WO1990011975A1 - Revetements conducteurs transparents - Google Patents

Revetements conducteurs transparents Download PDF

Info

Publication number
WO1990011975A1
WO1990011975A1 PCT/US1990/001554 US9001554W WO9011975A1 WO 1990011975 A1 WO1990011975 A1 WO 1990011975A1 US 9001554 W US9001554 W US 9001554W WO 9011975 A1 WO9011975 A1 WO 9011975A1
Authority
WO
WIPO (PCT)
Prior art keywords
oxide
metal
layer
metal oxide
dielectric
Prior art date
Application number
PCT/US1990/001554
Other languages
English (en)
Inventor
Wilfred C. Kittler
Original Assignee
Andus Corporation
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
Application filed by Andus Corporation filed Critical Andus Corporation
Publication of WO1990011975A1 publication Critical patent/WO1990011975A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3613—Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3655—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing at least one conducting layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
    • C03C17/366—Low-emissivity or solar control coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3681—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens

Definitions

  • DMD Dielectric-metal-dielectric
  • a metal layer is sandwiched between two layers of dielectric material
  • DMD Dielectric-metal-dielectric
  • Berning et al., J __ Opt. Soc. Am. r H, 230 (1957) discloses a DMD coating having a silver layer and dielectric multilayer antireflection coatings on either side for use as band pass filters.
  • Holland et al., Brit. J. Appl. Phys. , _&, 359 (1958) discloses a gold DMD coating which is transparent to visible light but infrared reflective. Additional publications related to DMD coatings are Plumat et al., CA 840,513 (1970) and Asahi Glass, GB 1,307,642 (1973) .
  • Multilayer coatings are often used in architectural or automotive glazing applications, where high visible or solar light transmittance and infrared light reflectance are important, and in aircraft transparencies where high light transmittance and electrical conductivity are necessary. Further, it is very important that these coatings be environmentally stable, because of the harsh environments in which they are called to perform.
  • the metal layers therein are usually very thin, often only 50-200 angstroms thick, and relatively fragile.
  • Thin layers of certain metals such as silver are not particularly stable, especially at such extreme thinnesses, because of the metal's tendency to form sulfides or oxides (from reaction with chemicals in the environment) and to agglomerate.
  • Antireflection layers may provide some protection by serving as corrosion barriers, but they themselves are also usually very thin, typically 200- 1000 angstroms thick, and cannot afford adequate protection, unless the multilayer coating is further protected by placing it in a laminate or other protective structure.
  • this invention provides an article having a transparent, conductive, infra-red reflective coating with improved stability, comprising a substrate having on a surface thereof a transparent, conductive, infra-red reflective coating comprising a metallic layer sandwiched between two dielectric metal oxide layers, at least one of which is doped with a dopant metal selected from the group consisting of copper, gold, iron, nickel, cobalt, molybdenum, tungsten, platinum, vanadium, tantalum, titanium, chromium, magnesium, zirconium, nickel, aluminum, bismuth, lead, and alloys thereof.
  • a dopant metal selected from the group consisting of copper, gold, iron, nickel, cobalt, molybdenum, tungsten, platinum, vanadium, tantalum, titanium, chromium, magnesium, zirconium, nickel, aluminum, bismuth, lead, and alloys thereof.
  • an article having a transparent, conductive, infra-red reflective coating with improved stability comprising a substrate having on a surface thereof a transparent, conductive, infra-red reflective coating comprising a metallic layer and a dielectric metal oxide layer doped with a dopant metal as defined above.
  • Fig. 3 is an XPS depth profile of a coating according to this invention.
  • Fig. 4 is an XPS depth profile of another coating according to this invention.
  • Fig. 5 compares the reflectance and transmission characteristics of coatings of this invention and a prior art coating, before environmental stability testing.
  • Fig. 6 compares the reflectance and transmission characteristics of coatings of this invention and a prior art coating, after environmental stability testing.
  • Fig. la depicts in cross-section an article 1 comprising a substrate 2 having deposited thereon a DMD coating 3 comprising dielectric layers 4a and 4b and metallic layer 5.
  • At least one of dielectric layers is doped with a dopant as described in more detail hereinbelow, improving corrosion resistance of the metallic layer.
  • Both dielectric layers can be doped, although where the substrate is a relatively impervious material such as glass, the inner dielectric layer 4b need not be doped.
  • the substrate is a relatively pervious material such as a thin polymeric film, it is preferred that both dielectric layers be doped.
  • Article 6 comprises a substrate 7 having deposited thereon a coating 8 comprising a dielectric layer 9 and metallic layer 10, the dielectric layer being doped as discussed above.
  • this embodiment differs from the one shown in Fig. la in that there is no dielectric layer interposed between the substrate and the metallic layer.
  • This embodiment may advantageously be used where the substrate is a relatively impervious material, so that there is a lesser threat of environmental attack from the substrate-facing side.
  • Suitable dielectric materials for the dielectric layers include tin oxide, indium oxide, indium tin oxide, titanium oxide, zinc oxide and tantalum oxide. Preferred are tin, indium, or indium-tin oxide. While generally, as a matter of convenience, the dielectric layers are made of the same material, such is not a requirement.
  • Suitable dopant metals include transition metals such as copper, gold, manganese, iron, nickel, cobalt, molybdenum, tungsten, platinum, vanadium, tantalum, titanium, chromium, magnesium, zirconium, nickel, and aluminum; group Illa-Va elements, including bismuth, indium, tin, and lead; and alloys thereof. Copper and gold are preferred.
  • the metallic layer which is to be protected can be made of various metals. Silver, copper, and gold, which are often used in visible/solar transparent but infrared reflective, conductive coatings, are especially benefitted. Other metals which can be protected include platinum, palladium, nickel, and rhodium.
  • the dopant metal forms an oxide with a heat of formation greater than that of the metal oxide corresponding to the metal of the metallic layer but less than that of metal oxide of the dielectric layer.
  • the heats of formation preferably satisfy the following inequality: dielectric metal oxide > oxide of dopant metal
  • the metallic layer is silver and the dielectric layer is tin oxide
  • copper is a preferred dopant metal, as cupric oxide has a heat of formation of -167.5 kJ/mole, between that of silver oxide (-30.6 kJ/mole) and tin oxide (-580.7 kJ/mole) . While not wishing to be bound by theory, it is believed that in such an embodiment a corrosion protection effect is derived from the partial oxidation of the dopant metal in the dielectric layer.
  • dopant metal such as copper
  • doping levels of up to 28 atom % are possible, without seriously reducing the transmittance.
  • dopants which form more transparent oxides than copper, such as aluminum considerably higher doping levels, up to 50 atom %, are tolerated without serious reduction in transmittance, as shown in Ritchie et al., U.S. Pat. 4,710,441 (1987) .

Abstract

L'invention concerne un article comportant un revêtement de stabilité améliorée, transparent, conducteur, réfléchissant les rayons infrarouges, comprenant un substrat doté d'un revêtement composé d'une couche métallique d'une matière telle que l'argent, ledit revêtement comportant sur au moins une de ses surfaces une couche d'oxyde métallique diélectrique d'une matière telle que l'oxyde d'étain, dopée par un métal tel que le cuivre. Ladite couche métallique est facultativement prise en sandwich entre deux desdites couches d'oxyde métallique diélectriques.
PCT/US1990/001554 1989-04-11 1990-03-19 Revetements conducteurs transparents WO1990011975A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US33692489A 1989-04-11 1989-04-11
US336,924 1989-04-11

Publications (1)

Publication Number Publication Date
WO1990011975A1 true WO1990011975A1 (fr) 1990-10-18

Family

ID=23318301

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1990/001554 WO1990011975A1 (fr) 1989-04-11 1990-03-19 Revetements conducteurs transparents

Country Status (5)

Country Link
EP (1) EP0467955A1 (fr)
JP (1) JPH04504388A (fr)
AU (1) AU5437790A (fr)
CA (1) CA2051390A1 (fr)
WO (1) WO1990011975A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0599071A1 (fr) * 1992-11-24 1994-06-01 Leybold Aktiengesellschaft Substrat transparent avec un système de couches transparentes et procédé de production d'un tel système de couches
EP0733931A2 (fr) * 1995-03-22 1996-09-25 Toppan Printing Co., Ltd. Film conductif multicouche, substrat transparent muni d'électrodes et dispositif d'affichage à cristal liquide qui l'utilisent
EP0789005A1 (fr) * 1996-02-09 1997-08-13 Saint-Gobain Vitrage Substrat transparent muni d'un empilement de couches minces à propriétés dans l'infrarouge
WO2000055656A1 (fr) 1999-03-17 2000-09-21 General Electric Company Revetements anti-infrarouge
WO2000055655A1 (fr) * 1999-03-17 2000-09-21 General Electric Company Couche d'adhesion pour filtres uv a oxyde metallique
WO2002046491A2 (fr) * 2000-12-04 2002-06-13 Guardian Industries Corp. Couche d'oxyde d'argent absorbant/reflechissant les uv et procede de formation de cette derniere
EP1163544B1 (fr) * 1999-03-17 2010-12-29 SABIC Innovative Plastics IP B.V. procede de production de filtres anti-ultraviolets a resistance aux intemperies amelioree
JP2014500223A (ja) * 2010-12-13 2014-01-09 サウスウォール テクノロジーズ インコーポレイティド 耐亀裂性で低放射性の浮設フィルムを備えた絶縁ガラスユニット
JP2015219690A (ja) * 2014-05-16 2015-12-07 コニカミノルタ株式会社 透明導電デバイス、及び、タッチパネル
EP1501768B1 (fr) * 2002-05-03 2017-04-19 Vitro, S.A.B. de C.V. Substrat presentant un revetement de gestion thermique pour une unite de vitrage isolant
CN112941476A (zh) * 2021-01-28 2021-06-11 山东省科学院能源研究所 一种二氧化锡/铜/二氧化锡多层透明导电薄膜及其制备方法与应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE72285T1 (de) * 1989-06-20 1992-02-15 Flachglas Ag Fassadenplatte, verfahren zu ihrer herstellung sowie verwendung derselben.

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2750500A1 (de) * 1977-11-11 1979-05-17 Leybold Heraeus Gmbh & Co Kg Verfahren zur herstellung von infrarotreflektierenden, fuer sichtbares licht weitgehend transparenten scheiben und durch die verfahren hergestellte scheibe
EP0106223A2 (fr) * 1982-10-08 1984-04-25 Optical Coating Laboratory, Inc. Système de films pour fenêtre à contrôle d'énergie et méthodes pour les fabriquer
US4462883A (en) * 1982-09-21 1984-07-31 Pilkington Brothers P.L.C. Low emissivity coatings on transparent substrates
DE3211753C2 (de) * 1982-03-30 1985-03-28 Interpane Entwicklungs- und Beratungsgesellschaft mbH & Co. KG, 3471 Lauenförde Hochtransparenter, in Durch- als auch Außenansicht neutral wirkender und wärmedämmender Belag für ein Substrat aus transparentem Material sowie Verwendung des Belages
DE3628057A1 (de) * 1985-08-19 1987-02-19 Nippon Sheet Glass Co Ltd Verfahren zur herstellung von waermereflektierendem glas
EP0283881A1 (fr) * 1987-03-26 1988-09-28 Ppg Industries, Inc. Films pulvérisés d'oxydes d'étain et de bismuth
US4799745A (en) * 1986-06-30 1989-01-24 Southwall Technologies, Inc. Heat reflecting composite films and glazing products containing the same
EP0304234A2 (fr) * 1987-08-18 1989-02-22 Boc Technologies Limited Verre revêtu de films d'oxydes métalliques ayant des propriétes de barrière

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2750500A1 (de) * 1977-11-11 1979-05-17 Leybold Heraeus Gmbh & Co Kg Verfahren zur herstellung von infrarotreflektierenden, fuer sichtbares licht weitgehend transparenten scheiben und durch die verfahren hergestellte scheibe
DE3211753C2 (de) * 1982-03-30 1985-03-28 Interpane Entwicklungs- und Beratungsgesellschaft mbH & Co. KG, 3471 Lauenförde Hochtransparenter, in Durch- als auch Außenansicht neutral wirkender und wärmedämmender Belag für ein Substrat aus transparentem Material sowie Verwendung des Belages
US4462883A (en) * 1982-09-21 1984-07-31 Pilkington Brothers P.L.C. Low emissivity coatings on transparent substrates
EP0106223A2 (fr) * 1982-10-08 1984-04-25 Optical Coating Laboratory, Inc. Système de films pour fenêtre à contrôle d'énergie et méthodes pour les fabriquer
DE3628057A1 (de) * 1985-08-19 1987-02-19 Nippon Sheet Glass Co Ltd Verfahren zur herstellung von waermereflektierendem glas
US4799745A (en) * 1986-06-30 1989-01-24 Southwall Technologies, Inc. Heat reflecting composite films and glazing products containing the same
US4799745B1 (fr) * 1986-06-30 1992-02-25 Southwall Technologies Inc
EP0283881A1 (fr) * 1987-03-26 1988-09-28 Ppg Industries, Inc. Films pulvérisés d'oxydes d'étain et de bismuth
EP0304234A2 (fr) * 1987-08-18 1989-02-22 Boc Technologies Limited Verre revêtu de films d'oxydes métalliques ayant des propriétes de barrière

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0599071A1 (fr) * 1992-11-24 1994-06-01 Leybold Aktiengesellschaft Substrat transparent avec un système de couches transparentes et procédé de production d'un tel système de couches
EP0733931A2 (fr) * 1995-03-22 1996-09-25 Toppan Printing Co., Ltd. Film conductif multicouche, substrat transparent muni d'électrodes et dispositif d'affichage à cristal liquide qui l'utilisent
EP0733931A3 (fr) * 1995-03-22 1997-08-13 Toppan Printing Co Ltd Film conductif multicouche, substrat transparent muni d'électrodes et dispositif d'affichage à cristal liquide qui l'utilisent
EP0789005A1 (fr) * 1996-02-09 1997-08-13 Saint-Gobain Vitrage Substrat transparent muni d'un empilement de couches minces à propriétés dans l'infrarouge
US6420032B1 (en) 1999-03-17 2002-07-16 General Electric Company Adhesion layer for metal oxide UV filters
EP1163544B1 (fr) * 1999-03-17 2010-12-29 SABIC Innovative Plastics IP B.V. procede de production de filtres anti-ultraviolets a resistance aux intemperies amelioree
US6261694B1 (en) 1999-03-17 2001-07-17 General Electric Company Infrared reflecting coatings
EP2302423A3 (fr) * 1999-03-17 2011-07-20 SABIC Innovative Plastics IP B.V. Revêtements réfléchissant les infrarouges
WO2000055656A1 (fr) 1999-03-17 2000-09-21 General Electric Company Revetements anti-infrarouge
WO2000055655A1 (fr) * 1999-03-17 2000-09-21 General Electric Company Couche d'adhesion pour filtres uv a oxyde metallique
US6596399B2 (en) 2000-12-04 2003-07-22 Guardian Industries Corp. UV absorbing/reflecting silver oxide layer, and method of making same
WO2002046491A3 (fr) * 2000-12-04 2002-09-12 Guardian Industries Couche d'oxyde d'argent absorbant/reflechissant les uv et procede de formation de cette derniere
WO2002046491A2 (fr) * 2000-12-04 2002-06-13 Guardian Industries Corp. Couche d'oxyde d'argent absorbant/reflechissant les uv et procede de formation de cette derniere
EP1501768B1 (fr) * 2002-05-03 2017-04-19 Vitro, S.A.B. de C.V. Substrat presentant un revetement de gestion thermique pour une unite de vitrage isolant
JP2014500223A (ja) * 2010-12-13 2014-01-09 サウスウォール テクノロジーズ インコーポレイティド 耐亀裂性で低放射性の浮設フィルムを備えた絶縁ガラスユニット
JP2015219690A (ja) * 2014-05-16 2015-12-07 コニカミノルタ株式会社 透明導電デバイス、及び、タッチパネル
CN112941476A (zh) * 2021-01-28 2021-06-11 山东省科学院能源研究所 一种二氧化锡/铜/二氧化锡多层透明导电薄膜及其制备方法与应用
CN112941476B (zh) * 2021-01-28 2022-09-16 山东省科学院能源研究所 一种二氧化锡/铜/二氧化锡多层透明导电薄膜及其制备方法与应用

Also Published As

Publication number Publication date
CA2051390A1 (fr) 1990-10-12
EP0467955A1 (fr) 1992-01-29
JPH04504388A (ja) 1992-08-06
AU5437790A (en) 1990-11-05

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