Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3613—Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3639—Multilayers containing at least two functional metal layers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3652—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
  • C03C17/366—Low-emissivity or solar control coatings
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3681—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3689—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one oxide layer being obtained by oxidation of a metallic layer
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
  • C03C23/007—Other surface treatment of glass not in the form of fibres or filaments by thermal treatment

Definitions

• the invention relates to a substrate coated on one side of a stack of thin layers with infrared reflection properties and / or in solar radiation.
• the functional layer is thus disposed between two antireflection coatings each in general comprising several layers which are each made of a dielectric material of the nitride type, and in particular silicon nitride or aluminum oxide, or oxide. From the optical point of view, the purpose of these coatings that frame the or each metal functional layer is "anti-reflective" this functional metal layer.
• a blocking coating is however sometimes interposed between one or each antireflection coating and the functional metal layer, the blocking coating disposed under the functional layer towards the substrate protects it during a possible heat treatment at high temperature, the bending type and and / or quenching and the blocking coating disposed on the functional layer opposite the substrate protects this layer from possible degradation during the deposition of the upper antireflection coating and during a possible high temperature heat treatment, such as bending and / or quenching.
• the invention relates more particularly to the use of an end layer of the stack, the one furthest from the face of the substrate on which the stack is deposited and the implementation of a treatment of the stack of layers. thin complete with a source producing radiation and in particular infrared radiation. It is known, in particular from the international patent application No. WO 2010/142926, to provide an end-layer absorbent layer of a stack and to apply a treatment after the deposition of a stack to reduce the emissivity, or improve the optical properties of a low-emissive stack.
• a metallic end-layer makes it possible to increase the absorption and to reduce the power required for the treatment. As the end layer oxidizes during processing and becomes transparent, the optical characteristics of the stack after treatment are interesting (high light transmission can be obtained in particular).
• the object of the invention is to overcome the drawbacks of the prior art, by developing a new type of stack of layers with one or more functional layers, which stack has, after treatment, a low resistance per square (and thus a low emissivity), a high light transmission, as well as an aspect homogeneity, both in transmission and in reflection.
• Another important goal is to enable the treatment to be carried out more quickly, and thus to reduce its cost.
• the object of the invention is thus, in its broadest sense, a substrate according to claim 1.
• This substrate is coated on one side of a thin film stack with infrared reflection properties and / or in the radiation solar cell comprising at least one metallic functional layer, in particular based on silver or metal alloy containing silver and at least two antireflection coatings, said coatings each comprising at least one dielectric layer, said functional layer being disposed between the two antireflection coatings, said stack comprising on the one hand an end layer which is the layer of the stack which is furthest from said face, which comprises at least one metal M 2 , said metal being a reducer in an oxide / metal pair having a redox potential ⁇ 2 and said terminal layer being in the metallic state and secondly a pre-terminal layer which is the layer of the stack located just under and in contact with said terminal layer in the direction of said face, which comprises at least one metal Mi, said metal being a reducer in an oxide / metal pair having a redox potential ⁇ and said pre-terminal
• said redox potential ⁇ is greater than said redox potential ⁇ 2 , said oxidation-reduction potentials being measured by a normal hydrogen electrode.
• dielectric layer in the sense of the present invention, it should be understood that from the point of view of its nature, the material is “non-metallic", that is to say 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.
• absorbent layer in the sense of the present invention, it should be understood that the layer is a material having an average coefficient k, over the entire range of visible wavelength (380 nm to 780 nm), greater than 0 5 and having bulk electrical resistivity (as known in the literature) greater than 10 -6 ⁇ .cm.
• n denotes the actual refractive index of the material at a given wavelength and the coefficient k represents the imaginary part of the refractive index at a given wavelength; the ratio n / k being calculated at a given wavelength identical for n and for k.
• the term "metal layer” is understood to mean that the layer is absorbent as indicated above and that it does not comprise an oxygen atom or a nitrogen atom.
• the "redox potential” is the voltage obtained with the standard hydrogen electrode; this is the potential generally indicated in the reference works.
• the stack according to the invention thus comprises a last layer, called a "terminal layer” (or “overcoat” in English), that is to say a layer deposited in the metallic state, from a metal target. and in an atmosphere containing neither oxygen nor nitrogen, voluntarily introduced.
• This layer is found essentially oxidized stoichiometrically in the stack after treatment with a source producing radiation and in particular infrared radiation.
• Said pre-terminal layer in the at least partially oxidized state with respect to its known stable stoichiometry, acts as an oxygen donor layer for the layer immediately above (opposite the substrate).
• Said pre-terminal layer may be in the oxidized state, according to its known stable stoichiometry, or possibly in the over-oxidized state relative to its known stable stoichiometry.
• Said metallic end layer preferably has a thickness of between 0.5 nm and 5.0 nm, or even between 1.0 nm and 4.0 nm. This relatively small thickness makes it possible to obtain complete oxidation of the terminal layer during the treatment and thus a relatively high light transmission.
• Said end layer is chosen to have a high absorption at the wavelength ⁇ of the source producing a radiation during the treatment.
• the imaginary part of the index of a metal of the terminal layer k () satisfies: k ()> 3 (ex: Ti at 980 nm), even k ()> 4 (ex: Zn at 980 nm ), or even k ()> 7 (eg Sn, In at 980 nm).
• Said pre-terminal layer preferably has a thickness of between 5.0 and 20.0 nm, or even between 10.0 nm and 15.0 nm. This relatively average thickness makes it possible to produce an effective oxygen reservoir without greatly influencing the optical appearance of the stack.
• said pre-terminal layer is a tin oxide (that is to say a layer which has no element other than Sn and O) or an oxide of a mixture of metallic elements. comprising tin and preferably further comprising zinc.
• the atomic proportion of tin over zinc is different and said pre-terminal layer is richer in tin than said metallic end layer ; however, when said metallic end layer and said pre-terminal layer both comprise tin and zinc, the atomic proportion of tin over zinc may be the same for both layers.
• said pre-terminal layer is located directly on a dielectric layer based on silicon nitride; this dielectric layer based on silicon nitride preferably does not include oxygen.
• This dielectric layer based on silicon nitride preferably has a physical thickness of between 5.0 and 50.0 nm, or even between 8.0 and 20.0 nm; this layer preferably being made of aluminum nitride Si 3 N 4 doped with aluminum.
• This dielectric layer based on silicon nitride is a barrier layer which prevents the entry of oxygen from the atmosphere towards the substrate; since the metallic functional layer is located between this barrier layer and the substrate, it prevents the penetration of oxygen from the atmosphere towards the metallic functional layer.
• a dielectric layer based on silicon nitride is difficult to deposit because the silicon is difficult to spray due to its low conductivity.
• the presence of the pre-terminal layer also makes it possible to deposit a dielectric layer based on silicon nitride of a thickness that is lower than usual.
• the functional layer is deposited directly on a sub-blocking coating disposed between the functional layer and the dielectric coating underlying the functional layer and / or the functional layer is deposited directly under a over-locking coating disposed between the functional layer and the overlying dielectric coating to the functional layer and the underblocking coating and / or the overblocking coating comprises a thin layer of nickel or titanium having a physical thickness such that 0.2 nm ⁇ ⁇ 2.5 nm.
• the invention further relates to a method for obtaining a substrate coated on one side of a stack of thin films with infrared reflection properties and / or in solar radiation comprising at least one metallic functional layer, particular silver-based or silver-containing metal alloy and two anti-reflective coatings, comprising the following steps, in order:
• a thin film stack with infrared reflection properties and / or solar radiation comprising at least one metallic functional layer, in particular based on silver or metal alloy containing silver and at least two antireflection coatings, according to the invention
• thermoforming the pre-terminal layer it is possible that said treatment is performed in an atmosphere that does not include oxygen. It is also possible to provide a multiple glazing unit comprising at least two substrates which are held together by a frame structure, said glazing effecting a separation between an outer space and an interior space, in which at least one spacer gas strip is arranged. between the two substrates, a substrate being according to the invention.
• a single multiple glazing substrate having at least two substrates or multiple glazing having at least three substrates is coated on an inner face in contact with the interposed gas layer of a thin film stack with reflection properties in the substrate. infrared and / or in solar radiation.
• the glazing then incorporates at least the carrier substrate of the stack according to the invention, optionally associated with at least one other substrate.
• a multiple glazing unit comprising three substrates two substrates are each coated on an inner face in contact with the interlayer gas strip of a stack of thin layers with infrared reflection properties and / or in the radiation solar according to the invention.
• Each substrate can be clear or colored. At least one of the substrates may be colored glass in the mass. The choice of the type of coloration will depend on the level of light transmission and / or the colorimetric appearance sought for the glazing once its manufacture is complete.
• the glazing may have a laminated structure, combining in particular at least two rigid substrates of the glass type with at least one thermoplastic polymer sheet, in order to present a glass-like / thin-film / sheet (s) / glass / blade-type structure. interlayer gas / glass sheet.
• the polymer may especially be based on polyvinyl butyral PVB, ethylene vinyl acetate EVA, PET polyethylene terephthalate, PVC polyvinyl chloride.
• the present invention thus makes it possible to produce a stack of thin layers with one or more functional layers having a low emissivity (in particular ⁇ 1%) and a high solar factor which has a homogeneous optical appearance in transmission and reflection. after treatment of the stack using a source producing radiation and in particular infrared radiation.
• FIG. 1 a functional monolayer stack according to the invention, the functional layer being deposited directly on a sub-blocking coating and directly under an overblocking coating, the stack being illustrated during the treatment using a source producing radiation;
• FIG. 2 a double glazing solution incorporating a functional monolayer stack
• FIG. 1 illustrates a structure of a functional monolayer stack 14 according to the invention deposited on a face 29 of a transparent glass substrate 30, in which the single functional layer 140, in particular based on silver or alloy metal containing silver, is disposed between two antireflection coatings, the underlying antireflection coating 120 located below the functional layer 140 towards the substrate 30 and the overlying antireflection coating 160 disposed above the functional layer. 140 opposite the substrate 30.
• the single functional layer 140 in particular based on silver or alloy metal containing silver
• These two antireflection coatings 120, 160 each comprise at least one dielectric layer 122, 128; 162, 164, 166.
• the functional layer 140 may be deposited directly on a sub-blocking coating 130 placed between the underlying antireflection coating 120 and the functional layer 140 and, on the other hand, the functional layer 140 may be deposited directly under an overblocking coating 150 disposed between the functional layer 140 and the overlying antireflection coating 160.
• the layers of under and / or over-blocking although deposited in metallic form and presented as being metal layers, are sometimes in practice oxidized layers because one of their functions (in particular for the over-blocking layer) is to oxidize during the deposition of the stack to protect the functional layer.
• the antireflection coating 160 located above the metallic functional layer ends with a terminal layer 168, which is the layer of the stack that is furthest from face 29.
• a pre-terminal layer 167 is further provided just below this end layer 168, towards the face 29, this pre-terminal layer 167 being in contact with the terminal layer located thereon.
• this glazing comprises two substrates 10, 30 which are held together by a frame structure 90 and which are separated from one another. other by an interlayer gas blade 15.
• the glazing thus makes a separation between an outer space ES and an interior space IS.
• the stack can be positioned in face 3 (on the innermost sheet of the building by considering the incident sense of sunlight entering the building and on its face facing the gas blade).
• FIG. 2 illustrates this positioning (the incident direction of sunlight entering the building being illustrated by the double arrow) in face 3 of a stack of thin layers 14 positioned on an inner face 29 of the substrate 30 in contact with the spacer gas plate 15, the other face 31 of the substrate 30 being in contact with the interior space IS.
• one of the substrates has a laminated structure.
• the antireflection coating 120 comprises two dielectric layers 122, 128, the dielectric layer 122, in contact with the face 29 is a high refractive index layer and is in contact with a dielectric wetting layer 128 disposed just below the metal functional layer 140.
• the high refractive index dielectric layer 122 is based on titanium oxide; It has a refractive index between 2.3 and 2.7, which is here precisely 2.46.
• the dielectric layer 128 is called “wetting layer” because it improves the crystallization of the metal functional layer 140 which is here silver, which improves its conductivity.
• This dielectric layer 128 is zinc oxide ZnO (deposited from a ceramic target consisting of 50 atomic% of zinc and 50 atomic% of oxygen).
• the overlying antireflection coating 160 comprises a dielectric layer 162 of zinc oxide (deposited from a ceramic target consisting of 50 atomic% of doped zinc and 50 atomic% of oxygen), followed by a high index dielectric layer 164. in the same material as the dielectric layer 122.
• the next dielectric layer, 166 is made of Si 3 N 4 : Al nitride and is deposited from a metal target made of Si doped with 8% by weight of aluminum.
• the layer deposition conditions are:
• the deposited layers can thus be classified into four categories: i-layers of antireflection / dielectric material, having an n / k ratio over the entire visible wavelength range greater than 5: S13N4, Ti0 2 , ZnO, Sn0 2 , Sn x Zn y O z
• i-metal layer of absorbent material having an average coefficient k, over the entire range of wavelength of the visible, greater than 0.5 and a bulk electrical resistivity that is greater than 10 "6 ⁇ .cm : SnjZn j , Ti
• iii- metal functional layers made of material with infrared and / or solar radiation reflection properties: Ag
• Silver has been found to have a ratio of 0 ⁇ n / k ⁇ 5 over the entire visible wavelength range, but its bulk electrical resistivity is less than 10 "6 ⁇ .cm.
• the stack of thin layers is deposited on a clear soda-lime glass substrate of a thickness of 4 mm of the Planiclear brand, distributed by the company SAINT-GOBAIN.
• - R indicates the resistance per square of the stack, in ohms per square;
• - A L indicates the light absorption in the visible in%, measured according to the illuminant D65;
• - I T indicates the optical inhomogeneities in transmission; it is a score of 1, 2, 3 or 4, attributed by an operator: note 1 when no inhomogeneity is perceptible to the eye, note 2 when localized inhomogeneities, limited to certain areas of the sample, are perceptible to the eye under intense diffuse illumination (> 800 lux), note 3 when localized inhomogeneities limited to certain areas of the sample are perceptible to the eye under standard illumination ( ⁇ 500 lux ) and note 4 when inhomogeneities spread over the entire surface of the sample are perceptible to the eye under standard illumination ( ⁇ 500 lux).
• - I R indicates the optical inhomogeneities in reflection; it is a score of 1, 2, 3 or 4, attributed by an operator: note 1 when no inhomogeneity is perceptible to the eye, note 2 when localized inhomogeneities, limited to certain areas of the sample, are perceptible to the eye under intense diffuse illumination (> 800 lux), note 3 when localized inhomogeneities limited to certain areas of the sample are perceptible to the eye under standard illumination ( ⁇ 500 lux ) and note 4 when inhomogeneities spread over the entire surface of the sample are perceptible to the eye under standard illumination ( ⁇ 500 lux).
• Table 1 below illustrates the geometrical or physical thicknesses (and not the optical thicknesses) in nanometers, with reference to FIG. 1, of each of the layers of Examples 1 to 6: Layer Material Ex. 1, 3 Ex. 2, 4-6
• Table 2 below presents the materials tested for the end layers 168 and optionally the pre-terminal layers 167 of Examples 1 to 6, as well as their respective thicknesses (in nm):
• the metallic metal terminal layer 168 before the treatment comprises at least one metal M 2 (Zn, Ti) which is a reducing agent in an oxide / metal pair having a potential of redox ⁇ 2 and secondly the pre-terminal layer 167 comprises at least one metal Mi (Sn) which is an oxidant in an oxide / metal pair having a redox potential ⁇ and the oxidation-reduction potential Yi is thus greater at the redox potential ⁇ 2 .
• the pre-terminal layer 167 of Example 5 is a tin oxide deposited in its stable stoichiometric form SnO 2 .
• the pre-terminal layer 167 of Example 2 is a titanium oxide deposited in its stable stoichiometric TiO 2 form .
• the end layer 168 of Examples 3 and 6 is a metal layer made of titanium.
• Table 3 summarizes the main optical and energetic characteristics of these Examples 1 to 6, respectively before treatment (BT) and after treatment (AT):
• the processing here is a scrolling of the substrate 30 at a speed of 10 m / min under a laser line 20 of 60 ⁇ wide and power 25 W / mm with the laser line oriented perpendicular to the face 29 and towards the end layer 168, that is to say by arranging the laser line (illustrated by the right black arrow) above the stack and directing the laser toward the stack, as shown in Figure 1.
• Example 4 The reduction in square resistance to the treatment of Example 4 is excellent: 22.5%; The decrease in square resistance to the treatment of Examples 5 and 6 is slightly less good (respectively 18.4% and 15.7%). %), while being satisfactory; the emissivity obtained after treatment is weak, as desired.
• Examples 1 to 3 After treatment and oxidation of the end-layer 168, Examples 1 to 3 have a light absorption AL too high (greater than 15%) and are optically not sufficiently homogeneous, both in transmission and in reflection, with values of 1 T and l R equal to or greater than 2.
• Examples 4 and 5 After treatment and oxidation of the end layer 168, Examples 4 and 5 have an excellent light absorption AL (of the order of 6.5%) and are optically very homogeneous, both in transmission and in reflection, with values of l T and l R equal to 1.
• Example 6 After treatment and oxidation of the end layer 168, Example 6 has a slightly high light absorption AL but is optically very homogeneous, both in transmission and in reflection, with values of 1 T and 1 R equal to 1.
• the pre-terminal layer promotes optical stability in both transmission and reflection.
• a series of tests was carried out using the same stacks (same layer materials, same thicknesses) as for Examples 1, 4 and 5 but treating them at different speeds. treatment v; these series are noted respectively Examples 1 ', Examples 4' and Examples 5 'in Figure 3.
• FIG. 3 shows that the Al absorption after treatment is lower for the examples 4 'and 5' with a pre-terminal layer according to the invention under the end-layer than for the examples 1 'without a pre-terminal layer according to the invention. under the end-layer, regardless of the processing speed v.
• FIG. 3 shows that it is possible to increase the processing speed from 20% to 50% for Examples 4 'and 5', up to values of approximately 15 m / minute, without this being necessary. does not really influence the low absorption after treatment.
• the present invention can also be used for a stack of thin layers with several functional layers.
• the end layer according to the invention is the layer of the stack which is furthest from the face of the substrate on which the stack is deposited and the pre-terminal layer is the layer located just under the end layer in the direction of the face of the substrate on which is deposited the stack of thin layers and in contact with the terminal layer.

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• Surface Treatment Of Glass (AREA)
• Laminated Bodies (AREA)
• Heat Sensitive Colour Forming Recording (AREA)

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• 2015
  • 2015-05-29 FR FR1554852A patent/FR3036701B1/fr not_active Expired - Fee Related
• 2016
  • 2016-05-26 EP EP16733634.6A patent/EP3303242A1/de not_active Withdrawn
  • 2016-05-26 MX MX2017015275A patent/MX2017015275A/es unknown
  • 2016-05-26 KR KR1020177037199A patent/KR20180014749A/ko not_active Application Discontinuation
  • 2016-05-26 BR BR112017024097-1A patent/BR112017024097A2/pt active Search and Examination
  • 2016-05-26 JP JP2017562046A patent/JP6734875B2/ja not_active Expired - Fee Related
  • 2016-05-26 WO PCT/FR2016/051238 patent/WO2016193577A1/fr active Application Filing
  • 2016-05-26 EA EA201792607A patent/EA034718B1/ru not_active IP Right Cessation
  • 2016-05-26 US US15/577,025 patent/US20180141855A1/en not_active Abandoned
  • 2016-05-26 CN CN201680031333.8A patent/CN107667077B/zh not_active Expired - Fee Related
• 2017
  • 2017-11-02 CO CONC2017/0011292A patent/CO2017011292A2/es unknown

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