DE102008025108B4 - Process for the production of nanoscale electrically conductive multilayer systems - Google Patents

Process for the production of nanoscale electrically conductive multilayer systems Download PDF

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DE102008025108B4
DE102008025108B4 DE200810025108 DE102008025108A DE102008025108B4 DE 102008025108 B4 DE102008025108 B4 DE 102008025108B4 DE 200810025108 DE200810025108 DE 200810025108 DE 102008025108 A DE102008025108 A DE 102008025108A DE 102008025108 B4 DE102008025108 B4 DE 102008025108B4
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layer
precursor
burner
mol
coating
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DE102008025108A1 (en
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Dr. Heft Andreas
Thomas Struppert
Dr. Grünler Bernd
Dr. Pfuch Andreas
Alexander Jacob
Prof. Dr. Lang Heinrich
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VER ZUR FOERDERUNG VON INNOVATIONEN DURCH FORSCHUNG ENTWICKLUNG und TECHNOLOGIETRANSFER E V VEREIN I
Verein Zur Forderung Von Innovationen Durch Forschung Entwicklung und Technologietransfer Ev (verein Innovent Ev)
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VER ZUR FOERDERUNG VON INNOVATIONEN DURCH FORSCHUNG ENTWICKLUNG und TECHNOLOGIETRANSFER E V VEREIN I
Verein Zur Forderung Von Innovationen Durch Forschung Entwicklung und Technologietransfer Ev (verein Innovent Ev)
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    • C23COATING 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
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    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/453Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating passing the reaction gases through burners or torches, e.g. atmospheric pressure CVD
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
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    • C03C17/3655Surface 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
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/3602Surface 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
    • C03C17/3657Surface 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
    • C03C17/366Low-emissivity or solar control coatings
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
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    • C03C17/3602Surface 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
    • C03C17/3668Surface 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 electrical properties
    • C03C17/3673Surface 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 electrical properties specially adapted for use in heating devices for rear window of vehicles
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    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3681Surface 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
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    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • C23C16/18Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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    • C23COATING 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
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    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40Oxides
    • C23C16/405Oxides of refractory metals or yttrium
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    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/70Properties of coatings
    • C03C2217/78Coatings specially designed to be durable, e.g. scratch-resistant

Abstract

Verfahren zur Herstellung von nanoskaligen elektrisch leitfähigen Mehrschichtsystemen, welches aus einem Substrat und den darüber liegenden Schichten zur Haftvermittlung, zur Barrierewirkung und zum Schutz besteht, dadurch gekennzeichnet, dass – eine Flammenpyrolyse-Anlage mit einem temperierbaren Verfahrtisch und Brenner verwendet wird, wobei folgende Parameter einstellbar sind:Gas-Mischung: Brenngasgemisch (Propan/Luft) Volumenstrom Gas: 1–2 l/min Volumenstrom Luft: 20–50 l/min Brenner: Lochbrenner mit Homogenisatoraufsatz (Breite 220 mm) Vorheiztemperatur Verfahrtisch: 30–80°C Geschwindigkeit Verfahrtisch: 15–100 mm/s Abstand Substrat-Brenner: 4–8 mm – zur Abscheidung der Wolframoxidschicht ein Precursor in Form von Ammonium(meta)-wolframat, welches in Methanol/Wasser (2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,01 bis 0,5 mol/l eingestellt wird und die Beschichtung 5 bis 20 mal durchgeführt wird, so dass sich eine Schichtdicke bis maximal 30 nm einstellt, – zur Abscheidung der Zirkoniumoxidschicht ein Precursor in Form von Zirkonium(IV)acetylacetonat, welches in Ethanol/Wasser (2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,05 bis 0,5 mol/l eingestellt wird und die Beschichtung 5 bis 20 mal durchgeführt wird, so...Process for the production of nanoscale electrically conductive multi-layer systems, which consists of a substrate and the layers above for adhesion, for barrier effect and protection, characterized in that - a flame pyrolysis system with a temperature-controlled traversing table and burner is used, the following parameters being adjustable are: gas mixture: fuel gas mixture (propane / air) volume flow gas: 1–2 l / min volume flow air: 20–50 l / min burner: perforated burner with homogenizer attachment (width 220 mm) preheating temperature moving table: 30–80 ° C speed moving table : 15-100 mm / s distance substrate burner: 4-8 mm - a precursor in the form of ammonium (meta) tungstate, which is dissolved in methanol / water (2: 1), is used to deposit the tungsten oxide layer, whereby the precursor concentration is set to 0.01 to 0.5 mol / l and the coating is carried out 5 to 20 times, so that a layer thickness of up to max times 30 nm, - a precursor in the form of zirconium (IV) acetylacetonate, which is dissolved in ethanol / water (2: 1), is used to deposit the zirconium oxide layer, the precursor concentration being 0.05 to 0.5 mol / l is set and the coating is carried out 5 to 20 times, so ...

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von nanoskaligen elektrisch leitfähigen Mehrschichtsystemen auf Oberflächen, wobei die beschichteten Oberflächen insbesondere zum Wärme- oder Sonnenschutz bzw. in Heizelementen zur Anwendung kommen.The invention relates to a method for producing nanoscale electrically conductive multilayer systems on surfaces, wherein the coated surfaces are used in particular for heat or sun protection or in heating elements.

PVD-Verfahren (Physical vapor deposition) sind seit langem Stand der Technik. Durch Beschuss von Atomen eines Materials mit hochenergetischen Edelgasionen (Sputter-Prozess) ist es möglich, diese aus dem Verbund herauszureißen und auf dem Substrat abzuscheiden.PVD (Physical Vapor Deposition) methods have long been state of the art. By bombarding atoms of a material with high-energy noble gas ions (sputtering process), it is possible to rip them out of the composite and deposit them on the substrate.

Zum Abscheiden von Metallschichten werden vorwiegend diese PVD-Verfahren (z. B. DE 10 2004 001 655 A1 ) eingesetzt. Diese benötigen jedoch einen sehr aufwendigen und zugleich sehr kostenintensiven Apparaturaufbau, da sehr niedrige Drücke und/oder spezielle Atmosphären benötigt werden.For deposition of metal layers predominantly these PVD methods (eg. DE 10 2004 001 655 A1 ) used. However, these require a very complex and at the same time very expensive equipment construction, since very low pressures and / or special atmospheres are needed.

Bekannt sind auch Verfahren, bei denen in eine Flamme metallorganische und/oder metallanorganische Verbindungen (Precursor) eingebracht und durch Verbrennungsprozesse zersetzt und auf einer Oberfläche abgeschieden wurden. Diese Verfahren werden als Combustion-CVD-Verfahren oder Flammenpyrolyseverfahren bezeichnet. In der Patentanmeldung DE 10 2006 029 617 A1 sowie dem Patent US 6,193,911 B1 werden mittels dieses Verfahrens heiße Substratoberflächen beschichtet. Die Patentschriften US 4,292,347 A und US 4,401,474 A offenbaren eine pyrolytische Umsetzung von Metallorganylen, speziell Carboxylate und Diketonate, zu den entsprechenden Metalloxiden. Dabei werden die metallorganischen Verbindungen auf heiße Substratoberflächen gesprüht und bilden darauf eine haftfeste Schicht. Die Substrattemperaturen liegen dabei oberhalb von 500°C.Methods are also known in which organometallic and / or organometallic compounds (precursors) are introduced into a flame and decomposed by combustion processes and deposited on a surface. These processes are referred to as combustion CVD processes or flame pyrolysis processes. In the patent application DE 10 2006 029 617 A1 as well as the patent US 6,193,911 B1 hot substrate surfaces are coated by this method. The patents US 4,292,347 A and US 4,401,474 A disclose a pyrolytic reaction of organometallics, especially carboxylates and diketonates, to the corresponding metal oxides. The organometallic compounds are sprayed onto hot substrate surfaces and form an adherent layer thereon. The substrate temperatures are above 500 ° C.

Die thermische CVD benötigt hohe Substrattemperaturen und ist somit nur für wenige Materialen geeignet. (Lit.: H. J. Gläser, Dünnfilmtechnologie auf Flachglas, Schorndorf, Verlag Karl Hofman, 1999) The thermal CVD requires high substrate temperatures and is therefore only suitable for a few materials. (Lit .: H. J. Gläser, thin-film technology on flat glass, Schorndorf, Verlag Karl Hofman, 1999)

Ebenfalls sind aus der Patentanmeldung DE 43 20 931 A1 Beschichtungen mit elektrisch leitenden Schichten bekannt. Hierbei sind die Mehrschichtsysteme aus haftvermittelnden Schichten, Barriereschichten und Schutzschichten aufgebaut, zwischen denen die elektrisch leitende Schicht angeordnet ist. Ferner wird mit der DE 10 2005 061 248 B4 ein Verfahren zur Beschichtung eines Systemträgers mit einer Haftvermittlerschicht offenbart.Also are from the patent application DE 43 20 931 A1 Coatings with electrically conductive layers known. Here, the multilayer systems of adhesion-promoting layers, barrier layers and protective layers are constructed, between which the electrically conductive layer is arranged. Furthermore, with the DE 10 2005 061 248 B4 discloses a method of coating a system carrier with a primer layer.

Der Erfindung liegt die Aufgabe zugrunde, eine Möglichkeit anzugeben, welche die genannten Nachteile der etablierten Verfahren zur Abscheidung von elektrisch leitenden Schichten überwindet.The invention has for its object to provide a way that overcomes the disadvantages of the established methods for the deposition of electrically conductive layers.

Erfindungsgemäß wird diese Aufgabe bei einem Verfahren zur Herstellung von nanoskaligen elektrisch leitfähigen Mehrschichtsystemen, welche aus einem Substrat und den darüber liegenden Schichten zur Haftvermittlung, zur Barrierewirkung und zum Schutz bestehen dadurch gelöst, dass eine Flammenpyrolyse-Anlage mit einem temperierbaren Verfahrtisch und Brenner zur Abscheidung einer Wolframoxidschicht, Zirkoniumoxidschicht und Silberschicht verwendet wird, wobei folgende Parameter einstellbar sind: Gas-Mischung: Brenngasgemisch (Propan/Luft) Volumenstrom Gas: 1–2 l/min Volumenstrom Luft: 20–50 l/min Brenner: Lochbrenner mit Homogenisatoraufsatz (Breite 220 mm) Vorheiztemperatur Verfahrtisch: 30–80°C Geschwindigkeit Verfahrtisch: 15–100 mm/s Abstand Substrat-Brenner: 4–8 mm und zur Abscheidung der Wolframoxidschicht ein Precursor in Form von Ammonium(meta)-wolframat, welches in Methanol/Wasser (Volumenverhältnis 2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,01 bis 0,5 mol/l eingestellt wird und die Beschichtung 5 bis 20 mal durchgeführt wird, so dass sich eine Schichtdicke bis maximal 30 nm einstellt, ferner zur Abscheidung der Zirkoniumoxidschicht ein Precursor in Form von Zirkonium(IV)acetylacetonat, welches in Ethanol/Wasser (Volumenverhältnis 2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,05 bis 0,5 mol/l eingestellt wird und die Beschichtung 5 bis 20 mal durchgeführt wird, so dass sich eine Schichtdicke bis maximal 20 nm einstellt und zur Abscheidung der Silberschicht ein Precursor in Form von Silber(I)-carboxylat, welches in Ethanol/Wasser (2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,1 bis 0,2 mol/l eingestellt wird und die Beschichtung 10 bis 100 mal durchgeführt wird, so dass sich eine Schichtdicke bis maximal 70 nm einstellt.This object is achieved in a method for producing nanoscale electrically conductive multilayer systems, which consist of a substrate and the overlying layers for adhesion, barrier effect and protection in that a flame pyrolysis plant with a temperature-controlled traversing table and burner for the deposition of a Tungsten oxide layer, zirconium oxide layer and silver layer is used, wherein the following parameters are adjustable: Gas mixture: Fuel gas mixture (propane / air) Volume flow of gas: 1-2 l / min Volume flow air: 20-50 l / min Burner: Hole burner with homogenizer attachment (width 220 mm) Preheating temperature traversing table: 30-80 ° C Speed traversing: 15-100 mm / s Distance substrate burner: 4-8 mm and for depositing the tungsten oxide layer, a precursor in the form of ammonium (meta) tungstate dissolved in methanol / water (2: 1 by volume) is used, the precursor concentration being adjusted to 0.01 to 0.5 mol / l and the coating is carried out 5 to 20 times, so that a layer thickness of up to 30 nm sets in, further for depositing the zirconium oxide precursor in the form of zirconium (IV) acetylacetonate, which is dissolved in ethanol / water (volume ratio 2: 1) , is used, wherein the precursor concentration is adjusted to 0.05 to 0.5 mol / l and the coating is carried out 5 to 20 times, so that a layer thickness is set to a maximum of 20 nm and for deposition the silver layer is a precursor in the form of silver (I) carboxylate, which is dissolved in ethanol / water (2: 1) is used, wherein the precursor concentration is adjusted to 0.1 to 0.2 mol / l and the coating 10th is carried out to 100 times, so that sets a layer thickness up to 70 nm.

Der wesentliche Vorteil der Erfindung besteht in der verhältnismäßig einfachen und vor allem preiswerten Bauweise des Beschichtungsapparates. Das verwendete Combustion-CVD-Verfahren wird unter Atmosphärendruck und ohne Schutzgase betrieben. Ein weiterer Vorteil der Erfindung besteht in der Verwendung eines relativ kalten Substrates (maximal 80°C Vorwärmtemperatur) wodurch auch thermisch nicht hoch belastbare Materialen, wie Kunststoffe, beschichtet werden können. Zudem wird der Einsatz und die Kombination spezieller Precursoren benötigt, um die gewünschte Eigenschaft des Mehrschichtsystems zu erhalten.The main advantage of the invention is the relatively simple and above all inexpensive construction of the coating apparatus. The used Combustion-CVD process is operated under atmospheric pressure and without protective gases. Another advantage of the invention is the use of a relatively cold substrate (maximum of 80 ° C preheating) whereby also not highly resilient materials, such as plastics, can be coated. In addition, the use and the combination of special precursors is required to obtain the desired property of the multilayer system.

Erfindungsgemäß setzt sich das Mehrschichtsystem aus einzelnen Schichten zusammen, welche verschiedene Zwecke erfüllen. Dazu gehören Haftvermittlung, Barrierewirkung und Schutz. Zwischen diesen einzelnen Schichten wird mindestens eine elektrisch leitende Schicht, welche elementar oder oxidisch sein kann, eingebaut. Das Mehrschichtsystem kann ebenfalls aus mehreren solchen Basisbaugruppen aufgebaut sein. Die Gesamtschichtdicke des Mehrschichtsystems soll unter 200 nm betragen, wobei die Schichtdicken der einzelnen Schichten 10 bis 70 nm betragen.According to the invention, the multilayer system is composed of individual layers which fulfill different purposes. These include detention, barrier and protection. Between these individual layers, at least one electrically conductive layer, which may be elemental or oxidic, is incorporated. The multilayer system may also be constructed from a plurality of such basic modules. The total layer thickness of the multilayer system should be less than 200 nm, the layer thicknesses of the individual layers being 10 to 70 nm.

Die elektrisch leitenden Schichten bestehen aus Silber oder Gold, welche ab einer Schichtdicke von wenigen Nanometer (< 10 nm) eine gute elektrische Leitfähigkeit besitzen und damit für Anwendungen, bei denen eine hohe IR-Reflexion von Bedeutung ist, in Betracht kommen. Silberschichten bieten darüber hinaus bis zu einer bestimmten Schichtdicke (bis ca. 20 nm) eine hohe Transmission im UV- und sichtbaren Bereich.The electrically conductive layers are made of silver or gold, which have a good electrical conductivity from a layer thickness of a few nanometers (<10 nm) and thus come into consideration for applications in which high IR reflection is of importance. In addition, silver layers offer a high transmission in the UV and visible range up to a certain layer thickness (up to about 20 nm).

Erfindungsgemäß ist eine derartige Abscheidung auch mit einem Atmosphärendruck-Plasma denkbar. Die Schichtbildungsprozesse bei der Umwandlung der entsprechenden Precursoren sind denen in der Flamme sehr ähnlich, so dass auch damit elektrisch leitende nanoskalige Mehrschichtsysteme abgeschieden werden können.According to the invention, such a deposition is also conceivable with an atmospheric pressure plasma. The layer formation processes in the conversion of the corresponding precursors are very similar to those in the flame, so that electrically conductive nanoscale multilayer systems can be deposited therewith.

Die Erfindung soll nachstehend anhand von Ausführungsbeispielen näher erläutert werden. In der dazugehörigen Zeichnung zeigtThe invention will be explained below with reference to exemplary embodiments. In the accompanying drawing shows

1 den Aufbau eines Mehrschichtsystems. 1 the construction of a multi-layer system.

Das erfindungsgemäße Verfahren ist gerichtet auf die Herstellung eines Mehrschichtsystems 1 basierend auf Wolframoxid 3, Zirkoniumoxid 4, elektrisch leitende Schicht (Silber, Gold, ...) 5 und einer Schutzschicht 6 auf einem Substrat 2. Substrate 2 können dabei Glas, Kunststoff oder sogar Metalle sein.The inventive method is directed to the production of a multi-layer system 1 based on tungsten oxide 3 , Zirconium oxide 4 , electrically conductive layer (silver, gold, ...) 5 and a protective layer 6 on a substrate 2 , substrates 2 can be glass, plastic or even metals.

Beispiel 1example 1

Die Abscheidung eines Mehrschichtsystems 1 auf Glas kann als Wärmeschutzverglasung Anwendung finden. Die elektrisch leitende Schicht, welche vorrangig aber nicht zwangsläufig aus Silber besteht, trägt dabei die Eigenschaft der Reflexion der IR-Strahlung. Silber weist bei einer guten IR-Reflexion noch eine hohe Transmission im UV- und sichtbaren Bereich auf.The deposition of a multilayer system 1 on glass can be used as heat protection glazing application. The electrically conductive layer, which primarily but not necessarily consists of silver, thereby carries the property of the reflection of the IR radiation. Silver still has a high transmission in the UV and visible range with good IR reflection.

Inhalt der erfindungsgemäßen Lösung ist die Kopplung eines oxidischen Mehrschichtsystems mit einer Silberschicht 5. Diese Silberschicht 5 wird hierbei direkt auf das oxidische Mehrschichtsystem bestehend aus Wolframoxid 3 und Zirkoniumoxid 4 oder auf ein aus mehreren zusätzlichen Schichten bestehendes Mehrschichtsystem aufgebracht. Mindestens die Silberschicht 5 wird dabei flammenpyrolytisch abgeschieden. Als Precursorsubstanzen werden für die flammenpyrolytische Abscheidung der Metall- und Metalloxidschichten metallorganische und/oder metallanorganische Verbindungen, welche das entsprechende Element enthalten, verwendet. Jedoch ist es von Bedeutung, die einzelnen Precursoren aufeinander abzustimmen, um das gewünschte Mehrschichtsystem mit den gewünschten Eigenschaften zu erhalten.Contents of the solution according to the invention is the coupling of an oxide multilayer system with a silver layer 5 , This silver layer 5 is here directly on the oxide multilayer system consisting of tungsten oxide 3 and zirconium oxide 4 or applied to a multi-layer system consisting of several additional layers. At least the silver layer 5 is deposited by flame pyrolysis. As precursor substances, organometallic and / or organometallic compounds containing the corresponding element are used for the flame pyrolytic deposition of the metal and metal oxide layers. However, it is important to tailor the individual precursors in order to obtain the desired multilayer system with the desired properties.

Nachfolgend wird der Parameterbereich für die flammenpyrolytische Abscheidung der einzelnen Schichten angegeben: Flammenpyrolyse-Anlage mit temperierbaren Verfahrtisch und Brenner Gas-Mischung: Brenngasgemisch (Propan/Luft) Volumenstrom Gas: 1–2 l/min Volumenstrom Luft: 20–50 l/min Brenner: Lochbrenner mit Homogenisatoraufsatz (Breite 220 mm) Vorheiztemperatur Verfahrtisch: 30–80°C Geschwindigkeit Verfahrtisch: 15–100 mm/s Abstand Substrat-Brenner: 4–8 mm Parameterbereich für Wolframoxid-Schichtabscheidung Precursor: Ammonium(meta)-wolframat in Methanol/Wasser (2:1) Precursorkonzentration: 0,01–0,5 mol/l Anzahl an Durchlaufen: 5–20 Schichtdicke: bis 30 nm Parameterbereich für Zirkoniumoxid-Schichtabscheidung Precursor: Zirkonium(IV)acetylacetonat in Ethanol/Wasser Precursorkonzentration: 0,05–0,5 mol/l Anzahl an Durchläufen: 5–20 Schichtdicke: bis 20 nm Parameterbereich für Silber-Schichtabscheidung Precursor: Silber(I)-carboxylat in Ethanol/Wasser (2:1) Precursorkonzentration: 0,1–0,2 mol/l Anzahl an Durchlaufen: 10–100 Schichtdicke: bis 70 nm The parameter range for the flame pyrolytic deposition of the individual layers is given below: Flame pyrolysis plant with temperature-controlled travel table and burner Gas mixture: Fuel gas mixture (propane / air) Volume flow of gas: 1-2 l / min Volume flow air: 20-50 l / min Burner: Hole burner with homogenizer attachment (width 220 mm) Preheating temperature traversing table: 30-80 ° C Speed traversing: 15-100 mm / s Distance substrate burner: 4-8 mm Parameter range for tungsten oxide film deposition precursor: Ammonium (meta) tungstate in methanol / water (2: 1) precursor concentration: 0.01-0.5 mol / l Number of passes: 5-20 Layer thickness: up to 30 nm Parameter range for zirconia layer deposition precursor: Zirconium (IV) acetylacetonate in ethanol / water precursor concentration: 0.05-0.5 mol / l Number of passes: 5-20 Layer thickness: up to 20 nm Parameter range for silver layer deposition precursor: Silver (I) carboxylate in ethanol / water (2: 1) precursor concentration: 0.1-0.2 mol / l Number of passes: 10-100 Layer thickness: up to 70 nm

Beispiel 2Example 2

Auch der Einsatz von Gold als elektrisch leitende Schicht ist denkbar. Großtechnisch ist die Goldabscheidung eher unrealistisch, da die enorm hohen Rohstoffpreise eine Massenproduktion verhindern. Jedoch für geringe Stückzahlen und/oder nicht flächige Substrate, bei denen eine hohe IR-Reflexion benötigt wird, kann mit der Flammenpyrolyse dieses Mehrschichtsystem sehr kostengünstig aufgebracht werden.The use of gold as an electrically conductive layer is conceivable. On a large scale, the gold separation is rather unrealistic, because the enormously high raw material prices prevent mass production. However, for low volumes and / or non-planar substrates in which a high IR reflection is required, can be applied very inexpensively with the flame pyrolysis of this multilayer system.

Inhalt der erfindungsgemäßen Lösung ist die Kopplung eines oxidischen Mehrschichtsystems mit einer Goldschicht. Diese Goldschicht wird hierbei direkt auf das oxidische Mehrschichtsystem bestehend aus Wolframoxid 3 und Zirkoniumoxid 4 oder auf ein aus mehreren zusätzlichen Schichten bestehendes Mehrschichtsystem aufgebracht. Mindestens die Goldschicht 5 wird dabei flammenpyrolytisch abgeschieden. Als Precursorsubstanzen für die flammenpyrolytische Abscheidung der Metall- und Metalloxidschichten werden metallorganische und/oder metallanorganische Verbindungen, welche das entsprechende Element enthalten, verwendet. Jedoch ist es von Bedeutung, die einzelnen Precursoren aufeinander abzustimmen, um das gewünschte Mehrschichtsystem zu erhaltenContent of the solution according to the invention is the coupling of an oxide multilayer system with a gold layer. This gold layer is here directly on the oxide multilayer system consisting of tungsten oxide 3 and zirconium oxide 4 or applied to a multi-layer system consisting of several additional layers. At least the gold layer 5 is deposited by flame pyrolysis. As precursor substances for the flame pyrolytic deposition of the metal and metal oxide layers, organometallic and / or organometallic compounds containing the corresponding element are used. However, it is important to match the individual precursors to one another in order to obtain the desired multilayer system

Claims (3)

Verfahren zur Herstellung von nanoskaligen elektrisch leitfähigen Mehrschichtsystemen, welches aus einem Substrat und den darüber liegenden Schichten zur Haftvermittlung, zur Barrierewirkung und zum Schutz besteht, dadurch gekennzeichnet, dass – eine Flammenpyrolyse-Anlage mit einem temperierbaren Verfahrtisch und Brenner verwendet wird, wobei folgende Parameter einstellbar sind: Gas-Mischung: Brenngasgemisch (Propan/Luft) Volumenstrom Gas: 1–2 l/min Volumenstrom Luft: 20–50 l/min Brenner: Lochbrenner mit Homogenisatoraufsatz (Breite 220 mm) Vorheiztemperatur Verfahrtisch: 30–80°C Geschwindigkeit Verfahrtisch: 15–100 mm/s Abstand Substrat-Brenner: 4–8 mm
– zur Abscheidung der Wolframoxidschicht ein Precursor in Form von Ammonium(meta)-wolframat, welches in Methanol/Wasser (2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,01 bis 0,5 mol/l eingestellt wird und die Beschichtung 5 bis 20 mal durchgeführt wird, so dass sich eine Schichtdicke bis maximal 30 nm einstellt, – zur Abscheidung der Zirkoniumoxidschicht ein Precursor in Form von Zirkonium(IV)acetylacetonat, welches in Ethanol/Wasser (2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,05 bis 0,5 mol/l eingestellt wird und die Beschichtung 5 bis 20 mal durchgeführt wird, so dass sich eine Schichtdicke bis maximal 20 nm einstellt und – zur Abscheidung der Silberschicht ein Precursor in Form von Silber(I)-carboxylat, welches in Ethanol/Wasser (2:1) gelöst ist, verwendet wird, wobei die Precursorkonzentration auf 0,1 bis 0,2 mol/l eingestellt wird und die Beschichtung 10 bis 100 mal durchgeführt wird, so dass sich eine Schichtdicke bis maximal 70 nm einstellt.
Process for the production of nanoscale electrically conductive multilayer systems, which consists of a substrate and the overlying layers for adhesion, barrier and protection, characterized in that - a flame pyrolysis plant is used with a temperature-controlled travel table and burner, the following parameters adjustable are: Gas mixture: Fuel gas mixture (propane / air) Volume flow of gas: 1-2 l / min Volume flow air: 20-50 l / min Burner: Hole burner with homogenizer attachment (width 220 mm) Preheating temperature traversing table: 30-80 ° C Speed traversing: 15-100 mm / s Distance substrate burner: 4-8 mm
- For the deposition of tungsten oxide, a precursor in the form of ammonium (meta) tungstate, which is dissolved in methanol / water (2: 1) is used, wherein the precursor concentration is adjusted to 0.01 to 0.5 mol / l and the coating is carried out 5 to 20 times so that a layer thickness of up to 30 nm is established, - a precursor in the form of zirconium (IV) acetylacetonate, which is dissolved in ethanol / water (2: 1), is used to deposit the zirconium oxide layer is, wherein the precursor concentration is adjusted to 0.05 to 0.5 mol / l and the coating is carried out 5 to 20 times, so that a layer thickness is set to a maximum of 20 nm and - to deposit the silver layer, a precursor in the form of silver (I) carboxylate, which is dissolved in ethanol / water (2: 1) is used, wherein the precursor concentration is adjusted to 0.1 to 0.2 mol / l and the coating is carried out 10 to 100 times, so that a layer thickness to a maximum of 70 nm.
Verfahren nach Anspruch 1, durch gekennzeichnet, dass zuerst auf das Substrat zur Haftvermittlung eine Schicht aus Wolframoxid aufgebracht wird.A method according to claim 1, characterized in that first a layer of tungsten oxide is applied to the substrate for adhesion promotion. Verfahren nach Anspruch 1, durch gekennzeichnet, dass als zweite Schicht zur Barrierewirkung eine Schicht aus Zirkoniumoxid aufgebracht wird.A method according to claim 1, characterized in that a layer of zirconium oxide is applied as the second layer for barrier action.
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