Solar-control and / or low-emissivity glazing

Abstract

The invention relates to a material comprising a transparent substrate coated with a functional coating that can act on solar radiation and / or infrared radiation. The invention also relates to glazings comprising said materials and to the use of said kind of materials for manufacturing thermal insulation and / or solar protection glazings. The invention is specifically concerned with developing a material comprising a functional coating which has two silver-based functional layers and has a selectivity close to that of functional coatings with three functional layers, while maintaining excellent color neutrality.

Description

[0001] Title: Solar control and / or low-emissivity glazing

[0002] The invention relates to a material comprising a transparent substrate coated with a functional coating capable of acting on solar radiation and / or infrared radiation. The invention also relates to glazing comprising these materials as well as the use of such materials for manufacturing thermal insulation and / or solar protection glazing. In the remainder of the description, the term "functional" qualifying "functional coating" means "capable of acting on solar radiation and / or infrared radiation".

[0003] These glazings can be used to equip both buildings and vehicles, in particular for:

[0004] - reduce air conditioning effort and / or prevent excessive overheating, so-called “solar control” glazing and / or

[0005] - reduce the amount of energy dissipated to the outside, so-called “low emissive” glazing.

[0006] The selectivity "S" makes it possible to evaluate the performance of these glazings. It corresponds to the ratio of the light transmission TL VjS in the visible of the glazing on the solar factor FS of the glazing (S = TL VjS / FS). The solar factor "FS or g" corresponds to the ratio in % between the total energy entering the room through the glazing and the incident solar energy. The solar factor therefore measures the contribution of a glazing to heating the "room". The smaller the solar factor, the lower the solar gains.

[0007] Known selective glazings comprise transparent substrates coated with a functional coating comprising a stack of one or more metallic functional layers, each disposed between two dielectric coatings. Such glazings make it possible to improve solar protection while maintaining high light transmission. These functional coatings are generally obtained by a succession of deposits carried out by cathodic sputtering, possibly assisted by a magnetic field.

[0008] Conventionally, the faces of a glazing unit are designated starting from the exterior of the building and numbering the faces of the substrates from the outside to the inside of the dwelling or room it equips. This means that incident sunlight passes through the faces in ascending order of their number.

[0009] Known selective glazing is generally double glazing comprising the functional coating located on face 2, i.e. on the outermost substrate of the building on its face facing the interlayer gas layer.

[0010] Currently, the best performing materials have a selectivity greater than 2 and include a functional coating with at least three silver-based metal functional layers. For comparison:

[0011] - a material comprising a functional coating with two silver-based layers allows to obtain a selectivity of 1.7 up to 1.9,

[0012] - a material comprising a functional coating with a silver-based layer makes it possible to obtain a selectivity of up to 1.2,

[0013] - a material comprising a functional coating without a silver-based layer allows to obtain a selectivity of up to 1.

[0014] However, functional coatings comprising at least three functional layers are complex. Indeed, by multiplying the number of layers and materials constituting these functional coatings, it becomes increasingly difficult to adapt the settings of the deposition conditions in order to obtain functional coatings that are consistent in color and properties.

[0015] The invention is specifically concerned with developing a material comprising a functional coating with two silver-based functional layers exhibiting improved selectivity, while maintaining excellent color neutrality.

[0016] The subject of the invention is a material comprising a substrate coated with a functional coating comprising an alternation of only two silver-based metallic functional layers called, starting from the substrate, first and second functional layers and three dielectric coatings called, starting from the substrate, Di1, Di2 and Di3, each dielectric coating comprising at least one dielectric layer, so that each functional metallic layer is arranged between two dielectric coatings, characterized in that:

[0017] - the third dielectric coating Di3 located above the second functional layer comprises a titanium oxide-based layer located above and in contact with the second silver-based functional metal layer, this titanium oxide layer having a thickness greater than or equal to 3 nm, preferably a thickness of at least 5 nm,

[0018] - the first dielectric coating Di 1 located below the first functional layer comprises a high refractive index layer having a refractive index measured at 550 nm greater than 2.20 and a thickness greater than 3.0 nm, preferably greater than 5 nm.

[0019] The invention is suitable for any material with a light transmission greater than 40%. However, the invention is particularly suitable for materials with high light transmission.

[0020] The solution of the invention consists in using a thick high-index blocking layer in contact with the second functional layer and a high-index layer in the first dielectric coating.

[0021] The solution of the invention is suitable for materials whose stacking is intended to be used:

[0022] - as deposited, i.e. without any heat treatment whatsoever, - laser treated, i.e. only the stack is treated and not the substrate,

[0023] - heat treated such as quenching.

[0024] The applicant has discovered that the use of a thick, high-index layer in contact with the third functional layer makes it possible to further improve the selectivity provided that this layer is thick, preferably with a thickness greater than 5 nm, or even greater than 10 nm. This embodiment is particularly advantageous when it is desired to improve the selectivity of glazing with high light transmission, i.e. light transmission greater than 70%. Another alternative to this embodiment may be to use, in addition to or instead of the titanium oxide-based layer in contact with the silver, another layer with a high refractive index.

[0025] The applicant also discovered that the mechanical properties are improved when the thick titanium oxide-based blocking layer is combined with a tin oxide-based layer.

[0026] The invention also has the following features alone or in combination:

[0027] - the titanium oxide-based layer located above the second silver-based functional layer has a thickness of at least 5 nm,

[0028] - the second dielectric coating Di2 located above the first functional layer comprises a titanium oxide-based layer located above and in contact with the first silver-based functional metal layer having a thickness greater than or equal to 3 nm, preferably greater than 5 nm, or even greater than 10 nm,

[0029] - the second dielectric coating further comprises a tin oxide-based layer comprising at least 10%, or less than 20% or at least 30% by mass of tin relative to the total mass of elements other than nitrogen and oxygen, located above and in contact with the titanium oxide-based layer, this tin oxide-based layer generally has a thickness greater than 5 nm, or even greater than 10 nm and / or less than 40 nm, or even less than 30 nm,

[0030] - the second dielectric coating further comprises a layer based on tin oxide, preferably based on zinc and tin oxide comprising at least 10%, at least 20% or at least 30% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide, this layer based on tin oxide generally has a thickness greater than 5 nm, or even greater than 10 nm and / or less than 40 nm, or even less than 30 nm,

[0031] - the third dielectric coating Di3 located above the second functional layer comprises a high refractive index layer having a refractive index measured at 550 nm greater than 2.20 and a thickness greater than 5 nm, this layer is distinct from the titanium oxide-based layer in contact with the silver layer, - the second dielectric coating Di2 comprises a high refractive index layer having a refractive index measured at 550 nm greater than 2.20 and a thickness greater than 5 nm, preferably greater than 10 nm, this layer is distinct from the possible titanium oxide-based layer in contact with the silver layer,

[0032] - the high refractive index layers are chosen from titanium oxide-based layers, niobium oxide layers and silicon and zirconium nitride-based layers,

[0033] - layers with a refractive index greater than 2.20 other than layers based on titanium oxide in contact with functional layers have a thickness greater than 10 nm,

[0034] - the functional coating comprises one or more metal blocking layers preferably located in contact with and below the first and / or second metal functional layer,

[0035] - the dielectric coating located below the first functional layer comprises a zinc oxide-based layer located in contact with the first functional layer or separated from the first functional layer by a blocking layer,

[0036] - the dielectric coating located below the second functional layer comprises a zinc oxide-based layer located in contact with the second functional layer or separated from the second functional layer by a blocking layer,

[0037] - the material has a light transmission greater than 70%, greater than 75%, greater than 76% or greater than 78%,

[0038] - the material has a light transmission of less than 70%, preferably between 30 and 50%.

[0039] Advantageously, the layers with a refractive index greater than 2.20 other than the layers based on titanium oxide in contact with the functional layers, have a thickness greater than 10 nm.

[0040] The applicant has also discovered that the use of metal blocking layers, located below and in contact with the first and / or second silver-based functional layer, makes it possible to strengthen the mechanical properties. This results in better results in the EBT and TT-EBT tests. It also makes it easier to adjust the optics. This embodiment is more suitable for glazing with a light transmission of less than 70%, particularly with a light transmission of between 30 and 50%.

[0041] In particular, the dielectric coating located below the first functional layer comprises a zinc oxide-based layer located in contact with the first functional layer or separated from the first functional layer by a blocking layer. In particular, the dielectric coating located below the second functional layer comprises a zinc oxide-based layer located in contact with the second functional layer or separated from the second functional layer by a blocking layer.

[0042] The present invention also relates to glazing comprising a material as described above, said glazing possibly being in the form of multiple glazing or laminated glazing.

[0043] The invention also relates to:

[0044] - glazing comprising a material according to the invention,

[0045] - glazing comprising a material according to the invention mounted on a vehicle or on a building, and

[0046] - the process for preparing a material or glazing according to the invention,

[0047] - the use of glazing according to the invention as solar control and / or low-emissivity glazing for buildings or vehicles,

[0048] - a building, a vehicle or a device comprising glazing according to the invention.

[0049] Throughout the description, the substrate according to the invention is considered to be laid horizontally. The stack of thin layers is deposited above the substrate. The meaning of the expressions "above" and "below" and "lower" and "upper" is to be considered in relation to this orientation. In the absence of a specific stipulation, the expressions "above" and "below" do not necessarily mean that two layers and / or coatings are arranged in contact with each other. When it is specified that a layer is deposited "in contact" with another layer or a coating, this means that there cannot be one (or more) layer(s) interposed between these two layers (or layer and coating).

[0050] All the luminous characteristics described are obtained according to the principles and methods of European standards EN 410 relating to the determination of luminous and solar characteristics of glazing used in glass for construction. Sunlight entering a building is considered to go from the outside to the inside.

[0051] According to the invention, the luminous characteristics are measured according to illuminant D65 at 2° perpendicular to the material mounted in double glazing:

[0052] - TL corresponds to the light transmission in the visible range in %,

[0053] - Rext (or RL1) corresponds to the external light reflection in the visible in %, observer on the external space side,

[0054] - Rint (or RL2) corresponds to the interior light reflection in the visible in %, observer on the interior space side,

[0055] - a*T and b*T correspond to the transmission colors a* and b* in the L*a*b* system,

[0056] - a*Rext and b*Rext correspond to the reflected colors a* and b* in the L*a*b* system, observer on the exterior space side, - a*Rint (or a*RL1) and b*Rint (or b*RL2) correspond to the reflected colors a* and b* in the L*a*b* system, observer on the interior space side.

[0057] The coating is deposited by magnetic field-assisted sputtering (magnetron process). In this advantageous embodiment, all layers of the stack are deposited by magnetic field-assisted sputtering.

[0058] In the absence of a specific stipulation, the expressions "above" and "below" do not necessarily mean that two layers and / or coatings are placed 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).

[0059] Unless otherwise stated, thicknesses referred to in this document are physical thicknesses and layers are thin layers. A thin layer is defined as a layer with a thickness between 0.1 nm and 100 micrometers.

[0060] According to the invention, unless otherwise indicated, the expression "based on", used to qualify a material or a metallic layer as to what it contains, means that the mass fraction of the constituent that it comprises is at least 50%, in particular at least 70%, preferably at least 90%.

[0061] According to the invention, unless otherwise indicated, the expression "based on", used to qualify a material or a dielectric layer as to what it contains, means that the mass fraction of the constituent that it comprises is at least 50%, in particular at least 70%, preferably at least 90% by mass relative to the total mass of elements other than oxygen and nitrogen.

[0062] According to the invention, the term "distinct layers" means two layers of different chemical nature, i.e. made up of different chemical elements or two layers of the same nature but separated by at least one layer of different chemical nature.

[0063] The titanium oxide-based layer is advantageously deposited from a ceramic target, in particular under stoichiometric conditions, in a controlled atmosphere comprising oxygen. Preferably, a first thin layer of titanium oxide-based layer is deposited in contact with the silver layer, from a ceramic target, in a non-oxidizing or very weakly oxidizing atmosphere. Then, a thicker layer of titanium oxide-based layer is deposited from a ceramic target in an oxidizing atmosphere. The titanium oxide-based layer consists of these two parts. During deposition, the part of the titanium oxide-based layer in contact with the functional layer is less oxidized than the part furthest from the functional layer. By proceeding in this way, we obtain both: - a low resistance per square thanks to the Ag / TiOx interface deposited without oxygen and

[0064] - low absorption thanks to the second part of the titanium oxide layer.

[0065] This multi-step deposition makes it possible to obtain a predominantly titanium oxide layer in the stack with a large quantity of oxygen, while protecting the silver-based functional layer with a first, weakly oxidized titanium oxide layer. The absorption of the stack is then greatly reduced both in the absence of heat treatment and following heat treatment.

[0066] The layer is a titanium oxide-based layer over this entire thickness. According to the invention, this titanium oxide-based layer is part of a dielectric coating located above the silver layer. This means that when determining the thickness of this dielectric coating, the thickness of this layer is taken into consideration.

[0067] This thick titanium oxide-based layer near the silver contributes to obtaining the advantageous properties of the invention. This oxide layer is non-absorbent, especially when it is mainly deposited from a ceramic target in an oxidizing atmosphere.

[0068] The titanium oxide-based layers comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 95.0%, at least 96.5% and more preferably at least 98.0% by mass of titanium relative to the mass of all the elements constituting the titanium oxide-based layer other than oxygen.

[0069] Titanium oxide-based layers can have a thickness of:

[0070] - greater than or equal to 3 nm, greater than or equal to 4 nm, greater than or equal to 5 nm, and / or

[0071] - less than or equal to 30 nm, less than or equal to 25 nm, less than or equal to 20 nm, less than or equal to 15 nm, less than or equal to 10 nm, less than or equal to 8 nm, less than or equal to 6 nm.

[0072] Titanium oxide-based layers can have a thickness between 5 and 30 nm.

[0073] The titanium oxide-based layers may comprise or consist of elements other than titanium and oxygen. These elements may be chosen from silicon, chromium and zirconium. Preferably, the elements are chosen from zirconium. Preferably, the titanium oxide-based layer comprises at most 35%, at most 20% or at most 10% by mass of elements other than titanium relative to the mass of all the elements constituting the titanium oxide-based layer other than oxygen.

[0074] The titanium oxide-based layer is preferably deposited from a ceramic target, in particular under stoichiometric conditions in an oxidizing atmosphere, preferably in which the percentage of oxygen volume flow rate represents between 0 and 20%, preferably 2 to 15%.

[0075] According to the preferred embodiment, a titanium oxide-based layer is deposited from a ceramic target, in particular under stoichiometric. The titanium oxide-based layer can be deposited from a TiO ceramic target x substoichiometric, where x is a number different from the stoichiometry of titanium oxide TiCh, i.e. different from 2 and preferably less than 2, in particular between 0.75 times and 0.99 times the normal stoichiometry of the oxide. TiOx may in particular be such that 1.5 < x < 1.98 or 1.5 < x < 1.7, or even 1.7 < x < 1.95.

[0076] The material according to the invention may have the following characteristics alone or in combination:

[0077] - the titanium oxide-based layer is deposited from a ceramic target, in particular under stoichiometric conditions, preferably in an oxidizing atmosphere whose percentage in volume flow of oxygen represents between 0 and 20%, preferably 2 to 15%,

[0078] - the titanium oxide-based layer has a thickness between 5 and 30 nm,

[0079] - the titanium oxide-based layer located above the second silver-based functional layer has a thickness:

[0080] - greater than 5 nm, greater than 10 nm,

[0081] - less than 30 nm, less than 25 nm, less than 20 nm,

[0082] - the titanium oxide-based layer located above the first silver-based functional layer has a thickness:

[0083] - greater than 5 nm, greater than 10 nm,

[0084] - less than 30 nm, less than 25 nm, less than 20 nm,

[0085] - titanium oxide-based layers can be deposited from a ceramic target, particularly under stoichiometric conditions,

[0086] - the titanium oxide-based layer comprises an oxidation gradient, the part of the titanium oxide-based layer in contact with the zinc-based layer is more oxidized than the part furthest away,

[0087] - the dielectric coating located above the functional layer comprises a layer based on zinc and tin oxide comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide,

[0088] - the layer based on zinc and tin oxide has a thickness:

[0089] - greater than 5 nm,

[0090] - less than 40 nm.

[0091] - the dielectric coating located above the functional layer comprises a layer comprising silicon chosen from silicon nitride layers or silicon nitride and zirconium layers,

[0092] - the dielectric coating located below the functional layer comprises a zinc oxide-based layer located in contact with the functional layer,

[0093] - the dielectric coating located below the first metallic functional layer comprises a layer comprising silicon chosen from silicon nitride layers,

[0094] - the dielectric coating located above the first metallic functional layer comprises a layer comprising silicon chosen from silicon nitride layers,

[0095] - the dielectric coating located above the second metallic functional layer comprises a layer comprising silicon chosen from silicon nitride layers,

[0096] - each dielectric coating comprises a layer comprising silicon chosen from silicon nitride layers,

[0097] - the layer with a refractive index greater than 2.20 is chosen from layers based on titanium oxide and layers based on silicon and zirconium nitride,

[0098] - the coating has been subjected to rapid thermal annealing,

[0099] - the coating and the substrate have been subjected to heat treatment at a high temperature above 500°C such as quenching, annealing or bending.

[0100] Preferably, the sum of the thicknesses of all oxide-based layers present:

[0101] - in the dielectric coating Di 1 located between the substrate and the first functional metal layer is less than 60%, less than 50% or less than 40%, of the total thickness of the dielectric coating and / or

[0102] - in the dielectric coating located above the first silver-based functional layer is less than 60%, less than 50% or less than 40%, of the total thickness of the dielectric coating and / or

[0103] - in the dielectric coating located above the second silver-based functional layer is less than 60%, less than 50% or less than 40%, of the total thickness of the dielectric coating.

[0104] The silver-based metal functional layers comprise at least 95.0%, preferably at least 96.5% and more preferably at least 98.0% by mass of silver relative to the mass of the functional layer. Preferably, a silver-based metal functional layer comprises less than 1.0% by mass of metals other than silver relative to the mass of the silver-based metal functional layer.

[0105] The silver-based metal functional layers have a thickness:

[0106] - greater than 5 nm, 6 nm, 7 nm, 8 nm, 9 nm, 10 nm, 11 nm, 12 nm, 13 nm, 14 nm, 15 nm or 16 nm, and / or

[0107] - less than 25 nm, 22 nm, 20 nm, 18 nm.

[0108] By "dielectric coating" within the meaning of the present invention, it is understood that there may be a single layer or several layers of different materials inside the coating. A "dielectric coating" according to the invention mainly comprises dielectric layers. However, according to the invention these coatings may also comprise layers of other nature, in particular absorbent layers, for example metallic ones.

[0109] A "same" dielectric coating is considered to be located:

[0110] - between the substrate and the first functional layer,

[0111] - between each functional silver-based metal layer,

[0112] - above the last functional layer (furthest from the substrate).

[0113] Dielectric coatings comprise dielectric layers. By "dielectric layer" for the purposes of the present invention, it is to be understood that from the point of view of its nature, the material is "non-metallic", i.e. is not a metal. In the context of the invention, this term designates a material having an n / k ratio over the entire visible wavelength range (from 380 nm to 780 nm) equal to or greater than 5. n designates the real refractive index of the material at a given wavelength and k represents the imaginary part of the refractive index at a given wavelength; the n / k ratio being calculated at a given wavelength identical for n and for k.

[0114] The thickness of a dielectric coating corresponds to the sum of the thicknesses of the layers constituting it. Preferably, the dielectric coatings have a thickness greater than 10 nm, greater than 15 nm, between 15 and 200 nm, between 15 and 100 nm or between 15 and 70 nm.

[0115] The dielectric layers of the coatings have the following characteristics alone or in combination:

[0116] - they are deposited by magnetic field-assisted cathode sputtering,

[0117] - they are chosen from oxides, nitrides or oxynitrides of one or more elements chosen from titanium, silicon, aluminum, zirconium, tin and zinc,

[0118] - they have a thickness greater than 2 nm, preferably between 2 and 100 nm.

[0119] Dielectric layers, in addition to their optical function, can have various other functions. The choice of the nature and position of the dielectric layers within the dielectric coating depends on this function. For example, the following functions can be cited:

[0120] - stabilizer or wetting layers located in the immediate vicinity of silver-based functional layers such as zinc oxide-based layers,

[0121] - smoothing layers located below the wetting layers such as tin oxide-based layers,

[0122] - barrier or optical function layers.

[0123] A single dielectric layer generally performs several functions. In fact, each dielectric layer plays an optical role which depends on its refractive index and its thickness.

[0124] The dielectric layers are conventionally chosen from oxide-based, nitride-based or oxynitride-based layers. The oxide-based layers of one or more elements comprise essentially oxygen and very little nitrogen. The oxide-based layers comprise in particular at least 90% by atomic percentage of oxygen relative to the oxygen and nitrogen in said layer. The nitride-based layers comprise essentially nitrogen and very little oxygen. The nitride-based layers comprise at least 90% by atomic percentage of nitrogen relative to the oxygen and nitrogen in said layer. The oxynitride-based layers comprise a mixture of oxygen and nitrogen. The silicon oxynitride-based layers comprise 10 to 90% (limits excluded) by atomic percentage of nitrogen relative to the oxygen and nitrogen in said layer.

[0125] 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 under consideration.

[0126] The dielectric layers are classically chosen from:

[0127] - layers comprising silicon, aluminum and / or zirconium, optionally doped with at least one other element,

[0128] - tin oxide-based layers,

[0129] - layers based on titanium oxide,

[0130] - zinc oxide-based layers.

[0131] The stack may comprise at least one layer comprising silicon or aluminum. Preferably, the dielectric coating located above the functional layer may comprise a layer comprising silicon, in particular chosen from silicon nitride layers or silicon nitride and zirconium layers. Each dielectric coating may also comprise at least one layer comprising silicon.

[0132] Silicon-containing layers are extremely stable to heat treatments. For example, no migration of the elements that make them up is observed. Consequently, these elements are not likely to alter the silver layer. Silicon-containing layers therefore also contribute to the non-alteration of the silver layers and therefore to the achievement of low emissivity after heat treatment.

[0133] The layers comprising silicon comprise at least 50% by mass of silicon relative to the mass of all elements constituting the layer comprising silicon other than nitrogen and oxygen.

[0134] The layers comprising silicon may be selected from oxide-based, nitride-based or oxynitride-based layers such as silicon oxide-based layers, silicon nitride-based layers and silicon oxynitride-based layers.

[0135] The silicon oxide-based layers comprise at least 90 atomic percent oxygen relative to the oxygen and nitrogen in the silicon oxide-based layer. The silicon nitride-based layers comprise at least 90 atomic percent nitrogen relative to the oxygen and nitrogen in the silicon nitride-based layer. The silicon oxynitride-based layers comprise 10 to 90 atomic percent nitrogen relative to the oxygen and nitrogen in the silicon oxide-based layer. Preferably, the silicon oxide-based layers are characterized by a refractive index at 550 nm of less than or equal to 1.55. Preferably, the silicon nitride-based layers are characterized by a refractive index at 550 nm of greater than or equal to 1.95.

[0136] The layers comprising silicon may comprise or consist of elements other than silicon, oxygen and nitrogen. These elements may be selected from aluminum, boron, titanium, and zirconium. The layers comprising silicon may comprise at least 2%, at least 5% or at least 8% by mass of aluminum relative to the mass of all elements constituting the layer comprising silicon other than oxygen and nitrogen.

[0137] The layers comprising aluminum may be selected from oxide-based, nitride-based or oxynitride-based layers such as aluminum oxide-based layers such as AI2O3, aluminum nitride-based layers such as AIN and aluminum oxynitride-based layers such as AlOxNy.

[0138] Silicon nitride and zirconium Si-based layers x Zr y N zare part of the layers comprising silicon, in particular layers based on silicon nitride. The refractive index of the layers based on silicon nitride and zirconium increases with increasing proportions of zirconium in said layer.

[0139] Silicon nitride-based layers may comprise aluminum and / or zirconium. Such layers may comprise, in atomic proportions relative to the atomic proportions of Si, Zr and Al:

[0140] - 50 to 98%, 60 to 90%, 60 to 70% atomic silicon,

[0141] - 0 to 10%, 2 to 10% atomic aluminum,

[0142] - 0 to 40%, 10 to 40% or 15 to 30% atomic zirconium.

[0143] Preferably, at least one dielectric coating comprises a layer comprising silicon selected from silicon nitride-based layers. Preferably, the dielectric coating located above the silver-based functional layer comprises a layer comprising silicon selected from silicon nitride-based layers. Each dielectric coating may comprise a layer comprising silicon selected from silicon nitride-based layers.

[0144] Preferably, the sum of the thicknesses of all the layers comprising silicon based on silicon nitride in each dielectric coating located above the first silver-based functional metal layer may be greater than 35%, greater than 50%, of the total thickness of the dielectric coating. Preferably, the silver-based functional layer is located above a dielectric layer called a stabilizing or wetting layer made of a material capable of stabilizing the interface with the functional layer. These layers are generally based on zinc oxide.

[0145] Preferably, the silver-based functional layer is located below a dielectric layer called a stabilizing or wetting layer made of a material capable of stabilizing the interface with the functional layer. These layers are generally based on zinc oxide.

[0146] The zinc oxide-based layers may comprise at least 80% or at least 90% by mass of zinc relative to the total mass of all the elements constituting the zinc oxide-based layer excluding oxygen and nitrogen.

[0147] The zinc oxide-based layers may comprise one or more elements selected from aluminum, titanium, niobium, zirconium, magnesium, copper, silver, gold, silicon, molybdenum, nickel, chromium, platinum, indium, tin and hafnium, preferably aluminum.

[0148] Zinc oxide-based layers can optionally be doped with at least one other element, such as aluminum.

[0149] A priori, the zinc oxide-based layer is not nitrided, however traces may exist.

[0150] The zinc oxide-based layer comprises, in order of increasing 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.

[0151] The dielectric coating located between the substrate and the first functional metal 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.

[0152] 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.

[0153] Preferably, the dielectric coating directly below the silver-based functional metal layer comprises at least one zinc oxide-based dielectric layer, optionally doped with at least one other element, such as aluminum. The metal functional layer deposited above a zinc oxide-based layer is either directly in contact or separated by a blocking layer.

[0154] In all stacks, the dielectric coating closest to the substrate Di1 is also called the bottom coating and the dielectric coating furthest from the substrate Di3 is called the top coating. Two-layer silver stacks also include an intermediate dielectric coating Di2 located between the bottom and top coating.

[0155] Preferably, the first dielectric coating and the second dielectric coating corresponding to the lower or intermediate coatings, comprise a zinc oxide-based dielectric layer located below and directly in contact with a silver-based metal layer or separated from this layer by a blocking sub-layer.

[0156] Preferably, the dielectric coating directly above the silver-based functional metal layer comprises at least one zinc oxide-based dielectric layer, optionally doped with at least one other element, such as aluminum. The metal functional layer deposited below a zinc oxide-based layer is either directly in contact or separated by a blocking layer.

[0157] Preferably, the second dielectric coating and the third dielectric coating corresponding to the intermediate or upper coatings comprise a zinc oxide-based dielectric layer located above and directly in contact with the silver-based metal layer or separated from this layer by a blocking overlayer.

[0158] The zinc oxide layers have a thickness:

[0159] - 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

[0160] - not more than 25 nm, not more than 10 nm or not more than 8.0 nm.

[0161] Preferably, the material comprises one or more layers based on tin oxide, preferably zinc oxide and tin.

[0162] The zinc and tin oxide-based layers comprise at least 20% by mass of tin relative to the total mass of zinc and tin. The zinc and 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 and tin oxide-based layer comprises 40 to 80% by mass of tin relative to the total mass of zinc and tin.

[0163] The tin oxide layer has a thickness:

[0164] - greater than 5 nm, greater than 10 nm, greater than 15 nm, greater than 20 nm or greater than 25 nm,

[0165] - less than 50 nm, less than 40 nm or less than 35 nm.

[0166] The dielectric coating located between the substrate and the first functional metal layer and / or one or each dielectric coating located above the first silver-based functional layer comprises a layer based on tin oxide, preferably zinc oxide and tin comprising at least 20% by mass of tin relative to the total mass of zinc and tin. Each dielectric coating may comprise a layer of tin oxide, preferably based on zinc oxide and tin comprising at least 20% by mass of tin relative to the total mass of zinc and tin.

[0167] Dielectric layers are divided into low refractive index layers, intermediate refractive index layers, and high refractive index layers, depending on their refractive index at 550 nm. Low refractive index layers have a refractive index of less than 1.70. Intermediate refractive index layers have a refractive index between 1.70 and 2.2. High refractive index layers have a refractive index greater than 2.2.

[0168] The coating may include a layer with a refractive index greater than 2.20. The presence of high-index layers contributes to obtaining high light transmission.

[0169] High refractive index layers can be chosen from:

[0170] - layers based on titanium oxide (n550=2.4),

[0171] - layers based on mixed titanium oxide and another component chosen from the group consisting of Zn, Zr and Sn,

[0172] - layers based on a layer of zirconium nitride (n 550 = 2.55),

[0173] - layers based on silicon and zirconium nitride (n550 nm = 2.20 - 2.40),

[0174] - layers based on a layer of zirconium oxide,

[0175] - layers based on a layer of niobium oxide (n550 = 2.30),

[0176] - layers based on a layer of bismuth oxide (n 550 = 2.60).

[0177] Preferably, the high refractive index layer is chosen from titanium oxide-based layers and silicon and zirconium nitride-based layers.

[0178] The functional coating may comprise at least one blocking layer whose function is to protect the silver layers by preventing possible degradation linked to the deposition of a dielectric coating or linked to a heat treatment. These blocking layers are preferably located in contact with the silver-based functional metal layers.

[0179] According to advantageous embodiments, the stack may comprise at least one blocking layer, located below and directly in contact with a silver-based functional metal layer (blocking sub-layer) and / or at least one blocking layer located above and directly in contact with a silver-based functional metal layer (blocking over-layer).

[0180] A blocking layer above a silver-based functional metal layer is called a blocking overlayer. A blocking layer below a silver-based functional metal layer is called a blocking underlayer.

[0181] The blocking layers are selected from metal layers based on a metal or a metal alloy, metal nitride layers, metal oxide layers and metal oxynitride layers of one or more elements selected from titanium, nickel, chromium, tantalum and niobium such as Ti, TiN, TiOx, Nb, NbN, NbOx, Ni, NiN, NiOx, Cr, CrN, CrOx, NiCr, NiCrN, NiCrOx.

[0182] When these blocking layers are deposited in metallic, nitrided or oxynitrided form, these layers can 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.

[0183] The blocking layers can be chosen from metallic layers, in particular from a nickel and chromium alloy (NiCr) or titanium. The choice of this type of blocking layer is particularly suitable when the material or functional coating is intended to undergo heat treatment at high temperatures.

[0184] Advantageously, the blocking layers are nickel-based metal layers. The nickel-based metal blocking layers may comprise, (before heat treatment), at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% by mass of nickel relative to the mass of the nickel-based metal layer.

[0185] Nickel-based metal layers can be chosen from:

[0186] - the metallic layers of nickel,

[0187] - doped nickel metal layers,

[0188] - metallic layers based on nickel alloy.

[0189] Nickel alloy based metal layers can be based on nickel and chromium alloy.

[0190] Blocking layers can also be chosen from titanium metal layers or titanium oxide layers. The choice of this type of blocking layer is particularly suitable when the material or functional coating is used as is, i.e. without heat treatment.

[0191] Each blocking layer has a thickness between 0.1 and 5.0 nm. The thickness of these blocking layers can be:

[0192] - at least 0.1 nm, at least 0.2 nm or at least 0.4 nm and / or

[0193] - not more than 5.0 nm, not more than 2.0 nm, not more than 1.0 nm or not more than 0.5 nm.

[0194] The functional coating may optionally comprise a protective layer. The protective layer is preferably the last layer of the stack, i.e. the layer furthest from the coated substrate of the stack (before heat treatment). These layers generally have a thickness of between 0.5 and 10 nm, between 1 and 5 nm, between 1 and 3 nm or between 1 and 2.5 nm. This protective layer may be chosen from a layer of titanium, zirconium, hafnium, silicon, zinc and / or tin, this or these metals being in metallic, oxidized or nitrided form. According to one embodiment, the protective layer is based on zirconium oxide and / or titanium, preferably based on zirconium oxide, titanium oxide or titanium and zirconium oxide. When determining the thickness of a dielectric coating, the thickness of the protective layer is taken into account.

[0195] The transparent substrates according to the invention are preferably made of a rigid mineral material, such as glass, or organic polymer-based (or polymer).

[0196] The transparent organic substrates according to the invention may also be made of polymer, rigid or flexible. Examples of polymers suitable according to the invention include, in particular:

[0197] - polyethylene,

[0198] - polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN);

[0199] - polyacrylates such as polymethyl methacrylate (PMMA);

[0200] - polycarbonates;

[0201] - polyurethanes;

[0202] - polyamides;

[0203] - polyimides;

[0204] - fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);

[0205] - photocrosslinkable and / or photopolymerizable resins, such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate resins and

[0206] - polythiourethanes.

[0207] The substrate is preferably a sheet of glass or glass-ceramic. The substrate is preferably transparent, colorless (in which case it is a clear or extra-clear glass) or colored, for example blue, gray or bronze. The glass is preferably of the soda-lime-silica type, but it can also be of borosilicate or alumino-borosilicate type glass. According to a preferred embodiment, the substrate is made of glass, in particular soda-lime-silica or of polymeric organic material.

[0208] The substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and even 3 m. The thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, in particular between 2 and 8 mm, or even between 4 and 6 mm. The substrate can be flat or curved, or even flexible.

[0209] The present invention relates to the non-heat-treated material. The coating may not have undergone a heat treatment at a temperature above 500°C, preferably 300°C. The present invention also relates to the heat-treated material. The heat treatments are chosen from:

[0210] - annealing, for example rapid annealing,

[0211] - quenching and / or bending.

[0212] The material, i.e., the transparent substrate coated with the stack, may have undergone high temperature heat treatment. The stack and the substrate may have undergone high temperature heat treatment such as quenching, annealing, or bending.

[0213] It is also possible to heat treat only the stack. In this case, only the stack may have undergone heat treatment.

[0214] In both cases, the stack may have undergone heat treatment at a temperature above 300°C, preferably 500°C. The heat treatment temperature (at the stack) is above 300°C, preferably above 400°C, and better still above 500°C.

[0215] According to the invention, it is possible to carry out a rapid thermal annealing 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 stack 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 less than or equal to 150°C at any point on the face of the substrate opposite that on which the stack is located. This process has the advantage of heating only the stack, without significantly heating the entire substrate.

[0216] In the case of laser processing, the coated materials can be treated using a laser line formed from laser sources such as InGaAs laser diodes or Yb:YAG disk lasers. These continuous sources emit at a wavelength between 900 and 1100 nm. The laser line has a length of about 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.

[0217] The materials are arranged on a roller conveyor so as to travel in an X direction, parallel to its length. The laser line is fixed and positioned above the coated surface of the substrate with its longitudinal direction Y extending perpendicular to the X direction of travel of the substrate, i.e. along the width of the substrate, extending over this entire width.

[0218] The position of the focal plane of the laser line is adjusted to be within the thickness of the functional coating when the substrate is positioned on the conveyor. The power flux density of the laser line at the focal plane is less than 100kW / cm2. The substrate was moved under the laser line at a speed of approximately 8 m / min. The coating may therefore have been subjected to rapid thermal annealing in which each point of the stack is heated to a temperature of at least 300°C while maintaining a temperature less than or equal to 150°C at any point on the face of the substrate opposite that on which the stack is located.

[0219] It is also possible to combine heat treatments. For example, it is possible to perform rapid thermal annealing followed by quenching.

[0220] The coating and substrate may have been subjected to a heat treatment at an elevated temperature above 500°C such as tempering, annealing or bending. The coated substrate of the stack may be curved or tempered glass.

[0221] The invention also relates to a glazing comprising at least one material according to the invention. The invention relates to a glazing which may be in the form of monolithic, laminated and / or multiple glazing, in particular double glazing or triple glazing.

[0222] Double glazing has 4 sides, side 1 is on the outside of the building and therefore constitutes the outer wall of the glazing, side 4 is on the inside of the building and therefore constitutes the inner wall of the glazing, sides 2 and 3 being on the inside of the double glazing. The stack according to the invention is on side 2 or side 3.

[0223] Triple glazing has 6 faces, face 1 is on the outside of the building and therefore constitutes the outer wall of the glazing, face 6 is on the inside of the building and therefore constitutes the inner wall of the glazing, faces 2 and 3 and 4 and 5 being on the inside of the double glazing. The stack according to the invention can be on face 2, face 3 and / or face 5.

[0224] A laminated glazing unit comprises at least one structure of the first substrate / sheet(s) / second substrate type. The polymeric sheet may in particular be based on polyvinyl butyral PVB, ethylene vinyl acetate EVA, polyethylene terephthalate PET, polyvinyl chloride PVC. The stack of thin layers is positioned on at least one of the faces of one of the substrates.

[0225] The invention therefore relates to:

[0226] - multiple glazing of the double glazing type with stacking on face 2,

[0227] - multiple glazing of the double glazing type with stacking on face 3,

[0228] - multiple glazing of the triple glazing type with stacking on face 2 and face 5,

[0229] - laminated glazing with stacking on face 2 or 3.

[0230] These windows can be mounted on a building or a vehicle.

[0231] The following examples illustrate the invention.

[0232] Examples

[0233] 1. Preparation of the substrates: materials and deposition conditions Stacks of thin layers defined below are deposited on clear soda-lime glass substrates with a thickness of 6 mm. In the examples of the invention:

[0234] - the functional layers are silver (Ag) layers,

[0235] - the dielectric layers are based on aluminum-doped silicon nitride (SiaN4: Al), based on aluminum-doped silicon and zirconium nitride (SiZrN: Al), based on zinc and tin oxide, based on zinc oxide (ZnO).

[0236] The layers of titanium oxide TiOx, hereinafter referred to as TiOx (1), located above and in contact with the functional layers, are deposited from a ceramic target, in particular under stoichiometric conditions, in a controlled atmosphere comprising oxygen. A first thin layer of titanium oxide-based layer is deposited in contact with the silver layer, from a ceramic target, in a non-oxidizing or very weakly oxidizing atmosphere. Then, a thicker layer of titanium oxide-based layer is deposited from a ceramic target in an oxidizing atmosphere. The titanium oxide-based layer consists of these two parts. During deposition, the part of the titanium oxide-based layer in contact with the functional layer is less oxidized than the part furthest from the functional layer.

[0237] The layers of titanium oxide TiOx, hereinafter referred to as TiOx (2), are deposited from a ceramic target, in particular under stoichiometric conditions without varying the proportions of oxygen during their deposition. The deposition conditions of the layers, which were deposited by sputtering (so-called "magnetron cathode sputtering"), are summarized in Table 1.

[0238] [Table 1]

[0239] %wt: % by weight; at%: atomic.

[0240] In the examples, different materials according to the invention and comparative materials were tested. In all the tables setting out the optical characteristics and performances, the characteristics were measured on a double glazing having a 6 / 16 / 4 structure: 6 mm glass / 16 mm interlayer space filled with 90% argon and 10% air / 4 mm glass, the stack being positioned on face 2 (face 1 of the glazing being the outermost face of the glazing, as usual).

[0241] Light transmission levels ranging from 40% to 80% were tested. For this, a color box was defined for interior and exterior reflection for all glazing.

[0242] The color box varies only by the level of a* in transmission for the different light transmission levels. The color level (a*) in transmission, and more specifically the search for neutrality in transmission (a*T close to 0), regulates the selectivity of multi-Ag coatings. For TL cases of 40 and 50%, a*T is greater than -9. For TL cases of 60%, a*T is greater than -7. For TL >70%, a*T is greater than -4.

[0243] [Table 2]

[0244] The table below lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that constitutes the stacks according to their positions relative to the substrate carrying the stack.

[0245] Example 1

[0246] In this series of examples, the examples according to the invention comprise a functional coating which comprises a TiOx layer in the third dielectric coating, in contact with the second silver layer, and a high index layer in the first dielectric coating.

[0247] Light transmissions of 78.5%, 75%, 70%, 60%, 50% and 40% are respectively sought in Examples 1a, 1b, 1c, 1d, 1e and 1f.

[0248] Each functional coating according to the invention is compared to a coating achieving the same light transmission TL but comprising neither a TiOx layer in contact with a silver layer, nor a high-index layer in the first dielectric coating (M1).

[0249] Table 3 below lists the different functional coatings tested.

[0250] Example 2

[0251] As in the previous example series, the functional coatings according to the invention comprise a TiOx layer in the third dielectric coating, in contact with the second silver layer, and a high index layer in the first dielectric coating.

[0252] In this example, the functional coatings according to the invention additionally comprise a high index layer in the second dielectric coating.

[0253] Light transmissions of 78.5 and 70% are sought in Examples 2a and 2b respectively.

[0254] Each functional coating according to the invention is compared to a functional coating reaching the same TL but comprising neither a TiOx layer in contact with a silver layer, nor a high index layer.

[0255] Table 4 below lists the different functional coatings tested.

[0256]

[0257] The following coatings have been developed for use after undergoing a hardening type heat treatment. The heat treatments are carried out in a NABER furnace at a temperature of 650°C for 10 minutes.

[0258] 2. Optical Properties and Performance

[0259] Compared to a reference stack comprising the same TL, the presence of a high index layer in the first dielectric coating and a TiOx layer in the third dielectric coating, in contact with the second silver layer, makes it possible to significantly improve selectivity while remaining within the chosen color box, in transmission.

Claims

Claims 1. Material comprising a substrate coated with a functional coating comprising an alternation of only two silver-based metallic functional layers called, starting from the substrate, first and second functional layers and three dielectric coatings called, starting from the substrate, Di1, Di2 and Di3, each dielectric coating comprising at least one dielectric layer, so that each functional metallic layer is arranged between two dielectric coatings, characterized in that: - the dielectric coating Di1 located below the first functional layer comprises a high refractive index layer having a refractive index measured at 550 nm greater than 2.20 and a thickness greater than 3.0 nm, preferably greater than 5 nm, - the third dielectric coating Di3 located above the second functional layer comprises a titanium oxide-based layer located above and in contact with the second silver-based functional metal layer, this titanium oxide layer having a thickness greater than or equal to 3 nm.

2. Material according to the preceding claim, characterized in that the titanium oxide-based layer located above the second silver-based functional layer has a thickness of at least 5 nm.

3. Material according to any one of the preceding claims, characterized in that the second dielectric coating Di2 located above the first functional layer comprises a layer based on titanium oxide located above and in contact with the first functional metallic layer based on silver having a thickness greater than or equal to 3 nm.

4. Material according to the preceding claim, characterized in that the second dielectric coating Di2 further comprises a tin-based layer, preferably a zinc and tin oxide-based layer comprising at least 10% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the titanium oxide-based layer.

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

6. Material according to any one of the preceding claims, characterized in that the third dielectric coating Di3 located above the second functional layer comprises a high refractive index layer having an index of CORRECTED SHEET (RULE 91) ISA / EP refraction measured at 550 nm greater than 2.20 and a thickness greater than 5 nm, this layer is distinct from the titanium oxide-based layer in contact with the silver layer.

7. Material according to any one of the preceding claims, characterized in that the second dielectric coating Di2 comprises a high refractive index layer having a refractive index measured at 550 nm greater than 2.20 and a thickness greater than 5 nm, this layer is distinct from the possible layer based on titanium oxide in contact with the silver layer.

8. Material according to any one of the preceding claims, characterized in that the high refractive index layers are chosen from layers based on titanium oxide, layers of niobium oxide and layers based on silicon and zirconium nitride.

9. Material according to any one of the preceding claims, characterized in that the layers with a refractive index greater than 2.20 other than the layers based on titanium oxide in contact with the functional layers have a thickness greater than 10 nm.

10. Material according to any one of the preceding claims, characterized in that the functional coating comprises one or more metallic blocking layers preferably located in contact with and below the first and / or second metallic functional layer.

11. Material according to any one of the preceding claims, characterized in that the dielectric coating Di1 located below the first functional layer comprises a zinc oxide-based layer located in contact with the first functional layer or separated from the functional layer by a blocking layer.

12. Material according to any one of the preceding claims, characterized in that the dielectric coating located below the second functional layer Di2 comprises a zinc oxide-based layer located in contact with the second functional layer or separated from the functional layer by a blocking layer.

13. Material according to any one of the preceding claims, characterized in that the dielectric coating Di1 located below the first functional layer comprises a zinc oxide-based layer located in contact with the first functional layer or separated from the functional layer by a blocking layer and / or the dielectric coating Di2 located below the second functional layer comprises a zinc oxide-based layer located in contact with the second functional layer or separated from the functional layer by a blocking layer.

14. Material according to any one of the preceding claims, characterized in that: - the dielectric coating Di1 located below the first functional layer comprises a layer comprising silicon chosen from silicon nitride layers, CORRECTED SHEET (RULE 91) ISA / EP and / or - the dielectric coating Di2 located below the second functional layer comprises a layer comprising silicon chosen from silicon nitride layers, and / or - the dielectric coating Di3 located above the second functional layer comprises a layer comprising silicon chosen from silicon nitride layers.

15. Material according to any one of the preceding claims, characterized in that: the sum of the thicknesses of all the oxide-based layers present: - in the dielectric coating Di 1 located between the substrate and the first functional metal layer is less than 60% of the total thickness of the dielectric coating and / or - in the dielectric coating located above the first silver-based functional layer is less than 60 of the total thickness of the dielectric coating and / or - in the dielectric coating located above the second silver-based functional layer is less than 60% of the total thickness of the dielectric coating.

16. Material according to any one of the preceding claims, characterized in that it has a light transmission greater than 70%.

17. Material according to any one of claims 1 to 15, characterized in that it has a light transmission of less than 70%, preferably between 30 and 50%.

18. Glazing comprising material according to any one of claims 1 to 17 in the form of multiple glazing or laminated glazing. CORRECTED SHEET (RULE 91) ISA / EP

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