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
  • C03C17/3618—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
  • 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
• • 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
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]

Definitions

• the invention relates to a transparent substrate, in particular a mineral rigid material such as glass, said substrate being coated with a stack of thin layers comprising a metal-type functional layer that can act on the solar radiation and / or the infrared radiation of great length wave.
• the invention relates more particularly to the use of such substrates for manufacturing thermal insulation and / or sun protection glazings.
• These glazings can be intended both to equip buildings and vehicles, in particular to reduce the air conditioning effort and / or prevent excessive overheating (so-called “solar control” windows) and / or reduce the amount energy dissipated to the outside (glazing so-called “low emissive”) driven by the ever-increasing importance of glazed surfaces in buildings and vehicle interiors.
• a type of layer stack known to give substrates such properties consists of a functional metallic layer with infrared reflection properties and / or solar radiation, especially a metallic functional layer based on silver or of metal alloy containing silver.
• the functional layer is thus disposed between two antireflection coatings each in general having several layers which are each made of a dielectric material of the nitride type and in particular silicon nitride or aluminum or oxide. From an optical point of view, the purpose of these coatings which frame the functional metallic layer is to "antireflect" this metallic functional 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 promotes the crystalline growth of this layer and protects it during a possible heat treatment at high temperature, of the bending and / or quenching type 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 heat treatment at high temperature, of the bending and / or quenching type.
• the solar factor of a glazing is the ratio of the total energy entering the room through this glazing to the total incident solar energy.
• the most efficient solution then consists in using a multilayer stack which is functional, positioned on face 2 of the glazing and in particular a stack with two functional layers (hereinafter referred to as "functional bilayer stacking"), in order to keep a high light transmission in the visible, while maintaining a low light reflection in the visible. It is thus possible to obtain, for example, a selectivity> 1, 4, even> 1, 5 and even> 1, 6 and a luminous reflection of the order of 15%, or even of the order of 10%.
• the object of the invention is to overcome the drawbacks of the prior art, by developing a new type of stack of functional monolayer layers, stack which has a low - A - resistance by square (and therefore a low emissivity), a high light transmission and a relatively neutral color, in particular in reflection side layers (may also opposite side: "substrate side >>), and that these properties are preferably retained in a restricted range that the stack undergoes or not, a (or) heat treatment (s) at high temperature of the bending and / or quenching and / or annealing type.
• Another important goal is to propose a functional monolayer stack which has a low emissivity while having a low light reflection in the visible, as well as an acceptable coloration, especially in reflection, in particular which is not in the red.
• the object of the invention is therefore, in its widest sense, a glass substrate according to claim 1.
• optical thickness e 6 o in nm of the overlying antireflection coating is meant in the sense of the invention the total optical thickness of the or all the dielectric layers of this coating which is or are disposed above the functional metal layer, opposite the substrate, or above the overblocking coating if present.
• optical thickness e 20 nm of the underlying antireflection coating means in the sense of the invention the total optical thickness of the or all the dielectric layers of this coating which is or are arranged between the substrate and the functional metal layer or between the substrate and the sub-blocking coating if present.
• the silicon nitride-based dielectric layer optionally doped with at least one other element, such as aluminum which is at least included in each antireflection coating, as defined above, has an optical index measured at 550 nm between 1, 8 and 2.5 including these values, or preferably between 1, 9 and 2.3 or even between 1, 9 and 2.1 including these values.
• the refractive indices, and consequently the optical thicknesses obtained from the refractive indices, are considered here at the wavelength of 550 nm.
• the metallic functional layer is all the better crystallized that A is small and this layer then has a lower absorption in the infrared and a reflection in the infrared even higher.
• the ratio E of the optical thickness e of 20 nm Underlying antireflection coating on the optical thickness e 6 o in nm of the overlying antireflection coating is preferably such that: 0.3 ⁇ E ⁇ 0.7, or even 0.4 ⁇ E ⁇ 0.6.
• said silicon nitride-based dielectric layers possibly doped with at least one other element, such as aluminum, respectively, have, for the silicon nitride-based dielectric layer, the sub-antireflection coating. a physical thickness of between 5 and 25 nm, or even between 10 and 20 nm, and for the silicon nitride-based dielectric layer of the overlying antireflection coating, a physical thickness of between 15 and 60 nm, or even between 25 and 55 nm, .
• the last layer of the underlying antireflection coating, the furthest away from the substrate is an oxide-based wetting layer, in particular based on zinc oxide, optionally doped with the aid of at least one other element, such as aluminum.
• the underlying antireflection coating comprises at least one dielectric layer based on nitride, in particular silicon nitride and / or aluminum nitride and at least one noncrystallized smoothing layer made of a mixed oxide, said smoothing layer being in contact with a crystallized overlying fountain layer.
• the underblocking coating and / or the overblocking coating comprises a thin layer of nickel or titanium having a geometric thickness e such that 0.2 nm ⁇ e ⁇ 1.8 nm.
• At least one nickel-based thin layer, and in particular that of the overblocking coating, comprises chromium, preferably in mass quantities of 80% of Ni and 20% of Cr.
• At least one nickel-based thin layer and in particular that of the overblocking coating, comprises titanium, preferably in mass quantities of 50% of Ni and 50% of Ti.
• the underblocking coating and / or the overblocking coating may comprise at least one nickel-based thin layer present in metallic form if the substrate provided with the thin-film stack has not undergone heat treatment. bending and / or quenching after deposition of the stack, this layer being at least partially oxidized if the substrate provided with the stack of thin layers has undergone at least one bending and / or quenching heat treatment after deposition of the stacking.
• the thin nickel-based layer of the underblocking coating and / or the thin nickel-based layer of the overblocking coating when present is preferably directly in contact with the functional layer.
• the last layer of the overlying antireflection coating is preferably based on oxide, preferably deposited under stoichiometric, and in particular is based on titanium (TiO x ) or based on zinc and tin mixed oxide (SnZnO x ), possibly by another element at a rate of 10% by mass at most.
• the stack can thus comprise a last layer ("overcoat” in English), that is to say a protective layer, deposited preferably stoichiometric. This layer is found oxidized essentially stoichiometrically in the stack after deposition.
• This protective layer preferably has a thickness of between 0.5 and 10 nm.
• the glazing according to the invention incorporates at least the carrier substrate of the stack according to the invention, optionally associated with at least one other substrate.
• 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 according to the invention may have a laminated structure, in particular associating at least two rigid substrates of the glass type with at least one thermoplastic polymer sheet, in order to present a glass-like structure / thin-film stack / sheet (s) / glass.
• the polymer may especially be based on polyvinyl butyral PVB, ethylene vinyl acetate EVA, PET polyethylene terephthalate, PVC polyvinyl chloride.
• the glazing may then have a glass-like structure / stack of thin layers / sheet (s) of polymer.
• the glazings according to the invention are capable of undergoing heat treatment without damage for the stack of thin layers. They are therefore optionally curved and / or tempered.
• the glazing may be curved and / or tempered by being constituted by a single substrate, the one provided with the stack. It is then a glazing said
• the stack of thin layers is preferably on an at least partially non-flat face.
• the glazing may also be a multiple glazing, in particular a double glazing, at least the carrier substrate of the stack being curved and / or tempered. It is preferable in a multiple glazing configuration that the stack is disposed so as to be turned towards the interleaved gas blade side. In a laminated structure, the carrier substrate of the stack may be in contact with the polymer sheet.
• the glazing may also be a triple glazing consisting of three glass sheets separated two by two by a gas blade.
• the carrier substrate of the stack may be in front of the face and / or opposite
• the carrier substrate of the stack may be curved or tempered glass, this substrate can be curved or tempered before or after the deposition of the stacking.
• this glazing is mounted in double-glazing, it preferably has a selectivity S> 1, 4 or even S> 1, 4, or S> 1, even S> 1.5.
• the invention also relates to the method of manufacturing the substrates according to the invention, which consists in depositing the stack of thin layers on its substrate by a vacuum technique of the cathode sputtering type possibly assisted by magnetic field.
• the first layer (s) of the stack may be deposited by another technique, for example by a pyrolysis type thermal decomposition technique.
• the invention furthermore relates to the use of the substrate according to the invention, for producing a double glazing which has a selectivity S> 1, 4, or even S> 1, 4, or S> 1, 5 or even S> 1, 5 .
• the substrate according to the invention can be used in particular to produce a transparent electrode of a heating glazing unit or of an electrochromic glazing unit or of a lighting device or a display device or a photovoltaic cell.
• the present invention thus makes it possible to produce a stack of functional monolayer thin layers having in a multiple glazing configuration, and in particular double glazing, a high selectivity (S> 1, 40), a low emissivity ( ⁇ N ⁇ 3%) and a favorable aesthetics (T Lv , s> 60%, R Lv , s ⁇ 30%, neutral colors in reflection), whereas until now, only functional bilayer stacks allowed to obtain this combination of criteria.
• the functional monolayer stack according to the invention is less expensive to produce than a functional bilayer stack with similar characteristics.
• FIG. 1 illustrating a functional monolayer stack according to the invention, the functional layer being provided with a coating of undercoating. blocking and over-blocking coating and the stack being further provided with an optional protective coating.
• the stack of thin layers is deposited on a substrate 10 of soda-lime glass with a thickness of 4 mm.
• FIG. 1 illustrates a functional monolayer stack structure deposited on a transparent glass substrate, in which the single functional layer 40 is disposed between two antireflection coatings, the underlying antireflection coating 20 located beneath the functional layer 40. direction of the substrate 10 and the overlying antireflection coating 60 disposed above the functional layer 40 opposite the substrate 10.
• These two antireflection coatings 20, 60 each comprise at least one dielectric layer 22, 24, 26; 62, 64, 66.
• the functional layer 40 may be deposited on a sub-blocking coating 30 placed between the underlying antireflection coating 20 and the functional layer 40 and, on the other hand, the functional layer 40 may be deposited directly under a Overblock coating 50 disposed between the functional layer 40 and the overlying antireflection coating 60.
• the lower antireflection coating 20 has three antireflection layers 22, 24 and 26, which the upper antireflection coating 60 has two layers.
• the square resistance R in ohms per square of the functional layer 40 in nm is such that:
• resistance per square of a conductive thin film depends on its thickness according to the law of Fuchs-Sondheimer which expresses itself:
• R c 2 xt + Y. pxt
• R c denotes the resistance per square
• t denotes the thickness of the thin film in nm
• p denotes the intrinsic resistivity of the material forming the thin layer
• Y corresponds to the specular or diffuse reflection of the charge carriers at the level of interfaces.
• the invention makes it possible to obtain an intrinsic resistivity p such that p is of the order of 25 ⁇ .nm and an improvement of the reflection of the carriers such that Y is equal to or less than 600 (nm) 20 ohms. Very low values of Y can be obtained for example by implementing the technology disclosed in the international patent application published under the number: WO 2005/070540.
• the E of the optical thickness ratio e 20 nm of the antireflection coating 20 of the underlying optical thickness e o 6 in nm of the overlying antireflective coating 60 is such that:
• Example 4 A numerical simulation was initially performed (Examples 1, 2 and 3 below), and then a stack of thin layers was effectively deposited: Example 4.
• Table 1 below illustrates the thicknesses in nanometers of each of the layers or coatings of Examples 1 to 3 and the main characteristics of these examples:
• Example 4 was carried out on the basis of the functional monolayer stacking structure illustrated in FIG. 1 in which the functional layer 40 is provided with a sub-blocking coating 30 and an over-blocking coating 50 respectively immediately under and immediately on the functional layer 40.
• Example 4 there was no underblocking coating 30.
• a lower antireflection coating is deposited immediately under the underblocking coating. 30 and in contact with the substrate 10 and an upper antireflection coating 60 is deposited immediately on the overblocking coating 50.
• Table 2 below illustrates the geometrical thicknesses (and not the optical thicknesses) in nanometers of each of the layers of Example 4:
• the underlying antireflection coating 20 comprises a silicon nitride dielectric layer 22 and at least one uncrystallized non-crystalline smoothing layer 24.
• a mixed oxide of zinc and tin which is here doped with antimony (deposited from a metal target consisting of mass ratios 65: 34: 1 respectively for Zn: Sn: Sb), said smoothing layer 24 being in contact with said overlying damping layer 26.
• the zinc oxide damping layer 26 doped with aluminum ZnO: Al (deposited from a metal target consisting of zinc doped with 2% by weight of aluminum) makes it possible to improve the crystallization of money, which improves its conductivity; this effect is accentuated by the use of the SnZnO x : Sb amorphous smoothing layer, which improves the growth of ZnO and thus of silver.
• the silicon nitride layers 22, 64 are made of Si 3 N 4 doped with 10% by weight of aluminum. This stack also has the advantage of being heatable.
• the thickness of the overlying antireflection coating 60 satisfies the relationship (1).
• selectivity S T Lv , s / FS and which is> 1, 4, and even> 1.5, the light transmission T Lv , s, the light reflection R Lv , s, the solar factor FS and the selectivity S being considered in a double-glazed configuration 4-16 (Ar 90%) - 4.
• Example 4 the resistance per square of the stack both before and after heat treatment of Example 4 according to the invention is always less than 3 ohms per square and it results in a normal emissivity ⁇ N in the range of 1 to 2.5% before heat treatment and in the range of 1 to 2% after heat treatment.
• This example shows that it is possible to combine high selectivity and low emissivity, with a stack comprising a single functional silver metal layer, while maintaining a suitable aesthetic (the T Lv , s is greater than 60%, the R Lv , s is less than 30% and the colors are neutral in reflection).
• the light reflection R Lv , s, the light transmission T Lv , s measured according to the illuminant D65 and the reflection colors a * and b * in the LAB system measured according to the illuminant D65 on the substrate side do not vary from really significant way during heat treatment.
• Example 4 Comparing the optical and energy characteristics before heat treatment with these same characteristics after heat treatment, no major degradation was found.
• the stack of Example 4 is thus a quenchable stack within the meaning of the invention since the variation in light transmission in the visible range is less than and even less than 3.
• This transparent electrode substrate may be suitable for an organic electroluminescent device, in particular by replacing the silicon nitride layer 64 of Example 4 with a conductive layer (with in particular a resistivity of less than 10 5 ⁇ .cm) and in particular a layer based on oxide.
• This layer may be, for example, tin oxide or zinc oxide oxide optionally doped with Al or Ga, or based on mixed oxide and in particular with indium tin oxide, ITO oxide, Indium and zinc IZO, tin oxide and zinc SnZn possibly doped (for example with Sb,
• This organic electroluminescent device can be used to produce a lighting device or a display device (screen).
• the transparent electrode substrate may be suitable for heating glazing, for any electrochromic glazing, any display screen, or for a photovoltaic cell and in particular for a transparent photovoltaic cell rear face.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Surface Treatment Of Glass (AREA)
• Laminated Bodies (AREA)

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• 2008
  • 2008-03-18 FR FR0851731A patent/FR2928913B1/fr not_active Expired - Fee Related
• 2009
  • 2009-03-17 US US12/933,240 patent/US20110070417A1/en not_active Abandoned
  • 2009-03-17 CN CN200980117939.3A patent/CN102036930B/zh not_active Expired - Fee Related
  • 2009-03-17 BR BRPI0908713-3A patent/BRPI0908713A2/pt not_active IP Right Cessation
  • 2009-03-17 EP EP09726740A patent/EP2268588A2/de not_active Withdrawn
  • 2009-03-17 WO PCT/FR2009/050444 patent/WO2009122090A2/fr not_active Ceased
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