DE10152211C1 - Layer system used for transparent substrates comprises a partial layer of a mixed oxide of zinc oxide, titanium oxide and a further oxide, and further metal and/or oxide layers with functional silver layers - Google Patents

Layer system used for transparent substrates comprises a partial layer of a mixed oxide of zinc oxide, titanium oxide and a further oxide, and further metal and/or oxide layers with functional silver layers

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Publication number
DE10152211C1
DE10152211C1 DE10152211A DE10152211A DE10152211C1 DE 10152211 C1 DE10152211 C1 DE 10152211C1 DE 10152211 A DE10152211 A DE 10152211A DE 10152211 A DE10152211 A DE 10152211A DE 10152211 C1 DE10152211 C1 DE 10152211C1
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Prior art keywords
layer
oxide
weight
mixed oxide
layer system
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Heinz Schicht
Herbert Schindler
Uwe Schmidt
Lars Ihlo
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Saint Gobain Glass Deutschland GmbH
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Saint Gobain Glass Deutschland GmbH
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    • 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
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3652—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 coating stack containing at least one sacrificial layer to protect the metal from oxidation
    • 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
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • 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
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/21—Oxides
    • C03C2217/23—Mixtures
    • 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

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

Abstract

Layer system, especially low energy layer system for transparent substrates, especially glass panes, comprises at least one partial layer of a mixed oxide of ZnO, TiO2 and at least one further oxide, and further metal and/or oxide layers, especially with one or more functional silver layers. Preferred Features: The mixed oxide layer is 2-20 nm thick and is produced by reactive cathode sputtering from a metal alloy target having 90-40 weight % Zn, 10-60 weight % Ti, and 0.5-8 weight % of one or more of the metals Al, Ga and Sb. The alloy target consists of 71 weight % Zn, 27 weight % Ti and 2 weight % Al, or 56 weight % Zn, 42 weight % Ti and 2 weight % Al.

Description

Die Erfindung betrifft ein Schichtsystem für transparente Substrate, insbesondere für Glasscheiben, mit wenigstens einer aus einem metallischen Legierungstarget durch reak­ tive Katodenzerstäubung hergestellten Mischoxidschicht aus ZnO, TiO2 und wenigstens einem weiteren Metalloxid.The invention relates to a layer system for transparent substrates, in particular for glass panes, with at least one mixed oxide layer made of a ZnO, TiO 2 and at least one further metal oxide produced from a metallic alloy target by reactive cathode sputtering.

Schichtsysteme für Glasscheiben oder andere transparente Substrate weisen in der Re­ gel als Funktionsschicht eine oder mehrere Silberschichten sowie eine obere und eine un­ tere Entspiegelungsschicht aus Metalloxid auf. Zwischen den Entspiegelungsschichten und der Silberschicht oder den Silberschichten können eine oder mehrere weitere Schich­ ten angeordnet sein, die den Aufbau der Silberschicht begünstigen und/oder das Eindif­ fundieren störender Elemente in die Silberschicht verhindern. Bei den Schichtsystemen kann es sich um Low-E-Schichtsysteme mit Wärmedämmfunktion und/oder um solche mit Sonnenschutzfunktion handeln. Low-E-Schichtsysteme sind farbneutrale Systeme mit ho­ her Lichttransmission und hoher Transmission für die Strahlungswärme der Sonne zur Energieeinsparung im Bauwesen. Bei der industriellen Herstellung werden die Schicht­ systeme mit Hilfe der magnetfeldunterstützten Katodenzerstäubung (Sputtern) aufge­ bracht.Layer systems for glass panes or other transparent substrates show in the Re gel as a functional layer one or more silver layers as well as an upper and an un tere anti-reflective coating made of metal oxide. Between the anti-reflective layers and the silver layer or layers can include one or more additional layers ten arranged to favor the build-up of the silver layer and / or the diff prevent the formation of disturbing elements in the silver layer. With the layer systems can be low-E layer systems with thermal insulation function and / or with Act sun protection function. Low-E coating systems are color-neutral systems with ho forth light transmission and high transmission for the radiant heat of the sun Energy savings in construction. In industrial manufacturing, the layer systems with the help of magnetic field assisted sputtering introduced.

Während des Transports und der Lagerung sind die Oberflächenschichten mechanischen Beanspruchungen, und vor allem in Ländern mit maritimem Klima auch aggressiven che­ mischen Beanspruchungen ausgesetzt. Um die mechanische und die chemische Wider­ standsfähigkeit des Schichtsystems zu erhöhen, ist es bekannt, eine oder mehrere der Oxidschichten, insbesondere die obere Entspiegelungsschicht oder eine Teilschicht der oberen Entspiegelungsschicht, insbesondere die oberste Deckschicht, als Mischoxid­ schicht auszubilden, das heißt als eine aus mehreren Oxiden zusammengesetzte Schicht. Dadurch können die Härte und die chemische Beständigkeit des Schichtsystems verbes­ sert werden.The surface layers are mechanical during transport and storage Stresses, and especially in countries with a maritime climate also aggressive che mix exposed to stress. To counter the mechanical and chemical To increase the durability of the layer system, it is known to use one or more of the Oxide layers, especially the top anti-reflective layer or a partial layer of the top anti-reflective layer, especially the top cover layer, as a mixed oxide to form a layer, that is to say as a layer composed of several oxides. As a result, the hardness and chemical resistance of the coating system can change be tested.

DE-C1-198 52 358 befasst sich mit einem thermisch hoch belastbaren Low-E-Schichtsys­ tem auf thermisch vorzuspannenden Glasscheiben, das als Deckschicht ein ZnO-haltiges Mischoxid mit Spinellstruktur und der allgemeinen Formel ZnxMeyOz umfasst. Als Metall­ oxide sind SnO2, TiO2, Bi2O3 und ZnO genannt. Die Mischoxidschicht kann darüber hinaus Aluminiumoxid enthalten, wenn die Deckschicht reaktiv aus einem metallischen Legie­ rungstarget der Zusammensetzung 68 Gew.-% Zn, 30 Gew.-% Sn und 2 Gew.-% Al ge­ sputtert wird.DE-C1-198 52 358 is concerned with a thermally highly resilient low-E layer system on thermally toughened glass panes, which comprises a ZnO-containing mixed oxide with spinel structure and the general formula Zn x Me y O z as the top layer. SnO 2 , TiO 2 , Bi 2 O 3 and ZnO are mentioned as metal oxides. The mixed oxide layer can also contain aluminum oxide if the cover layer is reactively sputtered from a metallic alloy target of the composition 68% by weight Zn, 30% by weight Sn and 2% by weight Al.

DE-C1-197 32 978 und DE-C1-197 32 977 beschreiben jeweils aus Zn, Al und Si enthal­ tenden Legierungstargets herstellbare und als Deck- und/oder Entspiegelungsschichten eingesetzte Metall-Mischoxid-Teilschichten von Low-E-Schichtsystemen.DE-C1-197 32 978 and DE-C1-197 32 977 each contain Zn, Al and Si tendency alloy targets can be produced and as top and / or anti-reflective layers Metal mixed oxide partial layers of low-E layer systems used.

Ein weiteres Schichtsystem mit einer Mischoxidschicht der eingangs genannten Art ist aus EP-B1-0 304 234 bekannt. Auch dort besteht die Mischoxidschicht aus wenigstens zwei Metalloxiden, von denen ein Metalloxid ein Oxid von Ti, Zr oder Hf, und das andere Metalloxid ein Oxid von Zn, Sn, In oder Bi ist. Die Mischoxidschicht kann dabei durch gleichzeitiges Aufstäuben aus verschiedenen Metalltargets oder aus einem beide Metalle enthaltenden Legierungstarget hergestellt werden.Another layer system with a mixed oxide layer of the type mentioned above is made EP-B1-0 304 234 known. There, too, the mixed oxide layer consists of at least two Metal oxides, one of which is an oxide of Ti, Zr or Hf, and the other Metal oxide is an oxide of Zn, Sn, In or Bi. The mixed oxide layer can Dusting simultaneously from different metal targets or from both metals containing alloy target can be produced.

JP 2000 119 062 A offenbart ein oxidisches Sputtertarget mit den Anteilen 0,1 bis 20 Gew.-% Al2O3 + Ga2O3, 0,01 bis 5 Gew.-% TiO2, 0,01 bis 10 Gew.-% Nb2O5, V2O5, B2O3, SiO2 oder P2O5, Rest ZnO, und JP 2000 195 101 A erörtert ein weiteres oxidisches Sputtertarget mit der Hauptkomponente ZnO sowie den Anteilen 0,1 bis 20 Gew.-% Al2O3 + Ga2O3, 0,01 bis 5 Gew.-% TiO2. Diese bekannten Sputtertargets sind zum Erzeugen von Schutz­ schichten auf optischen Datenträgern (CD, DVD) vorgesehen.JP 2000 119 062 A discloses an oxidic sputtering target with the proportions 0.1 to 20 wt.% Al 2 O 3 + Ga 2 O 3 , 0.01 to 5 wt.% TiO 2 , 0.01 to 10 wt. % Nb 2 O 5 , V 2 O 5 , B 2 O 3 , SiO 2 or P 2 O 5 , rest ZnO, and JP 2000 195 101 A discusses another oxidic sputtering target with the main component ZnO and the proportions 0.1 to 20% by weight Al 2 O 3 + Ga 2 O 3 , 0.01 to 5% by weight TiO 2 . These known sputtering targets are provided to generate protective layers on optical data carriers (CD, DVD).

Aus EP-A1-0 922 681 ist es bekannt, zur Erhöhung der mechanischen und der chemi­ schen Beständigkeit die obere Entspiegelungsschicht aus zwei Teilschichten auszubilden, von denen die obere Teilschicht aus einem Mischoxid auf der Basis von Zink und Alumini­ um besteht, insbesondere mit Spinellstruktur vom Typ ZnAl2O4.From EP-A1-0 922 681 it is known to increase the mechanical and chemical resistance of the upper anti-reflective layer from two sub-layers, of which the upper sub-layer consists of a mixed oxide based on zinc and aluminum, in particular with a spinel structure of the type ZnAl 2 O 4 .

In DE-C1-198 48 751 ist ein Schichtsystem mit einer Mischoxidschicht beschrieben, die bezogen auf den gesamten Metallanteil 35 bis 70 Gew.-% Zn, 29 bis 64,5 Gew.-% Sn und 0,5 bis 6,5 Gew.-% eines oder mehrerer der Elemente Al, Ga, In, B, Y, La, Ge, Si, As, Sb, Bi, Ce, Ti, Zr, Nb und Ta enthält. DE-C1-198 48 751 describes a layer system with a mixed oxide layer which based on the total metal content 35 to 70 wt .-% Zn, 29 to 64.5 wt .-% Sn and 0.5 to 6.5% by weight of one or more of the elements Al, Ga, In, B, Y, La, Ge, Si, As, Sb, Bi, Ce, Ti, Zr, Nb and Ta contains.  

Zum Stand der Technik gehört auch das in dem Dokument EP-A1-0 593 883 beschriebe­ ne Schichtsystem, bei dem die obere Entspiegelungsschicht als eine nichtmetallische Dreifachschicht ausgebildet ist, die aus zwei Zinkoxidschichten und einer zwischen diesen angeordneten Titanoxidschicht besteht, die nacheinander aufgestäubt werden. Die Drei­ fachschicht kann mit einer weiteren Deckschicht aus Titanoxid bedeckt sein. Die Verfas­ ser des Dokuments nehmen an, dass sich während des Beschichtungsvorgangs zwischen den Zinkoxidschichten und der Titanoxidschicht eine im Subnanometerbereich liegende Zinktitanatschicht bildet, durch die die Schutzwirkung gegenüber Umgebungseinflüssen verstärkt wird. Analytisch sind jedoch Zwischenschichten aus Zinktitanat bei diesem Schichtsystem nicht nachweisbar.The state of the art also includes that described in document EP-A1-0 593 883 ne layer system, in which the top anti-reflective layer as a non-metallic Triple layer is formed, which consists of two zinc oxide layers and one between them arranged titanium oxide layer, which are dusted one after the other. The three compartment layer can be covered with a further cover layer made of titanium oxide. The author of the document assume that during the coating process between the zinc oxide layers and the titanium oxide layer are in the subnanometer range Zinc titanate layer forms through which the protective effect against environmental influences is reinforced. Intermediate layers of zinc titanate are, however, analytical for this Layer system not detectable.

Bei industriellen Beschichtungsanlagen ist das Aufstäuben von Zinktitanat-Schichten aus Zn-Ti-Legierungstargets mit Schwierigkeiten verbunden. Insbesondere zu Beginn des Sputterprozesses kommt es nämlich bei diesem Material am Target und an den Teilen der Sputterkammer zu elektrisch isolierenden Ablagerungen, die fehlerhafte Produkte und da­ mit Produktionsausschuss zur Folge haben.Dusting of zinc titanate layers is a thing of the past in industrial coating systems Zn-Ti alloy targets are difficult. Especially at the beginning of the Sputtering process occurs with this material on the target and on the parts of the Sputtering chamber for electrically insulating deposits, the faulty products and there with production scrap.

Der Erfindung liegt die Aufgabe zugrunde, Schichtsysteme mit wenigstens einer Misch­ oxidschicht aus ZnO und TiO2 einerseits hinsichtlich ihrer Härte und ihrer chemischen Be­ ständigkeit weiter zu verbessern und andererseits die beim Sputterprozess von ZnTi-Le­ gierungen auftretenden Schwierigkeiten zu vermeiden.The invention has for its object to further improve layer systems with at least one mixed oxide layer of ZnO and TiO 2 on the one hand with regard to their hardness and chemical resistance and on the other hand to avoid the difficulties encountered in the sputtering process of ZnTi alloys.

Diese Aufgabe wird mit den Merkmalen des Patentanspruchs 1 erfindungsgemäß gelöst.This object is achieved according to the invention with the features of patent claim 1.

Die erfindungsgemäß zusammengesetzte Mischoxidschicht kann innerhalb des Schicht­ systems grundsätzlich an beliebiger Stelle angeordnet sein. Zweckmäßigerweise bildet sie jedoch als Teilschicht der oberen Entspiegelungsschicht die eigentliche Deckschicht des Schichtsystems. Die untere Entspiegelungsschicht und die andere Teilschicht der oberen Entspiegelungsschicht können beispielsweise aus SnO2, ZnO, TiO2 und/oder Bi2O3 bestehen.The composite oxide layer composed according to the invention can in principle be arranged anywhere in the layer system. However, it expediently forms the actual top layer of the layer system as a partial layer of the upper anti-reflective layer. The lower anti-reflective layer and the other partial layer of the upper anti-reflective layer can consist, for example, of SnO 2 , ZnO, TiO 2 and / or Bi 2 O 3 .

Legierungstargets, mit denen derartige, bevorzugt zwischen 2 bis 20 nm dicke Mischoxid­ schichten hergestellt werden, weisen dementsprechend 90 bis 40 Gew.-% Zn, 10 bis 60 Gew.-% Ti und 0,5 bis 8 Gew.-% eines oder mehrere der Metalle Al, Ga und Sb auf.Alloy targets with which such mixed oxide, preferably between 2 to 20 nm thick layers are produced, accordingly have 90 to 40 wt .-% Zn, 10 to 60 wt .-% Ti and 0.5 to 8% by weight of one or more of the metals Al, Ga and Sb.

Nachfolgend werden drei Vergleichsbeispiele für Schichtsysteme mit Mischoxidschichten nach dem Stand der Technik einem erfindungsgemäßen Ausführungsbeispiel gegenüber gestellt. Dabei weisen die Schichtsysteme bei allen Beispielen dieselbe Schichtenfolge auf, und die Mischoxidschicht bildet in allen Fällen die oberste Deckschicht. The following are three comparative examples for layer systems with mixed oxide layers according to the prior art compared to an embodiment of the invention posed. The layer systems have the same layer sequence in all examples and the mixed oxide layer forms the top cover layer in all cases.  

Zur Bewertung der Schichteigenschaften wurden bei allen Beispielen acht verschiedene Tests durchgeführt, nämlichTo evaluate the layer properties, eight different ones were used in all examples Tests carried out, namely

1. Ritzhärtetest1. Scratch hardness test

Hierbei wird eine gewichtsbelastete Nadel mit definierter Geschwindigkeit über die Schicht gezogen. Das Gewicht, bei dem Ritzspuren sichtbar werden, dient als Maß für die Ritz­ härte.Here, a weight-loaded needle is passed over the layer at a defined speed drawn. The weight at which scratch marks become visible serves as a measure of the scratch hardness.

2. Tabertest2. Tabertest

Die Schicht wird mit einer reibenden Rolle definierter Körnung unter definiertem Anpress­ druck und vorgegebener Umdrehungszahl belastet. Die angegriffene Schicht wird mikro­ skopisch ausgewertet. Der nicht zerstörte Schichtanteil wird in % angegeben.The layer is applied with a grinding roll of defined grain under a defined contact pressure pressure and given number of revolutions. The attacked layer becomes micro scopically evaluated. The percentage of layers not destroyed is given in%.

3. Erichsen-Waschtest nach ASTM 24863. Erichsen wash test according to ASTM 2486

Visuelle Beurteilung der Kratzer nach 1000 Hüben.Visual assessment of the scratches after 1000 strokes.

4. Schwitzwassertest nach DIN 500214. Condensation water test according to DIN 50021

Visuelle Beurteilung der Schichtveränderungen nach 240 Stunden.Visual assessment of shift changes after 240 hours.

5. Streulichtmessung5. Scattered light measurement

Nach dem Schwitzwassertest wird mit einem Streulichtmeßgerät der Firma Gardner der sich aufgrund von Schichtveränderungen ergebende Streulichtanteil gemessen. Der Anteil des Streulichts wird in % angegeben.After the condensation water test, the scattered light component resulting from layer changes measured. The amount of the scattered light is given in%.

6. EMK-Test6. EMF test

Dieser Test ist beschrieben in Z. Silikattechnik 32 (1981) S. 216. Er erlaubt eine Aussage über die Passivierungsqualität der Deckschicht oberhalb der Silberschicht sowie über das Korrosionsverhalten der Ag-Schicht. Je geringer die Potentialdifferenz (in mV) zwischen dem Schichtsystem und der Bezugselektrode ist, umso besser ist die Schichtqualität.This test is described in Z. Silikattechnik 32 (1981) p. 216. It allows a statement about the passivation quality of the top layer above the silver layer and about the Corrosion behavior of the Ag layer. The smaller the potential difference (in mV) between the layer system and the reference electrode, the better the layer quality.

7. Salzsprühtest nach DIN 50021/Visuelle Beurteilung der Schichtveränderungen7. Salt spray test according to DIN 50021 / visual assessment of changes in the layer 8. Klimawechseltest nach DIN 52344/Visuelle Beurteilung der Schichtveränderungen8. Climate change test according to DIN 52344 / visual assessment of the layer changes

Auf diese Tests wird im folgenden durch Angabe ihrer Nummerierung Bezug genommen.These tests are referred to below by specifying their numbering.

Vergleichsbeispiel 1Comparative Example 1

In einer industriellen Durchlauf-Magnetronanlage wurde auf 4 mm dicke Floatglas-Schei­ ben ein Schichtsystem nach dem Stand der Technik mit folgender Schichtenfolge aufge­ bracht:
In a continuous industrial magnetron system, a layer system according to the state of the art with the following layer sequence was applied to 4 mm thick float glass panes:

Glas-20 nm SnO2-17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO2-2 nm ZnxSnySbzOn.Glass-20 nm SnO 2 -17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO 2 -2 nm Zn x Sn y Sb z O n .

Die die Deckschicht bildende Mischoxidschicht wurde entsprechend der DE-C1-198 48 751 von einem metallischen Target der Zusammensetzung 68 Gew.-% Zn, 30 Gew.-% Sn und 2 Gew.-% Sb in einer Ar/O2-Arbeitsgasatmosphäre gesputtert.The mixed oxide layer forming the cover layer was sputtered in accordance with DE-C1-198 48 751 from a metallic target of the composition 68% by weight Zn, 30% by weight Sn and 2% by weight Sb in an Ar / O 2 working gas atmosphere ,

Die an diesem Schichtsystem durchgeführten Tests Nr. 1 bis 8 ergaben folgende Werte:
Tests No. 1 to 8 carried out on this layer system gave the following values:

  • 1. 30-175 g1. 30-175 g
  • 2. 87%2. 87%
  • 3. 11 kleine Kratzer3. 11 small scratches
  • 4. rote Flecken4. red spots
  • 5. 0,23%5. 0.23%
  • 6. 111 mV6. 111 mV
  • 7. nach 24 Stunden punktförmige Defekte 7. Spot defects after 24 hours  
  • 8. nach 24 Stunden matte Stellen8. matt spots after 24 hours
Vergleichsbeispiel 2Comparative Example 2

Auf derselben Beschichtungsanlage wurde die gleiche Schichtfolge auf 4 mm dicken Floatglasscheiben abgeschieden mit dem einzigen Unterschied, daß die Mischoxid-Deck­ schicht durch ein stöchiometrisches Mischoxid ersetzt wurde, das entsprechend EP-A1-0 922 681 von einem metallischen Legierungstarget der Zusammensetzung 55 Gew.-% Zn und 45 Gew.-% Al gesputtert wurde. Die Schichtenfolge war wie folgt:
The same layer sequence was deposited on 4 mm thick float glass panes on the same coating system with the only difference that the mixed oxide cover layer was replaced by a stoichiometric mixed oxide which, according to EP-A1-0 922 681, had a metal alloy target with a composition of 55% by weight. % Zn and 45% by weight Al was sputtered. The layer sequence was as follows:

Glas-20 nm SnO2-17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO2-3 nm ZnAl2O4 Glass-20 nm SnO 2 -17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO 2 -3 nm ZnAl 2 O 4

Die Tests ergaben folgende Schichtbewertung:
The tests gave the following shift evaluation:

  • 1. 49-119 g1. 49-119 g
  • 2. 83-90%2. 83-90%
  • 3. keine Kratzer3. no scratches
  • 4. ein punktförmiger Defekt4. a punctiform defect
  • 5. 0,26%5. 0.26%
  • 6. 190 mV6. 190 mV
  • 7. nach 24 Stunden punktförmige Defekte7. Spot defects after 24 hours
  • 8. nach 24 Stunden Korrosionspunkte8. after 24 hours corrosion spots
Vergleichsbeispiel 3Comparative Example 3

Bei grundsätzlich gleichem Schichtaufbau wie in den vorangegangenen Beispielen wurde eine Mischoxid-Deckschicht aus ZnO und TiO2 aufgebracht, bei der die Mischoxidschicht 3 At.-% Ti bezogen auf ihren gesamten Metallgehalt enthielt. Eine solche Deckschicht ist in der EP-A1-0751099 beschrieben. Sie wurde von einem Target der Zusammensetzung 97 At.-% Zn und 3 At.-% Ti das auf derselben Sputteranlage in einer reaktiven Ar/O2-Ar­ beitsgasatmosphäre aufgebracht und führte zu einer nichtstöchiometrischen Mischoxid­ schicht der qualitativen Zusammensetzung ZnO/Zn2TiO4. Das Schichtsystem hatte folgen­ den Aufbau:
With basically the same layer structure as in the previous examples, a mixed oxide cover layer made of ZnO and TiO 2 was applied, in which the mixed oxide layer contained 3 at.% Ti based on its total metal content. Such a cover layer is described in EP-A1-0751099. It was applied by a target with the composition 97 at.% Zn and 3 at.% Ti to the same sputtering system in a reactive Ar / O 2 working gas atmosphere and resulted in a non-stoichiometric mixed oxide layer of the qualitative composition ZnO / Zn 2 TiO 4th The layer system had the following structure:

Glas-20 nm SnO2-17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO2-3 nm ZnO/Zn2TiO4.Glass-20 nm SnO 2 -17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO 2 -3 nm ZnO / Zn 2 TiO 4 .

Während der Schichtabscheidung im reaktiven Sputterbetrieb gab es nach ca. 2 tägigem Betrieb mit diesem Targetmaterial erhebliche Probleme in der entsprechenden Sputter­ kammer, so daß der Prozess abgebrochen werden musste.During the shift deposition in reactive sputtering operation, there was after about 2 days Operation with this target material poses significant problems in the corresponding sputter chamber, so that the process had to be stopped.

Dieses Schichtsystem zeigte folgende Eigenschaften:
This layer system showed the following properties:

  • 1. 112-193 g 1. 112-193 g  
  • 2. 90-91%2. 90-91%
  • 3. 2 mittlere und 10 kleine Kratzer3. 2 medium and 10 small scratches
  • 4. rote Flecken4. red spots
  • 5. 0,33%5. 0.33%
  • 6. 130 mV6. 130 mV
  • 7. nach 24 Stunden punktförmige Defekte7. Spot defects after 24 hours
  • 8. nach 24 Stunden Korrosionpunkte8. after 24 hours corrosion points
Ausführungsbeispielembodiment

Ebenso wie bei den Vergleichsbeispielen wurde auf die gleiche Schichtenfolge als Deck­ schicht die erfindungsgemäße Schicht gesputtert, und zwar von einem Target der Zusam­ mensetzung 71 Gew.-% Zn, 27 Gew.-% Ti und 2 Gew.-% Al.As with the comparative examples, the same layer sequence was used as the deck layer sputtered the layer according to the invention, specifically from a target of the composite composition 71% by weight of Zn, 27% by weight of Ti and 2% by weight of Al.

Bei einem Ar/O2-Verhältnis des Arbeitsgases von 70 : 30 konnte eine im wesentlichen stö­ chiometrische Zn2TiO4-Schicht abgeschieden werden mit hoher Oberflächenglätte. Der Sputterbetrieb verlief problemlos. Das Schichtsystem hatte folgenden Aufbau:
With an Ar / O 2 ratio of the working gas of 70:30, an essentially stoichiometric Zn 2 TiO 4 layer could be deposited with high surface smoothness. The sputtering operation went smoothly. The layer system had the following structure:

Glas-20 nm SnO2-17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO2-3 nm Zn2TiO4 : AlGlass-20 nm SnO 2 -17 nm ZnO-11 nm Ag-2 nm CrNi-38 nm SnO 2 -3 nm Zn 2 TiO 4 : Al

Die Tests ergaben folgende Eigenschaften dieses Schichtsystems:
The tests revealed the following properties of this layer system:

  • 1. 136-241 g1. 136-241 g
  • 2. 91-92%2. 91-92%
  • 3. 1 mittlerer und 3 kleine Kratzer3. 1 medium and 3 small scratches
  • 4. nach 360 Stunden keine Fehler4. No errors after 360 hours
  • 5. 0,25%5. 0.25%
  • 6. 60 mV6. 60 mV
  • 7. nach 48 Stunden keine Fehler, ab 55 Stunden erste Fehler7. No mistakes after 48 hours, first mistakes after 55 hours
  • 8. nach 24 Stunden keine Fehler, nach 48 Stunden erste Fehler8. No errors after 24 hours, first errors after 48 hours

Die folgende Tabelle fasst die Testergebnisse der vier Beispiele der Übersichtlichkeit halber noch einmal zusammen:
The following table summarizes the test results of the four examples for the sake of clarity:

Der Vergleich mit den Ergebnissen der Beispiele nach dem Stand der Technik zeigt, dass eine Zn2TiO4 : Al-Mischoxidschicht im Schichtsystem zu folgenden ausgezeichneten Eigenschaften führt:
A comparison with the results of the prior art examples shows that a Zn 2 TiO 4 : Al mixed oxide layer in the layer system leads to the following excellent properties:

  • - problemloser Sputterbetrieb,- trouble-free sputtering,
  • - hohe Härte der Schicht,- high hardness of the layer,
  • - sehr gute elektrochemische Passivierung,- very good electrochemical passivation,
  • - hohe Beständigkeit gegenüber Feuchtigkeit und gegenüber Elektrolyten wie zum Beispiel einer NaCl-Lösung, woraus auf eine sehr gute Beständigkeit im Meerwasserklima geschlossen werden kann.- high resistance to moisture and to electrolytes such as Example of a NaCl solution, indicating very good resistance in the Seawater climate can be closed.

Claims (8)

1. Schichtsystem, insbesondere Low-E-Schichtsystem, für transparente Sub­ strate, insbesondere für Glasscheiben, mit wenigstens einer Teilschicht aus einem Mischoxid von ZnO, TiO2 und wenigstens einem weiteren Oxid sowie weiteren metallischen und/oder oxidischen Schichten, insbesondere mit einer oder mehre­ ren Funktionsschichten aus Silber, dadurch gekennzeichnet, dass in der Misch­ oxidschicht ZnO und TiO2 im wesentlichen in molaren Verhältnissen von 1 : 1 oder 2 : 1 vorhanden sind, das weitere Oxid Al2O3, Ga2O3, und/oder Sb2O3 ist und der Anteil der weiteren Oxide Al2O3, Ga2O3, und/oder Sb2O3 in der Mischoxidschicht 0,5 bis 8 Gew.-% beträgt.1. Layer system, in particular low-E layer system, for transparent substrates, in particular for glass panes, with at least one partial layer composed of a mixed oxide of ZnO, TiO 2 and at least one further oxide and further metallic and / or oxide layers, in particular with one or Several functional layers made of silver, characterized in that the mixed oxide layer ZnO and TiO 2 are essentially in molar ratios of 1: 1 or 2: 1, the further oxide Al 2 O 3 , Ga 2 O 3 , and / or Sb 2 O 3 and the proportion of the further oxides Al 2 O 3 , Ga 2 O 3 , and / or Sb 2 O 3 in the mixed oxide layer is 0.5 to 8% by weight. 2. Schichtsystem nach Anspruch 1, dadurch gekennzeichnet, dass die Dicke der Mischoxidschicht 2 bis 20 nm beträgt.2. Layer system according to claim 1, characterized in that the thickness the mixed oxide layer is 2 to 20 nm. 3. Schichtsystem nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die Mischoxidschicht in einem eine oder mehrere Funktionsschichten aus Silber auf­ weisenden Low-E-Schichtsystem eine untere und/oder eine obere Entspiege­ lungsschicht oder eine Teilschicht einer solchen Entspiegelungsschicht ist.3. Layer system according to claim 1 or 2, characterized in that the Mixed oxide layer in one or more functional layers made of silver pointing low-E layer system a lower and / or an upper relaxation Coating layer or a partial layer of such an anti-reflective layer. 4. Schichtsystem nach Anspruch 1 oder 2 oder 3, dadurch gekennzeichnet, dass die Mischoxidschicht die eigentliche Deckschicht des Schichtsystems ist.4. Layer system according to claim 1 or 2 or 3, characterized in that the mixed oxide layer is the actual top layer of the layer system. 5. Schichtsystem nach einem der Ansprüche 1 bis 4, gekennzeichnet durch den Schichtaufbau: Substrat-SnO2-ZnO-Ag-CrNi-SnO2-Zn2TiO4 : Al. 5. Layer system according to one of claims 1 to 4, characterized by the layer structure: substrate-SnO 2 -ZnO-Ag-CrNi-SnO 2 -Zn 2 TiO 4 : Al. 6. Schichtsystem nach einem der Ansprüche 1 bis 5, dadurch gekennzeich­ net, dass die Mischoxidschicht durch reaktive Katodenzerstäubung aus einem metallischen Legierungstarget mit 90 bis 40 Gew.-% Zn, 10 bis 60 Gew.-% Ti und 0,5 bis 8 Gew.-% eines oder mehrerer der Metalle Al, Ga, und Sb hergestellt ist.6. Layer system according to one of claims 1 to 5, characterized in net that the mixed oxide layer by reactive sputtering from a metallic alloy target with 90 to 40 wt.% Zn, 10 to 60 wt.% Ti and 0.5 to 8 wt .-% of one or more of the metals Al, Ga, and Sb is produced. 7. Schichtsystem nach Anspruch 6, dadurch gekennzeichnet, dass das Legie­ rungstarget 71 Gew.-% Zn, 27 Gew.-% Ti und 2 Gew.-% Al enthält.7. Layer system according to claim 6, characterized in that the alloy contains about 71% by weight of Zn, 27% by weight of Ti and 2% by weight of Al. 8. Schichtsystem nach Anspruch 6, dadurch gekennzeichnet, dass das Legie­ rungstarget für die Herstellung der Mischoxidschicht 56 Gew.-% Zn, 42 Gew.-% Ti und 2 Gew.-% Al enthält.8. Layer system according to claim 6, characterized in that the alloy target for the production of the mixed oxide layer 56 wt .-% Zn, 42 wt .-% Ti and contains 2% by weight of Al.
DE10152211A 2001-10-23 2001-10-23 Layer system used for transparent substrates comprises a partial layer of a mixed oxide of zinc oxide, titanium oxide and a further oxide, and further metal and/or oxide layers with functional silver layers Expired - Fee Related DE10152211C1 (en)

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