Material comprising a two-layer silver-based functional coating and an absorbent layered element

Abstract

The invention relates to a material comprising a transparent substrate coated with a functional coating comprising, successively from the substrate, an alternation of two continuous functional silver-based metallic layers and three dielectric coatings. The second dielectric coating comprises a layered element comprising: - a first layer comprising silicon selected from a nitride, oxide, or oxynitride layer, - a discontinuous silver-based layer deposited directly on the first silicon-based layer comprising nanometric silver particles, - a second layer comprising silicon selected from a nitride, oxide, or oxynitride layer deposited directly on the discontinuous silver-based layer.

Description

Title of the invention: Material comprising a two-layer silver-based functional coating and an absorbent layered element

[0001] The invention relates to a material comprising a transparent substrate coated with a functional coating capable of acting on solar radiation and / or infrared (IR) radiation, consisting of two silver-based functional layers, the functional coating further comprising a layered element having particular absorption properties. The invention also relates to glazing comprising these materials and to the use of such materials for manufacturing thermal insulation and / or solar protection glazing.

[0002] In the following description, the term "functional" qualifying "functional coating" or "functional layer" means "able to act on solar radiation and / or infrared radiation".

[0003] Glazing can be intended to equip both buildings and vehicles, in particular to prevent excessive overheating, so-called "solar control" glazing and / or to reduce the effort of air conditioning.

[0004] The selectivity “S” allows for the evaluation of the performance of these glazings. It corresponds to the ratio of the visible light transmission TLvis of the glazing to the solar factor FS of the glazing (S = TLvis / FS). The solar factor “FS or g” corresponds to the ratio, expressed as a percentage, between the total energy entering the room through the glazing and the incident solar energy. High selectivity corresponds to achieving high visible light transmission combined with selective filtering of UV and IR radiation.

[0005] Achieving high selectivity must not be at the expense of aesthetics, and in particular color. Generally, the aim is to obtain the most neutral aesthetic possible in terms of transmission, external reflection, and internal reflection. This color neutrality must also be achieved regardless of the viewing angle relative to the glazing.

[0006] Known selective glazing comprises transparent substrates coated with a functional coating. Functional coatings comprising silver-based functional layers are generally more efficient in terms of selectivity compared to other known infrared-reflecting functional coatings such as coatings comprising conductive oxide-based layers, layers based on other metallic layers, or IR-absorbing layers.

[0007] When seeking to increase selectivity, the aim is to selectively reduce transmission in the infrared region (above 750 nm). One solution consists of increasing the number of silver-based functional layers. When determining the transmission curves as a function of wavelength, the following observations are made. The greater the number of silver-based functional layers, the sharper the transmission profile is over the visible wavelength range, and the narrower the base of the peak corresponding to absorption. However, the cutoff is not sharp and often extends into the visible red wavelength range. Absorption therefore becomes significant at the extreme values ​​of the visible spectrum corresponding to red absorption around 700 nm.

[0008] Absorbing in this visible region does not lead to a significant decrease in light transmission. This phenomenon is explained by the fact that the determination of light transmission takes into account the sensitivity of the human eye, or visual acuity.The eye's sensitivity to wavelength gradually decreases on either side of a maximum between 495 and 555 nanometers (nm). The human eye is therefore less sensitive to the extreme wavelengths of the visible spectrum, particularly those in the 630 to 780 nm range. Light transmission is only slightly affected by absorption between 630 and 780 nm because absorption occurs in a region where the human eye is less sensitive. However, absorption in this range significantly reduces the total energy entering the room or vehicle, thus lowering the solar factor without significantly decreasing light transmission.

[0009] In conclusion, the small decrease in light transmission coupled with the large reduction in energy transmission leads to a clear improvement in selectivity.

[0010] By way of example, the selectivities achieved in double glazing thanks to functional coatings comprising 1, 2, 3 or 4 silver-based layers are respectively approximately 1.2, 1.7, 2.0 and 2.25.

[0011] However, absorbing in the range of wavelengths of visible red between 630 and 780 nm has a significant impact on color perception. When light rays reach the eyes, they are captured by photoreceptors in the retina. There are three types of photoreceptors, each with a spectral sensitivity to a specific region of the color spectrum: cones more sensitive to blue light (peak centered at approximately 420 nm), others to green light (peak centered at 530 nm), and a third type of cone to red light (peak centered at 565 nm). Absorbing light between 630 and 780 nm, that is, in the region corresponding to the predominant absorption of red light, results in the perception of complementary colors, particularly green. In conclusion, reducing red transmission gives the glass a green tint in terms of transmission.

[0012] To limit this green coloration, several approaches are possible. A traditional approach to achieving both high selectivity and color neutrality involves developing increasingly complex functional coatings. These coatings comprise several silver-based metallic functional layers, each sandwiched between two dielectric coatings consisting of multiple dielectric layers. Such glazing improves solar protection while maintaining high light transmission.

[0013] Colors are optimized by exploiting optical interference phenomena. However, for high levels of selectivity, this solution is insufficient. A compromise between neutrality and selectivity must then be found.

[0014] Indeed, two-layer functional silver-based coatings are extremely complex. Improving neutrality can only be achieved at the expense of selectivity.

[0015] The invention is concerned with obtaining materials and glazing that are selective, neutral in reflection and neutral in transmission.

[0016] To characterize the color of a material or glazing in transmission, reflection, or absorption, the reflection, transmission, or absorption spectrum is determined. From this spectrum, the color can be defined by the parameters a* and b* in the Lab system with illuminant D65 and CIE 2° 1931 as the observer.

[0017] In this case, a material or glazing with an excessively blue-green appearance means that the values ​​of a* are too negative. If we consider transmitted colors, this means that the values ​​of a*T are too negative.

[0018] Theoretically, seeking neutrality means aiming for zero values ​​of a* and b*. However, in practice, these results cannot be achieved. Furthermore, it is preferable not to be too close to 0 in order to avoid positive values. It is preferable to have values ​​of a* that are less close to 0 but strictly negative rather than close to 0 but alternately positive or negative. In the latter case, undesirable color shifts are observed, for example, between slightly red and slightly green. Consequently, if perfect neutrality is not possible, it is preferable for the color to tend towards a blue-green rather than towards red.

[0019] To achieve this, we seek to obtain negative values ​​of a* as close to 0 as possible, particularly in transmission, and ideally for all observation angles. According to the invention, different levels of transmission neutrality can be defined as a function of transmission values ​​of a*T: - Level 4: a*T between -8 and -6, - Level 3: a*T between -6 and -4, - Level 2: a*T between -4 and -2, - Level 1: a*T between -2 and -0. The more one seeks to achieve greater neutrality (level 1), the more selectivity is negatively impacted.

[0020] The values ​​of b*T can be positive or negative but preferably as close as possible to 0.

[0021] The applicant has discovered a new layered element that absorbs selectively in the green range, i.e., between 490 and 550 nm. The invention therefore relates to a new functional coating comprising two continuous silver-based functional metallic layers and an absorbing layered element, enabling the combination of high selectivity and excellent color neutrality in transmission and reflection, at normal or angled incidence.

[0022] The behavior of the absorbing layer element of the invention differs from the visible-absorbing elements traditionally used in functional coatings, such as metallic layers or metal nitride-based layers. These layers do not absorb specifically in the green range but rather relatively homogeneously across the entire visible spectrum (350-750 nm). Consequently, they do not allow for the selective neutralization of the green color. These absorbing layers do not provide both high selectivity and good neutrality.

[0023] By selectively absorbing in the green range, the effect of red light absorption is neutralized without significantly impacting light transmission and therefore without reducing selectivity. Using the absorbing layered element according to the invention, at the same level of selectivity, allows for better neutrality.

[0024] The mechanism is as follows. In the absence of an element specifically absorbing green light, to become less green, the transmission window towards red must be "enlarged" to capture more of it. In doing so, a significant amount of red / infrared radiation is allowed to pass through, which greatly increases the solar factor and thus reduces selectivity.

[0025] The behavior of the layered element according to the invention is also different from the layered elements based on discontinuous layers described in the prior art.

[0026] Document WO2018 / 197821 describes colored glazing composed of a clear glass substrate onto which a colored coating is deposited. The coating comprises metallic nanoparticles in an inorganic matrix of an oxide of at least one element selected from the titanium, silicon, or zirconium group, for example TiOx:Ag. The colored coating exhibits an absorption peak whose maximum is between 350 and 800 nm. The position of the absorption peak maximum varies depending on the thickness of the colored coating, the oxidation levels, or the density of the metallic particles.

[0027] Document WO2019 / 239312 discloses functional coatings comprising a discontinuous silver layer encapsulated in an inorganic matrix based of niobium or silicon oxide.

[0028] Document WO2011 / 123402 discloses functional coatings comprising a discontinuous silver layer located between a dielectric zinc stannate layer and a nickel-chromium alloy-based layer (“Inconel”) or between a zinc oxide layer and a titanium layer.

[0029] These documents disclose various layered elements comprising a discontinuous silver layer consisting of nanometric silver particles encapsulated in different environments such as an inorganic matrix or two dielectric and / or metallic layers. These layered elements do not simply allow for the achievement of satisfactory absorption properties in the green region, both before and after heat treatment.

[0030] Finally, nothing in these documents indicates how to modulate the absorption in the preferred range between 475 and 590 nm.

[0031] The layered element of the invention comprises a discontinuous silver layer including silver nanoparticles capable of generating a plasmonic effect. The plasmonic effect consists of a vibration of the electron cloud of nanoparticles when they are subjected to an electromagnetic field. "Plasmonic absorption" refers to absorption related to plasmonic resonance effects of silver nanoparticles in a dielectric matrix. The specific absorption of the layered element according to the invention results from the plasmonic effect generated by the interactions between these nanoparticles and their specific environment. This novel layered element specifically absorbs the color green. It is therefore particularly suitable for use in functional coatings with multiple continuous silver layers.

[0032] The invention therefore relates to a material comprising a transparent substrate coated with a functional coating comprising successively, from the substrate, an alternation of two continuous silver-based functional metallic layers, referred to from the substrate as the first and second functional layers, and three dielectric coatings referred to from the substrate as D1, Di2 and Di3, each dielectric coating comprising at least one dielectric layer, such that each continuous functional metallic layer is arranged between two dielectric coatings, the dielectric coating Di2 comprising a layered element comprising: - a first layer comprising silicon chosen from a nitride, oxide or oxynitride layer, - a discontinuous silver-based layer deposited directly onto the first silicon-based layer comprising nanometric silver particles, - a second layer comprising silicon selected from a nitride layer, of oxide or oxynitride deposited directly on the discontinuous silver-based layer, characterized in that: - the first or second layer containing silicon includes oxygen, and - the first or second layer containing silicon includes nitrogen.

[0033] According to this definition, the two layers in contact with the discontinuous silver-based layer cannot be two layers of silicon oxide or two layers of silicon nitride.

[0034] According to the invention, the layered element is judiciously placed in the second dielectric coating. The absorbing layered element placed in this dielectric coating makes it possible to obtain high selectivity coupled with the desired aesthetics, that is to say, excellent color neutrality in transmission and reflection, regardless of the viewing angle.

[0035] The preferred characteristics which appear in the rest of the description are applicable both to the material according to the invention and, where applicable, to the glazing, devices or process according to the invention.

[0036] Unless otherwise stated, the thicknesses referred to in this document are physical thicknesses and the layers are thin films. A thin film is defined as a layer having a thickness between 0.1 nm and 100 micrometers.

[0037] In this description, unless otherwise indicated, the expression "based on", used to describe a material or layer as to what it contains, means that the mass fraction of the constituent it comprises is at least 50%, in particular at least 70%, preferably at least 90%.

[0038] Throughout this description, the substrate according to the invention is considered to be laid horizontally. The coating or layered element is deposited on top of the substrate. The meaning of the terms "above" and "below," and "lower" and "upper," is to be understood in relation to this orientation. Unless otherwise specified, the terms "above" and "below" do not necessarily mean that two layers and / or coatings are in contact with each other. When it is specified that a layer is deposited "in contact" with another layer or coating, this means that there cannot be one (or more) layer(s) interposed between these two layers (or layer and coating).

[0039] The coating is deposited by magnetic field-assisted sputtering (magnetron process). According to this advantageous embodiment, all layers of the coating or layered element are deposited by magnetic field-assisted sputtering.

[0040] All the described luminous characteristics are obtained according to the principles and Methods of the European standard EN 410 relating to the determination of the luminous and solar characteristics of glazing used in glass for construction. Sunlight entering a building is considered to travel from the outside in.

[0041] The following luminous characteristics are measured with illuminant D65 at 2° perpendicular to the material: - AL corresponds to the light absorption in the visible spectrum in %, - a*abs and b*abs correspond to the colors in absorption a* and b* in the L*a*b* system, after removing the contribution of the substrate, with the observer on the layer side, - TL corresponds to the light transmission in the visible spectrum as a percentage - Rext corresponds to the external light reflection in the visible spectrum as a percentage, from the observer's perspective on the exterior space. - Rint corresponds to the internal light reflection in the visible spectrum as a percentage, from the observer's perspective on the interior space side. - a*T and b*T correspond to the colors in transmission a* and b* in the L*a*b* system, - a*Rext and b*Rext correspond to the reflected colors a* and b* in the L*a*b* system, observer on the outside space side. - a*Rint and b*Rint correspond to the colors in reflection a* and b* in the L*a*b* system, observer on the interior space side.

[0042] To evaluate angle neutrality, the angle colors corresponding to the colors a* and b* in the L*a*b* system are also determined at an angle of 60° according to the illuminant D65. The angle colors can be determined in transmission a*60°T and b*60°T, in external reflection a*60°Rext and b*60°Rext or internal reflection a*60°Rint and b*60°Rint.

[0043] To characterize the absorption of the layered element, its absorption colors can be determined. For this purpose, the layered element is deposited on a 4 to 6 mm thick clear glass substrate. Its absorption spectrum is then determined, and the colors are calculated in the Lab system with illuminant D65 and CIE 2° 1931 as the observer. It is then possible to calculate the light absorption AL and its specific colorimetric parameters a*abs and b*abs.

[0044] According to the invention, the absorbing layered element must absorb specifically in the green range without having excessively high light absorption so as not to significantly impact light transmission and therefore selectivity. Neutralization is considered good when the layered element exhibits very negative a*abs values ​​and light absorption of less than 15%. Preferably: - a*abs is less than -5, or less than -10, and / or - b*abs varies between -10 and +10, and / or - AL is between 10 and 15%.

[0045] Another way to evaluate the neutralization efficiency is to determine the neutralization factor corresponding to the product of the light absorption AL and a*abs. The neutralization efficiency is proportional to the neutralization factor.

[0046] Different results are obtained depending on whether or not the layered element undergoes high-temperature heat treatment. When the layered element undergoes quenching-type heat treatment, neutralization factors of -100 can be obtained. When the layered element does not undergo quenching-type heat treatment, neutralization factors on the order of -40 can be obtained. Preferably, the neutralization factor is less than -50, or even less than -100.

[0047] The layered element of the invention may also have the following characteristics alone or in combination: - the second layer containing silicon is a silicon oxynitride layer, - The first layer containing silicon is a silicon oxynitride layer, - The first layer containing silicon contains oxygen, - the first and second layers comprising silicon both contain oxygen, and in that the first layer comprising silicon comprises a larger proportion of oxygen than the second layer comprising silicon, - The first and second layers have a different chemical composition, - The first and second layers have the same chemical composition. - the first layer containing silicon has a thickness of between 2 and 30 nm, between 4 and 20 nm, preferably from 5 to 15 nm, - the second layer, comprising silicon, has a thickness between 2 and 30 nm, between 4 and 20 nm, preferably from 5 to 15 nm, - the silver-based discontinuous layer has a thickness of less than 5 nm, preferably less than 4.0 nm, less than 3.0 nm or less than 2.0 nm, - the discontinuous silver-based layer deposited by sputtering in an atmosphere comprising argon or krypton, preferably krypton, - the layered element has a visible absorption peak with a maximum between 490 and 550 nm, preferably between 500 and 525 nm, - the layered element has a visible absorption peak with a full width at half maximum (FWHM) of less than 350 nm, preferably less than 300 nm, or even less than 270 nm, - the layered element has a light absorption in the visible range of between 8 and 20%, preferably between 10 and 17%, absorption measured on the layered element side on a 4 mm thick clear glass substrate.

[0048] According to the invention, two layers of different chemical composition means that they are composed of different chemical elements or of the same elements in different proportions. According to the invention, two layers of the same chemical composition means that they are composed of the same chemical elements present in the same proportions.

[0049] The layered element exhibits its advantageous absorption properties both: - when the layered element or the substrate carrying the layered element has not undergone high-temperature heat treatment and - when the layered element or the substrate carrying the layered element undergoes high-temperature heat treatment.

[0050] Obtaining the properties regardless of whether or not heat treatment is present allows for greater flexibility and simplicity in production lines. For example, it is possible to use the same cathode sequence for coatings used in both untempered and tempered applications.

[0051] According to the invention, the discontinuous silver particles are encapsulated between two specific dielectric layers that constitute the particular environment. The applicant has discovered that the advantageous absorption properties, both before and after heat treatment, of the layered element of the invention derive directly from this environment. Indeed, it is this environment, comprising silicon, nitrogen, and oxygen, in contact with the discontinuous silver-based layer, that enables specific absorption in the green region, particularly in the wavelength range from 490 to 550 nm.

[0052] Such a system not only allows for the selective absorption of certain colors, but also for the modulation of absorption properties within an advantageous wavelength range. By selectively absorbing certain wavelengths, light transmission is less affected. This allows for the maintenance of high selectivity. The ability to modulate the position of the absorption peak on demand also makes color control easier.

[0053] Another advantage of the layered element according to the invention is that the colors, particularly the b*abs values, can be adjusted by modifying the amounts of oxygen during the deposition of the layer(s) located below and / or above the silver particles. This color adjustment could not be achieved with the prior art materials encapsulating the silver particles. By varying the oxidation rate of the silicon-containing layers, certain trends were identified. For example, increasing the oxidation rate of the second silicon-containing layer results in a shift from very positive b*abs values ​​to less positive values ​​without a significant change in the a*abs values, which remain negative. It is therefore possible to modulate the color very easily by simply adjusting the oxidation level of the second layer containing silicon.

[0054] Another advantage of using such silicon-based layers is that they exhibit absorption parameters close to those required even before or without heat treatment.

[0055] In order to demonstrate that the nature of the layers is an essential feature of the invention, other configurations were tested. These included configurations comprising titanium-based or nickel-chromium alloy metallic layers over the discontinuous silver layer and configurations comprising dielectric layers of a different nature than those claimed. These configurations have the following drawbacks: - excessive light absorption in the visible spectrum - an absent or non-centered absorption peak between 490 and 550 nm, and / or - unsatisfactory colours with absorption values ​​of a*abs not negative enough and of b*abs too positive.

[0056] The layered element has a thickness: - greater than or equal to 5 nm, greater than or equal to 8 nm, greater than or equal to 10 nm or greater than or equal to 15 nm, - less than or equal to 100 nm, less than or equal to 30 nm, less than or equal to 20 nm or less than or equal to 15 nm. Preferably, the layered element has a thickness between 5 nm and 15 nm. The thickness of the layered element corresponds to the sum of the thicknesses of the first, the second layer comprising silicon and the equivalent thickness of the discontinuous silver-based layer.

[0057] The layered element comprises a discontinuous silver layer. According to the invention, a layer of a material is considered continuous when the layer is present over the entire surface and consists of a non-zero thickness of the material in question over the entire surface. In contrast, a discontinuous layer is not present over the entire surface. The coverage ratio characterizes this discontinuity. The coverage ratio corresponds to the percentage ratio, in a square of arbitrary dimensions, of the surface area occupied by the discontinuous layer to the surface area of ​​the material. The discontinuous layer represents 10% to 98%, 40% to 95%, 50% to 90%, 53% to 83%, or 63% to 83% of the surface area of ​​the square.

[0058] For each material and depending on its environment, there is a minimum thickness below which the layer will not be continuous.

[0059] For silver-based coatings deposited by sputtering, the minimum thickness beyond which a continuous layer is not obtained is approximately 5 nm. This means that when choosing to parameterize the sputtering device ca By methodically aiming for a continuous layer 5 nm thick, one actually obtains a discontinuous layer containing areas without silver and areas with silver particles thicker than 5 nm. There is a rearrangement in the form of nanometric silver particles, which then form nanometric patterns.

[0060] According to the invention, the equivalent thickness of a discontinuous layer is defined as the thickness of that layer if it were continuous. This equivalent thickness can, for example, be determined by secondary ion mass spectrometry (SIMS) analysis of the layered element using a microprobe. This allows the amount of substance to be quantified in terms of the number of silver atoms per unit area. This value can then be converted into an equivalent thickness. To obtain an equivalent thickness, the corresponding thickness is determined for a high feed rate. Then, a simple proportion is applied to the feed rate to obtain the desired equivalent thickness. For example, a thickness of 10 nm is measured for a silver layer deposited at a feed rate of 10 m / min. Therefore, if a silver layer with an equivalent thickness of 1 nm is desired, a feed rate of 10 m / min should be chosen.

[0061] The discontinuous silver-based layer has an equivalent thickness: - greater than 0.3 nm, greater than 0.5 nm, greater than 0.8 nm, greater than 1 nm, and / or - less than 5 nm, less than 4.5 nm, less than 4.0 nm, less than 3.0, less than 2.5 nm, less than 2.0 nm, less than 1.5 nm.

[0062] The silver-based discontinuous layer comprises 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 discontinuous layer. Preferably, the silver-based discontinuous layer comprises less than 1.0% by mass of metals other than silver relative to the mass of the functional silver-based metallic layer. To obtain a sharp absorption peak, it is preferable to have discontinuous layers of pure or lightly doped silver. The silver particles are preferably pure silver-based.

[0063] The discontinuous layer is deposited above and in contact with a first layer comprising silicon and below and in contact with a second layer comprising silicon.

[0064] Each layer comprising silicon in contact with the discontinuous silver-based layer has a thickness greater than or equal to 2 nm, greater than or equal to 3 nm, greater than or equal to 4 nm or greater than or equal to 5 nm.

[0065] Each layer comprising silicon in contact with the discontinuous silver-based layer has a thickness less than or equal to 25 nm, less than or equal to 20 nm or less than or equal to 15 nm.

[0066] The layers comprising silicon can be chosen from the layers based of oxide, silicon nitride-based or silicon oxynitride-based such as silicon oxide-based layers, silicon nitride-based layers and silicon oxynitride-based layers.

[0067] The quantities of oxygen and nitrogen in a layer are determined as atomic percentages relative to the total quantities of oxygen and nitrogen in the layer considered.

[0068] According to the invention: - Silicon oxide-based layers consist primarily of oxygen and very little nitrogen, - Silicon nitride-based layers consist primarily of nitrogen and very little oxygen, - Silicon oxynitride-based layers comprise a mixture of oxygen and nitrogen.

[0069] Silicon oxide-based layers comprise at least 90% atomic percentage of oxygen relative to the oxygen and nitrogen in the silicon oxide-based layer. Silicon nitride-based layers comprise at least 90% atomic percentage of nitrogen relative to the oxygen and nitrogen in the silicon nitride-based layer. Silicon oxynitride-based layers comprise 10 to 90% (exclusive) atomic percentage of nitrogen relative to the oxygen and nitrogen in the silicon oxynitride-based layer.

[0070] According to one embodiment, the first and second silicon layers both contain oxygen. Preferably, the first silicon layer contains a higher proportion of oxygen than the second silicon layer. This means, for example, that the atomic percentage of oxygen relative to oxygen and nitrogen in the first silicon layer is 5%, 10%, or even 20% higher than the atomic percentage of oxygen relative to oxygen and nitrogen in the second silicon layer.

[0071] The color of the layered element is modifiable within a certain advantageous range by changing the oxidation rate of the first and second layers comprising silicon and / or the thickness of the discontinuous silver layer.

[0072] To illustrate this phenomenon simply, we will use layers comprising 100% silicon by mass relative to the mass of all the elements constituting the layer containing silicon other than nitrogen and oxygen. However, the invention is not limited to the exclusive presence of silicon. The layer may include other elements.

[0073] The composition of the first and second layers comprising silicon in contact with the discontinuous silver-based layer can vary stoichiometrically between SiO2 and Si3N4 via oxynitride layers. Such layers containing silicon can be defined by the formula SiON(x) = x Si3N4 + (1-x) SiO2 with the parameter x characteristic of the effective mixture being between 0 and 1. Stoichiometry is assessed using the optical index at 550 nm (2.0 for SiN, 1.5 for SiO2).

[0074] The quantity of nitrogen N2 is kept more or less constant. It is the quantity of O2 that determines the oxidation rate of the layer.

[0075] The first layer comprising silicon preferably has a parameter x which varies between 0 and 0.5 or between 0.1 and 0.4.

[0076] The second layer comprising silicon preferably has a parameter x which varies between 0.2 and 1, between 0.1 and 1 or between 0.2 and 0.9.

[0077] By manipulating the oxynitriding of these two layers, it is possible to shift the maximum of the absorption peak. By doing so, the colors can be modified on demand.

[0078] In the case of an unheat-treated material, there is a thickness range for the discontinuous silver layer where the absorption a*abs is negative and stable. However, when the thickness of the silver layer is increased: - The neutralization potential (AL*a*abs) increases because the light absorption AL increases, - the b*abs increases which may not be desirable for the colors of the stack. To prevent the increase in b*abs, it is possible to increase the oxidation rate of the second layer containing silicon. This has the effect of reducing b*abs and therefore modifying the color rendering. Finally, the absorption peak is sharper when the oxidation rate of the first layer containing silicon is high.

[0079] In the case of a heat-treated material, the heat treatment helps to refine the absorption peak. The higher the oxidation rate in the first and second silicon layers, the more the peak is refined and shifted towards the blue end (compared to the unheat-treated material). This allows for adjusting the b*abs and obtaining a very negative a*abs. Conversely, if there is too much oxygen, the light absorption AL becomes too low and the neutralization insufficient.

[0080] Layers comprising silicon, having at least 90% silicon by mass relative to the mass of all elements constituting the silicon layer other than nitrogen and oxygen, exhibit refractive indices as defined below, depending on whether they are oxide, nitride, or oxynitride layers. Silicon oxide-based layers are characterized by a refractive index at 550 nm of 1.55 or less. Silicon nitride-based layers These coatings are characterized by a refractive index at 550 nm greater than or equal to 1.95. Silicon oxynitride-based coatings are characterized by a refractive index at 550 nm intermediate between that of a non-nitrided oxide coating and a non-oxidized nitride coating. Silicon oxynitride-based coatings preferably have a refractive index at 550 nm greater than 1.55, 1.60, or 1.70, or between 1.55 and 1.95, 1.60 and 2.00, 1.70 and 2.00, or 1.70 and 1.90. These refractive indices can vary to a certain extent (± 0.1) depending on the deposition conditions. Indeed, by adjusting certain parameters such as pressure or the presence of dopants, it is possible to obtain coatings of varying densities and therefore a variation in refractive index.

[0081] The layers comprising silicon may comprise or be made of elements other than silicon, oxygen and nitrogen. These elements may be selected from aluminium, boron, titanium and zirconium.

[0082] The layers comprising silicon may comprise at least 50%, at least 60%, at least 65%, at least 70%, at least 75.0%, at least 80% or at least 90% by mass of silicon relative to the mass of all the elements constituting the layer comprising silicon other than nitrogen and oxygen.

[0083] Preferably, the layer comprising silicon comprises at most 35%, at most 20% or at most 10% by mass of elements other than silicon relative to the mass of all the elements constituting the layer comprising silicon other than oxygen and nitrogen.

[0084] The silicon-based layer may comprise at least 2%, at least 5.0% or at least 8% by mass of aluminium relative to the mass of all the elements constituting the silicon oxide-based layer other than oxygen and nitrogen.

[0085] Silicon zirconium nitride-based layers SixZryNz are among the layers comprising silicon, in particular silicon nitride-based layers. The refractive index of silicon zirconium nitride-based layers increases with increasing proportions of zirconium in said layer.

[0086] Silicon nitride-based layers may include aluminum and / or zirconium. Such layers may include, in atomic proportions relative to the atomic proportions 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 15 to 30% atomic zirconium.

[0087] According to the invention, the first and second silicon layers are deposited from a silicon metallic target. Deposition takes place in an atmosphere comprising an optimized amount of oxygen and nitrogen to obtain the desired properties. The deposition atmosphere comprises a mixture of noble gases (He, Ne, Xe, Ar, Kr) and oxygen and / or nitrogen. The noble gas is preferably argon. The layers The following parameters allow us to define the conditions for a sputtering deposition:

[0088] - the deposition pressure, - the composition of gases in volumetric flow rate (unit sccm "standard cubic centimeter per minute").

[0089] According to the invention, the following parameters were used:

[0090] - the pressure in the deposition chamber is between 1 and 15 pbar, preferably 2 and 10 pbar or 2 and 8 pbar, - the deposition atmosphere comprises a mixture of argon, oxygen and nitrogen. The optimal oxygen threshold can vary to some extent depending on, for example: - power, - the configuration of the sputtering deposition chamber (geometry, locations of gas inlets... A person skilled in the art can define a satisfactory atmosphere by varying these parameters to a certain extent. In particular, a person skilled in the art is perfectly capable of determining the power to be applied to the target and the volumetric flow rates of oxygen, nitrogen, and noble gases.

[0091] Unless otherwise stated, the thicknesses referred to in this document without further specification are physical, real, or geometric thicknesses denoted Ep and are expressed in nanometers (and not optical thicknesses). The optical thickness Eo is defined as the physical thickness of the layer in question multiplied by its refractive index at a wavelength of 550 nm: Eo = n*Ep. Since the refractive index is a dimensionless value, the unit of the optical thickness can be considered to be the same as that chosen for the physical thickness.

[0092] According to the invention, a dielectric coating corresponds to a sequence of layers comprising at least one dielectric layer, located between the substrate and the first functional layer (Dil), between two functional layers (Di2 or Di3) or above the last functional layer (Di4).

[0093] If a dielectric coating is composed of several dielectric layers, the optical thickness of the dielectric coating corresponds to the sum of the optical thicknesses of the different dielectric layers constituting the dielectric coating. If a dielectric coating includes an absorbing layer for which the refractive index at 550 nm includes a non-zero (or non-negligible) imaginary part of the dielectric function, for example a metallic layer, the thickness of this layer is not taken into account for the calculation of the optical thickness of the dielectric coating.

[0094] The thickness of the blocking layers is not taken into account for the calculation of the optical thickness of the dielectric coating.

[0095] When a dielectric coating includes a layered element, the thickness of the dielectric layers of the layered element is taken into account in the calculation of the optical or physical thickness of the dielectric coating.

[0096] For the purposes of the present invention, the terms "first," "second," and "third" for functional layers or dielectric coatings are defined starting from the substrate carrying the stack and referring to the layers or coatings with the same function. For example, the functional layer closest to the substrate is the first functional layer, the next one moving away from the substrate is the second functional layer, and so on.

[0097] The functional coating comprises two continuous silver-based metallic functional layers (Fl and F2), each disposed between two dielectric coatings (Dil, Di2, Di3). The functional coating may comprise only two continuous silver-based metallic functional layers.

[0098] Continuous silver-based metallic 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 metallic functional layer comprises less than 1.0% by mass of metals other than silver relative to the mass of the silver-based metallic functional layer.

[0099] The first functional layer has a thickness between 7 and 20 nm or between 10 and 18 nm. The second functional layer has a thickness between 7 and 20 nm or between 10 and 18 nm.

[0100] The functional coating comprises one or more blocking layers located in contact below and / or above one or more functional layers.

[0101] The blocking layers traditionally serve to protect the functional layers from possible degradation during the deposition of the upper dielectric coating and during possible high-temperature heat treatment, such as annealing, bending and / or quenching.

[0102] The blocking layers are chosen from: - metallic coatings based on a metal or metallic alloy, metallic nitride coatings, and metallic oxynitride coatings of one or more elements selected from titanium, zinc, tin, nickel, chromium, and niobium, - the metallic oxide layers of one or more elements chosen from titanium, nickel, chromium and niobium.

[0103] The blocking layers may, in particular, be layers of Ti, TiN, TiOx, Nb, NbN, Ni, NiN, Cr, CrN, NiCr, NiCrN, SnZnN. When these blocking layers are deposited in metallic, nitrided, or oxynitrided form, these layers may undergo partial or total oxidation depending on their thickness and the nature of the layers surrounding them, for example, at the time of deposition of the next layer or by oxidation in contact with the underlying layer.

[0104] According to advantageous embodiments of the invention, the blocking layer(s) satisfy one or more of the following conditions: - each functional metallic layer is in contact with at least one blocking layer chosen from a blocking sublayer and a blocking overlayer, and / or - each functional metallic layer is in contact with a blocking overlayer, and / or - the thickness of each blocking layer is at least 0.05 nm, or between 0.05 and 2.0 nm, or between 0.05 and 1 nm, and / or - the sum of the thicknesses of all the blocking layers is greater than or equal to 0.5 nm or greater than or equal to 0.8 nm or greater than or equal to 1.0 nm, and / or - the sum of the thicknesses of all the blocking layers is less than or equal to 5.0 nm or less than or equal to 3.0 nm or less than or equal to 2.0 nm,

[0105] For the blocking layers, the thicknesses correspond to the thicknesses of the layers as deposited, i.e. before heat treatment or before any oxidation during the deposition of the overlying layer.

[0106] According to the invention, the blocking layers are considered not to be part of a dielectric coating. This means that their thickness is not taken into account in the calculation of the optical or geometric thickness of the dielectric coating in contact with them.

[0107] For the purposes of this invention, "dielectric layer" means that, from the point of view of its nature, the material is "non-metallic," that is, not a metal. In the context of the invention, this term refers to 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.

[0108] Preferably, each dielectric coating consists solely of one or more dielectric layers. Preferably, there is therefore no absorbing layer in the dielectric coatings so as not to reduce light transmission.

[0109] For the purposes of this invention, "dielectric coating" means that there may be one or more layers of different materials within the coating. A "dielectric coating" according to the invention comprises primarily dielectric layers. However, according to the invention, these coatings may also comprise layers of other types, in particular absorbent layers, for example, metallic layers.

[0110] A "same" dielectric coating is considered to be located: - between the substrate and the first functional layer, - between each functional silver-based metallic layer, - above the last functional layer (the one furthest from the substrate).

[0111] For the purposes of this invention, "dielectric layer" means a material that is "non-metallic" in nature, i.e., not a metal. In the context of this invention, the term refers to 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 denotes the actual 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, which is the same for both n and k.

[0112] The thickness of a dielectric coating corresponds to the sum of the thicknesses of the layers constituting it.

[0113] The coatings have a thickness greater than 15 nm, preferably between 15 and 200 nm.

[0114] The dielectric layers of the coatings have the following characteristics, alone or in combination: - They are deposited by magnetic field-assisted sputtering, - They are chosen from oxides, nitrides or oxynitrides of one or more elements chosen from titanium, silicon, aluminium, zirconium, tin and zinc, - they have a thickness greater than 2 nm, preferably between 4 and 100 nm.

[0115] Dielectric layers, in addition to their optical function, can have various other functions. The choice of the type and position of the dielectric layers within the dielectric coating depends on this function. Examples include the following functions: - Stabilizing or wetting layers located in the immediate vicinity of silver-based functional layers such as zinc oxide-based layers, - Smoothing layers located below wetting layers such as tin oxide-based layers, - barrier layers or layers with optical function.

[0116] A single dielectric layer generally performs several functions. Indeed, each dielectric layer plays an optical role that depends on its refractive index and its thickness.

[0117] Dielectric layers are conventionally chosen from oxide-based, nitride-based, or oxynitride-based layers. Oxide-based layers of one or more elements consist essentially of oxygen and very little nitrogen. Oxide-based layers comprise, in particular, at least 90% atomic percentage of oxygen relative to oxygen and nitrogen in said layer. Nitride-based layers consist primarily of nitrogen and very little oxygen. Nitride-based layers consist of at least 90% atomic percentage of nitrogen relative to oxygen and nitrogen in said layer. Oxynitride-based layers consist of a mixture of oxygen and nitrogen. Silicon oxynitride-based layers consist of 10 to 90% (exclusive limits) atomic percentage of nitrogen relative to oxygen and nitrogen in said layer.

[0118] 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 considered.

[0119] The dielectric layers are conventionally chosen from: - layers comprising silicon, aluminum and / or zirconium, possibly doped with at least one other element, - Tin oxide-based coatings, - Titanium oxide-based coatings, - Zinc oxide-based coatings.

[0120] Preferably, the silver-based functional layer is located above a dielectric layer, referred to as a stabilizing or wetting layer, made of a material suitable for stabilizing the interface with the functional layer. These layers are generally zinc oxide-based.

[0121] Preferably, the silver-based functional layer is located beneath a dielectric layer, referred to as a stabilizing or wetting layer, made of a material suitable for stabilizing the interface with the functional layer. These layers are generally zinc oxide-based.

[0122] Zinc oxide-based layers may comprise at least 80% or at least 90% by mass of zinc relative to the total mass of all elements constituting the zinc oxide-based layer, excluding oxygen and nitrogen.

[0123] Zinc oxide-based layers may comprise one or more elements selected from aluminium, titanium, niobium, zirconium, magnesium, copper, silver, gold, silicon, molybdenum, nickel, chromium, platinum, indium, tin and hafnium, preferably aluminium.

[0124] Zinc oxide-based layers may optionally be doped with at least one other element, such as aluminium.

[0125] A priori, the zinc oxide-based layer is not nitrided, however traces may exist.

[0126] The zinc oxide-based layer comprises, in increasing order of preference, at least 80%, at least 90%, at least 95%, at least 98% or at least 100%, by mass of oxygen relative to the total mass of oxygen and nitrogen.

[0127] The dielectric coating located between the substrate and the first functional metallic layer and / or one or each dielectric coating located above the first silver-based functional layer comprises a zinc oxide-based layer comprising at least 80% by mass of zinc relative to the mass of all elements other than oxygen.

[0128] Preferably, each dielectric coating comprises a zinc oxide-based layer comprising at least 80% by mass of zinc relative to the mass of all elements other than oxygen.

[0129] Preferably, the dielectric coatings located directly below a continuous silver-based functional metallic layer comprise at least one zinc oxide-based dielectric layer, optionally doped with at least one other element, such as aluminum. The metallic functional layer deposited above a zinc oxide-based layer is either in direct contact or separated by a blocking layer.

[0130] Preferably, the dielectric coatings located directly above a continuous silver-based functional metallic layer comprise at least one zinc oxide-based dielectric layer, optionally doped with at least one other element, such as aluminum. The metallic functional layer deposited below a zinc oxide-based layer is either in direct contact or separated by a blocking layer.

[0131] The zinc oxide layers have a thickness: - of at least 1.0 nm, at least 2.0 nm, at least 3.0 nm, at least 4.0 nm or at least 5.0 nm, and / or - at most 25 nm, at most 10 nm or at most 8.0 nm.

[0132] Preferably, the material comprises one or more layers based on tin oxide, preferably zinc oxide and tin.

[0133] Tin oxide-based layers comprise at least 20% by mass of tin relative to the mass of elements other than oxygen or nitrogen. Zinc tin oxide-based layers comprise at least 20% by mass of tin relative to the total mass of zinc and tin. The zinc tin oxide-based layer comprises, relative to the total mass of zinc and tin, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, or at least 80% by mass of tin. Preferably, the zinc tin oxide-based layer comprises 40 to 80% by mass of tin relative to the total mass of zinc and tin.

[0134] The tin oxide-based layer has a thickness of: - greater than 5 nm, greater than 10 nm, greater than 15 nm, greater than 20 nm or greater than 25 nm, - less than 50 nm, less than 40 nm or less than 35 nm.

[0135] The dielectric coating located between the substrate and the first continuous functional metallic layer and / or one or each of the dielectric coatings located above the first continuous silver-based functional layer comprises a tin oxide-based layer, preferably a zinc tin oxide-based layer, comprising at least 20% by mass of tin relative to the total mass of zinc and tin. Each dielectric coating may comprise a tin oxide-based layer, preferably a zinc tin oxide-based layer, comprising at least 20% by mass of tin relative to the total mass of zinc and tin.

[0136] Dielectric coatings may include layers comprising silicon as defined for the layered element.

[0137] Each layer comprising silicon has a thickness greater than or equal to 2 nm, greater than or equal to 3 nm, greater than or equal to 4 nm or greater than or equal to 5 nm.

[0138] Each layer comprising silicon has a thickness less than or equal to 25 nm, less than or equal to 20 nm or less than or equal to 15 nm.

[0139] Layers comprising silicon can be obtained: - by sputtering, - from a silicon metallic target or a silicon oxide-based ceramic target.

[0140] The dielectric coating furthest from the substrate may include a protective layer. These layers generally have a thickness of between 0.5 and 10 nm, preferably between 1 and 5 nm. This protective layer may be selected from a layer based on titanium, zirconium, hafnium, silicon, zinc and / or tin and mixtures thereof, this or these metals being in metallic, oxidized or nitrided form.

[0141] The functional coating advantageously has one or more of the following characteristics: - each dielectric coating located below a functional layer comprises a zinc oxide-based layer situated below, in contact with, or separated by a blocking layer from the functional layer, having a thickness greater than or equal to 3 nm, - Each dielectric coating located above a functional layer comprises a zinc oxide-based layer situated above, in contact with, or separated from by a blocking layer by the functional layer, - The first functional layer has a thickness between 7 and 20 nm, - The second functional layer has a thickness between 7 and 20 nm, - The first dielectric coating (Dil) has an optical thickness between 60 and 120 nm. - the second dielectric coating Di2 has an optical thickness between 120 and 250 nm, - the third dielectric coating Di3 has an optical thickness between 40 and 120 nm, - The first dielectric coating Dil comprises, in this order: - a layer based on silicon nitride or titanium oxide, 20 to 50 nm thick, - a layer based on zinc and tin oxide, 0 to 30 nm thick, - a zinc oxide-based layer of 2 to 24 nm, The second dielectric coating Di2 comprises, in this order: - a zinc oxide-based layer of 4 to 24 nm, - a silicon nitride-based layer of 30 to 100 nm, - a silicon oxide-based layer from 0 to 30 nm, - the layered element, - a silicon nitride-based layer of 30 to 100 nm, - a zinc and tin oxide-based layer from 0 to 40 nm, - a zinc oxide-based layer of 4 to 24 nm, The third dielectric coating Di3 comprises, in this order: - a zinc oxide-based layer of 4 to 24 nm, - one or more layers based on silicon nitride, the thickness of all these layers based on silicon nitride is 30 to 75 nm or 20 to 45 nm, - a top protective layer of 0 to 5 nm, all these thicknesses being optical thicknesses.

[0142] According to one embodiment, the protective layer is based on zirconium oxide and / or titanium, preferably based on zirconium oxide, titanium oxide or titanium oxide and zirconium.

[0143] The material, i.e. the coated transparent substrate, is intended to undergo high-temperature heat treatment. Therefore, the coating and the substrate have preferably been subjected to high-temperature heat treatment such as quenching, annealing, or bending.

[0144] The material of the invention has the advantage that these advantageous properties are obtained even when the material coated with the functional coating or the functional coating alone has not undergone high-temperature heat treatment. The materials according to the invention can be used interchangeably: - as deposited, that is to say without having been subjected to any high-temperature heat treatment; in this case, neither the substrate coated with the functional coating, nor the functional coating alone, has undergone high-temperature heat treatment. - treated by laser radiation; in this case, only the functional coating undergoes high-temperature heat treatment. - treated by annealing or quenching, in this case the substrate and the functional coating undergo heat treatment at high temperature.

[0145] As explained previously, according to the invention the properties must be obtained even when the functional coating or the substrate bearing the functional coating has not undergone high-temperature heat treatment.

[0146] The present invention therefore relates to the coated substrate without heat treatment. The functional coating may not have undergone heat treatment at a temperature exceeding 500 °C, preferably 300 °C.

[0147] The present invention also relates to the heat-treated material. The heat treatments are selected from: - annealing, for example rapid annealing, - quenching and / or dome making.

[0148] The material, i.e., the transparent substrate coated with the functional coating, may have undergone high-temperature heat treatment. Both the functional coating and the substrate may have been subjected to high-temperature heat treatment such as quenching, annealing, or bending.

[0149] It is also possible to heat-treat only the stack. In this case, only the functional coating may have undergone heat treatment.

[0150] In both cases, the functional coating may have undergone heat treatment at a temperature above 300 °C, preferably 500 °C. The heat treatment temperature (at the level of the functional coating) is above 300 °C, preferably above 400 °C, and better above 500 °C.

[0151] According to the invention, it is possible to perform a rapid thermal process (“Rapid Thermal Process”) such as laser or flash lamp annealing. Rapid thermal annealing is described, for example, in applications WO2008 / 096089 and WO2015 / 185848. In these cases, only the functional coating is subjected to heat treatment. During this type of treatment, each point of the stack is heated to a temperature of at least 300°C while maintaining a temperature of 150°C or less at any point on the substrate face opposite to that on which the functional coating is located. This process has the advantage of heating only the functional coating, without significant heating of the entire substrate.

[0152] In the case of laser treatment, the coated materials can be treated using a laser line formed from InGaAs laser diode or Yb:YAG disc laser sources. These continuous sources emit at a wavelength between 900 and 1100 nm. The laser line has a length of approximately 3.3 m, equal to the width 1 of the substrate, and an average full width at half maximum (FWHM) between 45 and 100 pm.

[0153] The materials are arranged on a roller conveyor so as to move along an X direction, parallel to its length. The laser line is fixed and positioned at the- above the coated surface of the substrate with its longitudinal direction Y extending perpendicularly to the direction X of the substrate's scrolling, that is, along the width of the substrate, extending over its entire width. 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 100 kW / cm². The substrate was moved under the laser line at a speed of approximately 8 m / min.

[0154] The functional coating 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 every point of the substrate face opposite to that on which the stack is located.

[0155] It is also possible to combine heat treatments. For example, it is possible to carry out rapid thermal annealing followed by quenching.

[0156] The functional coating and the substrate may have been subjected to heat treatment at a high temperature exceeding 500 °C, such as quenching, annealing, or bending. The substrate coated with the functional coating may be bent or tempered glass.

[0157] The transparent organic substrates according to the invention may also be made of polymer, rigid or flexible. Examples of suitable polymers 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 like ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP); - photocurable and / or photopolymerizable resins, such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate resins and - polythiomethanes.

[0158] The substrate is preferably a sheet of glass or glass-ceramic.

[0159] The substrate is preferably transparent, colorless (in which case it is clear glass or extra clear) or colored, for example in blue, gray or bronze. The glass is preferably of the soda-lime silicate type, but it can also be of the borosilicate or aluminoborosilicate type.

[0160] According to a preferred embodiment, the substrate is made of glass, in particular silico-sodo-calcic or of polymeric organic matter.

[0161] The substrate advantageously has a 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 2.8 and 6 mm. The substrate may be flat or convex, or even flexible.

[0162] The invention also relates to glazing comprising at least one material according to the invention. Depending on the intended applications and, in particular, the desired properties, this glazing may be in the form of monolithic glazing, multiple glazing, laminated glazing, or multiple and laminated glazing. The glazing may comprise at least one material according to the invention and an additional substrate assembled in the form of multiple glazing.

[0163] Conventionally, the faces of a glazing are designated from the outside of the building and by numbering the faces of the substrates from the outside towards the inside of the dwelling or room it equips. This means that the incident sunlight passes through the faces in ascending order of their number.

[0164] The best performing known selective glazings are generally double glazings comprising a functional coating located on face 2, i.e. on the substrate furthest outside the building; on its face turned towards the intercalated gas layer.

[0165] The materials according to the invention mounted in the form of double glazing with the functional coating positioned on face 2, exhibit a high selectivity in particular greater than 1.70, greater than 1.75, greater than 1.80, greater than 1.85.

[0166] A double-glazed unit has four faces: face 1 is on the exterior of the building and therefore constitutes the outer pane of the glazing; face 4 is on the interior of the building and therefore constitutes the inner pane of the glazing; and faces 2 and 3 are on the interior of the double glazing. The functional coating according to the invention is located on face 2 or face 3.

[0167] Triple glazing has 6 faces; face 1 is on the exterior of the building and therefore constitutes the outer wall of the glazing; face 6 is on the interior of the building and therefore constitutes the inner wall of the glazing; faces 2, 3, 4, and 5 are on the interior of the double glazing. The functional coating according to the invention can be located on face 2, face 3, and / or face 5.

[0168] A laminated glazing comprises at least one first substrate / sheet(s) / second substrate structure. The polymer sheet may, in particular, be based on Polyvinyl butyral (PVB), ethylene vinyl acetate (EVA), polyethylene terephthalate (PET), polyvinyl chloride (PVC). The thin-film functional coating is positioned on at least one face of one of the substrates.

[0169] The invention therefore relates to: - a double-glazed unit with the functional coating on surface 2, - a double-glazed unit with the functional coating on surface 3, - a triple-glazed unit with the functional coating on both surface 2 and surface 5. - laminated glazing with the functional coating on face 2 or 3. These windows can be mounted on a building or a vehicle. Examples

[0170] In all tables showing optical characteristics and performance, the following designations are used: DGU: the characteristics are measured in double glazing with a 6 / 12 / 4 structure: 6 mm glass / 12 mm air-filled space / 4 mm glass, the functional stacking coating being positioned on face 2 (face 1 of the glazing being the outermost face of the glazing, as usual). SGU: The measured characteristics are sometimes in single glazing with the functional coating positioned on face 2, in particular the parameters a*60° and b*60°.

[0171] A colour box (“colourbox”) has been defined in external reflection and in internal reflection for all glazing. Tab.la*, min a*, max b*, min b*, max TL -50 variable 0 -XX RL1 <18 -3.0 -1.0 -10.0 0 RL2 <16 -6.0 0 -5.0 1 I. Materials and Deposition Conditions

[0172] In these examples, the glass substrates are 4 mm alu-minosilicate type clear glass substrates. Continuous functional metallic layers (F) are silver (Ag) layers. For discontinuous silver layers, equivalent thicknesses are considered. The blocking layers are metallic layers made of nickel-chromium alloy (NiCr). The dielectric coatings of functional coatings include barrier layers and stabilizing layers as dielectric layers. The dielectric layers are selected from: - titanium oxide-based layers (TiOx, n = 2.4), - zinc tin oxide-based layers (SnZnO, n = 2.0), - zinc oxide-based layers (ZnO, n = 2.0). - layers based on silicon nitride (Si3N4, n = 2.0), - layers based on silicon oxide (SiO2, n = 1.5), - layers of silicon oxynitride (SiON).

[0173] The conditions for depositing the layers by sputtering (so-called "magnetron cathodic sputtering") are summarized in Table 1. Table 2 Material Stoichiometry Index TiO₂ Titanium dioxide TiO₂ 2.44 SnZnO₂ Zinc tin oxide SneZnfO₂ 2.00 ZnO₂ Zinc oxide ZnO₂ 2.00 SiN Aluminum-doped silicon nitride Si₃N₄:Al 2.07 SiO₂ Aluminum-doped silicon dioxide SiO₂:Al 1.55 SiON 50% silicon oxynitride SiO₂ / Si₃N₄ 1.80 Ag Ag⁻ NiCr Nickel-chromium alloy NiO₂,₈Cr₂

[0174] The deposition conditions of the layers, which were deposited by sputtering (so-called "magnetron cathode sputtering"), are summarized in Table 2. Table 3 Target used Deposition pressure Gas TiO₂ TiO₂ 2.103 mbar Ar / (Ar + O₂) at 95% SnZnO Zn:Sn at 64:36% at. 2.103 mbar Ar / (Ar + O2) at 50% ZnO Zn:Al at 98:2% wt 1.8.10-3 mbar Ar / (Ar + O2) at 63% Si3N4 Si:Al at 92:8% wt 3.2-6.10-3 mbar Ar / (Ar + N2) at 55% SiO2 Si:Al at 92:8% wt 2.103 mbar Ar / (Ar + O2) at 62.5% SiON Si:Al at 92:8% wt 4.103 mbar Ar XX% / O2 XX% / N2 XX% SiON* Si:Al at 92:8% wt 4.103 mbar variable NiCr Ni:Cr at 80:20% at. 2-3 x 10³ mbar Ar at 100% Ag cont Ag 2-8 x 10³ mbar Ar or Kr at 100% Ag says. Ag 2-8.103 mbar Ar or Kr at 100%

[0175] At. = atomic; Pds: Weight. II. First set of examples

[0176] The following tables list the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that constitutes the coatings according to their position with respect to the substrate carrying the stack (last line at the bottom of the table). Tab. 4 Inv.l Inv.2 Inv.3 Inv.4 Inv.5 Cp.l Cp.2 Cp.3 Cp.4 RD : M3 Si3N4 31,4 31,9 30,7 32,4 32,2 28,1 29,0 29,4 29,3 ZnO 9,0 9,0 9,0 9,0 9,0 9,0 9,0 9,0 9,0 CB: OB2 0,1 0,1 0,1 0,2 0,2 ​​0,1 0,1 0,1 0,1 CF: Ag2 17,0 17,2 16,6 16,2 16,4 12,0 12,5 12,9 15,3 RD: M2 ZnO 8,0 8,0 8,0 ECA* ECA1 ECA2 ECA3 ECA 4 ECA5 0 0 0 0 NiCr 0 0 0 0 0 1,1 1,2 1,1 1,2 Si3N4 23 26,75 29,1 15,24 12,14 20,9 22,7 23,1 25,5 ZnO 9 ​​9 9 9 9 9,0 9,0 9,0 9.0 CB : OBI 0.2 0.1 1.1 1.8 2.0 2.0 2.0 2.0 2.0 CF : Agi 16.0 15.9 14.6 13.3 12.7 11.0 11.0 11.6 12.3 CB : UB1 0 0 0 0 0 0.0 0.0 0.0 0.0 RD : Ml ZnO 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 5.0 SnZnO 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 8.0 Si3N 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0 Si3N4 12.3 5.9 6.0 5.7 0.0 22.7 21.3 20.5 7.7 SiON 12,0 12,0 12,0 12,0 12,0 12,0 12,0 12,0 12,0 Sub. mm 4,0 4,0 4,0 4,0 4,0 4,0 4,0 4,0 4,0

[0177] *ECA: Absorbent layer element Table 5 Material ECA1 ECA2 ECA3 ECA4 ECA5 ECA SiON 8 8 8 8 8 Ag dise. 1.2 1.0 0.8 0.7 0.6 SiON 6 6 6 6 6

[0178] The coated substrates undergo a heat treatment of the quenching type. Tab. 6 Inv.l Inv.2 Inv.3 Inv.4 Inv.5 Cp.l Cp.2 Cp.3 Cp.4 DG U TL% 49.1 50.9 51.0 50.7 51.0 51.0 50.7 50.7 49.4 - a*T -0.5 -0.8 -2.0 -3.2 -3.9 -3.1 -4.0 -4.4 -5.9 -b*T 0.2 0.7 -0.8 -0.1 -0.7 -3.4 -3.2 -2.9 -3.2 Rext% 16.0 16.0 16.0 15.9 16.0 16.3 15.5 16.0 16.0 - a*Rext -2.8 -2.0 -2.6 -0.6 -0.4 -3.5 -1.3 -0.5 -1.5 - b*Rext -4.9 -5.0 -5.0 -11.0 -11.9 0.8 -1.7 -2.9 -5.0 s 1.76 1.77 1.77 1.77 1.79 1.64 1.67 1.69 1.78 FS 27.9 28.8 28.8 28.6 28.5 31.1 30.4 30.0 27.8 SG U a*60°Rint 1.1 0.0 0.0 -1.5 0.0 0.0 -0.1 0.0 0.0 b*60°int -8.9 -7.8 -9.0 -10.0 -10.2 -9.9 -9.9 -10.0 -10.0

[0179] Fig. 1 represents the selectivity as a function of the values ​​of a*T. In this figure: - the curve of points represents the examples Cp.1, Cp.2, Cp.3, Cp.4, - the triangle curve represents the examples Inv.1, Inv.2, Inv.3, Inv.4, Inv.5.

[0180] The level of colour in transmission, and more particularly the search for neutrality in transmission (a*T close to 0), regulates the selectivity of bi-Ag coatings.

[0181] It is observed that with an absorbing layer based on NiCr placed in the second dielectric coating, the improvement of neutrality with values ​​of a*T going from a level 3 (a* [-6,-4]) to a level 2 (a* [-4,-2]), can only be at the expense of selectivity which goes from 1.77 to 1.64 (A = 0.13).

[0182] The layered element allows for improved neutrality with a*T values ​​going from level 2 (a* [-4,-2]) to level 1 (a* [-2,-0]), without harming the selectivity which goes from 1.78 to 1.76 (A = 0.02). III. Second set of examples

[0183] Table 7 Inv.6 Comp.l Comp.2 RD: M3 -SnZnO 3.0 3.0 3.0 - Si3N4 26.0 26.0 25.3 -ZnO 8.0 8.0 8.0 CB: NiCr 0.2 0.2 0.2 CF: Ag2 17.2 17.2 16.0 RD: M2 -ZnO 7.0 7.0 7.0 -SnZnO 30.0 30.0 30.0 - Si3N4 19.1 16.4 16.7 ECA6 8.0 - - NiCr - 1.2 1.2 - Si3N4 14.7 25.0 24.5 -ZnO 6.5 6.5 6.5 CB: NiCr 1.2 1.2 0.6 CF: Ag 16.3 16.3 15.4 RD: Ml -ZnO 5 5 5 -SnZnO 5 5 5 - TiO2 16.8 16.8 15.2 Substrate (mm) 6 6 6

[0184] CB: Blocking layer; CF: Functional layer; RD: Dielectric coating. Table 8 ECA6 Material EC SiON 8 Ag dise. 1,0 SiON 6 Tab. 9 Inv.6 Comp. 1 Comp.2 DG U TL% 51.1 47.9 52.0 - a*T -1.9 -6.2 -5.0 -b*T 3.0 3.5 2.0 Rext% 17.0 17.7 17.0 - a*Rext -3.5 -0.6 -1.7 - b*Rext -9.4 -12.5 -7.1 a*60°T -6.1 -9.2 -7.8 b*60°T 5.8 4.5 4.3 FS 27.8 25.6 28.7 s 1.84 1.87 1.81 SG U a*60° -2.0 -0.5 -2.0 b*60 -11.0 -13.8 -11.0

[0185] Only the glazing of the invention makes it possible to obtain both level 1 neutralization with an a*T value less than 2 and high selectivity, in particular greater than 1.8. III. Absorbent Layer Elements

[0186] The table below lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that constitutes the layered element according to their position with respect to the substrate carrying the stack (last line at the bottom of the table). Table 10 Material Inv.l' Inv.2' Cp.r Cp2' Cp.3' Cp.4' Cp.5' Cp.6' EC 2nd CD 10 nm SiON* SiON* TiOx ZnO SnZnO ZnO SiN SiO CB met. 1-2 nm - - - NiCr Ti - - - Ag says. 1 nm* Ag Ag Ag Ag Ag Ag Ag Ag lere CD 10 nm Si3N4 SiON* TiOx SnZnO SnZnO SnZnO SiN SiO Substrate 4 mm - - - - - -

[0187] EC: Layered element, CD: Dielectric layer, dise.: discontinuous, CB: Metallic blocking layer, *: equivalent thickness.

[0188] These materials can be used: - as is, that is to say without undergoing additional high-temperature heat treatment (hereinafter Ann.), - following heat treatment at a high temperature, hereinafter heat-treated material, carried out in a NABER oven at a temperature of 650°C for 10 minutes (hereinafter TT).

[0189] The specific optical absorption characteristics of heat-treated absorbing elements are determined from their absorption spectrum. For this purpose, the absorption of the substrate coated with the layered element is calculated. Then, the absorption of the substrate is subtracted.

[0190] We determine: - the position of the maximum of the absorption peak (c), - its maximum absorption (max), - its width at half height (W), - light absorption in the visible (AL) range, - the colors (a*abs, b*abs) and - the neutralization factor Fn (AL xa*abs).

[0191] The table below shows the results obtained for the elements in layers Inv. 1 and Inv.2 and comparatives. Tab.ll Inv.l Inv.2 Cp.l Cp2 Cp.3 Cp.4 TT max (%) 17.8 18.3 22.3 25.0 17.9 25.9 W (nm) 260 220 310 220 290 215 c (nm) 520 515 580 515 535 535 AL 15.41 14.9 19.93 20.75 16.12 22.61 a* -13.13 -16.74 -4.71 -18.62 -10.28 -17.03 b* 5.55 3.01 23.4 4.06 6.15 12.71 Fn -202 -249 -93 -386 -165 -385

[0192] According to the invention, a good absorbent coating in green is considered to have the following characteristics, preferably in combination: - a peak centered between 490 and 550 nm, preferably around 515, - a maximum absorption rate of less than 20% - a low half-width because if the width is too large, the a* can no longer be very negative, - absorption in the visible spectrum of less than 16% - a*abs as negative as possible, preferably less than -5, -6, -7, -8, -9, or even -10, and - a b* less than +10.

[0193] With heat treatment, a*abs less than -10 can easily be obtained. The comparative example Cp.l does not show a peak centered between 490 and 550. Comparative examples Cp.2 and Cp.4 exhibit excessive absorption. Consequently, they will have a very negative impact on selectivity if used to modify the color of a functional coating. Example Cp.3 is suitable but less satisfactory than the materials of invention Inv.1 and Inv.2. The cp.5 material, comprising a layered element with the sequence SiN / Ag dise. / SiN, exhibits an extremely broad absorption peak and excessively high light absorption. The a*abs. values ​​are not sufficiently negative. The neutralization factor is too low. The cp.6 material, comprising a layered element with the sequence SiO2 / Ag dise. / SiO2, is not absorbent. It appears that the high oxygen content generates defects in the discontinuous silver layer, which then loses its plasmonic absorption function.

[0194] These examples highlight that the following prior art configurations are less advantageous than that of the invention: - TiOx dielectric layer / Discontinuous silver layer / TiOx dielectric layer, - SnZnO dielectric layer / Discontinuous silver layer / Metallic NiCr layer / ZnO dielectric layer, - SnZnO dielectric layer / Discontinuous silver layer / Metallic Ti layer / SnZnO dielectric layer, - SnZnO dielectric layer / Discontinuous silver layer / ZnO dielectric layer, - SiN dielectric layer / Discontinuous silver layer / SiN dielectric layer, - SiO dielectric layer / Discontinuous silver layer / SiO dielectric layer.

Claims

Demands

1. A material comprising a transparent substrate coated with a functional coating comprising successively, from the substrate, an alternation of two continuous silver-based functional metal layers, designated from the substrate as the first and second functional layers, and three dielectric coatings designated from the substrate as D1, Di2, and Di3, each dielectric coating comprising at least one dielectric layer, such that each continuous functional metal layer is disposed between two dielectric coatings, the dielectric coating Di2 comprising a layered element comprising: - a first layer comprising silicon selected from a nitride, oxide, or oxynitride layer, - a discontinuous silver-based layer deposited directly on the first silicon-based layer comprising nanometric silver particles,- a second layer comprising silicon selected from a nitride, oxide or oxynitride layer deposited directly on the discontinuous silver-based layer, characterized in that: - the first or second layer comprising silicon comprises oxygen, and - the first or second layer comprising silicon comprises nitrogen.

2. Material according to the preceding claim characterized in that the second layer comprising silicon is a silicon oxynitride layer and / or the first layer comprising silicon is a silicon oxynitride layer.

3. Material according to any one of the preceding claims characterized in that the first and second layers comprising silicon both comprise oxygen and in that the first layer comprising silicon comprises a greater proportion of oxygen than the second layer comprising silicon.

4. Material according to any one of the preceding claims characterized in that the first layer comprising silicon has a thickness of between 4 and 20 nm and / or the second layer comprising silicon has a thickness of between 4 and 20 nm.

5. Material according to any one of the preceding claims characterized in that the silver-based discontinuous layer has an equivalent thickness of less than 5 nm, preferably less than 4.0 nm, or even less than 3.0 nm or less than 2.0 nm.

6. Material according to any one of the preceding claims characterized in that the layered element has a visible absorption peak having a maximum between 490 and 550 nm.

7. Material according to any one of the preceding claims characterized in that the layered element has a visible absorption peak whose full width at half maximum is less than 350 nm.

8. Material according to any one of the preceding claims characterized in that the layered element has a visible light absorption of between 8 and 20%, absorption measured on the layered element side on a 4 mm thick clear glass substrate.

9. Material according to any one of the preceding claims characterized in that each dielectric coating located below a functional layer comprises a zinc oxide-based layer located below, in contact with, or separated by a blocking layer from the functional layer having a thickness greater than or equal to 3 nm.

10. Material according to any one of the preceding claims characterized in that each dielectric coating situated above a functional layer comprises a zinc oxide-based layer situated above, in contact with, or separated by a blocking layer from the functional layer.

11. Material according to any one of the preceding claims characterized in that: - the first functional layer has a thickness between 7 and 20 nm, and / or - the second functional layer has a thickness between 7 and 20 nm.

12. Material according to any one of the preceding claims characterized in that: - the first dielectric coating Dil has an optical thickness of between 60 and 120 nm, - the second dielectric coating Di2 has an optical thickness of between 120 and 250 nm, - the third dielectric coating Di3 has an optical thickness between 40 and 120 nm.

13. 13. Material according to any one of the preceding claims characterized in that: the first dielectric coating D1 comprises, in this order: - a silicon nitride or titanium oxide layer from 20 to 50 nm, - a zinc tin oxide layer from 0 to 30 nm, - a zinc oxide layer from 2 to 24 nm; the second dielectric coating Di2 comprises, in this order: - a zinc oxide layer from 4 to 24 nm, - a silicon nitride layer from 30 to 100 nm, - a silicon oxide layer from 0 to 30 nm, - the layered element, - a silicon nitride layer from 30 to 100 nm, - a zinc tin oxide layer from 0 to 40 nm, - a zinc oxide layer From 4 to 24 nm, the third dielectric coating Di3 comprises, in this order: - a zinc oxide-based layer from 4 to 24 nm, - one or more silicon nitride-based layers,The thickness of all these silicon nitride-based layers is 30 to 75 nm or 20 to 45 nm, with a top protective layer of 0 to 5 nm; all these thicknesses are optical thicknesses.

14. Material according to any one of the preceding claims characterized in that the substrate is made of glass, in particular soda-lime silico-glass or of polymeric organic matter.

15. Glazing comprising at least one material according to any one of claims 1 to 14 and an additional substrate assembled in the form of multiple glazing.

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