WO2003029511A1 - Procede de depot de couches metalliques transparentes contenant de l'argent - Google Patents

Procede de depot de couches metalliques transparentes contenant de l'argent Download PDF

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Publication number
WO2003029511A1
WO2003029511A1 PCT/EP2002/009798 EP0209798W WO03029511A1 WO 2003029511 A1 WO2003029511 A1 WO 2003029511A1 EP 0209798 W EP0209798 W EP 0209798W WO 03029511 A1 WO03029511 A1 WO 03029511A1
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WO
WIPO (PCT)
Prior art keywords
silver
layer
layers
deposition
containing metal
Prior art date
Application number
PCT/EP2002/009798
Other languages
German (de)
English (en)
Inventor
Matthias Fahland
Christoph Charton
Patrik Karlsson
Original Assignee
Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V.
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 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V. filed Critical Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e. V.
Publication of WO2003029511A1 publication Critical patent/WO2003029511A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/20—Metallic material, boron or silicon on organic substrates
    • C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering

Definitions

  • the invention relates to a method for the deposition of thin transparent silver-containing metal layers of high conductivity in a vacuum. Such layers can pass through
  • Evaporation of the metal or by cathode sputtering, also called sputtering, are deposited.
  • Thin transparent silver-containing metal layers of high conductivity are further understood to be layers of pure silver or a silver alloy with a layer thickness below 20 nm and a sheet resistance below 30 ⁇ D. These are characterized by the fact that they are not optically dense, that is to say a considerable part of the incident
  • Such thin silver-containing metal layers are found as components of layer systems
  • Transparent electrodes are used today in a wide variety of devices. Their use is particularly widespread in flat screens which are used both for displays at computer workstations and in various mobile devices. Regardless of the special technology of image generation, a transparent electrode is required, which is located between the viewer and the self-illuminating components of the flat screen, or components that modify the external light.
  • transparent electrodes are used are solar cells, flat lamps based on organic or inorganic electroluminescence, electrochromic glasses or mirrors.
  • transparent electrodes are usually made from the semiconductor indium tin oxide (90% ln 2 0 3 , 10% Sn0 2 : short name ITO). This material is transparent in the visible spectral range and has an electrical conductivity in the range 10 "4 ... ⁇ " 3 ⁇ cm. Although this is far less than with the metals used in electrical engineering such as copper, aluminum and silver, it is nevertheless sufficient for most applications today.
  • Indium is required as the raw material for the production of the layer. This material is only available to a limited extent. Therefore and from the fact that an expected increase in demand can be expected, the price of the target material will increase in the next few years. This makes many economic assessments based on today's information uncertain or uneconomical from the start.
  • ITO In high-quality ITO, it is necessary to work with very low operating voltages of approx. 100 V in the case of sputtering. This can only be achieved by using a specially designed magnetic field or by coupling additional electrical energy.
  • Another possibility for producing transparent electrodes is to store a thin metal layer, in most cases made of silver, or a silver-containing layer in two transparent layers, for example consisting of ITO.
  • This increases the conductivity of the overall system with the same thickness of the overall system, since the metal, as already explained above, has a significantly higher conductivity than the transparent material.
  • significantly lower layer thicknesses of the ITO layers are required, since the conductivity of the layer system is essentially determined by the silver layer. Therefore, such layer systems can gain importance in display technology, for example on glass substrates, because they help to save the expensive coating material ITO. [M. Bender et al. Thin Solid Films 326 (1998), 76-71).
  • this layer system can also be used as a high-quality transparent electrode on plastics, for example polyethylene terephalate (PET) (M. Fahland et al. Proceedings of ICCG 2000).
  • PET polyethylene terephalate
  • a disadvantage of this method is that the transparency of the overall system is reduced by using a pure metal layer. For this reason, it is important that the metal layer itself has the highest possible transparency in order to reduce the transparency of the electrode as little as possible.
  • a thin silver layer is deposited by sputtering.
  • a magnetron with a Silver target installed in a coating chamber.
  • the chamber is then evacuated and argon is introduced into the chamber as the working gas.
  • the target is connected to a sputter power supply.
  • a gas discharge is ignited by the energy supply. Due to the potential conditions in the discharge plasma, individual atoms are knocked out of the target material by ion bombardment and can deposit as a layer on the substrate.
  • the power of the sputtering power supply is usually fixed.
  • current and voltage are set according to the impedance conditions in the discharge chamber.
  • a voltage between 200 and 500 V is usually set for silver targets. The exact value depends on the size of the target area, the argon pressure and the magnetic field of the magnetron.
  • the optical and electrical parameters of the layer differ significantly from those of the closed layer.
  • the aggregated state is characterized by an increased electrical resistance and an increased optical absorption.
  • the transition can be influenced by superimposing an RF discharge and a DC discharge.
  • the disadvantage of this method is that one station has to be equipped with several sputter power supplies. Furthermore, it is technically extremely complex to provide large-area magnetrons with RF sputtering power supplies.
  • a reduction in the layer thickness of a silver-containing layer is only sensible or economical to a certain degree according to the prior art for the applications mentioned.
  • a certain transition layer thickness which for silver can be between 10 and 18 nm depending on the process conditions, there is no continuous layer, but a conglomerate of individual layer islands. This shows itself on the one hand in a drastic increase in the electrical resistance and on the other hand also leads to an increasing absorption within the layer despite the further decrease in the layer thickness.
  • the transparency of the silver-containing layer also determines the transparency of the entire layer system which contains the silver-containing layer, that is to say, for example, a transparent electrode for electroluminescent systems.
  • the invention is based on the object of specifying a method which is improved compared to the prior art and which permits the production of a thin silver-containing layer with the highest possible optical transparency and good conductivity.
  • the atomization of a silver-containing target ensures that the magnetron discharge at voltages between the cathode and the anode of more than 700 V. is operated. It is irrelevant whether a special electrode or another magnetron connected as an anode is used as the anode. It was surprisingly found that thin silver-containing metal layers, which are deposited under these circumstances, have a significantly higher transparency than silver-containing metal layers of the same layer thickness, which have been deposited by conventional sputtering processes, in particular by magnetron sputtering at lower discharge voltages. The invention is apparently based on the effect that a significant increase in the discharge voltage compared to the values customary in the atomization of silver targets apparently leads to closed silver-containing layers even with smaller layer thicknesses.
  • Such a high voltage can advantageously be realized at low plasma impedances, such as are present in the case of silver sputtering, if the power supply is pulsed, i. H. if it is interrupted before the current has reached a value that can damage the target. Furthermore, it was surprisingly found that the transparency can be increased even further if in addition to the
  • the inlet of nitrogen has proven to be particularly effective.
  • a further increase in the discharge voltage to 850 V or 900 V also led to a further increase in the transparency with the same layer thickness of the silver-containing layer.
  • Technological requirements for transparent electrodes namely surface resistances between 10 ⁇ D and 30 ⁇ 0 for layer thicknesses that do not yet cause damage to the layer due to internal stresses, can be met with the method according to the invention, with a high optical transparency being achieved.
  • a pure silver layer is deposited as a silver-containing layer by sputtering a silver target. It is also particularly advantageous if the coating is carried out in such a way that the thickness of the silver-containing layer is less than 15 nm.
  • a polymer film made of polyethylene terephthalate PET is coated in a vacuum recipient by magnetron sputtering.
  • the film is wrapped in this recipient from an unwinding roll over a chill roll to a winding roll. While the slide passed over the chill roll, it passes through three coating stations one after the other in which it is coated with the ITO-Silver-ITO coating system.
  • the two ITO layers have a layer thickness of 40 nm.
  • the silver layer is applied by magnetron sputtering.
  • the magnetron in the coating station in which the silver coating takes place, is connected to a DC sputtering power supply, which is operated in constant voltage mode. 900 V are permanently set as the output voltage.
  • An electrical circuit between the DC sputter power supply alternately connects the DC sputter power supply to the magnetron for 10 ⁇ s and then the connection is interrupted for 80 ⁇ s. It is thereby achieved that the three-layer system ITO-silver-ITO deposited on polyethylene terephthalate has a transparency of 84% at a wavelength of 550 nm and an area resistance of 14 ⁇ D.
  • These layers are particularly suitable as transparent electrodes for use in flat screen technology or electroluminescent systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

Dans de nombreuses applications techniques, on a besoin de couches de grande transparence optique et de bonne conductivité électrique, sachant que l'on cherche souvent à obtenir les couches les plus minces possibles ayant ces propriétés. On utilise fréquemment le procédé par pulvérisation magnétron pour produire ces couches. L'application d'une tension de décharge supérieure à 700 V permet de réduire nettement l'épaisseur de couche des couches contenant de l'argent tout en conservant la même résistance de surface et en améliorant la transparence optique. Production d'écrans plats, de cellules solaires mince couche, de systèmes à électroluminescence etc.
PCT/EP2002/009798 2001-09-27 2002-09-03 Procede de depot de couches metalliques transparentes contenant de l'argent WO2003029511A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10147861.5 2001-09-27
DE2001147861 DE10147861A1 (de) 2001-09-27 2001-09-27 Verfahren zur Abscheidung transparenter silberhaltiger Metallschichten hoher Leitfähigkeit im Vakuum und Verwendung des Verfahrens

Publications (1)

Publication Number Publication Date
WO2003029511A1 true WO2003029511A1 (fr) 2003-04-10

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Application Number Title Priority Date Filing Date
PCT/EP2002/009798 WO2003029511A1 (fr) 2001-09-27 2002-09-03 Procede de depot de couches metalliques transparentes contenant de l'argent

Country Status (2)

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DE (1) DE10147861A1 (fr)
WO (1) WO2003029511A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05162227A (ja) * 1991-12-18 1993-06-29 Mitsui Toatsu Chem Inc 反射体
DE19726966C1 (de) * 1997-06-25 1999-01-28 Flachglas Ag Verfahren zur Herstellung einer transparenten Silberschicht mit hoher spezifischer elektrischer Leitfähigkeit , Glasscheibe mit einem Dünnschichtsystem mit einer solchen Silberschicht und deren Verwendung

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05162227A (ja) * 1991-12-18 1993-06-29 Mitsui Toatsu Chem Inc 反射体
DE19726966C1 (de) * 1997-06-25 1999-01-28 Flachglas Ag Verfahren zur Herstellung einer transparenten Silberschicht mit hoher spezifischer elektrischer Leitfähigkeit , Glasscheibe mit einem Dünnschichtsystem mit einer solchen Silberschicht und deren Verwendung

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Section Ch Week 199330, Derwent World Patents Index; Class A89, AN 1993-239595, XP002226457 *

Also Published As

Publication number Publication date
DE10147861A1 (de) 2003-04-24

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