[go: up one dir, main page]

WO2019244650A1 - Film d'oxyde de tungstène composite et son procédé de production, et matériau de base de formation de film et article comportant ledit film - Google Patents

Film d'oxyde de tungstène composite et son procédé de production, et matériau de base de formation de film et article comportant ledit film Download PDF

Info

Publication number
WO2019244650A1
WO2019244650A1 PCT/JP2019/022481 JP2019022481W WO2019244650A1 WO 2019244650 A1 WO2019244650 A1 WO 2019244650A1 JP 2019022481 W JP2019022481 W JP 2019022481W WO 2019244650 A1 WO2019244650 A1 WO 2019244650A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
tungsten oxide
composite tungsten
oxide film
present
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/022481
Other languages
English (en)
Japanese (ja)
Inventor
佐藤　啓一
勲雄 安東
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
Original Assignee
Sumitomo Metal Mining Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2019024926A external-priority patent/JP7395826B2/ja
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Priority to CN201980040623.2A priority Critical patent/CN112313359B/zh
Priority to KR1020207037653A priority patent/KR102787402B1/ko
Priority to EP19822399.2A priority patent/EP3812480A4/fr
Priority to CN202311298716.XA priority patent/CN117326592A/zh
Priority to US17/252,936 priority patent/US12006566B2/en
Publication of WO2019244650A1 publication Critical patent/WO2019244650A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • 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
    • C01G41/00—Compounds of tungsten
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G41/00—Compounds of tungsten
    • C01G41/006—Compounds containing tungsten, with or without oxygen or hydrogen, and containing two or more other elements
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/009—Compounds containing iron, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—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
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • 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
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • 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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • C23C14/58—After-treatment
    • 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
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal 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
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of 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
    • 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
    • C03C2218/32—After-treatment

Definitions

  • the present invention relates to a composite tungsten oxide film and a method for producing the same, and further relates to a film-forming substrate having the composite tungsten oxide film and an article utilizing the function of the composite tungsten oxide film.
  • This application is based on Japanese Patent Application No. 2018-117340 filed in Japan on June 20, 2018 and Japanese Patent Application No. 2019-24926 filed on February 14, 2019. Which is incorporated herein by reference.
  • Patent Literature 1 discloses a light-shielding member having a mirror surface state formed by vapor deposition of a metal such as aluminum as a light-shielding member such as a window material.
  • a light-shielding member of a film formed by sputtering silver or the like the appearance becomes a half-mirror shape, so that when used outdoors, the reflection is dazzling and there is a problem in view.
  • a light-shielding member using reflection generally has a feature that it reflects far-infrared rays and also has heat insulation. The reflection of the light from the light-shielding member including far-infrared rays is caused by the action of free electrons.
  • the applicant has proposed an infrared shielding fine particle dispersion having composite tungsten oxide fine particles described in Patent Document 2.
  • the composite tungsten oxide fine particles efficiently absorb sunlight, particularly light in the near infrared region, and have high transparency to visible light.
  • composite tungsten oxide fine particles are dispersed in an appropriate solvent to form a dispersion, and after adding a medium resin to the obtained dispersion, a coating is formed on the substrate surface to form a thin film. And has a very high thermal barrier.
  • the infrared shielding fine particle dispersion has high heat shielding properties due to its excellent light absorption properties, it has little reflection properties and therefore cannot be expected to have much heat insulating properties.
  • Patent Document 3 discloses a composite tungsten oxide film manufactured by applying a solution containing a compound compound of a composite tungsten oxide to a substrate and then heat-treating the solution.
  • a part of the film disclosed herein has a reflectance of about 30% at a wavelength of 1400 nm as shown by broken lines in FIGS. 2 and 3 of the document, and is expected to have some heat insulating properties.
  • Patent Literature 4 discloses a Na x WO 3 film in which a solution containing a compound compound of a composite tungsten oxide is dropped on a rotating substrate, formed into a film by centrifugal force, and then fired in a reducing atmosphere. See FIG. According to No. 1, the film almost reflects light in the infrared region, and seems to have both a shielding property and a heat insulating property.
  • such a composite tungsten oxide film is sometimes optically designed for the purpose of adjusting color tone, preventing reflection, and the like.
  • the film thickness of the laminated film is extremely several nm to several hundred nm. thin. Therefore, it is necessary to control the thickness of the composite tungsten oxide film to be less than 100 nm, but it is difficult to control a region having a thickness of less than 100 nm by a coating method.
  • the surface roughness of the laminated composite tungsten oxide film is required to be smooth, and if the surface roughness of the film formation surface is large, a desired optical design effect cannot be obtained.
  • a physical method such as a vapor deposition method or a sputtering method which is disclosed in the example of Patent Document 1.
  • the thin film formed by the physical film formation method can be a film from which elements other than the target composition are excluded.
  • a dispersant or a medium resin that is not suitable for high-temperature treatment it can be provided to, for example, a tempered glass manufacturing process to be subjected to high-temperature heat treatment.
  • the thickness of a thin film formed by a physical film formation method can be easily controlled even when the thickness is less than 100 nm, and a very smooth surface having an arithmetic average roughness of several nm or less can be formed.
  • the structure is easily possible.
  • Patent Document 5 proposes a window glass for a vehicle and a method for manufacturing the same, and uses a large-size in-line type sputtering apparatus capable of processing a large-area substrate such as a window for a vehicle. If such a manufacturing facility can be used, a high-quality and stable film having a uniform film thickness can be easily obtained, and the productivity is high.
  • the film formation source of the physical film formation method (for example, a target material in the case of the sputtering method) may not be a single compound, but may be, for example, a combination of a single element composition or a mixture of a plurality of compounds. The flexibility of composition selection is extremely wide.
  • Patent Document 6 proposes a composite tungsten oxide film formed by a sputtering method.
  • a composite tungsten oxide film made of tungsten and at least one element selected from the group consisting of group IVa, group IIIa, group VIIb, group VIb and group Vb of the periodic table is formed on a glass substrate.
  • the oxide film of this composition has an infrared transmittance of 40% or more and does not have sufficient heat ray shielding performance, and has a problem that its function cannot be exhibited unless it is formed as a multilayer film with another transparent dielectric film.
  • the heat ray shielding performance of the composite tungsten oxide film formed by the physical film formation method is not yet sufficient.
  • the film formed by the coating method has a high function of absorbing light and shielding heat rays, but cannot expect much heat insulation.
  • there is a problem that the smoothness of the film is poor.
  • the present invention has been made to solve such a situation, and has a function of reflecting and shielding infrared light, that is, a function of shielding heat rays by heat insulation, while maintaining transparency in a visible light region.
  • the present invention provides a composite tungsten film having high film smoothness and a method for producing the same, and further provides a film-forming substrate or an article utilizing these functions.
  • the present inventors have intensively studied a composite tungsten oxide film with respect to the above-mentioned problems, and according to a physical film forming method, have excellent visible light transmittance by optimizing conditions at the time of film formation. While exhibiting the function of reflecting infrared rays to insulate heat while maintaining the above, and in addition, a composite tungsten film having an extremely smooth film was obtained.
  • one embodiment of the present invention provides a compound represented by the general formula M x W y O z (where M is one or more elements selected from alkali metals, alkaline earth metals, Fe, In, Tl, and Sn; (W is tungsten, O is oxygen) is a composite tungsten oxide film having a composition represented by the following formula: 0.001 ⁇ x / y ⁇ 1, 2.2 ⁇ z / y ⁇ 3.0 It contains substantially no organic components, has a transmittance of 50% or more at a wavelength of 550 nm, a transmittance of 30% or less at a wavelength of 1400 nm, and a reflectance of 35% or more at a wavelength of 1400 nm.
  • a composite tungsten oxide film having a function of reflecting and shielding infrared light, that is, a function of shielding heat rays by heat insulation, while maintaining transparency in a visible light region.
  • the surface roughness Sa may be 20 nm or less.
  • the sheet resistance may be less than 10 5 ⁇ / ⁇ .
  • the composite tungsten oxide film may be derived from sputtering.
  • M is at least one element selected from Cs, Rb, K, Tl, In, Ba, Li, Na, Ca, Sr, Fe, and Sn. Is also good.
  • the composite tungsten oxide film may have a hexagonal crystal structure.
  • the hexagonal phase Since the hexagonal phase has a greater reflection in the infrared region, it can be efficiently reflected.
  • one embodiment of the present invention provides an intensity ratio of the diffraction intensity I (002) of the hexagonal (002) plane to the diffraction intensity I (200) of the hexagonal (200) plane by X-ray diffraction using CuK ⁇ radiation.
  • Is I (002) / I (200), I (002) / I (200) is 0.30 or more and 0.50 or less, and the a-axis of hexagonal crystal by X-ray diffraction using CuK ⁇ ray is The ratio c / a to the c-axis may be 1.018 to 1.029.
  • a composite tungsten oxide film that satisfies the above requirements by X-ray diffraction analysis is a composite tungsten oxide film that functions to reflect infrared rays and to insulate heat while maintaining excellent visible light transmittance.
  • one embodiment of the present invention provides a compound represented by the general formula M x W y O z (where M is one or more elements selected from an alkali metal, an alkaline earth metal, Fe, In, Tl, and Sn; (W is tungsten, O is oxygen) is a composite tungsten oxide film having a composition represented by the following formula: 0.001 ⁇ x / y ⁇ 1, 2.2 ⁇ z / y ⁇ 3.0
  • the composite tungsten oxide film has a hexagonal crystal structure, and has a diffraction intensity I (002) of a hexagonal (002) plane and a diffraction intensity of a hexagonal (200) plane by X-ray diffraction using CuK ⁇ radiation.
  • I (200) When the intensity ratio of I (200) is I (002) / I (200), I (002) / I (200) is 0.30 or more and 0.50 or less, and X-ray diffraction using CuK ⁇ ray
  • the ratio c / a between the a-axis and the c-axis of the hexagonal crystal is 1.018 to 1.029.
  • a composite tungsten oxide film that satisfies the above requirements by X-ray diffraction analysis is a composite tungsten oxide film that functions to reflect infrared rays and to insulate heat while maintaining excellent visible light transmittance.
  • M may be one or more elements selected from Cs, Rb, K, Tl, and Ba.
  • the composite tungsten oxide film can have a thickness greater than 20 nm.
  • ⁇ ⁇ Another embodiment of the present invention is a film-forming substrate having the above-described composite tungsten oxide film formed on at least one surface of a substrate on which a film is to be formed.
  • the substrate on which the film is to be formed may have a softening point or a heat distortion temperature of 400 ° C. or higher.
  • a film-forming substrate having more excellent functions can be obtained by heat treatment after film formation.
  • the substrate on which the film is to be formed can be glass.
  • glass By using glass as the base material for film formation, it is used in glass windows for vehicle windows and architectural windows, glass fibers, glass for solar power generation, glass for displays, glass for lenses and mirrors, semiconductors and MEMS, and the like.
  • Equipment using glass used in a wide range of fields, such as glass substrates, can be provided with an infrared shielding function.
  • Another aspect of the present invention is an article having one or more of the composite tungsten oxide film and / or the film-forming substrate described above.
  • another aspect of the present invention is a method for producing a composite tungsten oxide film, comprising a film forming step of forming a film by a physical film forming method, and a heat treatment step of heat treating the film.
  • a film is formed in an inert gas, and in the heat treatment process, heat treatment is performed at 400 to 700 ° C. in an inert gas containing an inert gas or a reducing gas.
  • a composite tungsten oxide film as an infrared reflecting film having transparency in a visible light region and having reflectivity in an infrared light region. Further, according to the present invention, such a composite tungsten oxide film is widely used industrially, is relatively harmless at the time of film formation, furthermore, the raw material used is excellent in long-term storage, and is useful for storage of dangerous substances and transportation. It can be provided in an unrestricted physical manufacturing method.
  • FIG. 1 is a diagram showing the difference in optical characteristics (transmittance) between the composite tungsten oxide film of the present invention and the infrared shielding material fine particle dispersion described in Patent Document 2.
  • FIG. 2 is a view showing a difference in optical characteristics (reflectance) between the composite tungsten oxide film of the present invention and the infrared ray shielding material fine particle dispersion described in Patent Document 2.
  • FIG. 3 is a process diagram schematically showing a process in a method for manufacturing a composite tungsten oxide film according to one embodiment of the present invention.
  • Composite Tungsten Oxide Film> A composite tungsten oxide film according to one embodiment of the present invention will be described.
  • Composite tungsten oxide film according to an embodiment of the present invention have the general formula M x W y O z (however, M is selected alkali metal, alkaline earth metal, Fe, an In, Tl, from among Sn One or more elements, W is tungsten, and O is oxygen).
  • the film has a composition represented by the following formula: x: y is 0.001 ⁇ x / y ⁇ 1, z: y is The configuration is in the range of 2.2 ⁇ z / y ⁇ 3.0.
  • composition range Details of the composition range are shown in Patent Document 2 by the present applicant, and the main component of the composite tungsten oxide having this composition range is a film having high transparency and infrared light absorption. It is necessary to make it.
  • the basic optical characteristics of the composite tungsten oxide film originate from the theoretically calculated atomic arrangement of the element M, tungsten W and oxygen O.
  • one embodiment of the present invention is a composite tungsten oxide film having characteristics different from those of the infrared shield described in Patent Literature 2, and will be described in detail below while appropriately comparing with the invention according to Patent Literature 2. I do.
  • the element M of the composite tungsten oxide film according to one embodiment of the present invention is at least one element selected from alkali metals, alkaline earth metals, Fe, In, Tl, and Sn, and more preferably. , Cs, Rb, K, Tl, In, Ba, Li, Na, Ca, Sr, Fe, and Sn. Although this is a range narrower than the constituent elements described in Patent Document 2, this is only an element whose effect was confirmed according to the Examples, and is not included in the present invention. However, it may have a similar function.
  • the element M of the composite tungsten oxide film according to one embodiment of the present invention is more preferably one or more elements selected from Cs, Rb, K, Tl, and Ba.
  • the composite tungsten film can have a crystal structure including a hexagonal crystal as described later.
  • the element M may have a crystal structure other than hexagonal depending on the x / y ratio. For example, K becomes tetragonal when the ratio of x / y is 0.5 or more. Since the structure containing the hexagonal phase has higher reflection in the infrared region, it can reflect efficiently.
  • Composite tungsten oxide film according to an embodiment of the present invention are the compounds of formula M x W y O z, the atomic ratio x / y of the element M and W (tungsten) is at 0.001 ⁇ x / y ⁇ 1 Yes, the atomic ratio z / y between O (oxygen) and W (tungsten) satisfies 2.2 ⁇ z / y ⁇ 3.0.
  • x / y is less than 0.001, a sufficient amount of free electrons is not generated, and an infrared shielding effect cannot be obtained. If x / y exceeds 1, an impurity phase is formed in the composite tungsten oxide film.
  • the composite tungsten oxide film according to one embodiment of the present invention does not substantially include an organic component.
  • a dispersant or a medium resin as disclosed in Patent Documents 2 and 3 is used.
  • surfactants or solvents there is no need to use surfactants or solvents.
  • substantially not containing an organic component means that it does not contain an organic component that is intentionally added, such as a polymer dispersant, in the process of producing the film.
  • Patent Document 3 describes a method for producing a transparent conductive film using a composite tungsten oxide in paragraph 0060.
  • the transparent conductive film disclosed in Patent Document 3 is coated with a solution containing a composite tungsten compound as a starting tungsten raw material solution on a substrate, and then coated with an inert gas, an inert gas and a reducing gas, or an atmosphere of a reducing gas. It has been shown that it can be obtained by heat treatment in a medium.
  • a surfactant having a polysiloxane skeleton containing an organic component is added to an aqueous solution of ammonium metatungstate and an aqueous solution of chloride of element M to form a solution.
  • a film composed of a fine particle dispersion containing composite tungsten oxide fine particles of Patent Document 2 absorbs light, particularly in a near infrared region. It has been shown that the absorption in the above serves as an excellent heat ray shielding film.
  • FIGS. 1 and 2 are diagrams showing a difference in optical characteristics between the composite tungsten oxide film of the present invention and the infrared ray shielding material fine particle dispersion described in Patent Document 2.
  • FIG. FIG. 4 is a diagram showing the reflectance.
  • the composite tungsten oxide film according to one embodiment of the present invention has optical characteristics different from those of the film made of a fine particle dispersion (fine particle dispersed film) according to Patent Document 2.
  • the composite tungsten oxide film according to the present invention largely reflects light in the infrared region of 1400 nm or less. The reason for this is presumed to be the difference between the fine particle dispersed film and the continuous film, as described later, but the details have not yet been determined.
  • the composite tungsten oxide film according to one embodiment of the present invention has a transmittance of 50% or more at a wavelength of 550 nm, a transmittance of 30% or less at a wavelength of 1400 nm, and a reflectance of 35% or more at a wavelength of 1400 nm.
  • a rear window is preferably black or dark gray from the viewpoint of privacy protection, and a pigment or the like may be intentionally used together with the heat ray shielding material.
  • the transparency index of the present invention indicates the film properties in a state where the above-mentioned intentional pigments and the like are not included. If the index of transparency is lower than the above-mentioned value, lighting becomes poor, which leads to, for example, darkening of an indoor space or making it difficult to see an external scenery.
  • the transmittance at a wavelength of 1400 nm and the reflectance at a wavelength of 1400 nm which are used as indices of the light shielding performance and the reflection performance, may be configured not to satisfy the above-mentioned values.
  • the reflection of the present invention since the reflection of the present invention is reflection by free electrons, it reflects light below the plasma frequency. In other words, light having a wavelength equal to or greater than the wavelength corresponding to the plasma frequency is reflected. That is, when the reflectance at a wavelength of 1400 nm is low, the reflectance of far-infrared rays having a longer wavelength is also low, the heat insulation property is low, and the effect of confining heat such as indoor heating is low. In order to obtain effective heat insulating properties, the reflectance at a wavelength of 1400 nm needs to be 35% or more.
  • the surface roughness Sa of the composite tungsten oxide film according to one embodiment of the present invention is 20 nm or less.
  • optical thin film design when laminating films, the reflection of a specific wavelength is strengthened or weakened by using interference to obtain a steep transmission profile (adjustment of the color of the film) or reflection in the visible light region. Can be used for prevention.
  • the influence of the surface roughness is that the above optical thin film design (in the case of laminating the films) has a small surface roughness, so that a stable laminated film with little disturbance of the optical path length is possible.
  • the composite tungsten oxide film according to one embodiment of the present invention is a film formed by a physical method obtained by film formation by a sputtering method or the like as described later, the surface roughness Sa of the film should be 20 nm or less. Can be. If it is 20 nm or less, there is a low possibility that a problem in designing the optical thin film will occur. When the surface roughness exceeds 20 nm, a uniform lamination state is not obtained, and it is difficult to obtain the effect of optical thin film design (lamination).
  • the composite tungsten oxide film according to one embodiment of the present invention is preferably formed with a thickness exceeding 20 nm.
  • the composite tungsten oxide film according to one embodiment of the present invention is a film formed by a physical method obtained by film formation by a sputtering method or the like, as described later, for example, heat-treated after applying a solution described in Patent Document 3.
  • components such as a solvent and a resin, which are indispensable for the film formation, are formed by volatilization, so that a residual stress is generated in the film.
  • defects such as residual volatile components and voids may be present.
  • the composite tungsten oxide film according to one embodiment of the present invention is formed without containing a volatile component, the residual stress of the film accompanying the film formation can be reduced, and the residual volatile component and voids can be reduced. No defects occur. For this reason, a film without cracks or peeling can be formed.
  • the film thickness is 20 nm or less, sufficient reflection performance in the infrared region cannot be obtained, and the infrared transmittance at 1400 nm exceeds 30%.
  • the thickness exceeds the above film thickness.
  • the transmittance in the visible light region at a wavelength of 550 nm is less than 50%, so that the visible light transmittance may be deteriorated, or the film may be peeled off due to the residual stress during film formation. .
  • the transmittance of the film can be measured using a spectrophotometer.
  • the composite tungsten oxide film according to one embodiment of the present invention has a sheet resistance of less than 1.0 ⁇ 10 5 ⁇ / ⁇ (read as ohm-per-square), more preferably 1.0 ⁇ 10 3 ⁇ / ⁇ . Is less than.
  • the sheet resistance can be adjusted by film formation conditions and heat treatment conditions described later. The sheet resistance can be measured using, for example, a resistivity meter.
  • the composite tungsten oxide film according to one embodiment of the present invention is usually formed as a continuous film, but has a form in which reflection is controlled by patterning, and a form in which irregularities are provided to provide a lens function.
  • the shape of the film, the shape of the unevenness, and the like may be any shape as long as it has the features of the present invention.
  • the composite tungsten oxide according to one embodiment of the present invention preferably has a hexagonal crystal structure.
  • the inclusion of the hexagonal crystal structure can be known by analyzing the film by X-ray diffraction.
  • the composite tungsten oxide is known to have a crystal structure such as hexagonal, cubic, tetragonal, and orthorhombic, and an amorphous structure, but the composite tungsten oxide film according to one embodiment of the present invention has a hexagonal crystal structure.
  • a crystal structure other than hexagonal such as cubic, tetragonal, orthorhombic, or an amorphous structure.
  • the ratio c / a of the a-axis length to the c-axis length of the hexagonal crystal obtained by X-ray diffraction using CuK ⁇ ray is 1.018 to 1.029. It is preferable that According to the ICDD reference code 01-081-1244 of the crystal structure database, c / a is 1.028. It is considered that when the number of atoms becomes excessive or insufficient compared with the standard hexagonal structure, the a-axis length and the c-axis length change.
  • the diffraction intensity I (002) of the hexagonal (002) plane and the diffraction intensity of the hexagonal (200) plane by X-ray diffraction using CuK ⁇ rays When the intensity ratio of I (200) is I (002) / I (200), it is preferable that I (002) / I (200) be 0.30 or more and 0.50 or less. Since the relative intensity of the (002) plane to the (200) plane is described as 26.2% in the above-described ICDD reference code 01-081-1244, the standard intensity ratio I (002) / I (200) Is 0.26.
  • the intensity ratio of the composite tungsten oxide film produced by the coating and firing method is this standard value, but the intensity ratio of the present invention is 0.30 or more and 0.50 or less. Since the intensity ratio is larger than the standard intensity ratio, it is considered that the growth of the hexagonal a and b planes is suppressed and the c-plane orientation tends to occur. If the above-mentioned c / a deviates from 1.018 to 1.029 and the intensity ratio I (002) / I (200) deviates from 0.30 or more to 0.50 or less, the heat ray reflection function decreases.
  • the crystal structure is trigonal.
  • the ratio c / a between the a-axis length and the c-axis length of the hexagonal crystal is the a-axis length and the c-axis length of the trigonal crystal. It is calculated by the ratio 2c / a.
  • the composite tungsten oxide film has characteristics different from those of the composite tungsten oxide films described in Patent Literature 2 and Patent Literature 3, and exhibits transparency in a visible light region.
  • a composite tungsten oxide film as an infrared reflecting film having reflectivity in the infrared light region.
  • FIG. 3 is a process diagram schematically showing a method for manufacturing a composite tungsten oxide film according to one embodiment of the present invention.
  • One embodiment of the present invention is a method for producing a composite tungsten oxide film containing the element M, tungsten W, and oxygen O as main components, and a film forming step S1 for forming a film using a physical film forming method. And a heat treatment step S2 for heat treating the film.
  • each step will be described in detail.
  • a film is formed using a physical film forming method.
  • the physical film forming method of the composite tungsten oxide film according to one embodiment of the present invention include a vacuum deposition method, a sputtering method, an ion plating method, and an ion beam method.
  • the sputtering method has a large energy of a film-forming particle, a strong adhesive force, a dense film and a strong film quality, a stable film-forming process, and high-precision control of the film quality and the film thickness.
  • the sputtering method has the advantages that films of high melting point metals, alloys and compounds can be formed, oxides and nitrides can be formed by introducing a reactive gas, and composition adjustment is relatively easy. It is preferable because it is widely used in a wide range of fields, such as electronic devices such as liquid crystal display elements and hard disks, and general-purpose products such as wind films and mirrors, and has many manufacturing devices.
  • the sputtering target for forming the composite tungsten oxide film represented by the general formula M x W y O z is, for example, a sputtering target including the element M and the element W, and a sputtering target including the element M and the compound of the element W and the element O.
  • a sputtering target formed in advance as a compound phase is used. If the sputtering target is formed as a compound phase in advance, the dependence of the film composition on the difference in vapor pressure of each element can be reduced, and stable film formation can be achieved.
  • the sputtering target may be used in the form of, for example, a compact formed by compacting powder composed of particles of the sputtering target composition or a sintered body formed by sintering the sputtering target composition.
  • the sputtering target since the sputtering target is formed of a compact or a sintered body as described above, it does not substantially include an organic component, and a film formed using the target does not substantially include an organic component. .
  • substantially not contained means that it does not contain intentionally added components such as a polymer dispersant.
  • the sputtering target is a conductor having a specific resistance of, for example, 1 ⁇ ⁇ cm or less, a DC sputtering apparatus with high productivity can be used. Further, when the sputtering target is a sintered body having a relative density of 70% or more, for example, cracks due to vibration during transportation are reduced, and it is not necessary to take extreme care in handling such as mounting to an apparatus. It is a form suitable for general production.
  • the atmosphere in the film forming step is variously selected, but preferably in an inert gas atmosphere.
  • the inert gas for example, a rare gas such as a helium gas or an argon gas, a nitrogen gas, or the like may be used.
  • a nitrogen gas a nitride may be formed depending on the selected element M.
  • Argon gas which is used and easily available is more preferable.
  • the purity of the gas used is preferably 99% or more, and the mixing of oxidizing gas such as oxygen is preferably less than 1%.
  • a composite tungsten oxide film having a high reflectance can be obtained by forming a film in an inert atmosphere and performing a heat treatment under the conditions described later.
  • the ratio of the oxidizing gas exceeds 1%, the reflectance of the composite tungsten oxide film after the heat treatment decreases.
  • the film after film formation is usually amorphous, a diffraction peak based on crystals may appear when subjected to X-ray diffraction analysis.
  • a heat treatment step S2 the film obtained in the film formation step S1 is heat-treated.
  • the heat treatment step S2 is performed in an inert or reducing atmosphere.
  • the heat treatment temperature is preferably 400 to 700 ° C. If the heat treatment temperature is lower than 400 ° C., the film remains amorphous and does not crystallize, or even when crystallized, the hexagonal diffraction peak in X-ray diffraction is extremely weak, and the heat shielding properties in the infrared region are low. Further, even if the heat treatment temperature is higher than 700 ° C., the characteristics of the film of the present invention can be obtained. However, practically, the film reacts with the substrate, the film peels off from the substrate, and the surface roughness increases. Will occur.
  • the heat treatment time may be sufficient to complete the crystallization of the composite tungsten oxide, and depends on the balance between the heat conduction of the base material and the productivity. It may be adjusted appropriately in about a minute.
  • the heat treatment is performed in an inert atmosphere or a reducing atmosphere.
  • the inert atmosphere include nitrogen and argon
  • examples of the reducing atmosphere include a mixed gas of nitrogen and hydrogen and a mixed gas of argon and hydrogen.
  • a composite tungsten oxide film having the above-described characteristics is widely used industrially and is relatively harmless during film formation.
  • the raw material can be provided by a physical production method that is excellent in long-term storage of the raw material and has no restrictions during transportation.
  • a film-forming substrate according to one embodiment of the present invention is one in which the above-described composite tungsten oxide film is formed on at least one surface of a film-forming substrate.
  • the substrate on which the film is to be formed is not particularly limited as long as the composite tungsten oxide film according to one embodiment of the present invention can be formed.
  • the substrate on which the film is to be formed is preferably a substrate having a softening point or heat deformation temperature of 400 ° C. or higher.
  • a substrate having a softening point or a heat deformation temperature of less than 400 ° C. is used, problems such as peeling of the film from the substrate on which the film is to be formed and cracking of the film occur during the heat treatment.
  • the thermal expansion coefficient of the film-forming substrate is closer to the thermal expansion coefficient of the film.
  • a base material that melts at 400 ° C. or lower may be used.
  • Examples of the base material having a softening point or heat distortion temperature of 400 ° C. or higher include glass, ceramics, and single crystals.
  • the substrate on which the film is to be formed is not necessarily required to be transparent. However, when the composite tungsten oxide film of the present invention is used together with the substrate, a transparent substrate is required.
  • Examples of the transparent substrate include glass, transparent ceramics such as YAG and Y 2 O 3, and single crystals such as sapphire. Above all, it is preferable to use a glass having a softening point of 400 ° C. or higher as a substrate on which a film is to be formed, from the viewpoints of easy availability, low cost, weather resistance, chemical resistance and the like.
  • the substrate is not limited to a flat surface but may have a curved surface or an uneven surface without deteriorating the features of the present invention.
  • the film-forming substrate has transparency in the visible light region, and has an infrared reflective film having reflectivity in the infrared light region. be able to.
  • An article according to one embodiment of the present invention has one or more of the above-described composite tungsten oxide film and / or film-forming substrate.
  • the article according to one embodiment of the present invention may be any article as long as the composite tungsten oxide film has a function of reflecting light.
  • the composite tungsten oxide film and / or the film-forming substrate of the present invention is used together with, for example, a film or a particle having another function, the composite tungsten oxide film and / or the film-forming substrate is included in an article utilizing the function described in the present invention. .
  • the composite tungsten oxide film of the present invention is an infrared reflective film having reflectivity in an infrared light region.
  • the article having a function of reflecting and shielding light include heat-insulating glass.
  • the heat insulating and insulating glass has a feature of shielding and insulating heat while being transparent, and reduces a rise in indoor temperature and a rise in vehicle temperature due to sunlight in summer. In addition, the heat of the heating in winter can be reflected and kept indoors.
  • a composite tungsten oxide film having transparency in the visible light region and having reflectivity in the infrared light region, and the formation of such a film.
  • the article can be provided with a substrate.
  • Example 1 In Example 1, a cesium tungsten oxide powder having a Cs / W atomic ratio of 0.33 (YM-01 manufactured by Sumitomo Metal Mining Co., Ltd.) was charged into a hot press apparatus, and a vacuum atmosphere, a temperature of 950 ° C., and a pressing pressure of 250 kgf / It was sintered under the condition of cm 2 to produce a cesium tungsten oxide sintered body. As a result of chemical analysis of the sintered body composition, Cs / W was 0.33.
  • This oxide sintered body was ground by machining to a diameter of 153 mm and a thickness of 5 mm, and joined to a stainless steel backing plate using a metal indium brazing material, to produce a cesium tungsten oxide sputtering target.
  • this sputtering target was attached to a DC sputtering apparatus (SBH2306 manufactured by ULVAC, Inc.), the ultimate vacuum was 5 ⁇ 10 ⁇ 3 Pa or less, the atmosphere during film formation was an argon gas atmosphere, and the gas pressure was 0.6 Pa.
  • a cesium tungsten oxide film was formed on a glass substrate (EXG manufactured by Corning, thickness 0.7 mm). The film thickness after film formation was 100 nm (film formation step S1).
  • the structure of the film after film formation was examined using an X-ray diffractometer (X'Pert-PRO (manufactured by PANalytical).)
  • the film after film formation was an amorphous film having no diffraction peak derived from the crystal structure. It was a structure.
  • the crystal structure, the X-ray diffraction intensity ratio, and the ratio c / a between the a-axis and the c-axis were examined using an X-ray diffractometer (X'Pert-PRO, manufactured by PANalytical).
  • the transmittance and the reflectance were measured using a spectrophotometer (manufactured by Hitachi, model number V-670).
  • the crystal structure of the film after heat treatment was a structure containing hexagonal crystals.
  • the X-ray diffraction intensity ratio was 0.401, and the ratio c / a between the a-axis and the c-axis was 1.028.
  • the transmittance at a wavelength of 550 nm was 71.3%, the transmittance at a wavelength of 1400 nm was 11.3%, and the reflectance at a wavelength of 1400 nm was 44.5%.
  • the sheet resistance of the film after the heat treatment was 3.0 ⁇ 10 3 ⁇ / ⁇ as a result of measurement using a resistivity meter (manufactured by Mitsubishi Chemical Corporation, Loresta), and the film after the heat treatment had high conductivity and low resistance. (The resistance was measured using Mitsubishi Chemical Loresta or Hiresta according to the resistivity).
  • Examples 2 to 17 and Comparative Examples 1 to 13 Using the same apparatus as in Example 1, the composite tungsten oxide film was changed by changing the element M, the composition ratio, the film thickness, the film formation atmosphere, the heat treatment atmosphere, the temperature, and the time as described in Tables 1 and 2. Was prepared and the characteristics of the film were examined. Tables 1 and 2 show the results of the examples together with the results of the comparative examples.
  • the transmittance at a wavelength of 550 nm is 50% or more
  • the transmittance at a wavelength of 1400 nm is 30% or less
  • the wavelength is It was confirmed that the film had a characteristic that the reflectance at 1400 nm was 35% or more.
  • the sheet resistance was less than 1.0 ⁇ 10 5 ⁇ / ⁇
  • the surface roughness Sa was 20 nm or less.
  • Comparative Examples 1 to 13 which are not included in the method for manufacturing a composite tungsten oxide film according to the present invention, the optical characteristics do not satisfy the above requirements, and the sheet resistance is 1.0 ⁇ 10 5 ⁇ / ⁇ . That's all.
  • the composite tungsten oxide film according to the present invention has high transparency in the visible light region, excellent light reflectivity in the infrared region, and high film smoothness, it is used for a wide range of applications utilizing the function of reflecting light. Have the potential to do so.

Landscapes

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

Abstract

La présente invention concerne : un film de tungstène composite qui a la fonction de réfléchir et bloquer la lumière infrarouge, c'est-à-dire, une fonction de blocage de rayonnement thermique obtenue par isolation thermique, et présente encore une transparence dans la région de lumière visible, et qui a un lissé de film élevé ; un procédé de production du film de tungstène composite ; et un matériau de base de formation de film ou un article utilisant ces fonctions. Ce film composite d'oxyde de tungstène comprend, en tant que composant principal, une composition représentée par la formule générale MxWyOz (où M représente un ou plusieurs éléments choisis parmi des métaux alcalins, des métaux alcalino-terreux, Fe, In, Tl et Sn, W représente le tungstène et O représente l'oxygène), où 0,001 ≤ x/y ≤ 1 et 2,2 ≤ z/y ≤ 3,0 et le film d'oxyde de tungstène composite ne contient pratiquement aucun composant de matière organique et présente une transmittance de 50 % ou plus à une longueur d'onde de 550 nm, une transmittance de 30 % ou moins à une longueur d'onde de 1400 nm et un facteur de réflexion de 35 % ou plus à une longueur d'onde de 1400 nm.
PCT/JP2019/022481 2018-06-20 2019-06-06 Film d'oxyde de tungstène composite et son procédé de production, et matériau de base de formation de film et article comportant ledit film Ceased WO2019244650A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
CN201980040623.2A CN112313359B (zh) 2018-06-20 2019-06-06 复合钨氧化物膜及其制造方法以及具有该膜的膜形成基材和物品
KR1020207037653A KR102787402B1 (ko) 2018-06-20 2019-06-06 복합 텅스텐 산화물막 및 그 제조 방법, 및 그 막을 갖는 막형성 기재 및 물품
EP19822399.2A EP3812480A4 (fr) 2018-06-20 2019-06-06 Film d'oxyde de tungstène composite et son procédé de production, et matériau de base de formation de film et article comportant ledit film
CN202311298716.XA CN117326592A (zh) 2018-06-20 2019-06-06 复合钨氧化物膜及其制造方法以及具有该膜的膜形成基材和物品
US17/252,936 US12006566B2 (en) 2018-06-20 2019-06-06 Composite tungsten oxide film and method for producing same, and film-deposited base material and article each provided with said film

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2018117340 2018-06-20
JP2018-117340 2018-06-20
JP2019024926A JP7395826B2 (ja) 2018-06-20 2019-02-14 複合タングステン酸化物膜及びその製造方法、並びに該膜を有する膜形成基材及び物品
JP2019-024926 2019-02-14

Publications (1)

Publication Number Publication Date
WO2019244650A1 true WO2019244650A1 (fr) 2019-12-26

Family

ID=68983958

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2019/022481 Ceased WO2019244650A1 (fr) 2018-06-20 2019-06-06 Film d'oxyde de tungstène composite et son procédé de production, et matériau de base de formation de film et article comportant ledit film

Country Status (3)

Country Link
JP (1) JP7662000B2 (fr)
CN (1) CN117326592A (fr)
WO (1) WO2019244650A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095983A1 (fr) * 2022-10-31 2024-05-10 住友金属鉱山株式会社 Film d'alignement de cristaux, structure et procédé de fabrication de film d'alignement de cristaux
WO2025041569A1 (fr) * 2023-08-18 2025-02-27 住友金属鉱山株式会社 Film de verre avec film de blocage d'infrarouge proche, stratifié de film de blocage d'infrarouge proche, procédé de fabrication de film de verre avec film de blocage d'infrarouge proche, et procédé de fabrication de stratifié de film de blocage d'infrarouge proche

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505108A (en) 1964-06-26 1970-04-07 Corning Glass Works Tungsten bronze films
JPH05113085A (ja) 1991-10-21 1993-05-07 Dainippon Printing Co Ltd 遮光フイルム
JPH0812378A (ja) 1994-06-30 1996-01-16 Nissan Motor Co Ltd 熱線遮断ガラス及びその製造方法
US6040939A (en) * 1998-06-16 2000-03-21 Turkiye Sise Ve Cam Fabrikalari A.S. Anti-solar and low emissivity functioning multi-layer coatings on transparent substrates
JP2002020142A (ja) 2000-06-29 2002-01-23 Nippon Sheet Glass Co Ltd 車両用窓ガラスおよびその製造方法
JP2006096656A (ja) 2004-08-31 2006-04-13 Sumitomo Metal Mining Co Ltd 透明導電膜およびその製造方法、透明導電物品、並びに赤外線遮蔽物品
JP2006347807A (ja) * 2005-06-15 2006-12-28 Sumitomo Metal Mining Co Ltd 酸化物焼結体、酸化物透明導電膜、およびこれらの製造方法
JP4096205B2 (ja) 2003-10-20 2008-06-04 住友金属鉱山株式会社 赤外線遮蔽材料微粒子分散体、赤外線遮蔽体、及び赤外線遮蔽材料微粒子の製造方法、並びに赤外線遮蔽材料微粒子
JP2010180449A (ja) * 2009-02-04 2010-08-19 Sumitomo Metal Mining Co Ltd 複合タングステン酸化物ターゲット材とその製造方法
KR20150088551A (ko) * 2014-01-24 2015-08-03 (주)석경에이티 알칼리금속산화물이 도핑된 텅스텐산화물 복합체, 투명전도성 조성물, 코팅필름 및 이를 포함하는 광학소자
WO2017159790A1 (fr) * 2016-03-16 2017-09-21 住友金属鉱山株式会社 Microparticules de matériau bloquant les rayons infrarouges proches ainsi que procédé de fabrication de celles-ci, et dispersion liquide de microparticules de matériau bloquant les rayons infrarouges proches
JP2018117340A (ja) 2016-11-28 2018-07-26 エスエスホー コミュニケーションズ セキュリティ オサケユイチアユルキネン コンピュータネットワーク内のユーザの認証
JP2019024926A (ja) 2017-07-28 2019-02-21 キヤノン株式会社 放射線撮像装置および放射線撮像方法
WO2019058737A1 (fr) * 2017-09-22 2019-03-28 住友金属鉱山株式会社 Film d'oxyde de césium-tungstène et son procédé de fabrication

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101023498B (zh) * 2004-08-31 2012-02-29 住友金属矿山株式会社 导电性粒子、可见光透过型粒子分散导电体及其制造方法、透明导电薄膜及其制造方法、使用它的透明导电物品、红外线屏蔽物品
JP5585046B2 (ja) * 2009-10-27 2014-09-10 東ソー株式会社 複合酸化物焼結体、ターゲット及び酸化物透明導電膜
CN110510674B (zh) * 2013-03-15 2022-09-09 株式会社东芝 电池用电极材料及电池用基板、蓄电池、色素增感太阳能电池、电容器、Li离子二次电池

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3505108A (en) 1964-06-26 1970-04-07 Corning Glass Works Tungsten bronze films
JPH05113085A (ja) 1991-10-21 1993-05-07 Dainippon Printing Co Ltd 遮光フイルム
JPH0812378A (ja) 1994-06-30 1996-01-16 Nissan Motor Co Ltd 熱線遮断ガラス及びその製造方法
US6040939A (en) * 1998-06-16 2000-03-21 Turkiye Sise Ve Cam Fabrikalari A.S. Anti-solar and low emissivity functioning multi-layer coatings on transparent substrates
JP2002020142A (ja) 2000-06-29 2002-01-23 Nippon Sheet Glass Co Ltd 車両用窓ガラスおよびその製造方法
JP4096205B2 (ja) 2003-10-20 2008-06-04 住友金属鉱山株式会社 赤外線遮蔽材料微粒子分散体、赤外線遮蔽体、及び赤外線遮蔽材料微粒子の製造方法、並びに赤外線遮蔽材料微粒子
JP2006096656A (ja) 2004-08-31 2006-04-13 Sumitomo Metal Mining Co Ltd 透明導電膜およびその製造方法、透明導電物品、並びに赤外線遮蔽物品
JP2006347807A (ja) * 2005-06-15 2006-12-28 Sumitomo Metal Mining Co Ltd 酸化物焼結体、酸化物透明導電膜、およびこれらの製造方法
JP2010180449A (ja) * 2009-02-04 2010-08-19 Sumitomo Metal Mining Co Ltd 複合タングステン酸化物ターゲット材とその製造方法
KR20150088551A (ko) * 2014-01-24 2015-08-03 (주)석경에이티 알칼리금속산화물이 도핑된 텅스텐산화물 복합체, 투명전도성 조성물, 코팅필름 및 이를 포함하는 광학소자
WO2017159790A1 (fr) * 2016-03-16 2017-09-21 住友金属鉱山株式会社 Microparticules de matériau bloquant les rayons infrarouges proches ainsi que procédé de fabrication de celles-ci, et dispersion liquide de microparticules de matériau bloquant les rayons infrarouges proches
JP2018117340A (ja) 2016-11-28 2018-07-26 エスエスホー コミュニケーションズ セキュリティ オサケユイチアユルキネン コンピュータネットワーク内のユーザの認証
JP2019024926A (ja) 2017-07-28 2019-02-21 キヤノン株式会社 放射線撮像装置および放射線撮像方法
WO2019058737A1 (fr) * 2017-09-22 2019-03-28 住友金属鉱山株式会社 Film d'oxyde de césium-tungstène et son procédé de fabrication

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024095983A1 (fr) * 2022-10-31 2024-05-10 住友金属鉱山株式会社 Film d'alignement de cristaux, structure et procédé de fabrication de film d'alignement de cristaux
WO2025041569A1 (fr) * 2023-08-18 2025-02-27 住友金属鉱山株式会社 Film de verre avec film de blocage d'infrarouge proche, stratifié de film de blocage d'infrarouge proche, procédé de fabrication de film de verre avec film de blocage d'infrarouge proche, et procédé de fabrication de stratifié de film de blocage d'infrarouge proche

Also Published As

Publication number Publication date
JP7662000B2 (ja) 2025-04-15
CN117326592A (zh) 2024-01-02
JP2023155281A (ja) 2023-10-20

Similar Documents

Publication Publication Date Title
JP6540859B1 (ja) 複合タングステン酸化物膜及びその製造方法、並びに該膜を有する膜形成基材及び物品
JP7081183B2 (ja) セシウムタングステン酸化物膜とその製造方法
KR102787402B1 (ko) 복합 텅스텐 산화물막 및 그 제조 방법, 및 그 막을 갖는 막형성 기재 및 물품
Fan et al. Thermal control properties of radiative cooling foil based on transparent fluorinated polyimide
WO2019058737A1 (fr) Film d'oxyde de césium-tungstène et son procédé de fabrication
JP7662000B2 (ja) 複合タングステン酸化物膜及び該膜を有する膜形成基材、並びに物品
JP2000067657A (ja) 赤外線透過に優れた透明導電膜及びその製造方法
JPWO2000051139A1 (ja) 透明導電積層体、その製造方法及びそれを用いた表示素子
Dang et al. Preparation and optical properties of W-doped VO2/AZO bilayer composite film
JP2003034828A (ja) 電磁波シールド用のＡｇ合金膜、電磁波シールド用Ａｇ合金膜形成体及び電磁波シールド用Ａｇ合金スパッタリングターゲット
CN115747740A (zh) 基于Ge2Sb2Te5的红外隐身与辐射散热薄膜及其制备方法
JP7004597B2 (ja) 放射冷却装置
JPH07333423A (ja) 選択透過膜
CN117062937A (zh) 透明导电膜、透明导电膜的制造方法、透明导电构件、电子显示器设备和太阳能电池
JP7737696B2 (ja) 調光ガラス及びその製造方法、並びに、前記調光ガラスを構成する多孔質モスアイ構造の二酸化バナジウム薄膜
Carrasco Hernández et al. Effect of silver on structural, optical, and electrical properties of ZnO: Al/Ag/ZnO: Al thin films.
Hossain et al. Production of angular-selective films by interdiffusion for novel spectral responses
Niaz et al. FABRICATION AND CHARACTERIZATION OF MULTILAYER HfO2/Ag/HfO2 FILMS
Zhan et al. High performance VO2 thin films fabricated by room-temperature reactive magnetron sputtering and rapid thermal annealing
Guan et al. Thickness dependence of Cr-doped VO2 thin films deposition by reactive pulsed magnetron sputtering
KR101506085B1 (ko) 나노 합금 박막 및 이의 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19822399

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207037653

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2019822399

Country of ref document: EP

Effective date: 20210120