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
  • 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
• • 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
  • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
• • 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
  • C03C17/3644—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
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/212—TiO2
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/216—ZnO
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/251—Al, Cu, Mg or noble metals
  • C03C2217/254—Noble metals
  • C03C2217/256—Ag
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/28—Other inorganic materials
  • C03C2217/281—Nitrides
• • 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
  • C03C2217/00—Coatings on glass
  • C03C2217/70—Properties of coatings
  • C03C2217/73—Anti-reflective coatings with specific characteristics
  • C03C2217/734—Anti-reflective coatings with specific characteristics comprising an alternation of high and low refractive indexes
• • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/154—Deposition methods from the vapour phase by sputtering
• • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/30—Aspects of methods for coating glass not covered above
  • C03C2218/31—Pre-treatment
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P40/00—Technologies relating to the processing of minerals
  • Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
  • Y02P40/57—Improving the yield, e-g- reduction of reject rates

Definitions

• the invention relates to a method for obtaining a material, such as a glazing unit, comprising a transparent substrate coated with a stack of thin layers comprising at least one silver-based functional metal layer.
• the material is intended to undergo heat treatment at elevated temperature.
• Functional metal layers based on silver (or silver layers) have advantageous electrical conduction and reflection properties of infrared (IR) radiation, hence their use in "solar control" glazing aimed at reducing the amount of incoming solar energy and / or in so-called “low emissivity” glazing aimed at reducing the amount of energy dissipated to the outside of a building or a vehicle.
• IR infrared
• These silver layers are deposited between antireflection coatings which generally comprise several dielectric layers for adjusting the optical properties of the stack. These dielectric layers also make it possible to protect the silver layer from chemical or mechanical aggression.
• optical and electrical properties of the material depend directly on the quality of the silver layers such as their crystalline state, their homogeneity and their environment such as the nature of the layers above and below the silver layer .
• the invention particularly relates to a material subjected to high temperature heat treatment such as annealing, bending and / or quenching. Heat treatments at high temperatures can cause changes within the silver layer and in particular generate defects. Some of these defects are in the form of a hole.
• the "hole” type defects correspond to the appearance of silver-free zones having a circular or dendritic shape, that is to say a partial dewetting of the silver layer.
• the object of the invention is to develop a method for obtaining a material comprising a substrate coated with a stack that can undergo high temperature heat treatments like bending, quenching and / or annealing while preserving good optical, mechanical and corrosion resistance properties.
• TiO 2 titanium oxide
• Nb 2 O 5 niobium oxide
• SnO 2 tin oxide
• the Applicant has discovered that the performance of a heat pretreatment of the layers likely to generate hole-like defects, before deposition of the silver layer, makes it possible to prevent these holes from appearing during the heat treatment of the complete stack.
• the invention relates to a method for obtaining a material comprising a transparent substrate coated with a stack of thin layers comprising at least one silver-based functional metal layer located above at least one antireflection coating,
• the transparent substrate coated with the stack is intended to undergo heat treatment at a temperature Tmax greater than 400 ° C.
• the antireflection coating comprises at least one dielectric layer capable of generating hole-type defects
• the method comprises the following sequence of steps: depositing the antireflection coating comprising at least one dielectric layer capable of generating hole-type defects on the transparent substrate, and then
• the dielectric layer liable to generate hole-type defects is subjected to thermal pretreatment, and then
• At least one functional metal layer based on silver is deposited.
• the method of the invention makes it possible to obtain the advantageous properties despite the presence in the stack of thin layers capable of generating hole-type defects.
• the maximum temperature Tmax corresponds to the highest temperature reached during the heat treatment to which the transparent substrate coated with the stack is subjected.
• the pretreatment of the layer capable of generating hole-like defects makes it possible to significantly prevent dewetting and the appearance of dendritic hole-type defects in the silver layer when the substrate coated with the stack is subjected to a heat treatment. .
• the stack is deposited by sputtering, in particular assisted by a magnetic field (magnetron process). Each layer of the stack can be deposited by sputtering.
• the thicknesses discussed herein are physical thicknesses.
• thin film is meant a layer having a thickness of between 0.1 nm and 100 micrometers.
• the substrate according to the invention is considered laid horizontally.
• the stack of thin layers is deposited above the substrate.
• the meaning of the terms “above” and “below” and “below” and “above” should be considered in relation to this orientation.
• the terms “above” and “below” do not necessarily mean that two layers and / or coatings are arranged in contact with each other.
• a layer is deposited "in contact” with another layer or a coating, this means that there can not be one or more layers interposed between these two layers.
• the dielectric layers capable of generating hole-type defects are chosen from titanium oxide (TiO 2 ), niobium oxide (Nb 2 O 5 ) and tin oxide (SnO 2 ) based layers. .
• the dielectric layers capable of generating hole-type defects are deposited by cathodic sputtering.
• the dielectric layers capable of generating hole-type defects have a thickness greater than 5 nm, preferably between 8 and 20 nm.
• the proposed solution according to the invention is suitable when the thin layer capable of generating hole-type defects is sufficiently close to the functional layer based on silver to induce defects. Indeed, in the case of complex stack comprising antireflection coatings with a number of dielectric layers, when the layer capable of generating hole-type defects is separated from the silver-based functional layer by a significant thickness of one or more layers not likely to generate defects or likely to generate dome-type defects, the ability to generate holes-type defects is reduced or canceled.
• the thin layer capable of generating hole-type defects of the antireflection coating is separated from the functional layer by one or more layers, the thickness of all the layers interposed between the layer capable of generating hole-type defects and the functional layer is at most 20 nm, preferably at most 15 nm.
• the thermal pretreatment of the thin layer capable of generating hole-like defects before deposition of the functional silver-based metallic layer can be achieved by any heating method. Pretreatment can be accomplished by placing the substrate in an oven or oven or subjecting the substrate to radiation.
• the thermal pretreatment is advantageously carried out by subjecting the substrate coated with the layer to be treated to radiation, preferably laser radiation focused on said layer in the form of at least one laser line.
• the thermal pretreatment may be performed by providing energy liable to each point of the thin film capable of generating hole type defects at a temperature of preferably at least 300 ° C, especially 350 ⁇ or 400 ⁇ , and even 500 ⁇ ⁇ or 600 ° C.
• Each point of the coating undergoes thermal pretreatment for a period of less than or equal to 1 second, or even 0.5 seconds, and advantageously in a range from 0.05 to 10 ms, in particular from 0.1 to 5 ms, or from 0 to , 1 to 2 ms.
• the wavelength of the radiation is preferably in a range from 500 to 2000 nm, in particular from 700 to 1100 nm, or even from 800 to 1000 nm.
• Power laser diodes emitting at one or more lengths Wavelengths selected from 808 nm, 880 nm, 915 nm, 940 nm or 980 nm have proved particularly suitable.
• Thermal pretreatment can also be achieved by subjecting the substrate to infrared radiation from conventional heaters such as infrared lamps.
• Thin layers capable of generating hole-like defects may be deposited from metal or ceramic targets comprising the elements for forming said layers. These layers may be deposited in an oxidizing or non-oxidizing atmosphere (that is to say without voluntary introduction of oxygen), preferably oxidizing preferably consisting of noble gas (s) (He, Ne, Xe, Ar, kr).
• s noble gas
• the thin layer capable of generating hole-type defects is a layer based on titanium oxide
• this layer may be totally oxidized in TiO 2 or partially under-oxidized form.
• This layer may also optionally be doped with zirconium, for example.
• it is partially under-oxidized, it is therefore not deposited in stoichiometric form, but in sub-stoichiometric form, of the TiO x type, where x is a different number of the stoichiometry of titanium oxide TiO 2 , that is to say, 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 can be in particular such that 1, 5 ⁇ x ⁇ 1, 98 or 1, 5 ⁇ x ⁇ 1, 7 or even 1, 7 ⁇ x ⁇ 1, 95.
• the titanium oxide layer can be deposited from a ceramic target or a titanium metal target.
• the niobium oxide layer can be deposited from a Nb 2 0 5 ceramic target or a niobium metal target.
• the tin oxide layer can be deposited from a Sn0 2 ceramic target or a tin metal target.
• the thickness of the silver-based functional layers is in order of increasing preference ranging from 5 to 20 nm, from 8 to 15 nm.
• Functional metal layers based on silver may be in contact with a blocking layer.
• a blocking sub-layer corresponds to a blocking layer disposed beneath a functional layer, a position defined with respect to the substrate.
• a blocking layer disposed on the functional layer opposite the substrate is called the blocking overlay.
• the blocking layers are chosen from NiCr, NiCrN, NiCrOx, NiO or NbN based layers.
• the thickness of each blocking layer is at least 0.5 nm and at most 4.0 nm.
• the stack comprises at least two antireflection coatings, each antireflection coating comprising at least one dielectric layer, so that each functional metal layer is disposed between two antireflection coatings.
• the method further includes the step of depositing an antireflection coating over the silver functional metal layer.
• Anti-reflective coatings may include barrier dielectric layers and / or dielectric layers with stabilizing function.
• the dielectric layers of the antireflection coatings may be chosen from oxides or nitrides of one or more elements chosen from titanium, silicon, aluminum, tin and zinc.
• the dielectric layers of the antireflection coating (s) are preferably deposited by magnetic field assisted sputtering.
• dielectric layers with stabilizing function means a layer made of a material capable of stabilizing the interface between the functional layer and this layer.
• the dielectric layers with a stabilizing function are preferably based on crystalline oxide, in particular based on zinc oxide, optionally doped with at least one other element, such as aluminum.
• the dielectric layer (s) with a stabilizing function are preferably zinc oxide layers. Indeed, it is advantageous to have a stabilizing function layer, for example, based on zinc oxide below a functional layer, because it facilitates the adhesion and crystallization of the functional layer based on and increases its quality and stability at high temperatures. It is also advantageous to have a stabilizing function layer, for example, based on zinc oxide over a functional layer.
• the stabilizing function dielectric layer (s) can therefore be above and / or below at least one functional silver-based metallic layer or each silver-based functional metal layer, either directly at its contact or be separated by a blocking layer.
• each silver-based functional metal layer is above an antireflection coating whose upper layer is a dielectric layer with a stabilizing function, preferably based on zinc oxide and / or below.
• This dielectric layer with a stabilizing function may have a thickness of at least 5 nm, in particular a thickness of between 5 and 25 nm and better still of 8 to 15 nm.
• the thin layer capable of generating holes-type defects of the antireflection coating is therefore generally separated from the functional layer by the stabilizing layer of the antireflection coating and optionally by a blocking layer.
• the thin layer capable of generating hole-type defects of the antireflection coating is separated from the functional layer by one or more layers, the thickness of all the layers interposed between the layer capable of generating hole-type defects and the functional layer is at least 6 nm, preferably at least 7.5 nm.
• Barrier dielectric layers are understood to mean a layer of a material capable of acting as a barrier to the diffusion of oxygen, alkalis and / or water at high temperature from the ambient atmosphere or the transparent substrate. to the functional layer.
• the barrier-type dielectric layers may be based on silicon compounds chosen from oxides such as SiO 2 , Si 3 N 4 silicon nitrides and SiO x N y oxynucleides , optionally doped with at least one other element, such as aluminum, based on aluminum nitrides AIN or based on zinc oxide and tin.
• the transparent substrate coated with the stack for heat treatment may comprise:
• an antireflection coating comprising at least one thin layer capable of generating hole-type defects
• the stack may comprise: an antireflection coating situated beneath the silver-based functional metal layer comprising at least one thin layer capable of generating hole-type defects and a dielectric layer at stabilizing function based on zinc oxide separating the layer having a stress jump from the silver-based metallic functional layer, - optionally a blocking layer, located immediately in contact with the dielectric layer with a stabilizing function based on zinc oxide,
• an antireflection coating located above the functional silver-based metallic layer
• the stack may comprise, starting from the substrate:
• an antireflection coating comprising at least one dielectric layer with a barrier function and at least one dielectric layer with a stabilizing function
• an antireflection coating comprising at least one dielectric layer with a stabilizing function and a dielectric layer with a barrier function.
• the stack may comprise an upper protective layer deposited as the last layer of the stack, in particular to give anti-scratch properties.
• These upper layers of protection preferably have a thickness of between 2 and 5 nm.
• the substrate may be any material capable of withstanding the high temperatures of the heat treatment.
• the transparent substrates according to the invention are preferably made of a mineral rigid material, such as glass, in particular silico-soda-lime.
• the thickness of the substrate generally varies between 0.5 mm and 19 mm.
• the thickness of the substrate is preferably less than or equal to 6 mm or even 4 mm.
• a stress jump corresponds to a significant change in the slope of the curve connecting the evolution of the stress as a function of temperature.
• the stress jump can be related to a crystallization of the material constituting the layer during the heat treatment. Indeed, after cooling the stress values of the material are higher than those before heat treatment. Once the stress jump has been achieved, the thin layer can be heated and cooled without again occurring stress jump.
• the stress jump generally occurs in a temperature range below the temperature Tmax of the heat treatment.
• the dielectric layer capable of generating hole-type defects is chosen from a dielectric layer having a stress jump occurring in a temperature range below the temperature Tmax of the heat treatment and corresponding to a variation of the stress values greater than 0, 1 GPa for a temperature variation of less than 50 ° C.
• the thermal pretreatment is carried out by providing an energy capable of carrying each point of said layer a temperature greater than or equal to a temperature situated in the temperature range in which the stress jump occurs.
• the thermal pretreatment is advantageously carried out so that each point of the layer is brought to a temperature of at least 300 ° C. while maintaining at all points the face of the substrate opposite to that comprising the stack at a lower temperature or equal to 150 ° C.
• point of the layer is meant an area of the layer undergoing treatment at a given time.
• the entire layer (and therefore each point) is brought to a temperature of at least 300 ° C, but each point of the layer is not necessarily treated simultaneously.
• the layer can be processed at the same time as a whole, each point of the layer being simultaneously heated to a temperature of at least 300 ° C.
• the layer can alternatively be treated with in such a way that the different points of the layer or sets of points are successively brought to a temperature of at least 300 ° C, this second mode being more often used in the case of a continuous implementation at the scale industrial.
• each point of the thin layer is subjected to the treatment according to the invention (that is to say brought to a temperature greater than or equal to 300 ° C) for a duration generally less than or equal to 1 second, or even 0 , 5 seconds.
• a temperature of 100 ° C. or less is preferably maintained throughout the treatment. 50 ° C, at any point on the face of the substrate opposite to the face on which is deposited the layer having a strain jump.
• the heating parameters such as the power of the heating means or the heating time are to be adapted case by case by those skilled in the art according to various parameters such as the nature of the heating process, the thickness of the layer the size and thickness of the substrates to be treated etc.
• the thermal pretreatment step preferably comprises subjecting the substrate coated with the layer to be treated to radiation, preferably laser radiation focused on said layer in the form of at least one laser line.
• radiation preferably laser radiation focused on said layer in the form of at least one laser line.
• the lasers can radiate only a small area (typically of the order of a fraction of mm 2 to a few hundred mm 2 ), it is necessary, in order to treat the entire surface, to provide a beam displacement system. laser in the plane of the substrate or a system forming an in-line laser beam simultaneously radiating the entire width of the substrate, and in which the latter comes to scroll.
• the maximum temperature is normally experienced when the point of the coating under consideration passes under the laser line. At a given moment, only the points of the surface of the coating located under the laser line and in its immediate vicinity (eg less than one millimeter) is normally at a temperature of at least 300 ° C. For distances to the laser line (measured in the direction of travel) greater than 2 mm, especially 5 mm, including downstream of the laser line, the coating temperature is normally at most 50 ° C, and even 40 ° C or 30 ° C.
• the laser radiation is preferably generated by modules comprising one or more laser sources as well as optical shaping and redirection.
• Laser sources are typically laser diodes or fiber or disk lasers.
• the laser diodes make it possible to economically achieve high power densities with respect to the electric power supply, for a small space requirement.
• the radiation from the laser sources is preferably continuous.
• the shaping and redirecting optics preferably comprise lenses and mirrors, and are used as means for positioning, homogenization and focusing of the radiation.
• the purpose of the positioning means is, where appropriate, to arrange the radiation emitted by the laser sources along a line. They preferably include mirrors.
• the aim of the homogenization means is to superpose the spatial profiles of the laser sources in order to obtain a homogeneous linear power along the line.
• the homogenization means preferably comprise lenses enabling the incident beams to be separated into secondary beams and the recombination of said secondary beams into a homogeneous line.
• the means for focusing the radiation make it possible to focus the radiation on the coating to be treated, in the form of a line of desired length and width.
• the focusing means preferably comprise a converging lens.
• the length of the line is advantageously equal to the width of the substrate.
• the linear power of the laser line is preferably at least 300 W / cm, advantageously 350 or 400 W / cm, in particular 450 W / cm, or even 500 W / cm and even 550 W / cm. It is even advantageously at least 600 W / cm, especially 800 W / cm or 1000 W / cm.
• the linear power is measured where the or each laser line is focused on the coating. It can be measured by placing a power detector along the line, for example a power meter calorimetric, such as in particular the power meter Beam Finder S / N 2000716 of the Company Coherent Inc.
• the power is advantageously distributed homogeneously over the entire length of the or each line. Preferably, the difference between the highest power and the lowest power is less than 10% of the average power.
• the energy density supplied to the coating is preferably at least
• the high power densities and densities make it possible to heat the coating very quickly, without heating the substrate significantly.
• the or each laser line is fixed, and the substrate is in motion, so that the relative speeds of movement will correspond to the speed of travel of the substrate.
• the heat pretreatment of the layer capable of generating hole-type defects may be performed during the deposition in the chamber, or after the deposition, outside the deposition chamber.
• the thermal pretreatment can be done under vacuum, under air and / or at atmospheric pressure. Thermal pretreatment outside the deposition chamber is not preferred because it can generate pollution problems.
• the heat treatment device can therefore be integrated in a layer deposition line, for example a magnetic field assisted sputtering deposition line (magnetron process).
• the line generally includes substrate handling devices, a deposition facility, optical control devices, stacking devices.
• the substrates scroll, for example on conveyor rollers, successively in front of each device or each installation.
• the heat treatment device can be integrated in the depot installation.
• the laser can be introduced into one of the chambers of a sputtering deposition installation, in particular in a chamber where the atmosphere is rarefied, in particular under a pressure of between 10 ⁇ 6 mbar and 10 ⁇ 2 mbar.
• the heat treatment device may also be disposed outside the deposition installation, but so as to treat a substrate located inside said installation. For this purpose, it suffices to provide a window that is transparent to the wavelength of the radiation used, through which the laser radiation would treat the layer. It is thus possible to treat a layer capable of generating hole-type defects before the subsequent deposit of another layer in the same installation.
• the thermal pretreatment is preferably a radiation laser treatment in a system where the laser is integrated in a magnetron device.
• the heat pretreatment is carried out under vacuum within the deposition chamber of the magnetron device.
• the thermal pretreatment can also be carried out by heating using infrared radiation, a plasma torch or a flame as described in application WO 2008/096089.
• Infrared lamp systems associated with a focusing device for example a cylindrical lens
• a focusing device for example a cylindrical lens
• the coated transparent substrate is intended to undergo heat treatment at a temperature Tmax greater than 400 ° C.
• the heat treatments are chosen from annealing, for example by flash annealing such as laser or flame annealing, quenching and / or bending.
• the temperature of the heat treatment is greater than 400 ° C, preferably greater than 450 ° C, and more preferably greater than 500 ° C.
• the substrate coated with the stack may be a curved and / or tempered glass.
• the material may be in the form of monolithic glazing, laminated glazing, asymmetrical glazing or multiple glazing including double glazing or triple glazing.
• Stacks of thin layers defined below are deposited on clear soda-lime glass substrates with a thickness of 2 or 4 mm.
• TiO 2 titanium oxide layers are deposited from a ceramic target in an oxidizing atmosphere.
• the layer of ⁇ 02 (30 nm) is deposited, then
• the layer is optionally subjected to thermal pretreatment, then
• the substrate coated with the complete stack is subjected to a heat treatment at a temperature Tmax greater than 400 ° C.
• the comparative glazing comprises the stack D comp., That is to say a stack comprising a layer of titanium oxide under the silver layer that has not been subjected to thermal pretreatment before deposition of the coating layer. money and heat treatment.
• the glazing of the invention comprises the stack D Inv., That is to say a stack comprising a layer of titanium oxide under the silver layer subjected to thermal pretreatment by laser annealing at 980 nm before deposit of the silver layer. The heat treatment corresponds to annealing at 620 ° C for 10 minutes.
• the dielectric layers that can generate hole-like defects can be identified by microscopic analysis. For this, a stack is deposited on a substrate comprising a dielectric layer capable of generating hole-type defects in contact with or near a silver layer. The assembly is subjected to a heat treatment. The observation of the images makes it possible to identify if faults are generated. If necessary, if these defects are hole type.
• FIGS. 1, 2a and 2b are glazing images comprising a stack comprising a layer capable of generating hole-type defects subjected to heat treatment in a Naber oven simulating quenching with an annealing at 620.degree. 10 minutes.
• the substrate is according to the prior art, that is to say obtained according to a method not comprising the heat pretreatment step before depositing the silver layer.
• Figure 1 shows black dendritic spots corresponding to the non-silver zones, i.e., hole-like defects obtained after quenching.
• Figure 2.a is a sectional image taken under a transmission microscope of a hole-type defect.
• Figure 2.b is an image taken with a scanning electron microscope which locates the section of Figure 2 by a white line.
• the glass substrate 1 is distinguished, the antireflection coating 2 comprising several dielectric layers located below the silver layer, the silver layer 3, the antireflection coating 4 situated above the silver and a protective layer 5.
• Figures 3 and 4 are images under a scanning electron microscope:
• a glazing unit comprising a stack D comp. corresponding to a stack comprising a silver layer located above an antireflection coating comprising a non-pretreated titanium oxide layer, the complete stack has been subjected to heat treatment at 620 ° C. for 10 min (FIG. 3) ,
• a glazing unit comprising a stack D Inv. corresponding to a stack comprising a silver layer located above an antireflection coating comprising a pretreated titanium oxide layer before deposition of the silver layer, the complete stack has undergone a heat treatment at 620 ° C. for 10 minutes (Figure 4). Numerous dendritic holes are observed in FIG.
• the presence of defects after heat treatment can be quantified by measuring the proportion of surface area including defects on heat-treated glazings. The measurement is to determine the percentage of area occupied by the holes.
• the solution of the invention therefore allows a decrease in significant blur. There is a clear decrease in the number of hole-type defects and therefore of the blur after heat treatment at high temperature.

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• 2014
  • 2014-05-28 FR FR1454870A patent/FR3021650A1/fr not_active Withdrawn
• 2015
  • 2015-05-27 US US15/313,742 patent/US20170137320A1/en not_active Abandoned
  • 2015-05-27 EA EA201692353A patent/EA032833B1/ru not_active IP Right Cessation
  • 2015-05-27 CN CN201580027531.2A patent/CN106458729A/zh active Pending
  • 2015-05-27 JP JP2016569416A patent/JP2017516919A/ja active Pending
  • 2015-05-27 EP EP15732815.4A patent/EP3148950A1/de not_active Withdrawn
  • 2015-05-27 WO PCT/FR2015/051404 patent/WO2015181501A1/fr active Application Filing
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