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WO2017099215A1 - Cible de pulvérisation, stratifié, corps multicouche et procédé de fabrication de stratifié - Google Patents

Cible de pulvérisation, stratifié, corps multicouche et procédé de fabrication de stratifié Download PDF

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Publication number
WO2017099215A1
WO2017099215A1 PCT/JP2016/086699 JP2016086699W WO2017099215A1 WO 2017099215 A1 WO2017099215 A1 WO 2017099215A1 JP 2016086699 W JP2016086699 W JP 2016086699W WO 2017099215 A1 WO2017099215 A1 WO 2017099215A1
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WIPO (PCT)
Prior art keywords
film
mass
oxide film
content
laminate
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Ceased
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PCT/JP2016/086699
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English (en)
Japanese (ja)
Inventor
雄斗 大越
俊成 渡邉
宮川　直通
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AGC Inc
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Asahi Glass Co Ltd
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Publication of WO2017099215A1 publication Critical patent/WO2017099215A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • 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

Definitions

  • the present invention relates to a sputtering target used for forming an oxide film by reactive sputtering, a laminate and a multilayer body having an oxide film formed using the sputtering target, and a method for manufacturing the laminate About.
  • Low-radiation membranes are widely used in windows for buildings and vehicles in order to reduce the burden of cooling and heating by suppressing the radiation of heat rays.
  • the low radioactive film is also called a Low-E (Low-Emissivity) film, and the glass on which the low-emission film is formed is called Low-E glass.
  • a low emissivity film is required to have a low emissivity of heat rays. For this reason, the low radioactive film is usually configured to include a metal film that is low radioactive.
  • a laminated structure of the low radioactive film in order from the transparent substrate side such as a glass substrate, (1) a three-layer structure in which three layers of a dielectric film, a metal film and a dielectric film are laminated, or (2) a dielectric film, A five-layer structure in which five layers of a metal film, a dielectric film, a metal film, and a dielectric film are stacked is known. Further, an Ag film having low radiation is preferably used as the metal film. On the other hand, an electrically insulating film such as an oxide film or a nitride film is used as the dielectric film, and the oxide film is most widely used. As the oxide film, a composite oxide film of Zn and Sn (Zn—Sn composite oxide film) is widely used.
  • the Zn—Sn composite oxide film is formed by reactive sputtering using, for example, a sputtering target (Zn—Sn alloy target) made of an alloy of Zn and Sn.
  • a sputtering target Zn—Sn alloy target
  • Zn—Sn alloy target made of an alloy of Zn and Sn.
  • Zn and Sn are included as essential elements, and Al, Ga, In, B, Y, La, Ge, Si, P, Sb, Bi, Ce, and Ti are included.
  • a method of forming a Zn—Sn composite oxide film by reactive sputtering using a metal target containing one or more elements selected from Zr, Zr, Nb, and Ta see, for example, Patent Document 1). .
  • the sputtering target of the present invention contains 5 to 88% by mass of Zn, 5 to 88% by mass of Sn, and 7 to 90% by mass of Bi with respect to the total amount of metals.
  • the laminate of the present invention is a laminate having a transparent substrate and an oxide film formed on the transparent substrate, and the oxide film contains 5 to 88 masses of Zn with respect to the total amount of metals. %, Sn is contained in an amount of 5 to 88% by mass, and Bi is contained in an amount of 7 to 90% by mass.
  • the multilayer body of the present invention includes the laminate and another transparent substrate disposed on the laminate via a gap.
  • the manufacturing method of the laminated body of this invention is a manufacturing method of the laminated body which has a transparent substrate and the oxide film formed on the said transparent substrate, Comprising: It is reactive using the said sputtering target on the said transparent substrate. It has the process of forming the said oxide film by sputtering.
  • the sputtering target of the present invention contains 5 to 88% by mass of Zn, 5 to 88% by mass of Sn, and 7 to 90% by mass of Bi with respect to the total amount of metal, the Zn—Sn composite oxide film is reacted.
  • the film can be formed at a high film formation rate by reactive sputtering.
  • the sputtering target according to an embodiment of the present invention contains 5 to 88% by mass of Zn, 5 to 88% by mass of Sn, and 7 to 90% by mass of Bi with respect to the total amount of metals.
  • the content of Zn is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more with respect to the total amount of metals.
  • the content of Zn is preferably 60% or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, and particularly preferably 37% or less with respect to the total amount of metals.
  • the content of Sn is preferably 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more based on the total amount of metals.
  • the Sn content is 88% by mass or less, the raw material cost is low.
  • the Sn content is preferably 60% or less, more preferably 45% by mass or less, still more preferably 40% by mass or less, and particularly preferably 35% by mass or less, based on the total amount of metals.
  • Bi improves the deposition rate when forming an oxide film by reactive sputtering.
  • oxidation so-called poisoning
  • the occurrence of poisoning is suppressed, and an oxide film can be formed at a high film formation rate by reactive sputtering.
  • Bi which is a heavy element
  • the surface of the oxide film is flattened. If the surface of the oxide film is planarized, when a metal film such as an Ag film is formed thereon, the film thickness of the metal film becomes uniform, and the scratch resistance and moisture resistance are improved.
  • the Bi content is 7% by mass or more, the film formation rate is sufficiently improved when an oxide film is formed by reactive sputtering. In addition, the surface of the oxide film is easily flattened.
  • the content of Bi is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more.
  • the Bi content is 90% by mass or less, the raw material cost is low.
  • the Bi content is preferably 60% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
  • the Zn content and the Sn content may be different, but the ratio of both in the total metal amount, that is, the Zn content (unit: mass%) in the total metal content is the Sn content (unit: mass%).
  • the value Zn / Sn divided by) is preferably 0.5 to 1.25. If Zn / Sn is 0.5 or more, the raw material cost is low. Zn / Sn is more preferably 0.7 or more, further preferably 0.9 or more, and particularly preferably 1.0 or more. On the other hand, when Zn / Sn is 1.25 or less, the deposition rate when the oxide film is deposited by reactive sputtering is high, and the productivity of the laminate is good. In addition, the oxide film is difficult to crystallize. Zn / Sn is more preferably 1.2 or less, and further preferably 1.1 or less.
  • the Zn content and Sn content may be different, but the smaller the difference, the better. If the difference between the Zn content and the Sn content is small, the surface becomes easy to flatten because it becomes amorphous when the oxide film is formed. In addition, the weather resistance, acid resistance, and base resistance of the oxide film are improved.
  • is 20 mass%.
  • the content is preferably 17% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less.
  • the sputtering target according to an embodiment of the present invention is preferably composed of three components of Zn, Sn, and Bi, but can contain other metals as necessary and within the scope of the present invention.
  • other metals include Cu, Fe, In, Pb, Sb, Cd, and Si.
  • the total content is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less based on the total amount of metals.
  • Other metals to be contained may be intentionally contained, but may be contained as inevitable impurities.
  • the method for producing the sputtering target is not particularly limited, and examples thereof include a cold isostatic pressing (CIP) method, a spraying (spraying) method, a melting method, and a high-temperature and high-pressure pressing method.
  • CIP cold isostatic pressing
  • spraying spraying
  • melting melting
  • high-temperature and high-pressure pressing method high-temperature and high-pressure pressing method
  • the CIP method for example, it can be produced as follows. First, raw material powders, that is, Zn powder, Sn powder, and Bi powder are mixed by a dry ball mill to form a mixed powder. Under the present circumstances, each content of Zn, Sn, and Bi in a sputtering target can be adjusted by adjusting the mixture ratio of each raw material powder.
  • a metal powder that is not alloyed (single element powder) as described above may be used, or a metal powder (alloyed powder) in which a part of metal or all of the metal is alloyed. May be used. Further, instead of the raw material powder, raw material grains having a particle size larger than that of the raw material powder may be used.
  • the raw material powder has a raw material particle size of less than 1 mm, and the raw material particle has a raw material particle size of 1 mm or more.
  • Use of raw material powder facilitates mixing of raw materials. Since the raw material grains have a small surface area, it is difficult to form an oxide film when the raw material grains are used.
  • this mixed powder is molded into a predetermined shape to obtain a molded body.
  • This molded body is pressed by the CIP method to form a pressure molded body.
  • this pressure-molded body is processed into a predetermined shape to obtain a sputtering target.
  • the sputtering target include a planar (flat plate) type and a cylindrical (cylindrical) type.
  • the sputtering target is fixed to the support by metal bonding, for example, and becomes a target bonded body.
  • the support for example, a support made of a metal such as copper and having a plate shape or a tube shape is used.
  • a low melting point metal such as indium or tin is used.
  • the number of sputtering targets fixed to the support may be single or plural, and can be appropriately selected as necessary.
  • the method of fixing a sputtering target to a support body is not limited to metal bonding, It can select suitably from various fixing methods.
  • the laminated body which concerns on one Embodiment of this invention has a transparent substrate and the oxide film formed on this transparent substrate.
  • the oxide film is formed by reactive sputtering using the sputtering target.
  • Such a laminated body is suitably used as a multi-layer glass, for example, disposed so as to face another glass substrate with a gap.
  • the oxide film is used as a dielectric film constituting a low-radiation film.
  • the low-emission film is usually configured to include a metal film such as an Ag film that is low-emission, but only the metal film reflects visible light. By including the dielectric film, the refractive index of the low-emission film is adjusted, visible light is transmitted, and daylighting is improved.
  • transparent substrates include inorganic glass substrates and plastic substrates.
  • plastic substrate include fluorine resin, acrylic resin, polycarbonate resin, triacetate resin, polyether sulfone resin, polyethylene naphthalate resin, polyimide resin, polyethylene terephthalate resin, and polyether ether ketone resin.
  • the oxide film is formed by reactive sputtering using the above sputtering target.
  • the oxide film is a composite oxide film of Zn, Sn, and Bi (Zn—Sn—Bi composite oxide film).
  • the Zn—Sn—Bi composite oxide film contains 5 to 88 mass% of Zn, 5 to 88 mass% of Sn, and 7 to 90 mass% of Bi with respect to the total metal amount.
  • the content of Zn in the oxide film is 5% by mass or more, the raw material cost is low.
  • the content of Zn is preferably 20% by mass or more, more preferably 30% by mass or more, and particularly preferably 35% by mass or more with respect to the total amount of metals.
  • the Zn content of the oxide film is 88% by mass or less, the oxide film is difficult to crystallize, so that grain boundaries are difficult to form, the bond of the oxide film becomes strong, and the oxide film is flattened. The Due to the difficulty in forming grain boundaries, the oxide film is less likely to pass moisture, so that the weather resistance, acid resistance, and base resistance of the oxide film are improved.
  • the Zn content is preferably 60% by mass or less, more preferably 45% by mass or less, still more preferably 40% or less, and particularly preferably 37% or less, based on the total amount of metals.
  • the content of Sn in the oxide film is 5% by mass or more, the film formation rate when forming the oxide film by reactive sputtering is high, and the productivity of the laminate is good. In addition, the oxide film is hardly crystallized, and the weather resistance, acid resistance, base resistance, scratch resistance, and moisture resistance of the oxide film are improved.
  • the content of Sn is preferably 20% by mass or more, more preferably 25% by mass or more, and particularly preferably 30% by mass or more based on the total amount of metals.
  • the Sn content of the oxide film is 88% by mass or less, the raw material cost is low.
  • the Sn content is preferably 60% by mass or less, more preferably 45% by mass or less, particularly preferably 40% by mass or less, and most preferably 35% by mass or less, based on the total amount of metals.
  • the oxide film is difficult to crystallize, and Bi collides with the oxide film when forming the oxide film.
  • the surface is easy to flatten. Therefore, the weather resistance, acid resistance, base resistance, scratch resistance, and moisture resistance of the oxide film are improved.
  • the deposition rate is high when the oxide film is formed, and the productivity of the stacked body is good.
  • the refractive index of the oxide film is increased, and the thickness of the oxide film can be reduced.
  • film stress of the oxide film is reduced and the scratch resistance is good.
  • film stress refers to the compressive stress of the film.
  • the content of Bi is preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, and particularly preferably 25% by mass or more from the viewpoint of increasing the film formation rate.
  • the Bi content of the oxide film is 90% by mass or less, the raw material cost is low.
  • the Bi content is preferably 60% by mass or less, more preferably 40% by mass or less, and particularly preferably 35% by mass or less.
  • the Zn content and Sn content of the oxide film may be different, but the ratio of both in the total metal amount, that is, the Zn content (unit: mass%) in the total metal amount is the Sn content (
  • the value Zn / Sn divided by (unit: mass%) is preferably 0.5 to 1.25.
  • Zn / Sn is 0.5 or more, the raw material cost is low.
  • Zn / Sn is more preferably 0.7 or more, further preferably 0.9 or more, and particularly preferably 1.0 or more.
  • Zn / Sn is 1.25 or less, the deposition rate when forming an oxide film by reactive sputtering is high, and the productivity of the laminate is good.
  • the oxide film is difficult to crystallize.
  • Zn / Sn is more preferably 1.2 or less, and further preferably 1.1 or less.
  • the Zn content and the Sn content in the oxide film may be different, but the smaller the difference between the two, the better. If the difference between the Zn content and the Sn content is small, the surface of the oxide film is likely to be flattened because it becomes amorphous when the oxide film is formed. In addition, the weather resistance, acid resistance, and base resistance of the oxide film are improved.
  • of the difference between the Zn content (unit: mass%) and the Sn content (unit: mass%) is 20 mass% or less. It is preferably 17% by mass or less, more preferably 10% by mass or less, still more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 2% by mass or less.
  • the oxide film is preferably composed of three components of Zn, Sn, and Bi.
  • It can contain metals.
  • other metals include Cu, Fe, In, Pb, Sb, Cd, and Si.
  • the total content is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less based on the total amount of metals.
  • Other metals to be contained may be intentionally contained, but may be contained as inevitable impurities.
  • the laminated body which concerns on one Embodiment of this invention may contain carbon in the oxide film. Carbon is inevitably mixed by forming an oxide film by, for example, reactive sputtering using CO 2 gas as a reaction gas as described later.
  • the carbon content is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less based on the total amount of metals.
  • the oxide film is preferably amorphous.
  • “the oxide film is amorphous” means that the oxide film does not give a sharp peak in the X-ray diffraction measurement.
  • the crystallite diameter (Scherrer diameter) obtained by the Scherrer formula represented by the following formula (1) is 5. 2 nm or less.
  • the Scherrer diameter L is a Scherrer constant K, an X-ray wavelength ⁇ , a half-value width ⁇ , and a peak position ⁇ .
  • L K ⁇ / ( ⁇ cos ⁇ ) (1) It is represented by If the oxide film is amorphous, grain boundaries cannot be formed, the oxide film is strongly bonded, and the oxide film is planarized. Due to the absence of grain boundaries, the oxide film is difficult to pass moisture, so that the weather resistance, acid resistance, and base resistance of the oxide film are improved. Further, since the surface of the oxide film is flattened, when a metal film such as an Ag film is formed on the oxide film, the film thickness of the metal film becomes uniform, and scratch resistance and moisture resistance are improved. It becomes good. An oxide film formed using a sputtering target having a small difference between the Zn content and the Sn content is likely to be amorphous.
  • the oxide film preferably has a refractive index at a wavelength of 600 nm of 2.0 to 2.5. If the refractive index of the laminate having a wavelength of 600 nm is 2.0 or more, the thickness of the oxide film can be reduced, and the productivity is improved.
  • the refractive index at a wavelength of 600 nm of the oxide film is more preferably 2.02 or more, and further preferably 2.03 or more.
  • the refractive index at a wavelength of 600 nm of the oxide film is 2.5 or less, the appropriate thickness of the oxide film does not become too thin and it is easy to form the oxide film.
  • the refractive index of the oxide film at a wavelength of 600 nm is more preferably 2.4 or less, and further preferably 2.3 or less. The refractive index is obtained by ellipsometry.
  • the Zn—Sn—Bi composite oxide film has good flatness, it is preferably used as a dielectric film of a low radiation film.
  • the laminated structure of the low radioactive film include (1) a three-layer structure and (2) a five-layer structure.
  • the three-layer structure has three layers of a first dielectric film, a first metal film, and a second dielectric film in order from the transparent substrate side.
  • the five-layer structure includes, in order from the transparent substrate side, the first dielectric film, the first metal film, the second dielectric film, the second metal film, and the third dielectric film. It has 5 layers.
  • the metal film an Ag film is preferable.
  • the Zn—Sn—Bi composite oxide film need not be included in all of the plurality of dielectric films, and may be included in some of the dielectric films. Further, this part of the dielectric film does not need to include the Zn—Sn—Bi composite oxide film in the entire thickness direction, and includes the Zn—Sn—Bi composite oxide film in a part of the thickness direction. But you can.
  • the dielectric film used in combination with the Zn—Sn—Bi composite oxide film is a composite oxide film of zinc and aluminum.
  • the Zn—Al composite oxide film has crystallinity, and an Ag film having high crystallinity can be obtained by forming an Ag film as a metal film thereon.
  • the Zn—Al composite oxide film has high flatness among crystalline zinc composite oxides, the film thickness of the Ag film as the metal film becomes uniform, and scratch resistance and moisture resistance are improved. .
  • the low-radiation film having the three-layer structure described above preferably has each layer as shown below.
  • the first dielectric film is preferably a Zn—Sn—Bi composite oxide film and a Zn—Al composite oxide film in this order from the transparent substrate side.
  • the first metal film is preferably an Ag film.
  • the second dielectric film is preferably a Zn—Al composite oxide film and a Zn—Sn—Bi composite oxide film in this order from the transparent substrate side.
  • the thicknesses of the Zn—Sn—Bi composite oxide film and the Zn—Al composite oxide film in the first dielectric film are preferably 3 to 80 nm and 1 to 20 nm, respectively.
  • the thickness of the Ag film in the first metal film is preferably 5 to 20 nm.
  • the thicknesses of the Zn—Al composite oxide film and the Zn—Sn—Bi composite oxide film in the second dielectric film are preferably 1 to 20 nm and 3 to 100 nm, respectively.
  • membrane is the geometric thickness calculated
  • the first metal film and the second dielectric are suppressed in order to suppress oxidation of the first metal film when the second dielectric film is formed.
  • a barrier film such as a Ti film may be provided between the body film.
  • a protective film such as a TiO 2 film may be provided on the opposite side of the second dielectric film from the transparent substrate in order to suppress oxidation of the second dielectric film and alteration due to water vapor.
  • the thickness of each of the barrier film and the protective film is preferably 1 to 100 nm, and more preferably 1 to 20 nm.
  • the low-radiation film having the five-layer structure described above preferably has each layer as shown below.
  • the first dielectric film is preferably a Zn—Sn—Bi composite oxide film and a Zn—Al composite oxide film in this order from the transparent substrate side.
  • the first metal film is preferably an Ag film.
  • the second dielectric film is preferably a Zn—Al composite oxide film, a Zn—Sn—Bi composite oxide film, and a Zn—Al composite oxide film in this order from the transparent substrate side.
  • the second metal film is preferably an Ag film.
  • the third dielectric film is preferably a Zn—Al composite oxide film and a Zn—Sn—Bi composite oxide film in this order from the transparent substrate side.
  • the thicknesses of the Zn—Sn—Bi composite oxide film and the Zn—Al composite oxide film in the first dielectric film are preferably 3 to 80 nm and 1 to 20 nm, respectively.
  • the thickness of the Ag film in the first metal film is preferably 5 to 20 nm.
  • Thickness of Zn—Al composite oxide film (first metal film side), Zn—Sn—Bi composite oxide film, Zn—Al composite oxide film (second metal film side) in the second dielectric film The thicknesses are preferably 1 to 20 nm, 3 to 100 nm, and 1 to 20 nm, respectively.
  • the thickness of the Ag film in the second metal film is preferably 5 to 20 nm.
  • the thicknesses of the Zn—Al composite oxide film and the Zn—Sn—Bi composite oxide film in the third dielectric film are preferably 1 to 20 nm and 3 to 100 nm, respectively.
  • the first metal film and the second dielectric are used in order to suppress oxidation of the first metal film when forming the second dielectric film.
  • a barrier film such as a Ti film may be provided between the body film.
  • a barrier film such as a Ti film is provided between the second metal film and the third dielectric film in order to suppress oxidation of the second metal film when the third dielectric film is formed. You may have.
  • a protective film such as a TiO 2 film may be provided on the opposite side of the third dielectric film from the transparent substrate in order to suppress oxidation of the third dielectric film and deterioration due to water vapor.
  • the thickness of each of the barrier film and the protective film is preferably 1 to 100 nm, and more preferably 1 to 20 nm.
  • the multilayer body which concerns on one Embodiment of this invention is equipped with an above described laminated body and the other transparent substrate arrange
  • a glass substrate is usually used as the transparent substrate and the other transparent substrate constituting the laminate, but may be a plastic substrate or the like.
  • the multilayer body is attached to a frame such as a window frame, and transmits outdoor light such as sunlight to the room.
  • the window can be, for example, a building window, a vehicle window, or the like.
  • the gap may be filled with an inert gas such as Ar or air.
  • the pressure in the gap may be the same as the atmospheric pressure or may be smaller than the atmospheric pressure.
  • the gap may be a vacuum.
  • the Zn—Sn—Bi composite oxide film in the above-described multilayer body is formed on the opposing surface of another transparent substrate.
  • the laminated body having the above-described Zn—Sn—Bi composite oxide film may be on the outdoor side or on the indoor side with respect to another transparent substrate.
  • the laminate is on the outdoor side, it is possible to block solar heat from the outside.
  • the laminate is on the indoor side, it is difficult to release indoor heat to the outside.
  • the above-described Zn—Sn—Bi composite oxide film is used as a dielectric film in the stacked body, so that the refractive index of the low-radiation film is high and the thickness can be reduced. . For this reason, the film formation time of the low radioactive film can be shortened, and the productivity is high.
  • the manufacturing method of the laminated body which concerns on one Embodiment of this invention has the process of forming the said oxide film by reactive sputtering using the sputtering target mentioned above on the transparent substrate, It is characterized by the above-mentioned.
  • the sputtering target is obtained by the method described above.
  • the oxide film is formed by reactive sputtering, and each layer is laminated on the transparent substrate so as to have the above-described laminated structure of the low radioactive film.
  • oxidation reactive gas is used as a reactive gas used for reactive sputtering.
  • the oxidation reactive gas one containing oxygen element is used, and specifically, O 2 gas, O 2 —Ar mixed gas, CO 2 gas, CO 2 —Ar mixed gas, or the like is used.
  • O 2 gas is preferable because the film forming rate is increased.
  • CO 2 gas is preferable because light absorption is small and a highly transparent oxide film can be obtained.
  • a DC (direct current) sputtering method for example, a DC (direct current) sputtering method, a DC pulse sputtering method which is a method of applying an intermittent negative voltage periodically repeated below 500 kHz, a low frequency (LF) to a medium frequency (MF). And alternating current (AC) sputtering method.
  • the sputtering method is not particularly limited, but the DC sputtering method is preferable because it has a high film formation rate and is suitable for film formation on a large-area transparent substrate.
  • the temperature of the transparent substrate during film formation is not particularly limited, and is, for example, in the range of room temperature to 700 ° C. Further, after film formation, heat treatment may be performed at a temperature of 700 ° C. or lower.
  • the first dielectric film is preferably formed with a Zn—Sn—Bi composite oxide film and a Zn—Al composite oxide film in this order from the transparent substrate side.
  • the first metal film is preferably an Ag film.
  • the second dielectric film is preferably formed with a Zn—Al composite oxide film and a Zn—Sn—Bi composite oxide film in this order from the transparent substrate side.
  • each layer is formed to have the thickness described above.
  • the first metal film and the second dielectric are used in order to suppress oxidation of the first metal film when forming the second dielectric film.
  • a barrier film such as a Ti film may be formed between the films.
  • a protective film such as a TiO 2 film may be formed after forming the second dielectric film.
  • the above-described (2) low-emission film having a five-layer structure is preferably formed as shown below.
  • the first dielectric film is preferably formed with a Zn—Sn—Bi composite oxide film and a Zn—Al composite oxide film in this order from the transparent substrate side.
  • the first metal film is preferably an Ag film.
  • the second dielectric film is preferably formed with a Zn—Al composite oxide film, a Zn—Sn—Bi composite oxide film, and a Zn—Al composite oxide film in this order from the transparent substrate side.
  • the second metal film is preferably an Ag film.
  • As the third dielectric film a Zn—Al composite oxide film and a Zn—Sn—Bi composite oxide film are preferably formed in this order from the transparent substrate side.
  • each layer is formed to have the thickness described above.
  • a third dielectric film is formed in order to suppress oxidation of the first metal film when forming the second dielectric film.
  • a barrier film such as a Ti film may be formed between them.
  • a protective film such as a TiO 2 film may be formed after the formation of the third dielectric film.
  • the oxide film is formed by reactive sputtering using the above-described sputtering target, so that the film can be formed at a high film formation rate.
  • Examples 1 to 9 are examples, and examples 10 to 11 are comparative examples.
  • Examples 1-2 As a raw material powder, Zn powder (manufactured by High Purity Chemical Laboratory, 3N grade, average particle size 75 ⁇ m or less), Sn powder (manufactured by High Purity Chemical Laboratory, 3N grade, average particle size 63 ⁇ m or less), Bi powder (high Purity Chemical Laboratory Co., Ltd., 4N grade, average particle size 75-150 ⁇ m) was weighed with an electronic balance so that the content shown in Table 1 was obtained. In addition, the content rate shown in Table 1 is the ratio (unit: mass%) of each metal with respect to the total metal amount, and is the ratio with respect to the total amount of Zn, Sn, and Bi here.
  • the ratio Zn / Sn of Zn and Sn contents (unit: mass%) in the total metal amount, and the Zn content (unit: mass%) and Sn content (unit: mass%) in the total metal amount Table 1 shows the absolute value
  • Example 3 to 9 As raw material grains, Zn grains (manufactured by High Purity Chemical Laboratory, 3N grade, average particle size 3-7 mm), Sn grains (manufactured by High Purity Chemical Laboratory, 3N grade, average particle diameter 2-4 mm), Bi grains (High purity chemical research company make, 4N grade, average particle size 2-5 mm) was weighed with an electronic balance so as to have the content shown in Table 1. These raw material grains were heated at 450 ° C. to obtain a Zn—Sn—Bi melt. Thereafter, a Zn—Sn—Bi melt was cast into a 51 mm diameter mold and cooled to obtain a Zn—Sn—Bi alloy disc. This alloy disk was processed to a thickness of 6 mm to obtain a sputtering target. Using this sputtering target, a target assembly was prepared and evaluated in the same manner as in Examples 1 and 2.
  • Example 10 A target joined body was prepared and evaluated in the same manner as in Examples 1 and 2 except that Bi powder was not added and the contents of Zn powder and Sn powder were 50 mass%, respectively.
  • Example 11 Except for using 1% by mass of Al powder (3N grade, average particle size 20 ⁇ m), instead of Bi powder, the content of Zn powder and Sn powder was 49.5% by mass, respectively. Were produced and evaluated in the same manner as in Examples 1 and 2.
  • a laminate was prepared from the obtained target joined bodies of Examples 1 to 11, and the film formation rate was measured. In some examples, the refractive index and film stress (compressive stress) were further measured. The measurement results are shown in Table 1. In Table 1, the blank represents “not measured”. The measuring method of each physical property is shown below.
  • the sputtering atmosphere was a CO 2 atmosphere at a pressure of 0.5 Pa
  • the sputtering system was a direct current magnetron sputtering system
  • the input power was 80 W.
  • Zn—Sn—Bi composite oxide films were obtained as oxide films. Thereafter, the thickness of the oxide film was measured by a stylus type film thickness method.
  • An oxide film having a thickness of 50 nm was formed on a 4-inch silicon wafer by a reactive sputtering method using the produced target bonded body to obtain a stacked body.
  • the sputtering atmosphere was a CO 2 atmosphere at a pressure of 0.5 Pa
  • the sputtering system was a direct current magnetron sputtering system
  • the input power was 500 W.
  • the film stress of the oxide film of the obtained laminate was measured by “FLX-2320 Thin Film Stress Measurement System (trade name)” manufactured by TEMOR.
  • the film formation rate of the laminate of Example 11 containing Al was about 10% slower than that of the laminate of Example 10 containing no Bi.
  • the laminates of Examples 1 to 9 containing Bi were at least 5% faster than the laminate of Example 10 containing no Bi.
  • the laminates of Examples 4 to 9 containing Bi in excess of 10.0% by mass increased the film forming rate by 20% or more compared to the laminate of Example 10 not containing Bi.
  • the laminates of Examples 6 to 7 containing Bi had smaller film stress and a higher refractive index than the laminate of Example 10 containing no Bi.
  • the oxide films of the laminates of Examples 1 to 9 containing Bi were measured by X-ray diffraction using an X-ray diffractometer (SmartLab manufactured by RIGAKU), no sharp peak was obtained, and the oxide film was amorphous. It was quality.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Ceramic Engineering (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

L'invention concerne une cible de pulvérisation avec laquelle un film peut être formé à une grande vitesse de formation de film par pulvérisation réactive d'un film d'oxyde complexe de Zn-Sn. En outre, l'invention concerne un stratifié et un corps multicouche ayant le film d'oxyde complexe de Zn-Sn formé en utilisant une telle cible de pulvérisation, ainsi qu'un procédé de fabrication d'un stratifié. La cible de pulvérisation contient de 5 à 88 % en masse de Zn, de 5 à 88 % en masse de Sn et de 7 à 90 % en masse de Bi, par rapport à la teneur totale en métal.
PCT/JP2016/086699 2015-12-11 2016-12-09 Cible de pulvérisation, stratifié, corps multicouche et procédé de fabrication de stratifié Ceased WO2017099215A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60182012A (ja) * 1984-02-28 1985-09-17 Sony Corp 薄膜磁気記録媒体
JPH1087350A (ja) * 1996-09-12 1998-04-07 Nippon Sheet Glass Co Ltd 断熱複層ガラス及び真空複層ガラス
JPH10237630A (ja) * 1996-04-12 1998-09-08 Asahi Glass Co Ltd 酸化物膜、積層体およびそれらの製造方法
JP2005206875A (ja) * 2004-01-22 2005-08-04 Ulvac Japan Ltd 成膜装置及び成膜方法
JP2008231445A (ja) * 2007-03-16 2008-10-02 Sumitomo Chemical Co Ltd 透明導電膜用材料
WO2014078054A1 (fr) * 2012-11-19 2014-05-22 Guardian Industries Corp. Article revêtu par un revêtement à faible émissivité comprenant une ou des couches comprenant de l'oxyde d'étain comportant des métaux supplémentaires
JP2015074788A (ja) * 2013-10-07 2015-04-20 三菱マテリアル株式会社 Ｉｎスパッタリングターゲット及びＩｎ膜
WO2016132825A1 (fr) * 2015-02-18 2016-08-25 三菱マテリアル株式会社 Cible de pulvérisation et film stratifié

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60182012A (ja) * 1984-02-28 1985-09-17 Sony Corp 薄膜磁気記録媒体
JPH10237630A (ja) * 1996-04-12 1998-09-08 Asahi Glass Co Ltd 酸化物膜、積層体およびそれらの製造方法
JPH1087350A (ja) * 1996-09-12 1998-04-07 Nippon Sheet Glass Co Ltd 断熱複層ガラス及び真空複層ガラス
JP2005206875A (ja) * 2004-01-22 2005-08-04 Ulvac Japan Ltd 成膜装置及び成膜方法
JP2008231445A (ja) * 2007-03-16 2008-10-02 Sumitomo Chemical Co Ltd 透明導電膜用材料
WO2014078054A1 (fr) * 2012-11-19 2014-05-22 Guardian Industries Corp. Article revêtu par un revêtement à faible émissivité comprenant une ou des couches comprenant de l'oxyde d'étain comportant des métaux supplémentaires
JP2015074788A (ja) * 2013-10-07 2015-04-20 三菱マテリアル株式会社 Ｉｎスパッタリングターゲット及びＩｎ膜
WO2016132825A1 (fr) * 2015-02-18 2016-08-25 三菱マテリアル株式会社 Cible de pulvérisation et film stratifié

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