniques, particularly when the coating is made of a complex stack of successive layers whose thicknesses do not exceed a few nanometers or a few tens of nanometers. More frequently, stacks made of thin films have solar control properties, primarily due to the intrinsic properties of one or more active layers, referred to as functional layers in this description. Thus, an “active” or “functional” layer is understood to be one that significantly affects the flow of solar radiation passing through the glazing unit. In a known way, such an active layer can operate either primarily by reflecting incident infrared radiation or primarily by absorbing infrared radiation. More often, these anti-solar layers work partly by reflection and partly by absorption, as explained earlier. In particular, the most efficient stacks currently on the market include at least one functional metallic layer made of silver that works substantially by reflecting a significant portion of the incident IR (infrared) radiation. The normal emissivity of the same does not exceed a small percentage. However, these stacks are mainly used as low-emissivity (or low-e) glazing units for the thermal insulation of buildings. However, these layers are sensitive to moisture and are therefore used exclusively in double-glazed units on face 2 or 3 of the unit to protect it from moisture. The stacks according to the invention do not comprise such silver layers or even gold or platinum layers, or only in very imperceptible quantities, particularly as unavoidable impurities. As described, for example, in WO01 / 21540, other metallic coatings with an anti-solar function have also been mentioned in the field. These include functional layers of Nb, Ta, or W, or nitrides of these metals. In such coatings, solar radiation is primarily absorbed non-selectively by the functional layers; that is, IR radiation (i.e., with a wavelength between approximately 780 nm and 2500 nm) and visible radiation (with a wavelength between approximately 380 and 780 nm) are absorbed / reflected indiscriminately. In such glazing units, the normal emissivity values ​​εη are generally higher. Lower emissivity values ​​can only be obtained when the functional layer is relatively thick, in particular at least 20 nm thick per metallic niobium layer. Due to the non-selective absorption of this layer, the light transmission coefficients of such glazing units are necessarily very low, generally below 30%.Finally, in view of such characteristics, it does not seem possible to obtain from stacks of solar control glazing units that combine relatively low normal emissivities, usually less than 50% and in particular around 40% or even 35%, while maintaining a sufficiently high light transmission, i.e., usually above 30%. The characteristics of light, and in particular the light transmission characteristics, are measured according to the present invention in accordance with the principles described in NF EN410 (2011). In other publications, it has been proposed to use a titanium nitride (TiN)-based material as a functional layer that also has low emissivity properties and is less prone to corrosion than silver-based layers. Particular examples include DE102014114330, DE102013112990, and JPH05124839. The object of the present invention relates to solar control glazing units incorporating stacks comprising such layers and more specifically aims to improve the properties thereof, particularly the combined properties of high light transmission and low emissivity of such glazing units. Therefore, the objective of the present invention is to provide glazing units comprising a stack of layers that provide them with solar control properties as described above, while having a light transmission Tl normally greater than 30%, preferably greater than or equal to 40% or even greater than or equal to 50% and a normal emissivity εη low, i.e. less than 50%, or less than 45% or even less than 40%, the stack being durable over time, particularly when placed directly on an exposed face of the glazing unit on the inside or even outside of the building or passenger compartment without any specific precautions. Therefore, within the meaning of the present invention, the objective is that the glazing units have the highest Tε / εη ratio, i.e., the selectivity of which is improved; a glazing unit within the meaning of the present invention thus allows a significant portion of light in the visible range to pass through while reflecting a significant portion of the near IR radiation after heat treatment, such as tempering, bending, annealing, etc. Thus, the present invention makes it possible to obtain anti-solar glazing units capable of undergoing a heat treatment such as tempering, bending or more generally a heat treatment at temperatures above 500°C; in particular, the treatment makes it possible to improve the optical and energy properties of the units and in particular, their selectivity. BRIEF DESCRIPTION OF THE INVENTION A glazing unit according to the invention also makes it possible to select the radiation that passes through it by favoring the transmission of light waves, i.e., with a wavelength between approximately 380 and 780 nm, and by limiting the passage of infrared radiation with a wavelength greater than 780 nm. The invention makes it possible to maintain strong lighting in the passenger room or compartment protected by the glazing unit, while minimizing the amount of heat that enters there. According to another aspect, the glazing unit according to the present invention also has thermal insulation properties by virtue of the low emissivity properties of the layer used, which makes it possible to limit heat exchanges between the interior and exterior of the building. According to another advantage of the present invention, the glazing unit provided with the batteries according to the invention is simple to produce, compared to other known glazing units that have anti-solar properties, in particular those comprising a silver-based battery. Furthermore, they are resistant to moisture, scratches, and acid attacks. In particular, the glazing units according to the invention exhibit improved longevity in that their initial solar or thermal insulation properties vary only very slightly under the chemical attacks to which they are subjected during their intended use. In this way, they can be used advantageously as a single glazing unit (just one glass substrate), preferably the stack is oriented on the inner face of the building or passenger compartment to be protected. More particularly, the present invention relates to a glass article having anti-solar properties comprising at least one glass substrate provided with a stack of layers, where the stack comprises and preferably consists successively, from the surface of the substrate: - a first module Mi consisting of a layer based on a dielectric material with a thickness ei or of a set of layers based on dielectric materials with a cumulative thickness ei between 1 and 100 nm, - a TNi layer comprising titanium nitride, preferably titanium nitride-based, with a thickness between 2 and 80 nanometers, preferably between 4 and 70 nanometers, more preferably between 10 and 50 nm, - a second M2 module consisting of a layer based on a dielectric material with a thickness of 62 nm or of a set of layers based on dielectric materials with a cumulative thickness between 1 and 100 nm, - Optionally, a protective layer comprises or is preferably based on a titanium oxide, a zirconium oxide, a titanium and zirconium oxide. According to the invention, the stack also comprises an intermediate layer comprising and preferably consisting substantially of or simply consisting of at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, the intermediate layer being deposited between the TN1 layer and the first module Mi and / or between the TN1 layer and the second module M2, the intermediate layer having a thickness between 0.2 nm and 6 nm and preferably between 0.5 nm and 5 nm, and more preferably between 1 and 4 nm. According to the preferred embodiments of the present invention, which of course may be combined with each other as appropriate: The deposited element that constitutes the intermediate layers is substantially aluminum. According to this modality, a layer consisting substantially of, or simply consisting of, aluminum is deposited between the TN1 layer and the first module Mi and / or the second module M2 to form the intermediate layer (in particular, by magnetron-assisted sputtering of an aluminum target in an atmosphere of a neutral gas, such as argon). The element deposited to constitute the intermediate layers is substantially silicon. According to this modality, a layer consisting substantially or simply of silicon is therefore deposited between the TN1 layer and the first module Mi and / or the second module M2 to form the intermediate layer (in particular, by magnetron-assisted sputtering of a silicon target in an atmosphere of a neutral gas such as argon). The element deposited to constitute the intermediate layers is substantially titanium. According to this embodiment, a layer consisting substantially of titanium is deposited between the TN1 layer and the first module Mi and / or the second module M2 to form the intermediate layer (in particular, by magnetron-assisted sputtering of a titanium target in an atmosphere of a neutral gas such as argon). Preferably, the titanium is deposited at least between the TN1 layer and the second module M2 to form the intermediate layer. According to another embodiment, a titanium layer is deposited between the TN1 layer and the first module Mi, and a titanium layer is deposited between the TN1 layer and the second module M2 to form two intermediate layers on either side of the TN1 layer. The element deposited to constitute the intermediate layer is substantially a mixture of aluminum and silicon. According to this embodiment, a layer consisting substantially or simply of aluminum and silicon is deposited between the TN1 layer and the first module M1 and / or the second module M2 to form the intermediate layer (in particular, by magnetron-assisted sputtering of a silicon target in an atmosphere of a neutral gas such as argon). According to this embodiment, the mass ratio of Si / Al can vary between 99:1 and 1:99. In particular, it can be between zocn Ln / zznz / E / YiAi 97 / 35 and 75 / 25, particularly between 95 / 5 and 80 / 20. The elements deposited to constitute the intermediate layers are silicon and titanium. According to this embodiment, a mixture consisting substantially of titanium is deposited between the TNi layer and the first module M1 and / or the second module M2 to form the intermediate layer (in particular, by magnetron-assisted sputtering of a target comprising a silicon-titanium mixture in an atmosphere of a neutral gas such as argon). According to this embodiment, the mass ratio of Si / Ti can vary between 99 / 1 and 1 / 99. In particular, it can be between 97 / 35 and 75 / 25, and specifically between 95 / 5 and 80 / 20. The elements deposited to constitute the intermediate layers are aluminum and titanium. According to this embodiment, a substantially consistent mixture of aluminum and titanium is deposited between the TN1 layer and the first module Mi and / or the second module Mz to form the intermediate layer (in particular, by magnetron-assisted sputtering of a target comprising a mixture of aluminum and titanium in an atmosphere of a neutral gas such as argon). According to this embodiment, the Al / Ti mass ratio can vary between 99 / 1 and 1 / 99. In particular, it can be between 97 / 35 and 75 / 25, and specifically between 95 / 5 and 80 / 20. - The layers based on dielectric materials that make up the set of layers with an accumulated thickness ei are deposited successively and are thus in contact with each other. - The layers based on dielectric materials that make up the set of layers with an accumulated thickness e2 are deposited successively and thus be in contact with each other. The TN1 layer and the intermediate layers are in contact with each other. The Mi module, the TN1 layer, the M2 module and the intermediate layer or layers are deposited successively and thus come into contact with each other. The M1 and M2 modules comprise and are preferably based on materials selected from silicon nitride, aluminum nitride, aluminum silicon nitride, tin oxide, zinc tin oxide, silicon oxide, titanium oxide, silicon oxynitride, aluminum oxynitride, or aluminum silicon oxynitride. More preferably, the M1 and M2 module(s) are based on materials selected from silicon nitride, aluminum silicon oxynitride, silicon oxynitride, or aluminum silicon oxynitride. - The first module Mi comprises and preferably consists of a layer comprising silicon nitride or aluminum silicon nitride, the layer comprising silicon nitride or aluminum silicon nitride, preferably still in contact with the intermediate layer. - The second module M2 comprises and preferably consists of a layer comprising silicon nitride or aluminum silicon nitride, the layer comprising silicon nitride or aluminum silicon nitride, preferably still in contact with the intermediate layer. - At least one of the M1 or M2 modules comprises or consists of a layer comprising and preferably consisting of silicon oxynitride and / or aluminum oxynitride, the layer comprising silicon oxynitride and / or aluminum oxynitride is preferably in contact with the intermediate layer. The refractive index at 550 nm of silicon oxynitride and / or aluminum oxynitride is between 1.60 and 1.99, preferably between 1.70 and 1.95. The index can be adjusted in particular according to the N / O ratio in the material. The battery comprises and preferably consists of the following sequence of layers, starting from the substrate surface: a silicon nitride-based or silicon oxynitride-based layer (optionally further comprising aluminum), the intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, the TN1 layer, optionally a second intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, a silicon nitride-based layer or a silicon oxynitride-based layer (optionally further comprising aluminum) and optionally a protective layer particularly selected from titanium oxides, zirconium oxides or a mixture of titanium and zirconium oxides. - The battery comprises and preferably consists of the following sequence of layers, starting from the substrate surface: a silicon nitride-based or silicon oxynitride-based layer (optionally further comprising aluminum), optionally another intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, the TNi layer, the intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, a silicon nitride-based layer or a silicon oxynitride-based layer (optionally further comprising aluminum) and optionally a protective layer particularly selected from titanium oxides, zirconium oxides or a mixture of titanium and zirconium. - The stack comprises the following layers in succession, starting from the substrate surface, each layer being successively in contact with the next: SiNx or SiON / AI, Si or Ti or S¡AI / T¡NX / optionally Al, Si, Ti or SiAI / SiNx or SiON, or SiNx or SiON / optionally Al, Si or Ti or SiAI / TINx / optionally Al, Si, Ti or SiAI / SINx or SiON, in which case - SiNx is a layer comprising or based on silicon nitride, - SiON is a layer comprising or based on silicon oxynitride, Al, Si or AISi is a respective layer obtained by deposition of aluminum, silicon or a mixture of aluminum and silicon, - TiNx is the TNi layer comprising or based on titanium nitride. - The battery comprises a plurality of layers comprising titanium nitride TNi, TN2..., in particular two layers (TN1 and TN2) comprising titanium nitride, each layer comprising titanium nitride that is separated from the next in the battery by a layer based on a dielectric material or by a set of layers based on dielectric materials and optionally by an intermediate layer comprising at least one element selected from silicon, aluminum, titanium and mixtures thereof. - The battery does not contain any silver, platinum, gold, or copper-based coating. The glass substrate is made of transparent glass. Without departing from the scope of the invention, it is also possible to deposit the battery on a substrate made of glass that is tinted or colored throughout. The expression “tinted throughout” is understood to mean that the substrate comprises elements in its vitreous composition that are intended to give it a coloration (i.e., different from so-called “transparent” glass), in particular elements such as cobalt, iron, selenium, or chromium, which are also intended to reduce its light transmission. - The glass substrate provided with the battery has been subjected to heat treatment after the battery deposition and in particular, it has been tempered, annealed or bent. - The thickness ei of the first module Mi is between 1 nm and 100 nanometers inclusive, and in particular between 10 and 70 nm. - The thickness of the second module M2 is between 5 nm and 100 nanometers inclusive, and in particular between 20 nm and 70 nm inclusive. - The glass article comprises two glass substrates bonded by a thermoplastic film, which consists of polyvinyl butyral PVB, at least one of the substrates is provided with the stack of layers, the stack being preferably arranged on one face of a substrate that is oriented inside the glazing unit or in contact with the thermoplastic film. Preferably, the functional layers according to the invention are based on titanium nitride or preferably consist substantially of titanium nitride. A layer based on titanium nitride (or other material) comprises, for example, at least 50% by weight of titanium nitride (or other material) or more than 60% by weight of titanium nitride (or other material) or even more than 80% by weight (or other material) or even more than 90% by weight of titanium nitride (or other material). The titanium nitride according to the invention is not necessarily stoichiometric (Ti / N atomic ratio of 1) but can be super- or sub-stoichiometric. According to an advantageous embodiment, the N / Ti ratio is between 1 and 1.2. Furthermore, the titanium nitride according to the invention can comprise a smaller amount of oxygen, for example, between 1 and 10 mol% oxygen, particularly between 1 and 5 mol% oxygen. According to a particularly preferred embodiment, the titanium nitride layers according to the invention have the general formula TiNxOy, wherein 1.00 < x < 1.20 and wherein 0.01 < y < 0.10.However, once deposited in thin layers, the dielectric materials can comprise additional elements that significantly increase their electrical conductivity and, for example, are useful for improving the sputtering efficiency of the precursor material that constitutes the magnetron target. The dielectric layers of the M1 and M2 modules according to the invention can be layers based on a material selected from silicon nitride, aluminum nitride, tin oxide, a mixture of zinc or tin oxide, silicon oxide, titanium oxide, and silicon oxynitride, and the M1 and M2 modules preferably consist of a single layer, and this layer is based on silicon nitride.A material based on silicon nitride, tin oxide, a zinc-tin oxide mixture, silicon oxide, titanium oxide, or silicon oxynitride is, for example, a material consisting predominantly and preferably substantially of such a compound but which may also contain other minor elements, particularly as a substitute for cations, for example, to promote its deposition in the form of thin films by conventional magnetron sputtering techniques as described above. By way of example, silicon nitride, silicon oxynitride, or silicon oxide layers according to the present invention, particularly those deposited by magnetron sputtering, typically comprise elements of the type Al, Zr, B, etc., in proportions, for example, up to 10 at.% or even sometimes up to 20 at.%, based on the silicon content of the layer.Similarly, and without departing from the scope of the present invention, titanium oxide layers may comprise minor metal cations such as zirconium as a substitute for titanium. The glazing unit according to the invention can be a single glazing unit in which the stack of thin layers is preferably arranged on face 2 of the single glazing unit when the substrate faces are numbered from the outside to the inside of the building or passenger compartment provided with the unit. According to the invention, the intermediate layers deposited from the metallic targets consisting of Ti, Si, Al or a mixture of at least two of these elements may comprise nitrogen or oxygen, even before any heat treatment. Thus, SIMS (secondary ion mass spectrometry) analyses have shown that the layers comprise a smaller quantity of such heteroatoms, even in the absence of nitrogen or oxidizing gas during spray deposition (particularly in a 100% argon atmosphere), without it being possible to determine the exact quantity of the heteroatom in the layer in question using currently available techniques. The same applies to the glass articles according to the invention. According to another embodiment, the glazing unit according to the invention may be a laminated glazing unit comprising two glass substrates bonded by a thermoplastic film, in particular a polyvinyl butyral or PVB film. The glazing unit is provided with a stack of layers as described above. Preferably, the stack is deposited on the face of the substrate that is oriented inward toward the laminated structure, in particular on face 2 of the glazing unit, and even more preferably is in contact with the thermoplastic film. Alternatively, it may be deposited on the inner face of the laminated glazing unit, i.e., on face 4 of the glazing unit. The faces are conventionally numbered from 1 to 4 from the outside to the inside of the glazing unit. The substrates described above can, of course, be thermally tempered and / or curved after the stack is depositioned according to the invention. A method for producing an article according to the invention comprises, for example, at least the following steps: - a glass substrate is introduced into a spray device, - at least one sublayer of a dielectric material is deposited in one or more first compartments, - In another compartment, a titanium target is sprayed by means of a plasma generated from a gas comprising nitrogen, preferably in a mixture with a rare gas such as argon, under the conditions to obtain a titanium nitride layer, zocn ίη / ζζηζ / E / γίΛΐ - at least one top layer of a dielectric material is deposited in one or more additional compartments. According to the present invention, in a compartment comprising a target consisting of aluminum, silicon, titanium or a mixture of at least two of these elements, in particular silicon and aluminum, located immediately before and / or after the compartment equipped with the titanium target, a thin layer of 1 to 6 nm of aluminum, silicon, titanium or a mixture of at least two of these elements, in particular silicon and aluminum, is deposited by spraying the target in the presence of a neutral gas, for example, exclusively argon. The term “top layer” in this description refers to the respective position of the layers relative to the functional layers in the stack, which is supported by the glass substrate. In particular, the top layer is the outermost layer of the stack, oriented away from the substrate. The thickness of a layer within the meaning of the present invention shall be understood to mean the actual geometric thickness of the layer, as can be measured in particular by conventional electron microscopy or other techniques. DETAILED DESCRIPTION OF THE INVENTION The invention and its advantages are described in more detail below by means of the following non-limiting examples in accordance with the invention. Unless otherwise specified, in all examples and descriptions, the thicknesses given are geometric. According to the invention, the properties and advantages of the glazing unit are illustrated by the following examples: In a well-known manner, in the following examples, the different successive layers are deposited in successive dedicated compartments of the spray device. Each compartment is provided with a specific metallic target consisting of Si, Ti, Al, Al, and Si, selected for the deposition of a specific stack layer and supplied with a specific gas composition of the desired composition for each layer. More precisely, the silicon nitride-based layers are deposited in the device compartments of a metallic silicon target (comprising 8 wt% aluminum) in a reactive atmosphere containing argon and nitrogen, according to well-established techniques. Therefore, the silicon nitride layers also contain aluminum. The silicon oxynitride-based layer is deposited in a compartment of the device from a silicon metal target (comprising 8 wt% aluminum) in a reactive atmosphere containing argon, nitrogen, and oxygen. The respective flow rates of the gases introduced into the compartment were 20 sccm (standard cubic centimeters per minute) of Ar, 5 sccm of O2, and 100 sccm of N2. The refractive index at 550 nm measured for this material was 1.88. Titanium nitride layers are deposited in other compartments of the device from a pure titanium metallic target in a reactive atmosphere containing nitrogen and argon. Layers of aluminum or aluminum-silicon alloys were deposited from the spraying of a target of the same composition in a neutral argon atmosphere. Titanium layers were deposited from a pure titanium metallic target in a zocn Ln / zznz / E / YiAi Table 1 ShN4 (Mi) IL* TIN (TNi) IL* SIN3N4 (M2) Deposition type IL Example 1 (reference): 30 - 20 - 30 - Example 2 (invention): 30 - 20 2 30 Al Example 3 (invention): 30 - 20 2 30 Si-Al Example 4 (invention): 30 2 20 - 30 Ti Example 5 (invention): 30 1 20 1 30 Ti Example 6 (comparative) 30 - 20 2 30 NiCr Example 7 (comparative) 30 - 20 2 30 NbN Example 8 (invention): 30 - 20 3 30** Al *IL: intermediate layer ** silicon oxynitride SiON with a refractive index of 1.88 at 550nm. zocn Ln / zznz / E / YiAi Therefore, all glazing units obtained according to examples 1 to 8 are then subjected to heat treatment at 650°C for 10 minutes. A - Measurement characteristics of glazing units The thermal and optical characteristics of the glazing units before and after tempering were measured according to the following principles and standards: °) Optical properties: The measurements were made in accordance with the aforementioned standard NF EN410 (2011). More precisely, the light transmission Tl was measured between 380 and 780 nm depending on the illuminant at Des. 2°) Thermal properties: The normal emissivity was measured in accordance with the ISO 10292 standard mentioned above. B - Results The results obtained by the monolithic glazing units according to the examples described above are compiled in Table 2 below: Table 2 Example Tl after tempering εη After tempering Κ / εη after tempering 1 (reference) 54.1 40.6 1.33 2 (invention) 54.5 37.9 1.44 3 (invention) 55.5 38.0 1.46 4 (invention) 52.7 34.8 1.51 5 (invention) 50.7 32.6 1.56 6 (comparative) 48.5 35.8 1.35 7 (comparative) 52.5 49 1.07 8 (invention) 53.5 34.9 1.53 zocn Ln / zznz / E / YiAi Examples 2 and 3 are examples according to the present invention. For these two examples, after tempering, a light transmission of approximately 55% was observed, which was surprisingly higher than that of the same battery without the intermediate aluminum layer or the Si-Al alloy according to the invention. In accordance with an advantageous feature, the emissivity at normal incidence was also significantly reduced compared to reference example 1. Examples 4 and 5 according to the present invention show a slight reduction in light transmission but also a much lower emissivity compared to the reference battery. Finally, the use of the intermediate layer in the stack according to the invention makes it possible to obtain a light transmission equal to or substantially comparable to that of the reference stack while improving the thermal properties of the glazing unit. Finally, it is observed that when the selectivity of the glazing unit is measured by the ratio Tu / εη, it is significantly improved by the glazing units according to the invention, especially after tempering. The comparative glazing unit according to example 6 comprising an intermediate layer made of a NiCr alloy has a substantially reduced light transmission compared to the reference example and the examples according to the invention and, finally, a selectivity that is substantially equal to that of the reference glazing unit. The comparative glazing unit according to example 7 comprising an NbN intermediate layer has degraded selectivity compared to the reference example. The glazing unit according to example 8, in which a silicon (and aluminum) oxynitride layer is used in contact with the intermediate layer, has also improved its selectivity compared to the reference example. When considering the selectivities of Tu / εη of the glazing units according to Examples 1 to 8, as reported in Table 2, it can be observed that the glazing units according to the invention have the best selectivities after being subjected to heat treatment. Based on other complementary examples, the aim is to determine the optimal thickness of aluminum used to form the intermediate layer for selectivity when varying the thickness in the stack described above, as per Example 2. The results obtained are compiled in Table 3 below: Table 3 Example Al layer thickness (nm). Tl after tempering εη after tempering Ti_ / εη after tempering 1 (reference) 0 54.1 40.6 1.33 2 2 54.5 37.9 1.44 2a 1 54.7 40.1 1.44 2b 3 54.9 34.1 1.61 2c 4 52.9 32.8 1.61 2d 5 51.3 32.9 1.56 Analysis of the data reported in Table 3 shows that the best results and compromises were obtained when the thickness of the intermediate aluminum layer was between 2 and 4 nm.

Claims

1. A glass article having anti-solar properties, characterized in that it comprises at least one glass substrate provided with a stack of layers, wherein the stack comprises successively from the surface of the substrate: - a first module M1 consisting of a layer based on a dielectric material with a thickness ei or of a set of layers based on dielectric materials with a cumulative thickness ei, the thickness ei being between 1 and 100 nm, preferably between 5 and 80 nm, in particular between 10 nm and 70 nm, - a TNi layer comprising titanium nitride and preferably titanium nitride-based with a thickness between 2 and 80 nanometers, preferably between 4 and 70 nanometers, more preferably between 10 and 50 nm, - a second module M2 consisting of a layer based on a dielectric material with a thickness or of a set of layers based on dielectric materials with a cumulative thickness e, the thickness being between 5 and 100 nm, preferably between 20 and 70 nm,and where an intermediate layer comprises and preferably consists substantially of at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements is deposited between the TN1 layer and the first module Mi and / or between the TN1 layer and the second module M2, the intermediate layers having a thickness between 0.2 nm and 6 nm, preferably between 0.5 and 5 nm and more preferably between 1 and 4 nm.

2. The glass article according to claim 1, further characterized in that the element deposited to constitute the intermediate layers is substantially aluminum.

3. The glass article according to claim 1, further characterized in that the element deposited to constitute the intermediate layers is substantially silicon.

4. The glass article according to claim 1, further characterized in that the element deposited to constitute the intermediate layer is substantially silicon and aluminum.

5. The glass article according to claim 1, further characterized in that the element deposited to constitute the intermediate layer is substantially titanium.

6. The glass article according to one of the preceding claims, further characterized in that the M1 or M2 modules comprise materials selected from silicon nitride, aluminum nitride, aluminum silicon nitride, tin oxide, mixed zinc and tin oxide, silicon oxide, titanium oxide, and silicon oxynitride.

7. The glass article according to the preceding claims, further characterized in that the first module Mi comprises and preferably consists of a layer comprising silicon nitride or aluminum silicon nitride, the layer comprising silicon nitride or aluminum silicon nitride still being in contact with the intermediate layer.

8. The glass article according to the preceding claims, further characterized in that the second module M2 comprises and preferably consists of a layer comprising silicon nitride or aluminum silicon nitride, the layer comprising silicon nitride or aluminum silicon nitride still in contact with the intermediate layer.

9. The glass article according to any one of the preceding claims, further characterized in that at least one of the modules M1 or M2 comprises and preferably consists of a layer comprising silicon oxynitride and / or aluminum silicon oxynitride, the silicon oxynitride and / or aluminum oxynitride layer still being in contact with an intermediate layer. zocn Ln / zznz / E / YiAi 10. The glass article according to any one of the preceding claims, further characterized in that the stack comprises and preferably consists of the following sequence of layers, starting from the substrate surface: a silicon nitride-based or silicon oxynitride-based layer, the intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, the TN1 layer, optionally a second intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, a silicon nitride-based or silicon oxynitride-based layer and optionally a protective layer selected in particular from titanium oxides, zirconium or a mixture of titanium and zirconium.

11. The glass article according to any one of claims 1 to 9, further characterized in that the stack comprises and preferably consists of the following sequence of layers, starting from the substrate surface: a layer based on silicon nitride or silicon oxynitride, titanium or a mixture of at least two of these elements, optionally another intermediate layer comprising at least one element selected from silicon, aluminum, titanium or a mixture of at least two of these elements, the TN1 layer, the intermediate layer comprising at least one element selected from silicon, aluminum, a silicon nitride-based layer or a silicon oxynitride-based layer and optionally a protective layer selected in particular from titanium oxides, zirconium or a mixture of titanium and zirconium.

12. The glass article according to one of the preceding claims, further characterized in that the stack comprises a plurality of layers comprising titanium nitride, each layer comprising titanium nitride being separated from the next in the stack by a layer based on a dielectric material or by a set of layers based on dielectric materials and optionally, an intermediate layer comprising at least one element selected from silicon and / or aluminum.

13. The glass article according to one of the preceding claims, further characterized in that the battery does not contain any silver, platinum or gold-based coating.

14. The glass article according to one of the preceding claims, further characterized in that the glass substrate is made of transparent glass.

15. The glass article according to one of the preceding claims, further characterized in that the glass substrate or substrates provided with the battery are tempered or curved.

16. The glass article according to one of the preceding claims, further characterized in that the Mi module, the TNi layer, the M2 module and the intermediate layers are deposited successively and are thus in contact with each other.