FR3098215A1 - DOUBLE-LAYER TIN GLASS FOR SOLAR CONTROL - Google Patents

Abstract

Glass article with sunscreen properties comprising at least one glass substrate provided with a stack of layers, in which the stack comprises successively from the surface of said substrate: a) a first layer TN1 comprising titanium nitride and preferably based on nitride titanium, with a thickness between 1 nanometers and 50 nanometers, preferably between 1 and 30 nanometers, more preferably between 2 and 25 nm, b) a first module M1 consisting of a layer based on a dielectric material of thickness e 1 or by a set of layers based on dielectric materials with a cumulative thickness e 1 of between 1 and 100 nm, c) a second layer TN2 comprising titanium nitride and preferably based on titanium nitride, thickness between 1 nanometers and 50 nanometers, preferably between 5 and 40 nanometers, more preferably between 10 and 40 nm, d) a second module M2 consisting of a layer based on a dielectric material of thickness e 2 or by a set of layers based on dielectric materials with a cumulative thickness e 2 of between 1 and 120 nm, and in which said layer TN1 is directly in contact with the surface of the substrate.

Description

DOUBLE LAYER TIN GLAZING FOR SOLAR CONTROL

The invention relates to so-called solar control insulating glazing, provided with stacks of so-called functional thin layers, that is to say acting on solar and/or thermal radiation essentially by reflection and/or absorption of near infrared radiation ( solar) or distant (thermal). The application more particularly targeted by the invention is firstly the field of building, as solar control glazing. Without departing from the scope of the invention, this glazing can also be used in vehicle glazing, such as side glasses, car roofs, rear windows.

“Functional” or even “active” layer is understood to mean, within the meaning of the present application, the layers of the stack which give the stack most of its thermal insulation properties. Most often, the stacks of thin layers with which the glazing unit gives it substantially improved insulation properties, very essentially through the intrinsic properties of said active layers. Said layers act on the flux of thermal infrared radiation passing through said glazing, as opposed to the other layers, generally made of dielectric material and most often mainly having the function of chemical or mechanical protection of said functional layers. The term “dielectric material” is understood to mean a material whose massive shape and devoid of impurities has a high resistivity, in particular a resistivity initially greater than 10 ¹⁰ ohms.meters (Ω.m).

Such glazing provided with stacks of thin layers act on the incident IR radiation either essentially by the absorption of said radiation by the functional layer or layers, or essentially by reflection by these same layers.

They are grouped under the designation of solar control glazing. They are mainly marketed and used:
- either to essentially protect the home from solar radiation or the passenger compartment (automobile) and avoid overheating, such glazing being qualified in the field of solar protection,
- either essentially to ensure thermal insulation of the dwelling and prevent heat loss, these glazing being qualified as insulating glazing.

By anti-sun, it is thus meant within the meaning of the present invention the ability of the glazing to limit the energy flow, in particular the solar infrared radiation (IRS) passing through it from the outside to the inside of the dwelling or the passenger compartment. .

By thermal insulation, we mean a glazing provided with at least one functional layer giving it reduced energy loss, said layer having properties of reflection of IR radiation of between 5 and 50 micrometers. The functional layers used in this function have a high IR radiation reflection coefficient and are called low-emissivity (or low-e according to the English term).

In some countries, the standards imply that the glazing has both solar protection and thermal insulation properties for building glazing.

Such a property is generally measured by the solar factor, denoted FS or more often g in the art.

In a known manner, the solar factor g is equal to the ratio of the energy passing through the glazing (i.e. entering the room) and the incident solar energy. More specifically, it corresponds to the sum of the flux transmitted directly through the glazing and the flux absorbed by the glazing (including the stacks of layers possibly present on one of its surfaces) then possibly re-emitted towards the interior (the local).

Within the meaning of the present invention, it is considered that a factor g of the order of 30 to 35% fulfills such an insulation function.

The most efficient stacks currently marketed to solve the above problems and deposited by magnetron sputtering techniques incorporate a metallic layer of the Silver type operating essentially in the mode of reflection of a major part of the IR (infrared) radiation. incident. These stacks are thus mainly used as low-emissivity (or low-e) glazing for the thermal insulation of buildings. These layers are however very sensitive to humidity and are therefore exclusively used in double glazing, facing 2 or 3 of them, to be protected from humidity. The stacks according to the invention do not include such layers of the silver type, or else of the gold or platinum type or even copper. More generally, the stacks according to the invention do not contain such precious metals, or else in very negligible quantities, in particular in the form of unavoidable impurities.

In general, all the light and thermal characteristics presented in this description are well known to those skilled in the art and can be obtained according to the principles and methods described in the standards NF EN 410 (2011) and ISO 9050 (2003 ), relating respectively to the determination of the light and energy characteristics of the glazing used in glass for construction.

According to another aspect which must be taken into account in certain applications, when they are associated with the glass substrate used (in particular with a clear glass), the coatings must moreover also be aesthetically pleasing, that is to say that the glazing fitted with its stack must have a colorimetry, both in transmission and in internal reflection, sufficiently neutral not to inconvenience the inhabitants of the building or the passengers of the vehicle in the CIE LAB colorimetry system (L*, a*, b*). In particular, the values of the coefficient a* of these two parameters must be as close as possible to 0 for the color to be considered sufficiently neutral. In particular, too high values of the coefficient a* in internal reflection, that is to say on the side of the stack (denoted a* _int in the rest of the description), translates an intense coloring of the glazing seen from the inside the building and the passenger compartment and are to be avoided. It will preferably be sought, for such a purpose, to obtain glass articles in which the parameter a* _int is between -10 and 10, preferably between -8 and 8, or even between -5 and 5. according to the invention the development of glass articles having a relatively neutral color in transmission, in order to ensure correct rendering of the colors from the exterior to the interior of the building. It will preferably be sought, again, to obtain glass articles in which the parameter a* _T is between -10 and 10, or even between -5 and 5 and more preferably between -5 and 0.

As indicated above, the coatings are conventionally deposited by deposition techniques of the vacuum sputtering type assisted by magnetic field of a cathode of the material or of a precursor of the material to be deposited, often called magnetron sputtering technique in the field. . Such a technique is now conventionally used, in particular when the coating to be deposited consists of a more complex stack of successive layers with thicknesses of a few nanometers or a few tens of nanometers.

Finally, it is also sought in current technologies for stacks whose colors in external reflection are adjustable, that is to say stacks which make it possible to obtain glazing whose color in external reflection is different, on the basis of the same sequence of successive layers. Concretely, stacks are sought according to which the modification of the thicknesses of its various constituent layers modifies the color rendered in exterior vision, while retaining a relatively neutral color in transmission and in interior reflection. Depending on the needs and during the production of such glazing, it is then possible to successively deposit in the magnetron device different stacks corresponding to different colors in reflection without the need to substantially modify said device (in particular the targets used for the deposition of each layer). Switching from one glazing production to another can thus be done by simply adjusting the spraying conditions to adjust the different thicknesses.

Patent application WO2018/129135 describes a stack of layers successively comprising the following sequence of layers: Si ₃ N ₄ /TiN/Si ₃ N ₄ /TiN/Si ₃ N ₄ . It is indicated in this publication that such a sequence, in which the functional TiN layers are encapsulated by dielectric layers based on silicon nitride, makes it possible to obtain a stack whose color is substantially neutral on the glass side (outside). .

The development of new stacks has become necessary for certain applications and in particular to solve the problems and objectives described above.

In particular, glazing that provides improved visual comfort is currently being sought, both in the field of construction (as building glazing) and in the automotive sector (as side glazing, rear window glazing or even as a glazed roof). One of the objects of the present invention to meet such a demand and to provide thermal insulating glass articles whose colors are relatively neutral in transmission and in internal reflection and whose color in external reflection can be easily adjusted during their production. .

According to the results obtained by the applicant company, the previous problems have been solved by glass articles as now described:

A glass article with sunscreen properties according to the invention comprises at least one glass substrate provided with a stack of layers, in which the stack successively comprises, from the surface of said substrate:

- a first layer TN ₁ comprising titanium nitride and preferably based on titanium nitride, with a thickness of between 1 nanometers and 50 nanometers, preferably between 1 and 30 nanometers, more preferably between 2 and 25 nm,

- a first module M ₁ constituted by a layer based on a dielectric material with a thickness e ₁ or by a set of layers based on dielectric materials with a cumulative thickness e ₁ between 1 and 100 nm,
- a second layer TN ₂ comprising titanium nitride and preferably based on titanium nitride, with a thickness of between 1 nanometer and 50 nanometer, preferably between 5 and 40 nanometer, more preferably between 10 and 40 nm,
- a second module M ₂ constituted by a layer based on a dielectric material with a thickness e ₂ or by a set of layers based on dielectric materials with a cumulative thickness e ₂ between 1 and 120 nm,

and wherein said TN layer ₁ is directly in contact with the surface of the substrate.

According to preferred embodiments of the present invention, which can obviously be combined if necessary with each other:

• Within the stack, the first module M ₁ is in contact with the first layer TN ₁ and the second layer TN _2.
• Within the stack, the second module M ₂ is in contact with the second layer TN _2.
• The module(s) M ₁ , M ₂ are based on materials chosen from among a silicon nitride, an aluminum nitride, a tin oxide, a mixed oxide of zinc and tin, a silicon oxide, an oxide of titanium, a silicon oxynitride,
• _M1 and M2 are single layers.
• M ₁ and M ₂ comprise silicon nitride.
• M ₁ and M ₂ are based on silicon nitride.
• The stack is formed by the following sequence of layers, starting from the surface of the substrate: layer based on titanium nitride/layer based on silicon nitride/layer based on titanium nitride/layer based on nitride of silicon/ optionally at least one protective layer preferably chosen from titanium oxide, zirconium oxide or a mixture of titanium and zirconium.
• The thickness e ₁ of the first module M ₁ is between 15 nm and 100 nanometers, limits included.
• The thickness e ₂ of the second module M ₂ is between 10 nm and 100 nanometers, limits included.
• The thickness of the TN ₂ layer is greater than the thickness of the TN ₁ layer.
• The thickness of TN layer ₁ is greater than the thickness of TN layer _2.
• In the glass article:

• the thickness of the TN layer ₁ is between 5 and 25 nm, preferably between 10 and 20 nm,
• the thickness e ₁ of the module M ₁ is between 20 and 45 nm, preferably between 25 and 40 nm,
• the thickness of the TN layer ₂ is between 5 and 30 nm, preferably between 10 and 20 nm,
• the thickness e ₂ of the module M ₂ is between 5 and 30 nm, preferably between 5 and 20 nm.
• In the glass article:
• the thickness of the TN layer ₁ is between 5 and 25 nm, preferably between 10 and 20 nm,
• the thickness e ₁ of the module M ₁ is between 40 and 65 nm, preferably between 45 and 60 nm,
• the thickness of the TN layer ₂ is between 5 and 30 nm, preferably between 10 and 20 nm,
• the thickness e ₂ of the module M ₂ is between 70 and 110 nm, preferably between 80 and 100 nm.
• In the glass article:
• the thickness of the TN layer ₁ is between 10 and 30 nm, preferably between 10 and 25 nm,
• the thickness e ₁ of the module M ₁ is between 40 and 65 nm, preferably between 45 and 60 nm,
• the thickness of the TN layer ₂ is between 10 and 30 nm, preferably between 15 and 25 nm,
• the thickness e2 of the module M2 is between 20 and 45 nm, preferably between 25 and 40 nm.

- The cumulative thickness TN ₁ + TN ₂ of the first layer based on titanium nitride and the second layer based on titanium nitride is less than 60 nm, preferably is less than 55 nm and more preferably is between 25 and 45nm.

- The coating does not contain any layer of a metallic nature, in particular based on silver or gold or copper.

- The glass substrate on which the stack is placed is made of clear glass. Without departing from the scope of the invention, it may also be envisaged to deposit the stack on a tinted glass substrate.

- The glass article comprises two glass substrates assembled by a thermoplastic sheet, in particular polyvinyl butyral PVB, at least one of said substrates being provided with said stack of layers, said stack being preferably arranged on a face of a substrate facing inwards said glazing, or in contact with the thermoplastic sheet.

- The previous glass article comprises a first glass substrate, preferably colored in its mass, bonded to a second substrate by an intermediate thermoplastic sheet, in particular of PVB, said second substrate being made of clear glass and provided with said stack of layers arranged preferably on its side exposed to the outside of said article. By colored in its mass, it is meant that the substrate includes in its glass composition elements aimed at giving it a color (i.e. different from that of a so-called "clear" glass), in particular elements such as cobalt, iron , selenium, or even chromium, which can also aim to reduce light transmission.

- In the glass article comprising two glass substrates:

• the thickness of the TN layer ₁ is between 10 and 30 nm, preferably between 15 and 25 nm,
• the thickness e ₁ of the module M ₁ is between 10 and 35 nm, preferably between 15 and 25 nm,
• the thickness of the TN layer ₂ is between 5 and 30 nm, preferably between 10 and 20 nm,
• the thickness e ₂ of the module M ₂ is between 50 and 90 nm, preferably between 60 and 80 nm.
• In the glass article comprising two glass substrates:
• the thickness of the TN layer ₁ is between 1 and 20 nm, preferably between 1 and 10 nm, more preferably between 2 and 8 nm,
• the thickness e ₁ of the module M ₁ is between 50 and 80 nm, preferably between 55 and 75 nm,
• the thickness of the TN layer ₂ is between 20 and 50 nm, preferably between 25 and 45 nm,
• the thickness e ₂ of the module M ₂ is between 40 and 80 nm, preferably between 55 and 75 nm.
• In the glass article comprising two glass substrates:
• the thickness of the TN layer ₁ is between 10 and 40 nm, preferably between 15 and 25 nm,
• the thickness e ₁ of the module M ₁ is between 60 and 100 nm, preferably between 75 and 95 nm,
• the thickness of the TN layer ₂ is between 10 and 30 nm, preferably between 15 and 25 nm,
• the thickness e ₂ of the module M ₂ is between 30 and 60 nm, preferably between 35 and 55 nm.

Preferably, the titanium nitride layers according to the invention are based on titanium nitride or more preferably consist essentially of titanium nitride.

A titanium nitride-based layer comprises, for example, at least 50% by weight of titanium nitride, or even more than 60% by weight of titanium nitride, or even more than 80% by weight, or even more than 90% by weight of titanium nitride. titanium.

The titanium nitride according to the invention is not necessarily stoichiometric (Ti/N atomic ratio of 1) but can be over- or under-stoichiometric. According to an advantageous mode, the N/Ti ratio is between 1 and 1.2. Also, the titanium nitride according to the invention can comprise a minor quantity of oxygen, for example between 1 and 10% molar of oxygen, in particular between 1 and 5% molar of oxygen.

According to a particularly preferred mode, the titanium nitride layers according to the invention correspond to the general formula TiN _x O _y , in which 1.00 <x <1.20 and in which 0.01 <y <0.10.

The dielectric materials, once deposited in thin layers, can however comprise additional elements which substantially increase their electrical conductivity, useful for example for improving the yield of cathode sputtering of the precursor material constituting the magnetron target. The dielectric layers of the modules M ₁ , M ₂ according to the invention can be layers based on a material chosen from among a silicon nitride, an aluminum nitride, a tin oxide, a mixed oxide of zinc or of tin, a silicon oxide, a titanium oxide, a silicon oxynitride, preferably the modules M1 and M2 consist of a single layer and this layer is based on silicon nitride. A material based on silicon nitride, tin oxide, mixed oxide of zinc and tin, silicon oxide, titanium oxide, silicon oxynitride is for example a material consisting predominantly, and preferably essentially, of such a compound but which may also nevertheless contain other minority elements, in particular as a substitute for the cations, for example to promote the deposition thereof in the form of thin layers by the usual techniques of magnetron sputtering as previously described. By way of example, the layers according to the present invention in silicon nitride (or in silicon oxynitride, or even in silicon oxide) in particular those deposited by magnetron, most often comprise elements of the type Al, Zr, B, etc. ., in proportions which can go for example up to 10 atomic % or even sometimes up to 20 atomic %, on the basis of the silicon content of the layer. Similarly, the titanium oxide layers may comprise, in substitution for titanium, other minority metal cations such as zirconium, without departing from the scope of the present invention.

The glazing according to the invention can be a single glazing in which the stack of thin layers being preferably arranged on face 2 of the single glazing by numbering the faces of the substrate from the outside towards the inside of the building or the passenger compartment that he team.

According to another embodiment, the glazing according to the invention can be laminated glazing, comprising two glass substrates assembled by a thermoplastic sheet, in particular a polyvinyl butyral or PVB sheet, said glazing being provided with a stack of layers as described above . Preferably, the stack is deposited on the side of the substrate facing the interior of the laminated structure, in particular on side 2 of the glazing, and more preferably still, it is in contact with the thermoplastic sheet. Alternatively, it can be deposited on the inside face of the laminated glazing, i.e. on face 4 of the glazing, the faces being conventionally numbered from 1 to 4 from the outside towards the inside of the glazing.

The substrates previously described can of course be heat-tempered and/or bent.

A method of manufacturing an article according to the invention comprises, for example, at least the following steps:
- a glass substrate is introduced into a sputtering device,
- in a first compartment, a titanium target is sputtered by means of a plasma generated from a gas comprising nitrogen, preferably mixed with a rare gas such as argon,
- in a subsequent compartment, at least one intermediate layer of a dielectric material is deposited,
- in a subsequent compartment, a titanium target is sputtered by means of a plasma generated from a gas comprising nitrogen, preferably mixed with a rare gas such as argon,
- In a subsequent compartment, at least one overlayer of a dielectric material is deposited.

The term “overlayer” refers in this description to the respective position of said layers relative to the functional layer(s) in the stack, said stack being supported by the glass substrate. In particular, the overlayer is the outermost layer of the stack, facing away from the substrate.

The term “intermediate layer” denotes the layer or layers arranged between two functional layers.

By thickness of a layer, is meant within the meaning of the present invention the actual geometric thickness of the layer, such as it can be measured in particular by the conventional techniques of electron microscopy or other.

The invention and its advantages are described in more detail, below, by means of the non-limiting examples below according to the invention. In all examples and description, unless otherwise specified, thicknesses given are geometric.

The properties and advantages of the glazing according to the invention are illustrated by the examples which follow.

In these examples, the glass substrate is covered successively with a stack of layers comprising two functional layers based on titanium nitride, an intermediate layer (first layer M ₁ between the two layers of TiN) based on silicon nitride and a over-layer (second layer M ₂ ) also based on silicon nitride (denoted for convenience Si ₃ N ₄ hereafter even if the actual stoichiometry of the layer is not necessarily this).

All substrates are 4 clear glass mm thick Planilux® marketed by Saint-Gobain Glass France. All the layers are deposited in a known manner by sputtering assisted by a magnetic field (often called a magnetron).

In a well-known way, the various successive layers are deposited in successive dedicated compartments of the cathode sputtering device, each compartment being provided with a specific metal target in Si, Ti, chosen for the deposition of a specific layer of the stack. .

More precisely, the silicon nitride layers are deposited in the device compartments from a metallic silicon target (doped with 8% by mass of aluminium), in a reactive atmosphere containing nitrogen. Silicon nitride layers therefore also contain aluminum.

The titanium nitride layers are deposited in other compartments of the device from a target of pure metallic titanium in a reactive atmosphere containing nitrogen and argon.

The magnetron deposition conditions of such layers, in particular for obtaining a desired thickness of each layer of the stack, are technically well known in the field.

The deposition conditions were adjusted according to conventional techniques for magnetron deposition to obtain different stacks, the succession of layers and their thicknesses (in nanometers nm) of which are reported in Table 1 below:

TiN
( _TN1 ) If ₃ N ₄
( _M1 ) TiN
( _TN2 ) If ₃ N ₄
( _M2 ) Color
sought-after exterior Example 1
(Invention) 15 32 16 10 Neutral Example 2 (invention) 15 54 16 99 Blue Example 3
(invention) 18 54 17 31 Bronze

A-Measurement of glazing characteristics

The thermal and optical characteristics of the glazing were measured according to the following principles and standards:

1°) Optical properties:

The measurements are carried out in accordance with the European standards ISO 9050 and NF EN410 mentioned above. More precisely, the light transmission T _L , the light reflection on the side of the stack R _int and the light reflection on the side of the uncoated glass face R _ext are measured between 380 and 780 nm depending on the illuminant D ₆₅ .

The parameters a* _int and b* _int (stack side in internal reflection, i.e. on the side of the glass on which the stack is deposited) are measured according to the colorimetry model (L, a*, b *).

The a* _ext and b* _ext parameter (glass side in external reflection, that is to say on the face of the glass that remains bare) is also measured according to the colorimetry model (L, a*, b*).

2°) Thermal properties:

The thermal insulation properties of the glazing are evaluated by determining the solar factor g, according to the conditions described in the previous standards.

B-Results

The results obtained for the monolithic glazing according to the examples described above are grouped together in Table 2 below:

Example T _L To* b* R _ext a* _ext b* _ext R _int a* _int b* _int g Exterior color 1 (invent.) 30 -4.3 1.8 14 -2.6 0 15 3.0 -2.0 31 Neutral 2 (invent.) 30 -4.6 3 9 -5 -19 20 1.1 -6.5 33 Blue 3 (invent.) 30 -3.7 1.5 12 9.6 10 8 -5 -5 31 Bronze

Examples 1 to 3 are examples according to the present invention. We observe for these three examples a light transmission of around 30%, and a relatively neutral or slightly bluish color in interior reflection, considered pleasant. The solar factor g is around 30 to 35%, which reflects the good thermal insulation properties of the glazing. The glazing according to example 1 has a neutral colorimetry in external reflection (on the side of the uncoated glazing). The glazing according to example 2, which has the same sequence of layers as example 1 but different thicknesses of the layers constituting the stack, has a pronounced blue colorimetry in external reflection. The glazing according to Example 3, for further modified thicknesses, has a pronounced bronze colorimetry in external reflection.

The glazings according to the invention thus comprise stacks whose colors in external reflection are adjustable, that is to say stacks whose color in external reflection is different, on the basis of the same sequence of successive layers.

According to other complementary examples, it is sought to obtain laminated glazing from simple glazing whose support is a clear glass of 4 mm thick Planilux® on which stacks according to the invention are deposited using the same techniques as previously described.

The characteristics of the stacks as deposited are reported in Table 3 below:

TiN
( _TN1 ) If ₃ N ₄
( _M1 ) TiN
( _TN2 ) If ₃ N ₄
( _M2 ) Color
sought-after exterior Example 4
(Invention) 20 23 13 70 Bronze Example 5
(Invention) 2 63 37 69 Neutral Example 6
(invention) 19 89 22 45 Blue

The glass substrate provided with its stack is assembled with another clear glass substrate of 4 mm thick Planilux®. The assembly is obtained by means of a sheet of untinted polyvinyl butyral (PVB) 0.38 mm thick, so that the stack of layers is found on face 2 of the laminated glazing, the faces being numbered 1. to 4 from the outer surface of the glazing, conventionally in the field.

The same parameters are measured on the final laminated glazing under the same conditions as previously described.

Example T _L To* b* R _ext a* _ext b* _ext R _int a* _int b* _int g reflection color 4 31 -4.6 1.1 16 7.5 15.3 9 -0.1 3 34 Bronze 5 30 -3.9 5.3 14 -1 -6 19 -1.4 3.4 33 Neutral 6 30 -5.2 2.0 21 -8.0 -13.4 10 -1.5 0 31 Blue

It is noted that the optical and energy characteristics of the laminated glazing of Examples 4 to 6 according to the invention, as reported in Table 3, allow the resolution of the technical problem previously exposed: The glazing has a substantially neutral color in transmission as in reflection interior (stack side) and an exterior color adaptable to the desired needs.

Thus, in the monolithic version as in the laminated version, it is possible according to the invention to obtain glazings that are substantially neutral in transmission as in internal reflection and whose color in external reflection can be adjusted, on the basis of the same stack, by the simple variation of the thicknesses of successive layers of said stack.

Claims (20)

Glass article with solar protection properties comprising at least one glass substrate provided with a stack of layers, in which the stack successively comprises, from the surface of the said substrate:
- a first layer TN ₁ comprising titanium nitride and preferably based on titanium nitride, with a thickness of between 1 nanometers and 50 nanometers, preferably between 1 and 30 nanometers, more preferably between 2 and 25 nm,
- a first module M ₁ constituted by a layer based on a dielectric material with a thickness e ₁ or by a set of layers based on dielectric materials with a cumulative thickness e ₁ between 1 and 100 nm,
- a second layer TN ₂ comprising titanium nitride and preferably based on titanium nitride, with a thickness of between 1 nanometer and 50 nanometer, preferably between 5 and 40 nanometer, more preferably between 10 and 40 nm,
- a second module M ₂ constituted by a layer based on a dielectric material with a thickness e ₂ or by a set of layers based on dielectric materials with a cumulative thickness e ₂ between 1 and 120 nm,
and wherein said TN layer ₁ is directly in contact with the surface of the substrate. Glass article according to claim 1, in which, within the stack, the first module M ₁ is in contact with the first layer TN ₁ and the second layer TN _2. Glass article according to one of the preceding claims, in which, within the stack, the second module M ₂ is in contact with the second layer TN _2. Glass article according to one of the preceding claims, in which the module or modules M ₁ , M ₂ are based on materials chosen from among a silicon nitride, an aluminum nitride, a tin oxide, a mixed zinc oxide and tin, silicon oxide, titanium oxide, silicon oxynitride. Glass article according to one of the preceding claims, in which M ₁ and M2 are single layers. Glass article according to one of the preceding claims, in which M ₁ and M ₂ comprise silicon nitride. Glass article according to one of the preceding claims, in which M ₁ and M ₂ are based on silicon nitride. Glass article according to one of the preceding claims, in which the stack is constituted by the following sequence of layers, starting from the surface of the substrate: layer based on titanium nitride/layer based on silicon nitride/layer with titanium nitride base/layer based on silicon nitride/optionally a protective layer chosen in particular from oxides of titanium, zirconium or a mixture of titanium and zirconium. Glass article according to one of the preceding claims, in which the thickness of the TN ₂ layer is greater than the thickness of the TN ₁ layer. Glass article according to one of Claims 1 to 8, in which the thickness of the TN layer ₁ is greater than the thickness of the TN layer _2. Glass article according to one of the preceding claims, in which the stack does not contain a layer based on silver or gold. Glass article according to one of the preceding claims, in which the glass substrate is made of clear glass. Glass article according to one of the preceding claims, in which:

• the thickness of the TN layer ₁ is between 5 and 25 nm, preferably between 10 and 20 nm,
• the thickness e ₁ of the module M ₁ is between 20 and 45 nm, preferably between 25 and 40 nm,
• the thickness of the TN layer ₂ is between 5 and 30 nm, preferably between 10 and 20 nm,
• the thickness e ₂ of the module M ₂ is between 5 and 30 nm, preferably between 5 and 20 nm.

Glass article according to one of Claims 1 to 12, in which:

• the thickness of the TN layer ₁ is between 5 and 25 nm, preferably between 10 and 20 nm,
• the thickness e ₁ of the module M ₁ is between 40 and 65 nm, preferably between 45 and 60 nm,
• the thickness of the TN layer ₂ is between 5 and 30 nm, preferably between 10 and 20 nm,
• the thickness e ₂ of the module M ₂ is between 70 and 110 nm, preferably between 80 and 100 nm.

Glass article according to one of Claims 1 to 12, in which:

• the thickness of the TN layer ₁ is between 10 and 30 nm, preferably between 10 and 25 nm,
• the thickness e ₁ of the module M ₁ is between 40 and 65 nm, preferably between 45 and 60 nm,
• the thickness of the TN layer ₂ is between 10 and 30 nm, preferably between 15 and 25 nm,
• the thickness e2 of the module M2 is between 20 and 45 nm, preferably between 25 and 40 nm.

Glass article according to one of the preceding claims, comprising two glass substrates assembled by a thermoplastic sheet, in particular of PVB, at least one of said substrates being provided with said stack of layers, said stack being preferably placed in contact with the thermoplastic sheet. Glass article according to one of claims 1 to 12, comprising two glass substrates assembled by a thermoplastic sheet, in particular of PVB, at least one of said substrates being provided with said stack of layers, said stack being preferably placed in contact with the thermoplastic sheet, in which :

• the thickness of the TN layer ₁ is between 10 and 30 nm, preferably between 15 and 25 nm,
• the thickness e ₁ of the module M ₁ is between 10 and 35 nm, preferably between 15 and 25 nm,
• the thickness of the TN layer ₂ is between 5 and 30 nm, preferably between 10 and 20 nm,
• the thickness e ₂ of the module M ₂ is between 50 and 90 nm, preferably between 60 and 80 nm.

Glass article according to one of Claims 1 to 9 and 11, comprising two glass substrates assembled by a thermoplastic sheet, in particular of PVB, at least one of the said substrates being provided with the said stack of layers, the said stack being preferably placed in contact with the sheet thermoplastic, in which:

• the thickness of the TN layer ₁ is between 1 and 20 nm, preferably between 1 and 10 nm, more preferably between 2 and 8 nm,
• the thickness e ₁ of the module M ₁ is between 50 and 80 nm, preferably between 55 and 75 nm,
• the thickness of the TN layer ₂ is between 20 and 50 nm, preferably between 25 and 45 nm,
• the thickness e ₂ of the module M ₂ is between 40 and 80 nm, preferably between 55 and 75 nm.

Glass article according to one of claims 1 to 12, comprising two glass substrates assembled by a thermoplastic sheet, in particular of PVB, at least one of said substrates being provided with said stack of layers, said stack being preferably placed in contact with the thermoplastic sheet, in which :

• the thickness of the TN layer ₁ is between 10 and 40 nm, preferably between 15 and 25 nm,
• the thickness e ₁ of the module M ₁ is between 60 and 100 nm, preferably between 75 and 95 nm,
• the thickness of the TN layer ₂ is between 10 and 30 nm, preferably between 15 and 25 nm,
• the thickness e ₂ of the module M ₂ is between 30 and 60 nm, preferably between 35 and 55 nm.

Glass article according to one of the preceding claims, in which the said glass substrate(s) are tempered or bent.