WO2008044531A1 - procédé de fabrication d'une couche mince de dioxyde de vanadium et son produit - Google Patents

procédé de fabrication d'une couche mince de dioxyde de vanadium et son produit Download PDF

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Publication number
WO2008044531A1
WO2008044531A1 PCT/JP2007/069225 JP2007069225W WO2008044531A1 WO 2008044531 A1 WO2008044531 A1 WO 2008044531A1 JP 2007069225 W JP2007069225 W JP 2007069225W WO 2008044531 A1 WO2008044531 A1 WO 2008044531A1
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Prior art keywords
thin film
vanadium dioxide
transparent conductive
heat
heating
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PCT/JP2007/069225
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English (en)
Japanese (ja)
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Ping Jin
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National Institute Of Advanced Industrial Science And Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/02—Oxides
    • 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
    • C03C17/3447—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 halide
    • C03C17/3452—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 halide comprising a fluoride
    • 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
    • C03C17/3621—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 fluoride
    • 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
    • C03C2217/00—Coatings on glass
    • C03C2217/90—Other aspects of coatings
    • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
    • 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]
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/154—Deposition methods from the vapour phase by sputtering
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/31—Pre-treatment
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/34—Masking

Definitions

  • the present invention relates to a process for producing a vanadium dioxide thin film and an electrically heated substrate provided with a transparent conductive film for use in forming the vanadium dioxide thin film. Efficiently form vanadium dioxide-based thin films used for light control glass and films with multifunctional functions such as health and comfort, energy saving, and environmental purification on windows of buildings and automobiles
  • the present invention relates to an electrically heated substrate provided with a transparent conductive film.
  • Non-patent Document 2 There are other window coating materials that are dimmed by heat.
  • Non-patent Document 2 an autonomous response type thermal light control glass using a special hide mouth gel
  • this material is difficult to apply to buildings that always require a clear view, and especially to window materials for moving objects such as automobiles.
  • Optical properties can be freely controlled by energizing and heating the organic reversible thermosensitive layer.
  • a dimmer and its control method have been proposed (Patent Document 1), but the organic crystal particles and polymer matrix, which are dimming materials at the time of dimming, become cloudy, and the original transparency of the window is lost. .
  • V vanadium dioxide
  • Non-patent Document 3 The vanadium dioxide dimming glass has a very simple structure and adjusts itself naturally and automatically according to changes in the environmental temperature, so no extra equipment is required.
  • thermochromic light-modulating materials have 1) low visible light transmittance due to strong absorption at short wavelengths including visible light, and 2) infrared for room temperature radiant heat. Low reflectivity and poor thermal insulation, 3) Since it is very difficult to form a vanadium dioxide single-phase thin film, it is usually necessary to raise the substrate temperature to 400 ° C or higher when making it by sputtering. In addition, the fabrication parameters must be finely controlled, and 4) the formation conditions of the single-phase light control film are severe, making it difficult to form a large area and optically uniform film. There was a problem.
  • substrate heating is still indispensable when forming a vanadium dioxide thin film, and its temperature is several hundred degrees Celsius, Basically it must be above 300 ° C.
  • substrate heating especially substrate heating at 200 ° C or higher, leads to enlargement of the film deposition equipment, and soon the current thin film coating equipment such as Low-E glass.
  • the coating equipment cannot be used without major modifications.
  • the conventional method results in an increase in cost and a decrease in efficiency. That is, the development of a more efficient and reliable thin film formation method, particularly an effective substrate heating method, which is a key point in the formation of vanadium dioxide, is awaited. Therefore, the present inventor paid attention not only to research, but also to the status of technological development in other fields.
  • Patent Document 1 JP-A-6-273807
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-176154
  • Patent Document 3 Japanese Patent Application Laid-Open No. 2004-306025
  • Patent Document 4 Japanese Patent Laid-Open No. 2005-202414
  • Non-Patent Document 1 Glass Engineering Handbook, Asakura Shoten, p. 449-452, 1999
  • Non-Patent Document 2 Haruo Watanabe: Solar Energy, 1997, 23, 49
  • Non-Patent Document 3 S.M Babulanam, T.S. Eriksson, G.A.Niklasson and C.G.Granqvist: Solar Energy Matrials 16 (1987) 347
  • the present inventor in view of the above-mentioned prior art, further energetically researches based on a series of inventions of vanadium dioxide monochromic thin films and functional products thereof.
  • some important points were found in the thin film body forming process.
  • 1) Use of a transparent conductive film in the vanadium dioxide thin film and its functional products is effective in improving product functionality.
  • the transparent conductive film is suitable as a base film for the vanadium dioxide thin film.
  • the transparent conductor thin film itself By making the transparent conductor thin film itself a heating element by energization heating, no additional substrate heating equipment is basically required for heating the substrate.
  • the transparent conductor is currently It can be used without large modifications such as an increase in heating space in a large-scale film deposition facility for forming low-E sputtered thin films.
  • the transparent conductor thin film itself generates heat.
  • a vanadium dioxide thin film is formed on top
  • an object of the present invention is to provide a substrate heating method and its substrate capable of efficiently forming a vanadium dioxide thermochromic thin film and its functional product.
  • the present invention for solving the above-described problems comprises the following technical means.
  • a heat resistant substrate with a transparent conductive thin film provided with a transparent conductive thin film is used.
  • Transparent conductive thin film is 1) Oxide-based (In O, SnO, Zn ⁇ , Cd ⁇ , TiO, Cdln O
  • Nitride TiN, ZrN, or HfN
  • the transparent conductive thin film has a current heating function and a structural template function that helps to form a vanadium dioxide thin film, a function that adjusts the optical characteristics of a thin film of a functional product including a vanadium dioxide thin film, or infrared reflection
  • the method according to the above (1) which has a plurality of functions of the heat insulation function.
  • the vanadium dioxide thin film is heated to a temperature above the transition temperature by natural temperature change or current heating, so that it has metallic properties, so that even if heat is removed, the metal properties are maintained with a large hysteresis width.
  • the vanadium dioxide thin film is cooled to below the transition temperature by natural temperature change or forced cooling so that it has semiconductor characteristics, so that the semiconductor characteristics can be maintained with a large hysteresis width even when heat is applied.
  • a heat-resistant substrate comprising a heat-resistant substrate with a thin film and a heating means for energizing and electrically heating the transparent conductive thin film.
  • the present invention relates to a method for producing a functional product including a vanadium dioxide-based thin film and / or a vanadium dioxide-based thin film, comprising: a heat-resistant substrate with a transparent conductive thin film provided with a transparent conductive thin film on the heat-resistant substrate.
  • the substrate is heated by conducting heating of the transparent conductive thin film when the vanadium dioxide thin film is formed. It is.
  • the substrate is heated by making an electrical connection between the heat-resistant substrate portion including the transparent conductive thin film and the heating portion including the power source and the temperature control device by means of a conductive wire.
  • the electrical connection with the heating part is detachable, and in order to uniformly control the heat generation of the transparent conductive thin film, the electrode and / or the conductive metal are arranged in a line or strip. Is preferred.
  • the vanadium dioxide type includes those added with elements.
  • the transparent conductive thin film is composed of (1) oxides (In 2 O 3, SnO 2, ZnO, CdO, TiO 2, Cdln 2 O 3, C
  • Nitride TiN, ZrN, or HfN
  • system includes, as a main component, a substance added with an element, or a mixture or compound.
  • the present invention is also a heat resistant substrate for forming a vanadium dioxide thin film and / or a vanadium dioxide thin film of a functional product including the vanadium dioxide thin film, wherein the transparent conductive thin film is disposed on the heat resistant substrate.
  • a heat-resistant substrate with a transparent conductive thin film and a heating means for energizing and electrically heating the transparent conductive thin film are provided inside or outside.
  • a preferred embodiment is that a transparent conductive film having a uniform surface resistance is provided on the substrate surface so that the heat generation distribution can be controlled uniformly.
  • the functional product including the vanadium dioxide thin film and / or the vanadium dioxide thin film includes a current heating function, a structural template function that assists in the formation of the vanadium dioxide thin film, and the vanadium dioxide thin film. It incorporates a transparent conductor thin film that has multiple functions, such as the function to adjust the optical properties of thin film systems of functional products (antireflection, adjustment of transmittance, etc.) or the heat insulation function by infrared reflection.
  • the transparent conductor thin film is actively used and used for substrate heating. More specifically, first, a transparent conductive thin film is coated on a heat-resistant substrate, and a vanadium dioxide light control thin film is formed thereon.
  • the substrate surface temperature due to the current heating of the transparent conductive thin film is preferably controlled between 50 and 700 ° C.
  • the transparent conductor thin film is formed on the transparent substrate by a general-purpose film forming method. Examples are a method of forming and a method of using a substrate provided with a transparent conductive film in advance by another method (for example, CVD or the like), for example, NESA glass or the like.
  • the composition and thickness of the transparent conductor thin film suitable for the target functional product are required, but the forming method is not particularly limited.
  • the present invention electrical, optical, crystallographic, or mechanical properties are provided between the transparent conductive thin film and the heat-resistant substrate and / or between the transparent conductive thin film and the vanadium dioxide thin film.
  • an intermediate layer is provided on the vanadium dioxide thin film.
  • a film is further formed to adjust properties or to add functions. Thin films of functional products including vanadium dioxide thin films. It is possible to appropriately control the optical characteristics of the system by natural temperature change or current heating of the transparent conductive thin film.
  • the vanadium dioxide thin film has a large thermal hysteresis width, and the width is at least 10 ° C or more.
  • An electrode such as a bus bar electrode is further formed on the transparent conductor film, and is electrically heated by a method that can be electrically connected to or easily detached from the temperature control unit or the power source by means of a current line, so that a heat resistant substrate can be obtained in a short period of time.
  • the surface transparent conductor film surface
  • a vanadium dioxide thin film is formed on the surface of the transparent conductor film that has reached a predetermined substrate temperature by a general-purpose thin film forming method (for example, sputtering or vacuum deposition). After forming the vanadium dioxide thin film, disconnect the electrical connection between the heat-resistant substrate and the current heating device so that the substrate can be moved to the next deposition process. If necessary, the process proceeds to the next film forming process as appropriate.
  • the substrate surface is heated only by electrical conduction to the transparent conductive thin film on the glass surface of the substrate. Therefore, an indirect heating method such as a conventional method, for example, heater heating is performed. No larger substrate heating equipment is needed than lamp heating.
  • the heat generated by the transparent conductive film on the glass surface itself provides the heat energy for forming the vanadium dioxide thin film, enabling efficient local heating and rapid heating without the need to heat the entire glass substrate. It is efficient and can heat the substrate.
  • the transparent conductive thin film for electric heating may be disposed on either side of the heat-resistant substrate, that is, on the same side as the vanadium dioxide thin film or on the opposite side. When placed on the opposite side, for example, the heat-resistant substrate is heated from below by energization, and a functional thin film is deposited thereon.
  • Figure 1 shows an overview of the present invention.
  • 1 is a transparent conductor target
  • 2 is a heat-resistant substrate
  • 3 is a transparent conductor film
  • 4 is a metal electrode target
  • 5 is a metal electrode film
  • 6 is a conductive wire
  • 7 is a power supply / temperature control unit
  • 8 is an acid Vanadium hydride film formation target
  • 9 represents a vanadium oxide film
  • 10 represents a titanium oxide film formation target
  • 11 represents a titanium oxide film.
  • a transparent conductive film (transparent conductive film 3) is coated on the heat-resistant substrate 2 (step 1).
  • a transparent conductor film 3 can be coated on a heat-resistant substrate 2 by a general-purpose thin film forming method as a part of a film forming process for forming a vanadium dioxide functional thin film product. It is also possible to directly use a commercially available transparent conductive substrate having appropriate characteristics in advance.
  • a metal electrode film (metal electrode film 5) is produced as a bus bar electrode or the like on the transparent conductive film (step 2).
  • a linear stripe-shaped conductive metal film or the like can be appropriately provided for adjusting the resistance value or uniform heat generation.
  • the electrodes are electrically connected to the external power supply and temperature controller by electric wires (process 3). It is assumed that the electrical connection can be removed at the stage of film formation (detachable), and the substrate can be moved to the next process.
  • External power supply ⁇ The transparent conductor film is energized and heated by the temperature controller to maintain the substrate temperature at a predetermined level.
  • the A vanadium dioxide-based film is formed on the transparent conductor base film that has reached a predetermined temperature. Disconnect the electrical connection and continue to form another functional film (Step 4). Continuous film formation is possible by transporting the substrate.
  • an example of the multifunctional automatic temperature control glass produced by the process of the present invention will be described. First, an ITO transparent conductor film is formed on a heat-resistant substrate by a sputtering method, and the substrate temperature is increased by energization heating. To form a vanadium dioxide thin film. Subsequently, a titanium oxide thin film is formed to form the multi-function automatic heat control glass (step 5) shown in FIG. 1 (the electrode portion is omitted).
  • the formed multifunctional automatic heat control glass functions in a plurality of functions as follows. For example, 1) UV blocking, 2) Visible light transmission, 3) Automatic solar thermal control (summer blocking, winter transmission, automatic switching by temperature or manual control by current heating), 4) High thermal insulation by infrared reflection, 5) Photocatalyst Examples are sex, etc.
  • a transparent conductive thin film for current heating may be disposed on the opposite side of the functional thin film of the heat-resistant substrate (step 4a). That is, the transparent conductive thin film is heated by energization heating, and a vanadium dioxide thin film or the like is formed on the opposite side of the heated heat-resistant substrate.
  • the multi-function automatic heat control glass structure shown on the left side of the figure is characterized by a large thermal hysteresis of the vanadium dioxide-based thin film, and its width ( ⁇ ) is 10 as shown on the right side of FIG. It is desirable to be over ° C.
  • 2 is a heat-resistant substrate
  • 3 is a transparent conductor film
  • 5 is a metal electrode
  • 9 is a vanadium dioxide film
  • 11 is a titanium oxide film
  • 6 is a conductive wire
  • 13 is a power supply / temperature control unit
  • T is a temperature rise Is the temperature at which the metal phase is reached
  • T is the temperature at which it returns to the semiconductor phase
  • ⁇ is the temperature hysteresis.
  • the transparent conductor film is energized and heated by natural heat or the power source / temperature control unit 13, and the vanadium dioxide thin film is heated to a temperature equal to or higher than the transition temperature (T) to the metal phase. Let it fall. If the vanadium dioxide thin film has a large thermal hysteresis, the metal characteristics are maintained if the temperature does not decrease to the transition temperature (T) to the semiconductor phase even if the heating is stopped.
  • the temperature is generally below T (not exceeding T), so it always has semiconductor characteristics and
  • the power source / temperature control unit in the left structure of FIG. 2 can be omitted.
  • the temperature of car windows under sunlight and building windows in the sun easily exceeds T and reflects solar radiation due to metallic properties. In winter, the temperature is always below T, so
  • the optical characteristics of the multifunctional automatic temperature control glass can be controlled by increasing the thermal hysteresis of the vanadium dioxide thin film.
  • the present invention has the following effects.
  • thermochromic thin film capable of efficiently forming a vanadium dioxide thermochromic thin film.
  • the heating time of the substrate is shortened by heat generation from the surface of the transparent conductive thin film.
  • the current heating structure is used as it is to control the optical characteristics of multifunctional automatic light control glass products.
  • a general-purpose magnetron sputtering apparatus was used for producing a thin film of vanadium oxide. Up to three force swords can be placed in the device, and power can be controlled arbitrarily with a high-frequency power source or a DC power source. The substrate can be rotated and the substrate temperature can be precisely set from room temperature to 800 ° C.
  • the size of the substrate used was 1 cm square and 2.5 cm square.
  • Figure 3 shows an outline of the experimental apparatus. ITO, vanadium oxide and silver were used as targets. Sales NESA glass (10 X 25 X lmm, FTO as a transparent conductive film with a coating of approximately 400 nm by CVD) was used as the substrate. First, an Ag electrode film was formed on both ends of a substrate masked with Ag by sputtering as shown in the right of FIG. The resistance between both electrodes was measured to be about 30 ⁇ .
  • the electrode was connected to a power source and a temperature control unit outside the vacuum through an energization terminal, and the substrate was heated by energization heating.
  • a thermocouple was brought into contact with the substrate surface for temperature measurement and control. Electric power from an external DC power supply was applied at 20V / 0.65A (13W), and the substrate temperature rose to 350 ° C in about 1 minute.
  • the substrate temperature was maintained at 350 ° C. with an automatic temperature controller, and a vanadium dioxide thin film was formed to about 70 nm by sputtering.
  • the FTO conductive film has the same structure as vanadium dioxide, and as a structural template, a VO thin film could be produced with good reproducibility at a substrate temperature of 350 ° C.
  • Example 2 Using the apparatus shown in FIG. 3, a thin film of vanadium oxide was formed using a commercially available quartz glass (10 ⁇ 10 ⁇ 0.5 mm) as a substrate.
  • a commercially available quartz glass (10 ⁇ 10 ⁇ 0.5 mm)
  • the transparent conductor thin film an ITO target was used, the substrate temperature was set to 100 ° C, and an ITO thin film was fabricated at about 10 nm. Subsequently, an Ag electrode film was produced. The surface resistance of the substrate was measured to be about 260 ⁇ .
  • the substrate temperature was raised by energization heating, and electric power was applied at 25V / 0.25A (6.25W), and the substrate temperature rose to 350 ° C in about 2 minutes. Since the ITO formation temperature is as low as 100 ° C, the resistance value at the time of fabrication was slightly high at 260 ⁇ , but the resistance value decreased slightly due to the annealing effect due to heating energization. Prepare 50nm VO on ITO thin film kept at 350 ° C
  • a titanium fluoride thin film was produced to 160 nm.
  • Fig. 4 shows the measured values of the thin film optical properties of vanadium dioxide on NESA glass and (b) shows vanadium dioxide on ITO-coated glass. Obviously, both showed changes in transmittance with temperature.
  • the infrared part of the spectral transmittance in Fig. 4 (a) shows a low value for both the metal phase and the semiconductor phase because the transparent conductive substrate coated with FTO has a high reflectance in the infrared region. This is interpreted as a decrease in transmittance.
  • the present invention relates to a manufacturing method and a product of a vanadium dioxide thin film.
  • solar radiation is automatically adjusted to a window of a house, a building, or a moving body only by a change in environmental temperature.
  • a substrate heating method required for forming a vanadium dioxide-based thin film which uses a transparent conductive thin film, can be provided.
  • the transparent conductive material By introducing a transparent conductive material into the basic structure of the heat control glass, the heat ray reflection effect is enhanced, and the transparent conductive material can promote the formation of the vanadium dioxide thin film.
  • the substrate can be heated easily and efficiently, and the formed heat-control glass structure can be controlled not only automatically but also manually.
  • FIG. 1 is an explanatory view showing an outline of the present invention.
  • FIG. 2 is an explanatory view showing an outline of a method for controlling optical characteristics of a multifunctional automatic heat control glass.
  • FIG. 3 is an explanatory diagram showing an outline of the experimental apparatus and examples.
  • FIG. 4 shows measured values of the optical properties of the thin film system of the example.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Surface Treatment Of Glass (AREA)
  • Surface Heating Bodies (AREA)
  • Resistance Heating (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

La présente invention concerne un procédé de chauffage de substrat dans lequel une couche mince thermochromique de dioxyde de vanadium et des produits fonctionnels de celle-ci peuvent être produits efficacement; et un procédé de fabrication d'un verre de contrôle thermique automatique à fonctions multiples destiné à être utilisé dans les vitrages de bâtiments et d'objets mobiles. L'invention concerne un procédé de fabrication d'une couche mince de dioxyde de vanadium et/ou un produit fonctionnel contenant une couche mince de dioxyde de vanadium, caractérisé en ce que l'on utilise un substrat résistant à la chaleur comportant une couche mince conductrice transparente disposée sur un substrat résistant à la chaleur, et en ce que lors de la formation d'une couche mince de dioxyde de vanadium, le chauffage du substrat est effectué par chauffage ohmique de la couche mince conductrice transparente. En conséquence, non seulement on peut réaliser un chauffage efficace du substrat par chauffage ohmique en utilisant la couche mince conductrice transparente introduite dans la structure du substrat, mais aussi on propose un procédé de contrôle des caractéristiques optiques d'un verre de contrôle thermique par l'utilisation d'une structure de substrat pouvant faire passer le courant.
PCT/JP2007/069225 2006-10-06 2007-10-01 procédé de fabrication d'une couche mince de dioxyde de vanadium et son produit WO2008044531A1 (fr)

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CN102785415A (zh) * 2012-07-26 2012-11-21 中国科学技术大学 二氧化钒基复合薄膜、包括其的透光结构及其应用
EP2679556A1 (fr) * 2012-06-27 2014-01-01 Samsung Corning Precision Materials Co., Ltd. Procédé de fabrication de fenêtre thermochromique
US11391467B2 (en) * 2018-11-01 2022-07-19 Samsung Electronics Co., Ltd. Cooking apparatus
CN115064679A (zh) * 2022-07-04 2022-09-16 佛山科学技术学院 一种氧化钒微米棒簇及其制备方法和应用
WO2024040429A1 (fr) * 2022-08-23 2024-02-29 中国科学院深圳先进技术研究院 Matériau composite de blindage électromagnétique ayant une caractéristique de réponse à la température, sa méthode de préparation et son application

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JP6948052B2 (ja) * 2016-11-25 2021-10-13 国立研究開発法人宇宙航空研究開発機構 探査機

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CN115064679A (zh) * 2022-07-04 2022-09-16 佛山科学技术学院 一种氧化钒微米棒簇及其制备方法和应用
CN115064679B (zh) * 2022-07-04 2024-04-23 佛山科学技术学院 一种氧化钒微米棒簇及其制备方法和应用
WO2024040429A1 (fr) * 2022-08-23 2024-02-29 中国科学院深圳先进技术研究院 Matériau composite de blindage électromagnétique ayant une caractéristique de réponse à la température, sa méthode de préparation et son application

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