US20020037421A1 - Glazing coated with at least one layer having thermochromic properties - Google Patents

Glazing coated with at least one layer having thermochromic properties Download PDF

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Publication number
US20020037421A1
US20020037421A1 US09/862,714 US86271401A US2002037421A1 US 20020037421 A1 US20020037421 A1 US 20020037421A1 US 86271401 A US86271401 A US 86271401A US 2002037421 A1 US2002037421 A1 US 2002037421A1
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Prior art keywords
layer
glazing according
properties
glazing
vanadium oxide
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Abandoned
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US09/862,714
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English (en)
Inventor
Alain Arnaud
Fabien Beteille
Jean-Christophe Giron
Francois Lerbet
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Saint Gobain Glass France SAS
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Saint Gobain Glass France SAS
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Assigned to SAINT-GOBAIN GLASS FRANCE reassignment SAINT-GOBAIN GLASS FRANCE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LERBET, FRANCOIS, GIRON, JEAN-CHRISTOPHE, ARNAUD, ALAIN, BETEILLE, FABIEN
Assigned to SAINT-GOBAIN GLASS FRANCE reassignment SAINT-GOBAIN GLASS FRANCE CORRECTIVE ASSIGNMENT TO CORRECT THE FIRST AND SECOND EXECUTION DATES OF ASSIGNOR PREVIOUSLY RECORDED ON REEL 012257 FRAME 0166 ASSIGNOR HEREBY CONFIRMS THE ASSIGNMENT OF THE ENTIRE INTEREST. Assignors: LERBET, FRANCOIS, ARNAUD, ALAIN, BETEILLE, FABIEN, GIRON, JEAN-CHRISTOPHE
Publication of US20020037421A1 publication Critical patent/US20020037421A1/en
Priority to US10/347,495 priority Critical patent/US6872453B2/en
Priority to US11/058,161 priority patent/US7311976B2/en
Abandoned legal-status Critical Current

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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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3441—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising carbon, a carbide or oxycarbide
    • 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
    • C03C17/3615—Coatings of the type glass/metal/other inorganic layers, at least one layer being non-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
    • C03C17/3618—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
    • C03C17/3639—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
    • C03C17/3657—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
    • C03C17/3668—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 electrical properties
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • C03C2217/948—Layers comprising indium tin oxide [ITO]
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate

Definitions

  • the present invention relates to glazing in the broad sense of the term (any substantially transparent substrate or assembly of substrates) which is provided with thin layers having thermochromic properties.
  • the invention relates more particularly to thermochromic layers based on vanadium oxide.
  • Vanadium oxide has already been much studied. It is a material which, as the temperature rises, switches at a temperature of about 70° C. from electrically insulating behaviour to electrically conducting behaviour due to a crystallographic distortion. This change in its electrical properties is accompanied by a change in its optical properties, essentially in the infrared (when the temperature of the layer exceeds the switch temperature, the layer becomes reflecting and absorbent in the infrared). This is one of the rare thermochromic compounds known to have such a transition at a temperature relatively close to room temperature, hence the interest that it has aroused in the production of glazing which can, for example, filter out solar radiation in hot weather.
  • thermochromic material it is therefore an object of the invention to provide greater flexibility in the various properties of this thermochromic material, especially so as to be able to give glazing which has been provided therewith more modifiable functionalities or even novel functionalities.
  • the invention is a glazing which is coated with at least one layer having thermochromic properties and comprising vanadium oxide, which can be substoichiometric in terms of oxygen, and at least one other layer having thermal properties, preferably at least partially reflecting in the infrared, and/or at least one other layer having optical properties, preferably antireflection properties in the visible, and/or at least one other layer having electrical conduction properties.
  • the term “glazing” as used herein is to be understood in its broadest sense, namely any essentially transparent substrate or assembly of substrates, examples of which will be explained in detail below and which may be of an inorganic nature (glass) or organic nature (polymer).
  • Such glazing may be rigid (glass or polycarbonate), semi-rigid or flexible (polyethylene terephthalate, polyvinyl chloride, etc.).
  • the glazing in question comprises at least one rigid or semi-rigid substrate. It may also be incomplete glazing, or glazing not yet assembled, and in this case it may comprise only one or more flexible substrates.
  • vanadium oxide as used herein is understood to mean one of the oxides of this metal which has thermochromic properties, namely, essentially vanadium dioxide VO 2 .
  • “substoichiometric in terms of oxygen” is understood to mean an oxide of vanadium having the formula VO x , where x ⁇ 2. This encompasses homogeneous structures (in which the layer is in a suboxidized state) or heterogeneous structures (in which the layer has a heterogeneous structure, with phases oxidized to a greater or lesser extent, such as containing vanadium inserts still in metallic form, as will be described in detail below).
  • thermochromic layer for example based on a metal oxide
  • a conducting layer for example based on a metal oxide
  • a suitable thickness and a suitable refractive index may in fact simultaneously fulfill at least two of these functions:
  • the invention has therefore developed an association, on the same glazing, of two very different types of layer, the properties of which can be combined to give very novel results. If the vanadium oxide layer is combined with one or more layers having thermal properties, the association comprises:
  • thermochromic layer the “active” layer—whose properties have two states depending on the operating temperature, but for which layer there is little room to maneuver in order to establish compromises, especially between thermal and optical properties;
  • a reflecting layer in that its properties remain substantially unchanged over the temperatures envisaged (normal outdoor temperatures throughout the year), which layer can interact, especially interferentially when the layers are within the same multilayer film, with the thermochromic layer in order to increase the number of possible variations in the properties conferred on the carrier glazing.
  • the abovementioned layer or layers having thermal properties may, in a first variant, be based on a metal or a metal alloy chosen from one or more of the following metals: gold (Au), silver (Ag), nickel (Ni) and chromium (Cr), or alloys such as steel or Inconel.
  • the metals or metal alloys may, moreover, be partially nitrified, especially in the case of nickel and chromium.
  • the preferred embodiment is silver—a selective metal—which offers a good compromise between optical properties (light transmission) and thermal properties (reflection in the infrared).
  • the layer or layers having thermal properties is or are based on one or more metal nitrides chosen from at least one of the following nitrides: titanium nitride (TiN), chromium nitride (CrN), niobium nitride (NbN) and zirconium nitride (ZrN).
  • TiN titanium nitride
  • CrN chromium nitride
  • NbN niobium nitride
  • ZrN zirconium nitride
  • the layer or layers based on vanadium oxide is or are modified so as to lower their switch temperature T s to a value below 60° C. or below 50° C. or 45° C., for example down to a range of values lying between 25° C. and 40° C.
  • the modification may be chemical, by adding a “dopant”, especially a metal chosen from titanium (Ti), niobium (Nb), molybdenum (Mo), iridium (Ir) and tungsten (W).
  • a dopant especially a metal chosen from titanium (Ti), niobium (Nb), molybdenum (Mo), iridium (Ir) and tungsten (W).
  • the dopant may also be chosen from halogens, especially fluorine. It is possible to use several dopants. In general, the amount of dopant in the layer is between 0.1 and 10 at % with respect to vanadium.
  • the modification may also be physical in nature, for example, by adjusting the deposition parameters for depositing the layer.
  • This (chemical or physical) modification will therefore lower the temperature at which the vanadium oxide completely fulfills its role of solar control layer, by making it effective as soon as the temperature reaches, for example, 25° C., 30° C., 50° C. or 60° C. It also has another consequence which, unexpectedly, proves to be attractive for the glazing user: it makes the switching of the layer visible, especially by appreciably increasing the light reflection when the switch temperature is exceeded. The user can then appreciate the change in functionality of the layer with his own eyes.
  • the layer or layers based on vanadium oxide must be at least partially crystallized in order to have the desired thermochromic properties.
  • This crystallization may be obtained during deposition of the layer or by a treatment after the deposition process.
  • This treatment, during or after deposition may comprise a heat treatment or a bombardment with a suitable ion beam.
  • a heat treatment may be carried out on the substrate before, during or after deposition of the layer.
  • This heat treatment may or may not be carried out in a vacuum when it precedes or follows the deposition.
  • the ion bombardment treatment may also be carried out during deposition of the layer or after deposition.
  • Another way of promoting the crystallization involves providing the layer with a suitable nucleation sublayer. This allows the temperature of the heat treatment required for crystallization to be lowered.
  • the sublayer may also act as a barrier layer with respect to species migrating from the materials adjacent to the layer, most particularly alkali metal ions migrating from glass substrates, or even have an optical function.
  • These sublayers may be made of silicon derivatives for example, especially silicon oxide (SiO x ) (0 ⁇ x ⁇ 2), silicon oxynitride (SiON) or silicon oxycarbide (SiOC). They may also be based on silicon nitride (possibly containing a minority metal of the Al type) or based on zinc oxide (ZnO).
  • thermochromic layer or at least one of the thermochromic layers may be based on vanadium oxide which is generally substoichiometric in terms of oxygen, especially with a formula of the VO x type in which x ⁇ 2 and especially between 1.50 and 1.95.
  • the layer may be homogeneous in its composition and be suboxide. It may also be heterogeneous, with phases rich in vanadium oxide and phases lean in oxidized vanadium, that is to say, phases in which the vanadium is in metallic or quasi-metallic form.
  • cermet type that is to say a structure comprising a ceramic (vanadium oxide, whether stoichiometric, substoichiometric or superstoichiometric with respect to oxygen) matrix with metallic (vanadium metal) inserts.
  • the advantage of this type of structure is that it is then possible to have a bifunctional layer: on the one hand, it is thermochromic as it contains vanadium oxide having this property and, on the other hand, it has thermal properties, especially infrared reflection properties, because of the presence of vanadium metal (having properties similar to silver). Consequently, there is no longer any need to add to the layer an Ag-type reflecting layer.
  • the invention is also glazing provided with such an overall oxygen substoichiometric thermochromic layer, a layer having a cermet-type structure, independently of any association with layers having functionalities other than a thermochromic functionality (a layer with an optical role, thermal role, electrical role, etc.).
  • the thickness of the layer or layers based on vanadium oxide is chosen so as to take into account various parameters: when it is used by itself, it is generally necessary to find the most acceptable compromise according to the application envisaged for the glazing. This as because vanadium oxide is absorbent and quite colored in the visible (a pronounced “bronze” color) and it is generally sought to have the highest possible contrast in terms of energy transmission T E , whereas the coloration in the visible and the energy transmission are increasing functions of the layer thickness.
  • the layers based on vanadium oxide according to the invention have a thickness of between 10 nm and 300 nm, preferably between 30 nm and 100 nm.
  • the layer(s) based on vanadium oxide and the layer(s) having thermal or optical properties form part of the same multilayer film of thin layers deposited on the same face of the constituent substrate or of one of the constituent substrates of the glazing. It is, of course, in this configuration that it is possible to obtain glazing with the most novel properties, by interferential interaction between the two types of layers. Preferably, they have a common interface. (Alternatively, one or more thin interlayers may be interposed between them).
  • the type of multilayer film capable of incorporating these two types of layers may be similar to the multilayer films with thermal properties already existing on the market or at the very least in the literature.
  • low-emissivity or solar-protection multilayer films with the following configuration are known:
  • dielectric/functional layer/dielectric/functional layer/dielectric with the functional layers being made, for example, of silver and the dielectrics (D) being in the form of layers or multilayer films based on a material of the metal-oxide type, on silicon oxide derivatives or on nitrides, such as AIN or Si 3 N 4 .
  • thermochromic vanadium oxide layer By therefore adopting this type of multilayer film, it is possible, according to the present invention, to substitute at least one of the constituent layers of the dielectrics with the vanadium-based thermochromic layer.
  • One of the dielectrics may thus be completely replaced with the vanadium oxide layer, or be in the form of a multilayer associating one or more conventional dielectric layers with a thermochromic vanadium oxide layer.
  • the dielectric D2 the one which lies against the two layers—which is thus completely or partially replaced.
  • the abovementioned conventional dielectrics may be chosen from ZnO, TiO 2 , SnO 2 , Nb 2 O 5 , Ta 2 O 5 , AIN, Si 3 N 4 , SiAlN, SiON, SiOC, SiO 2 , or a mixture of at least two of these materials.
  • the aforementioned multilayer films, using two silver layers and at least one vanadium oxide layer, are truly remarkable: they may give the glazing exceptional solar-protection properties when the weather starts to be hot, when the vanadium oxide switches to a metallic state. Furthermore, this switching from the thermal standpoint can be seen by the user, giving it an additional aesthetic aspect. It may thus provide enhanced visual comfort, within a building or a vehicle fitted with such glazing, by allowing the light to be screened in the event of strong sunshine.
  • Another variant of the invention involves depositing the layer(s) based on vanadium oxide and the layer(s) having thermal properties on both faces of the same constituent substrate of the glazing, or on one face of a first constituent substrate and on one face of a second constituent substrate of the said glazing. It is therefore possible to associate two types of layers in their known configurations on the same glazing (on one side, for example the vanadium oxide layer possibly associated with a nucleation sublayer/protective overlayer, and on the other side a multilayer film having one or two functional layers as described above). This simplifies the construction of the glazing, but limits the overall performance of the glazing by limiting the possible interferential interactions between the two types of layers.
  • thermochromic layer or layers with one or more electrically conducting layers.
  • These conducting layers may be made of a metal or a metal nitride, of the same type as the above-described infrared-reflecting layers.
  • thermochromic layer or layers to switch by heating using these conducting layers provided with suitable means of connection to a supply of electricity.
  • the conducting layer heats up by resistance heating when it is supplied with electricity, and it transmits this heat to the thermochromatic layer in order to make it switch to its reflecting/absorbent state when required.
  • thermochromatic layer in order to make it switch to its reflecting/absorbent state when required.
  • metal layers such as Ag layers, having a thickness ranging from 5 to 50 nm, especially 8 to 30 nm.
  • An ITO layer may have a thickness ranging from 50 to 500 nm, especially 100 to 300 nm.
  • the two types of layers are preferably located either on the same face of the substrate or of one of the constituent substrates, or on the opposed faces of the said substrate. This is because when the envisaged substrates are made of glass, it is preferable for there to be only at most one thickness of glass separating the conducting layer from the thermochromic layer (preferably a relatively thin glass sheet, for example at most 2 or 3 mm in thickness).
  • the type of connection system used for the conducting layer may comprise two metal shims deposited along two opposed sides of the conducting layer, as may be known in the case of heating layers for antifogging or defrosting applications, with which, for example, motor vehicle or aircraft windows are fitted. It is possible to chose a voltage supply or a current supply, with a signal initiating the switching of the electrochromic layer, which may be a square-wave signal, or to provide an increasing voltage rise, for example, an exponential rise.
  • thermochromic layer in two ways:
  • the electrical supply may be regulated by any electronic /computing means. If the vanadium oxide is not modified/doped and its switch temperature is high, this possibly regulated electrical control may thus make it possible to obtain switching at a lower ambient temperature, for example, around 30 or 40° C.
  • the association of a thermochromic layer with a conducting layer capable of being supplied with electricity therefore gives greater control of the switching state of the thermochromic layer, and greater flexibility.
  • a barrier layer of the SiO 2 or SiOC type which is a barrier to alkali metals, in configurations (1) and (2).
  • thermochromic layer it is possible to provide a barrier layer between the substrate (if it is made of glass) and the thermochromic layer.
  • thermochromic layer for example made of a metal oxide of the SnO 2 type, between the conducting layer and the thermochromic layer, particularly when the conducting layer is based on a doped oxide, such as ITO.
  • thermochromic layer on or under the conducting layer, between the two layers when they are superposed, etc.
  • the glazing according to the invention preferably comprises one or more rigid or semi-rigid substrates made of glass or of a polymer material of the polycarbonate (PC), polyvinyl chloride (PVC) or polymethyl methacrylate (PMMA) type.
  • PC polycarbonate
  • PVC polyvinyl chloride
  • PMMA polymethyl methacrylate
  • It may be “monolithic” glazing (a single substrate). It may also be laminated glazing or insulating multiple glazing of the double-glazing or triple-glazing type.
  • the glazing may include at least one curved and/or toughened glass pane.
  • the glazing according to the invention may have pronounced solar control properties, especially with a reduction in their energy transmission ⁇ T E of at least 5%, a reduction in their light transmission ⁇ T L of at least 5% and an increase in their light reflection ⁇ R L of at least 10% when they pass from a temperature below the switch temperature of the vanadium-oxide-based layers to a temperature above it.
  • the invention also provides solar control glazing whose thermal /optical behaviour is different, for example, depending on the season or the time of clay.
  • the invention provides glazing using at least one dielectric layer intended to antireflect the vanadium oxide layer in the visible.
  • the dielectric layer or layers are chosen by suitably selecting their refractive indexes, their positions in the multilayer film and their thicknesses. They may, for example, be metal oxides such as TiO 2 , SnO 2 , Ta 2 O 5 , Nb 2 O 5 , ZnO and/or silicon derivatives such as SiOC, SiO 2 , Si 3 N 4 , SiON and/or AIN.
  • the thin layers with which the glazing according to the invention is provided may be vacuum deposited, especially by sputtering (at least the layers based on a vanadium oxide and advantageously the other layers too).
  • the conducting layers based on a doped oxide, especially F:SnO 2 may also advantageously be deposited by pyrolysis, especially by CVD or powder pyrolysis, in a known manner.
  • Examples 1 to 3b relate to the first embodiment of the invention, associating a vanadium oxide layer with multilayer films comprising two silver layers.
  • the thin multilayer film is as follows:
  • the VO 2 is not doped.
  • the multilayer film is identical to Example 1, but the VO 2 layer in this case is 60 nm thick.
  • the thin multilayer film is as follows:
  • the “VO 2 ′” here is VO 2 modified with a level of fluorine such that its switch temperature is lowered to about 30° C.
  • the thin multilayer film is as follows:
  • Example 3a is identical to Example 3, except that the silver layers each have a thickness of 15 nm.
  • Example 3b is identical to Example 3, except that the silver layers each have a thickness of 14 nm.
  • the five coated glass panes were then mounted in a double-glazing configuration, with a second glass pane uncoated, made of clear silica-soda-lime glass 2 mm in thickness, and a gas layer of 12 mm thickness between the two glass panes.
  • T L means the light transmission, in %, using the D 65 illuminant:
  • Cold/hot means the color of the parameter in question, depending on whether the temperature is above or below the switch temperature of the vanadium-oxide-based layers;
  • T E means the energy transmission, in %
  • R L means the light reflection, in %
  • P a means the color purity in transmission, in %
  • ⁇ d means the dominant wavelength of the color in transmission, in nm.
  • TABLE 1 Example 1 1a 2 3 3a 3b T L (cold/hot) 32.4/ 24.7/ 26.3/ 21.6/11.4 24.4/13.3 26.2/15.4 28.8 21.7 14.6 ⁇ d (cold/hot) 576/ 577/ 526/ 499/480 508/481 529/482 563 567 483 P c (cold/hot) 29/20 41/32 5/25 7.6/34 4.9/31 4.5/27 T E (cold/hot) 22/15 19/11 13/8 10.6/6.5 12.2/7.5 14/8.6 R L (cold/hot) 22/25 24/25 31/46 22/38 18/34 15/30
  • the glazing according to the invention has an RL value, especially with regard to Examples 2 to 3b, which varies considerably depending on the state, “cold” or “hot”, of the glazing.
  • the glazing therefore becomes much more reflecting as soon as it switches to its “hot” state, allowing the user to “see” when the glazing becomes more filtering from the thermal standpoint. This effect is attractive and novel.
  • a useful criterion involves considering the T L (cold)/T E (hot) ratio, when it is sought to have the highest possible light transmission at low temperatures and to have the lowest possible energy transmission at high temperatures.
  • T L (cold)/T E (hot) ratio With a comparative example using a 50 nm VO 2 layer, this ratio is only 1.3, whereas this ratio is greater than or equal to 2 in the case of the examples according to the invention.
  • Examples 3a and 3b in particular have a color purity in transmission of less than 5% in the “cold” state. It is also possible in this state to have particularly neutral glazing with a low color intensity.
  • the invention has therefore made it possible to develop glazing which has a very high thermal adaptability and is optically attractive by varying the synergy between thermochromic layers and other layers. It allows the offering of summer/winter glazing by providing novel pairs of T L /T E values in the “cold” state and in the “hot” state.
  • thermochromic layers based on vanadium oxide with one or more layers having an essentially optical role.
  • thermochromic layers with overlayers and/or underlayers based on a dielectric having a suitable refractive index in order to improve/refine the optical performance.
  • Example 4 below thus relates to the second embodiment of the invention, associating the vanadium oxide layer with one or more dielectric layers intended for antireflection.
  • the multilayers film on the same glass as in the previous examples, is as follows:
  • the multilayer film again on the same type of glass, is produced by substituting the TiO 2 first layer of Example 4 with a ZnO layer of suitable optical thickness (or any other layer having a refractive index of less than 2.45, especially between 1.90 and 2.30).
  • the multilayer film again on the same type of glass, is produced by associating the VO 2 -based layer with an ITO conducting layer. This is:
  • the ITO layer is provided with two copper shims and supplied by a voltage generator: its thickness and the voltage are adjusted so as to be able to switch the VO 2 into its absorbent state as required, even when the ambient temperature is below its switch temperature.

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  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Laminated Bodies (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
US09/862,714 2000-05-23 2001-05-23 Glazing coated with at least one layer having thermochromic properties Abandoned US20020037421A1 (en)

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Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030228472A1 (en) * 2002-04-29 2003-12-11 Hoffman Wayne L. Coatings having low emissivity and low solar reflectance
US20040016202A1 (en) * 2002-05-16 2004-01-29 Hoffman Wayne L. High shading performance coatings
US20040071985A1 (en) * 2002-07-31 2004-04-15 Krisko Annette J. Temperable high shading performance coatings
US20040137234A1 (en) * 2003-01-09 2004-07-15 Grzegorz Stachowiak Heat treatable coated article with niobium nitride IR reflecting layer and method of making same
US20040155263A1 (en) * 1996-03-27 2004-08-12 Saint-Gobain Vitrage Electrochemical device
WO2004074531A3 (en) * 2003-02-13 2005-01-27 Guardian Industries Coated articles with nitrided layer and methods of making same
WO2005021627A1 (de) 2003-08-25 2005-03-10 Fraunhofer-Gesellschaft zur Förderung der Angwandten Forschung E.V. Thermochrome polymerschicht und verfahren zu deren herstellung
US20060199040A1 (en) * 2005-02-18 2006-09-07 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US20070006004A1 (en) * 2005-06-30 2007-01-04 Intel Corporation Dynamic bus parking
US20070020442A1 (en) * 2003-07-16 2007-01-25 Saint-Gobain Glass France Functionalized security glazing
US20070103761A1 (en) * 2003-07-09 2007-05-10 Saint-Gobain Glass France Electrically-controllable device with variable optical and/or energy properties
DE102007017791A1 (de) 2007-04-16 2008-10-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Komposit mit inversen thermochromen Eigenschaften, dieses enthaltender Verbundwerkstoff sowie dessen Verwendung
US20110080631A1 (en) * 2009-10-01 2011-04-07 Dong-Gun Moon Panel including thermochromic layer
US20110189389A1 (en) * 2005-02-18 2011-08-04 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US8017217B1 (en) * 2008-05-09 2011-09-13 Hrl Laboratories, Llc Variable emissivity material
US8248683B2 (en) 2010-08-05 2012-08-21 Samsung Sdi Co., Ltd. Variable light transmittance window
US20120263943A1 (en) * 2011-04-18 2012-10-18 Samsung Corning Precision Materials Co., Ltd. Post-heat-treatable substrate with thermochromic film
US20130149441A1 (en) * 2011-12-12 2013-06-13 Samsung Corning Precision Materials Co., Ltd. Method Of Manufacturing Thermochromic Substrate
EP2674404A1 (en) * 2012-06-15 2013-12-18 Samsung Corning Precision Materials Co., Ltd. Thermochromic window
WO2013189996A1 (de) * 2012-06-21 2013-12-27 Justus-Liebig-Universität Giessen Thermochromes glas mit beschichtung von farbneutralem vanadiumdioxid
EP2679556A1 (en) * 2012-06-27 2014-01-01 Samsung Corning Precision Materials Co., Ltd. Method of manufacturing thermochromic window
EP2679555A1 (en) * 2012-06-27 2014-01-01 Samsung Corning Precision Materials Co., Ltd. Thermochromic window doped with dopant and method of manufacturing the same
DE102012018813A1 (de) 2012-09-24 2014-03-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermochromes Material, dieses enthaltende Formkörper und deren Verwendung
US20140355639A1 (en) * 2012-12-03 2014-12-04 Indian Institute Of Technology Metamaterial structures for q-switching in lasers
US20150070755A1 (en) * 2012-03-21 2015-03-12 Saint-Gobain Glass France Solar control glazing
CN106045332A (zh) * 2016-06-02 2016-10-26 中国科学院广州能源研究所 一种低相变温度的热色智能调光膜及其制备方法
CN106082695A (zh) * 2016-06-02 2016-11-09 中国科学院广州能源研究所 一种智能调光膜及其制备与应用
US10133093B2 (en) 2007-12-20 2018-11-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Doping capsules, composite systems comprising these and also use thereof
US20190040520A1 (en) * 2016-02-04 2019-02-07 Ecole Polytechnique Federale De Lausanne (Epfl) Coating for optical and electronic applications
US10434846B2 (en) 2015-09-07 2019-10-08 Sabic Global Technologies B.V. Surfaces of plastic glazing of tailgates
US10597097B2 (en) 2015-09-07 2020-03-24 Sabic Global Technologies B.V. Aerodynamic features of plastic glazing of tailgates
US10690314B2 (en) 2015-09-07 2020-06-23 Sabic Global Technologies B.V. Lighting systems of tailgates with plastic glazing
EP3578529A4 (en) * 2017-01-31 2020-12-02 Sekisui Chemical Co., Ltd. INTERMEDIATE FILM INTENDED FOR LAMINATED GLASS HAVING THERMOCHROMIC PROPERTIES, LAMINATED GLASS AND LAMINATED GLASS SYSTEM
US11086054B2 (en) * 2016-07-28 2021-08-10 Commissariat A L'energie Atomique Et Aux Energies Alternatives Solid state thermochromic device, and method for producing said device
US11267173B2 (en) 2015-09-07 2022-03-08 Sabic Global Technologies B.V. Molding of plastic glazing of tailgates
US20220184927A1 (en) * 2019-09-09 2022-06-16 AGC Inc. Laminate and insulated glazing
US11466834B2 (en) 2015-11-23 2022-10-11 Sabic Global Technologies B.V. Lighting systems for windows having plastic glazing
CN115356866A (zh) * 2022-09-13 2022-11-18 中国科学技术大学 一种基于布拉格反射器结构的热致变色窗户组件及制备方法
US20240343924A1 (en) * 2023-04-05 2024-10-17 Teledyne Scientific & Imaging, Llc Variable thermal emissivity coating and method

Families Citing this family (74)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2809388B1 (fr) * 2000-05-23 2002-12-20 Saint Gobain Vitrage Vitrage comprenant au moins une couche a proprietes thermochromes
JPWO2002092529A1 (ja) * 2001-05-15 2004-08-26 日本板硝子株式会社 断熱・遮熱性ガラスパネル
US7154170B2 (en) * 2004-03-31 2006-12-26 Intel Corporation Semiconductor package security features using thermochromatic inks and three-dimensional identification coding
US7691458B2 (en) * 2004-03-31 2010-04-06 Intel Corporation Carrier substrate with a thermochromatic coating
JP4665153B2 (ja) * 2004-07-13 2011-04-06 独立行政法人産業技術総合研究所 高性能自動調光遮熱ガラス調光層膜厚の決定方法
EP1650173A1 (de) * 2004-10-19 2006-04-26 Applied Films GmbH & Co. KG Glasbeschichtung
CN100595608C (zh) * 2005-02-18 2010-03-24 佳能株式会社 光学透明部件和使用该光学透明部件的光学系统
AU2006327181A1 (en) 2005-12-22 2007-06-28 Hydra Biosciences, Inc. TRPA1 inhibitors for treating pain
US7637009B2 (en) * 2006-02-27 2009-12-29 Sv Probe Pte. Ltd. Approach for fabricating probe elements for probe card assemblies using a reusable substrate
US7761053B2 (en) * 2006-09-08 2010-07-20 Mpb Communications Inc. Variable emittance thermochromic material and satellite system
WO2008087077A1 (en) * 2007-01-16 2008-07-24 Nv Bekaert Sa A thermochromic device
US7973998B2 (en) 2007-05-18 2011-07-05 Serious Materials, Inc. Temperature activated optical films
KR101275805B1 (ko) * 2009-02-18 2013-06-18 한국전자통신연구원 대면적 바나듐 산화물 박막 성장장치 및 그 성장장치에서의 대면적 산화물 박막 성장방법
US20100209623A1 (en) * 2009-02-18 2010-08-19 Electronics And Telecommunications Research Institute Apparatus for growing large area vanadium dioxide thin film and method of growing large area oxide thin film in the apparatus
US10261381B2 (en) 2009-03-31 2019-04-16 View, Inc. Fabrication of low defectivity electrochromic devices
US8582193B2 (en) 2010-04-30 2013-11-12 View, Inc. Electrochromic devices
US12043890B2 (en) 2009-03-31 2024-07-23 View, Inc. Electrochromic devices
US8764951B2 (en) * 2010-04-30 2014-07-01 View, Inc. Electrochromic devices
US10591795B2 (en) 2009-03-31 2020-03-17 View, Inc. Counter electrode for electrochromic devices
US8764950B2 (en) * 2010-04-30 2014-07-01 View, Inc. Electrochromic devices
US9664974B2 (en) 2009-03-31 2017-05-30 View, Inc. Fabrication of low defectivity electrochromic devices
US9261751B2 (en) 2010-04-30 2016-02-16 View, Inc. Electrochromic devices
US8300298B2 (en) 2010-04-30 2012-10-30 Soladigm, Inc. Electrochromic devices
US11187954B2 (en) 2009-03-31 2021-11-30 View, Inc. Electrochromic cathode materials
US10852613B2 (en) 2009-03-31 2020-12-01 View, Inc. Counter electrode material for electrochromic devices
US10156762B2 (en) 2009-03-31 2018-12-18 View, Inc. Counter electrode for electrochromic devices
US8259381B2 (en) * 2009-06-05 2012-09-04 Exelis Inc. Phase-change materials and optical limiting devices utilizing phase-change materials
US8270060B2 (en) 2009-09-25 2012-09-18 Samsung Sdi Co., Ltd. Infrared ray transmittance controlling panel including color modifying layer
US20110111147A1 (en) * 2009-11-06 2011-05-12 Ajjer Llc Variable emissivity coatings and their applications
KR101137370B1 (ko) * 2009-11-18 2012-04-20 삼성에스디아이 주식회사 복층 창호
KR101127607B1 (ko) 2009-11-20 2012-03-22 삼성에스디아이 주식회사 전기 전도층이 포함된 써모크로믹 유리
KR20110072331A (ko) * 2009-12-22 2011-06-29 삼성전자주식회사 반도체 소자 및 그 제조 방법, 및 그것을 포함하는 반도체 모듈, 전자 회로 기판 및 전자 시스템
US12353109B2 (en) 2009-12-22 2025-07-08 View Operating Corporation Electrochromic cathode materials
US8381382B2 (en) * 2009-12-31 2013-02-26 Cardinal Ig Company Methods and equipment for assembling triple-pane insulating glass units
KR101137373B1 (ko) * 2010-01-07 2012-04-20 삼성에스디아이 주식회사 스마트 창호
US20110214357A1 (en) * 2010-03-04 2011-09-08 Sabin Ewing Energy saving roof
CN102934009B (zh) * 2010-04-30 2016-10-19 唯景公司 电致变色器件
WO2011137104A1 (en) * 2010-04-30 2011-11-03 Soladigm, Inc. Electrochromic devices
US9759975B2 (en) 2010-04-30 2017-09-12 View, Inc. Electrochromic devices
TW201210036A (en) * 2010-08-25 2012-03-01 An Ching New Energy Machinery & Equipment Co Ltd Enhanced intelligent thin film solar cell for temperature-oriented infrared light transmittance function
KR20120118303A (ko) * 2011-04-18 2012-10-26 삼성코닝정밀소재 주식회사 에너지절약형 창 및 복층유리
KR101260480B1 (ko) * 2011-04-18 2013-05-02 삼성코닝정밀소재 주식회사 시인성이 향상된 써모크로믹 코팅 기판
JP5781837B2 (ja) * 2011-06-03 2015-09-24 積水化学工業株式会社 サーモクロミック性フィルム、合わせガラス用中間膜、合わせガラス及び貼り付け用フィルム
KR101380509B1 (ko) 2011-08-12 2014-04-01 (주)엘지하우시스 저온 금속 증착공정을 적용한 열변색성 유리의 제조방법 및 이에 의한 열변색성 유리
KR101278058B1 (ko) 2011-12-08 2013-06-24 삼성코닝정밀소재 주식회사 써모크로믹 글라스 제조방법
KR101281467B1 (ko) 2011-12-15 2013-07-03 삼성코닝정밀소재 주식회사 써모크로믹 글라스 제조방법 및 이에 의해 제조된 써모크로믹 글라스
KR20130074156A (ko) * 2011-12-26 2013-07-04 삼성코닝정밀소재 주식회사 반사유리 및 이의 제조방법
KR101319263B1 (ko) 2012-05-22 2013-10-18 전자부품연구원 스마트 윈도우용 그래핀 기반 ｖｏ２ 적층체
KR101367828B1 (ko) 2012-07-16 2014-02-27 삼성코닝정밀소재 주식회사 써모크로믹 윈도우 제조방법
CN102785433A (zh) * 2012-07-26 2012-11-21 中国科学技术大学 红外调控力增强的透光结构及其应用
CN102910837A (zh) * 2012-10-16 2013-02-06 中国科学院上海技术物理研究所 一种离线可钢化智能低辐射镀膜玻璃及其制备方法
CN103770423B (zh) * 2012-10-22 2016-08-03 中国科学院上海硅酸盐研究所 一种同时具有调光和隔热保温功能的透明结构及其制备方法及应用
CN104768892A (zh) 2012-11-08 2015-07-08 法国圣戈班玻璃厂 具有可切换的光学性能的玻璃
US9170465B2 (en) 2012-11-26 2015-10-27 Guardian Industries Corp. Thermochromic window and method of manufacturing the same
KR101398602B1 (ko) * 2012-11-29 2014-05-23 코닝정밀소재 주식회사 써모크로믹 윈도우
FR2998981B1 (fr) * 2012-11-30 2015-02-06 Centre Nat Rech Scient Source de rayonnement infrarouge directionnelle commutable
CN103910495A (zh) * 2012-12-31 2014-07-09 中国南玻集团股份有限公司 双银热致变色玻璃及其制备方法
CN103896497A (zh) * 2012-12-31 2014-07-02 中国南玻集团股份有限公司 单银热致变色玻璃及其制备方法
KR20140144326A (ko) * 2013-05-03 2014-12-19 코닝정밀소재 주식회사 써모크로믹 윈도우 및 그 제조방법
US11891327B2 (en) 2014-05-02 2024-02-06 View, Inc. Fabrication of low defectivity electrochromic devices
US10345671B2 (en) 2014-09-05 2019-07-09 View, Inc. Counter electrode for electrochromic devices
US10816829B2 (en) 2014-10-03 2020-10-27 Konica Minolta, Inc. Optical film and method for producing optical film
CN116789175A (zh) 2014-11-26 2023-09-22 唯景公司 用于电致变色装置的对电极
CN105799276B (zh) * 2014-12-31 2018-03-16 中国科学院广州能源研究所 一种热色智能膜及其制备方法
CN105800955B (zh) * 2014-12-31 2018-12-07 中国科学院广州能源研究所 一种热色智能膜及其制备方法
CN105800951B (zh) * 2014-12-31 2018-10-23 中国科学院广州能源研究所 一种热色智能玻璃的制备方法
CN106145701A (zh) * 2015-03-27 2016-11-23 中国科学院广州能源研究所 一种节能夹层玻璃及其制备方法
KR101628256B1 (ko) 2015-09-15 2016-06-08 유니슨 주식회사 풍력발전장치
DE102016100355A1 (de) * 2016-01-11 2017-07-13 Institut Für Solarenergieforschung Gmbh Mehrschichtmaterialfolge zur Energiegewinnung aus Sonnenlicht, deren Herstellung sowie deren Verwendung
WO2018204640A1 (en) 2017-05-03 2018-11-08 University Of South Florida Microencapsulated thermochromic materials and uses thereof
EP3707104B1 (en) 2017-11-06 2024-05-15 Sage Electrochromics, Inc. Article including a non-light-emitting variable transmission device and a coating
JP2020012993A (ja) * 2018-07-18 2020-01-23 パナソニックＩｐマネジメント株式会社 光学フィルム及びそれを備える窓ガラス
KR102559753B1 (ko) * 2018-11-01 2023-07-27 삼성전자주식회사 조리장치
EP4530271A1 (en) 2023-09-26 2025-04-02 AGC Glass Europe Thermochromic glazing

Family Cites Families (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3483110A (en) * 1967-05-19 1969-12-09 Bell Telephone Labor Inc Preparation of thin films of vanadium dioxide
US3899449A (en) * 1973-05-11 1975-08-12 Globe Union Inc Low temperature coefficient of resistivity cermet resistors
US3834793A (en) * 1973-06-21 1974-09-10 Advance Technology Center Inc Dichromic mirror having multilayer thin films including vanadium dioxide
US4393095A (en) * 1982-02-01 1983-07-12 Ppg Industries, Inc. Chemical vapor deposition of vanadium oxide coatings
AU546405B2 (en) 1982-02-01 1985-08-29 Ppg Industries, Inc. Vanadium oxide coating
US4401690A (en) * 1982-02-01 1983-08-30 Ppg Industries, Inc. Thermochromic vanadium oxide with depressed switching temperature
US4960323A (en) * 1988-10-05 1990-10-02 Ford Motor Company Method for maintaining the electrochromic activity of an electrochromic material
US5506037A (en) * 1989-12-09 1996-04-09 Saint Gobain Vitrage International Heat-reflecting and/or electrically heatable laminated glass pane
GB9410261D0 (en) * 1994-05-20 1994-07-13 Glaverbel Optical cell
US5679283A (en) * 1994-07-22 1997-10-21 Gentex Corporation Electrochromic layer and devices comprising same
FR2728696A1 (fr) * 1994-12-23 1996-06-28 Saint Gobain Vitrage Procede d'alimentation electrique d'un vitrage electrocommandable
FR2736632B1 (fr) * 1995-07-12 1997-10-24 Saint Gobain Vitrage Vitrage muni d'une couche conductrice et/ou bas-emissive
FR2738813B1 (fr) * 1995-09-15 1997-10-17 Saint Gobain Vitrage Substrat a revetement photo-catalytique
US6358307B1 (en) * 1995-11-03 2002-03-19 Les Peintures Jefco Vanadium dioxide microparticles, method for preparing same, and use thereof, in particular for surface coating
FR2746934B1 (fr) 1996-03-27 1998-05-07 Saint Gobain Vitrage Dispositif electrochimique
FR2752570B1 (fr) * 1996-08-22 1998-10-02 Saint Gobain Vitrage Vitrage a proprietes optiques et/ou energetiques variables
GB9619134D0 (en) * 1996-09-13 1996-10-23 Pilkington Plc Improvements in or related to coated glass
FR2753545B1 (fr) * 1996-09-18 1998-10-16 Saint Gobain Vitrage Dispositif electrochimique
GB9619781D0 (en) * 1996-09-23 1996-11-06 Secr Defence Multi layer interference coatings
FR2757151B1 (fr) * 1996-12-12 1999-01-08 Saint Gobain Vitrage Vitrage comprenant un substrat muni d'un empilement de couches minces pour la protection solaire et/ou l'isolation thermique
FR2762541B1 (fr) * 1997-04-24 1999-07-02 Saint Gobain Vitrage Procede de fabrication d'un vitrage feuillete
ES2180308T3 (es) * 1998-06-03 2003-02-01 Bruno K Meyer Revestimiento termocromico.
DE19860026A1 (de) * 1998-06-03 1999-12-09 Bruno K Meyer Thermochrome Beschichtung
US6103353A (en) * 1998-07-08 2000-08-15 Eastman Kodak Company Copy restrictive documents
FR2781084B1 (fr) * 1998-07-10 2007-08-31 Saint Gobain Vitrage Procede de traitement d'un dispositif electrochimique
GB9816922D0 (en) * 1998-08-04 1998-09-30 Pilkington Plc Improvements in coating glass
US6218018B1 (en) * 1998-08-21 2001-04-17 Atofina Chemicals, Inc. Solar control coated glass
JP2000137251A (ja) * 1998-08-28 2000-05-16 Itaru Yasui サ―モクロミック体及びその製造方法
GB9822338D0 (en) * 1998-10-13 1998-12-09 Glaverbel Solar control coated glass
FR2809388B1 (fr) 2000-05-23 2002-12-20 Saint Gobain Vitrage Vitrage comprenant au moins une couche a proprietes thermochromes

Cited By (85)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040155263A1 (en) * 1996-03-27 2004-08-12 Saint-Gobain Vitrage Electrochemical device
US6940628B2 (en) * 1996-03-27 2005-09-06 Saint-Gobain Vitrage Electrochemical device
US7063893B2 (en) 2002-04-29 2006-06-20 Cardinal Cg Company Low-emissivity coating having low solar reflectance
US20040028955A1 (en) * 2002-04-29 2004-02-12 Hoffman Wayne L. Low-emissivity coating having low solar reflectance
US7670641B2 (en) 2002-04-29 2010-03-02 Cardinal Cg Company Coatings having low emissivity and low solar reflectance
US7758915B2 (en) 2002-04-29 2010-07-20 Cardinal Cg Company Low-emissivity coating having low solar reflectance
US20060222763A1 (en) * 2002-04-29 2006-10-05 Hoffman Wayne L Coatings having low emissivity and low solar reflectance
US20030228472A1 (en) * 2002-04-29 2003-12-11 Hoffman Wayne L. Coatings having low emissivity and low solar reflectance
US7067195B2 (en) 2002-04-29 2006-06-27 Cardinal Cg Company Coatings having low emissivity and low solar reflectance
US20040016202A1 (en) * 2002-05-16 2004-01-29 Hoffman Wayne L. High shading performance coatings
US7687149B2 (en) 2002-05-16 2010-03-30 Cardinal Cg Company High shading performance coatings
US7122252B2 (en) 2002-05-16 2006-10-17 Cardinal Cg Company High shading performance coatings
US7138182B2 (en) 2002-07-31 2006-11-21 Cardinal Cg Compay Temperable high shading performance coatings
US20040071985A1 (en) * 2002-07-31 2004-04-15 Krisko Annette J. Temperable high shading performance coatings
US7534497B2 (en) 2002-07-31 2009-05-19 Cardinal Cg Company Temperable high shading performance coatings
US6994910B2 (en) * 2003-01-09 2006-02-07 Guardian Industries Corp. Heat treatable coated article with niobium nitride IR reflecting layer
US20050205416A1 (en) * 2003-01-09 2005-09-22 Guardian Industries Corp. Heat treatable coated article with niobium nitride IR reflecting layer and method of making same
US20040137234A1 (en) * 2003-01-09 2004-07-15 Grzegorz Stachowiak Heat treatable coated article with niobium nitride IR reflecting layer and method of making same
WO2004074531A3 (en) * 2003-02-13 2005-01-27 Guardian Industries Coated articles with nitrided layer and methods of making same
US7037587B2 (en) 2003-02-13 2006-05-02 Guardian Industries Corp. Coated articles with nitrided layer and methods of making same
US7791784B2 (en) 2003-07-09 2010-09-07 Saint-Gobain Glass France Electrically-controllable device with variable optical and/or energy properties
US20070103761A1 (en) * 2003-07-09 2007-05-10 Saint-Gobain Glass France Electrically-controllable device with variable optical and/or energy properties
US8102585B2 (en) 2003-07-16 2012-01-24 Saint-Gobain Glass France Functionalized security glazing
US20070020442A1 (en) * 2003-07-16 2007-01-25 Saint-Gobain Glass France Functionalized security glazing
US20060246292A1 (en) * 2003-08-25 2006-11-02 Fraunhofer-Gesellschaft Zur Forderung Der Angwandten Forschung E.V. Thermochromic polymer layer and layer and method for production thereof
US7662466B2 (en) 2003-08-25 2010-02-16 Fraunhofer-Gesellschaft Zur Forderung Der Angwandten Forschung E.V. Thermochromic polymer layer and method for production thereof
WO2005021627A1 (de) 2003-08-25 2005-03-10 Fraunhofer-Gesellschaft zur Förderung der Angwandten Forschung E.V. Thermochrome polymerschicht und verfahren zu deren herstellung
US7931936B2 (en) 2005-02-18 2011-04-26 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US20060199040A1 (en) * 2005-02-18 2006-09-07 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US7811684B2 (en) 2005-02-18 2010-10-12 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US20090081361A1 (en) * 2005-02-18 2009-03-26 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US20110189389A1 (en) * 2005-02-18 2011-08-04 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US8501270B2 (en) 2005-02-18 2013-08-06 Canon Kabushiki Kaisha Optical transparent member and optical system using the same
US20070006004A1 (en) * 2005-06-30 2007-01-04 Intel Corporation Dynamic bus parking
US20100181541A1 (en) * 2007-04-16 2010-07-22 FRAUNHOFER-GESELLSCHAFT ZUR FÕRDERUNG DER ANGEWAND ANGEWANDTEN FORSCHUNG e .V. Composite with inverse thermochromic properties, composite material containing this and also use thereof
DE102007017791A1 (de) 2007-04-16 2008-10-30 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Komposit mit inversen thermochromen Eigenschaften, dieses enthaltender Verbundwerkstoff sowie dessen Verwendung
US8303857B2 (en) 2007-04-16 2012-11-06 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Composite with inverse thermochromic properties, composite material containing this and also use thereof
US10133093B2 (en) 2007-12-20 2018-11-20 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Doping capsules, composite systems comprising these and also use thereof
US8784151B1 (en) 2008-05-09 2014-07-22 Hrl Laboratories, Llc Variable emissivity material
US8017217B1 (en) * 2008-05-09 2011-09-13 Hrl Laboratories, Llc Variable emissivity material
US20110080631A1 (en) * 2009-10-01 2011-04-07 Dong-Gun Moon Panel including thermochromic layer
US8422113B2 (en) 2009-10-01 2013-04-16 Samsung Sdi Co., Ltd. Panel including thermochromic layer
US8248683B2 (en) 2010-08-05 2012-08-21 Samsung Sdi Co., Ltd. Variable light transmittance window
US20120263943A1 (en) * 2011-04-18 2012-10-18 Samsung Corning Precision Materials Co., Ltd. Post-heat-treatable substrate with thermochromic film
US20130149441A1 (en) * 2011-12-12 2013-06-13 Samsung Corning Precision Materials Co., Ltd. Method Of Manufacturing Thermochromic Substrate
US9657385B2 (en) * 2011-12-12 2017-05-23 Corning Precision Materials Co., Ltd. Method of manufacturing thermochromic substrate
US20150070755A1 (en) * 2012-03-21 2015-03-12 Saint-Gobain Glass France Solar control glazing
EP2674404A1 (en) * 2012-06-15 2013-12-18 Samsung Corning Precision Materials Co., Ltd. Thermochromic window
US9146408B2 (en) 2012-06-15 2015-09-29 Corning Precision Materials Co., Ltd. Thermochromic window
US9309147B2 (en) 2012-06-21 2016-04-12 Justus-Liebig-Universitaet Giessen Thermochromic glass comprising a coating of neutral-colour vanadium dioxide
WO2013189996A1 (de) * 2012-06-21 2013-12-27 Justus-Liebig-Universität Giessen Thermochromes glas mit beschichtung von farbneutralem vanadiumdioxid
US8988758B2 (en) 2012-06-27 2015-03-24 Samsung Corning Precision Materials Co., Ltd. Thermochromic window doped with dopant and method of manufacturing the same
CN103507389A (zh) * 2012-06-27 2014-01-15 三星康宁精密素材株式会社 制造热致变色窗户的方法
US20140001029A1 (en) * 2012-06-27 2014-01-02 Samsung Corning Precision Materials Co., Ltd. Method Of Manufacturing Thermochromic Window
EP2679556A1 (en) * 2012-06-27 2014-01-01 Samsung Corning Precision Materials Co., Ltd. Method of manufacturing thermochromic window
EP2679555A1 (en) * 2012-06-27 2014-01-01 Samsung Corning Precision Materials Co., Ltd. Thermochromic window doped with dopant and method of manufacturing the same
WO2014044462A1 (de) 2012-09-24 2014-03-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermochromes material, dieses enthaltende formkörper und deren verwendung
DE102012018813A1 (de) 2012-09-24 2014-03-27 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermochromes Material, dieses enthaltende Formkörper und deren Verwendung
US9193863B2 (en) 2012-09-24 2015-11-24 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Thermochromic material, molded article comprising said material and use thereof
US20140355639A1 (en) * 2012-12-03 2014-12-04 Indian Institute Of Technology Metamaterial structures for q-switching in lasers
US9627840B2 (en) * 2012-12-03 2017-04-18 Indian Institute Of Technology Kanpur Metamaterial structures for Q-switching in lasers
US11458709B2 (en) 2015-09-07 2022-10-04 Sabic Global Technologies B.V. Three shot plastic tailgate
US12390967B2 (en) 2015-09-07 2025-08-19 Sabic Global Technologies B.V. Molding of plastic glazing of tailgates
US12330397B2 (en) 2015-09-07 2025-06-17 Sabic Global Technologies B.V. Three shot plastic tailgate
US11267173B2 (en) 2015-09-07 2022-03-08 Sabic Global Technologies B.V. Molding of plastic glazing of tailgates
US10948152B2 (en) 2015-09-07 2021-03-16 Sabic Global Technologies B.V. Lighting systems of tailgates with plastic glazing
US10434846B2 (en) 2015-09-07 2019-10-08 Sabic Global Technologies B.V. Surfaces of plastic glazing of tailgates
US10597097B2 (en) 2015-09-07 2020-03-24 Sabic Global Technologies B.V. Aerodynamic features of plastic glazing of tailgates
US10690314B2 (en) 2015-09-07 2020-06-23 Sabic Global Technologies B.V. Lighting systems of tailgates with plastic glazing
US10717348B2 (en) 2015-09-07 2020-07-21 Sabic Global Technologies B.V. Surfaces of plastic glazing of tailgates
US11845240B2 (en) 2015-09-07 2023-12-19 Sabic Global Technologies B.V. Three shot plastic tailgate
US11466834B2 (en) 2015-11-23 2022-10-11 Sabic Global Technologies B.V. Lighting systems for windows having plastic glazing
US12145498B2 (en) 2015-11-23 2024-11-19 Sabic Global Technologies B.V. Illuminated graphic in an automotive plastic glazing
US11766965B2 (en) 2015-11-23 2023-09-26 Sabic Global Technologies B.V. Illuminated graphic in an automotive plastic glazing
US20190040520A1 (en) * 2016-02-04 2019-02-07 Ecole Polytechnique Federale De Lausanne (Epfl) Coating for optical and electronic applications
CN106045332B (zh) * 2016-06-02 2019-08-02 中国科学院广州能源研究所 一种低相变温度的热色智能调光膜及其制备方法
CN106082695A (zh) * 2016-06-02 2016-11-09 中国科学院广州能源研究所 一种智能调光膜及其制备与应用
CN106082695B (zh) * 2016-06-02 2019-01-08 中国科学院广州能源研究所 一种智能调光膜及其制备与应用
CN106045332A (zh) * 2016-06-02 2016-10-26 中国科学院广州能源研究所 一种低相变温度的热色智能调光膜及其制备方法
US11086054B2 (en) * 2016-07-28 2021-08-10 Commissariat A L'energie Atomique Et Aux Energies Alternatives Solid state thermochromic device, and method for producing said device
EP3578529A4 (en) * 2017-01-31 2020-12-02 Sekisui Chemical Co., Ltd. INTERMEDIATE FILM INTENDED FOR LAMINATED GLASS HAVING THERMOCHROMIC PROPERTIES, LAMINATED GLASS AND LAMINATED GLASS SYSTEM
US12240204B2 (en) * 2019-09-09 2025-03-04 AGC Inc. Laminate and insulated glazing
US20220184927A1 (en) * 2019-09-09 2022-06-16 AGC Inc. Laminate and insulated glazing
CN115356866A (zh) * 2022-09-13 2022-11-18 中国科学技术大学 一种基于布拉格反射器结构的热致变色窗户组件及制备方法
US20240343924A1 (en) * 2023-04-05 2024-10-17 Teledyne Scientific & Imaging, Llc Variable thermal emissivity coating and method

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FR2809388A1 (fr) 2001-11-30
JP2002086606A (ja) 2002-03-26
US6872453B2 (en) 2005-03-29
US20040005472A1 (en) 2004-01-08
US7311976B2 (en) 2007-12-25
EP1160214A1 (fr) 2001-12-05
US20050147825A1 (en) 2005-07-07

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