WO2006117118A1 - Procede pour appliquer un revetement de cuivre ou d'argent sur des substrats - Google Patents

Procede pour appliquer un revetement de cuivre ou d'argent sur des substrats Download PDF

Info

Publication number
WO2006117118A1
WO2006117118A1 PCT/EP2006/003885 EP2006003885W WO2006117118A1 WO 2006117118 A1 WO2006117118 A1 WO 2006117118A1 EP 2006003885 W EP2006003885 W EP 2006003885W WO 2006117118 A1 WO2006117118 A1 WO 2006117118A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
metal
copper
subgroup
borides
Prior art date
Application number
PCT/EP2006/003885
Other languages
German (de)
English (en)
Inventor
Dietrich Lange
Martin Seifert
Original Assignee
Esk Ceramics Gmbh & Co. Kg
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 Esk Ceramics Gmbh & Co. Kg filed Critical Esk Ceramics Gmbh & Co. Kg
Publication of WO2006117118A1 publication Critical patent/WO2006117118A1/fr

Links

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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/243—Crucibles for source material

Definitions

  • the invention relates to a process for coating substrates with copper or silver by evaporation of copper or silver using ceramic vaporizer boats and evaporator boats for use in such a process.
  • the substrate to be coated is passed over a cooled roller and thereby exposed to the aluminum vapor, which is reflected on the substrate surface as a thin metal layer.
  • evaporator so-called evaporator, in direct current passage at about 1450 0 C heated.
  • Aluminum wire is fed continuously, liquefied on the ceramic surface, and evaporated mbar at a vacuum of about 10 "4.
  • metallizing a series of evaporation boats are arranged such that over the entire width of the substrate a uniformly thick layer of aluminum deposited beat.
  • the chemical composition of the evaporator boats made of electrically conductive ceramic material usually consists of titanium diboride (TiB 2 ), boron nitride (BN) and optionally aluminum nitride (AlN).
  • TiB 2 is the electrically conductive component which allows the evaporator to be heated as if it had a resistance to ohms.
  • the tungsten Sheet metal boats have a completely different shape than the ceramic evaporator usually used in Bandbedampfungsanlagen, with the result that the restraints for the W-sheet metal boats must be designed completely different than the restraints for ceramic evaporator and a complex conversion of the restraints is required when the Bandevampfungsstrom from AI evaporation to Cu evaporation is to be converted.
  • Another disadvantage of the W-sheet metal boats is their deflection during operation, since tungsten and copper have different thermal expansion coefficients. This leads to tensions and deformations in the W-sheet metal boat. This deformation is known by the term "bimetallic effect".
  • DE 31 14 467 A1 describes a boat for evaporating metals from refractory oxide ceramics, such as ZrO 2 , wherein on the inside of the boat, a coating of tungsten and / or molybdenum is arranged.
  • refractory oxide ceramics such as ZrO 2
  • metals such as copper, iron, nickel or alloys of these metals can be applied to tape-shaped film materials.
  • ZrC> 2 oxide ceramics are brittle and sensitive to thermal shock and therefore unsuitable for evaporating metals. They are also not introduced to the market and have not prevailed in practice.
  • the invention is therefore based on the object to provide a method for coating substrates with copper or silver by evaporation of these metals using ceramic evaporator boats, in particular good initial wetting of the evaporator boats and thus a good running-in characteristic can be achieved. Further, evaporator boats are to be provided for use in such a process.
  • the evaporator boats used according to the invention show an excellent initial wetting by the metals to be evaporated copper and silver and therefore have a good Einfahr characterizing. They can be used without further modification in conventional vacuum belt vapor deposition systems. Due to the good wetting a maximum Badgrö_ße the Cu or Ag bath can be achieved and thus the highest possible Abdampf need be achieved.
  • the evaporation in the method according to the invention is low-spatter and uniform, so that a high layer uniformity of the metallized substrate is achieved.
  • the invention thus provides a process for coating substrates with a metal selected from copper and silver by evaporating the metal using ceramic evaporator boats, characterized in that one uses an evaporator boat of electrically conductive ceramic material whose surface from which the evaporation of the metal is provided with one of the following coatings: a) a coating of at least one transition metal of the 4th to 6th subgroup of the Periodic Table and / or their borides, b) a coating of a mixture of the metal to be evaporated and at least one transition metal the 4th to 6th subgroup of the Periodic Table and / or their borides, c) a first coating of at least one transition metal of the 4th to 6th subgroup of the Periodic Table and / or their borides and a coating thereon of the metal to be vaporized.
  • the invention furthermore relates to an evaporator boat for use in such a method, consisting of electrically conductive ceramic material whose surface, from which the vaporization of the metal takes place, is provided with one of the following coatings: a) a coating of at least one transition metal of the fourth b) a coating of a mixture of the metal to be vaporized and at least one transition metal of the 4th to 6th subgroup of the Periodic Table and / or their borides, c) a first coating of at least one Transition metal of the 4th to 6th subgroup of the Periodic Table and / or their borides and a coating applied thereon from the metal to be evaporated.
  • an evaporator boat made of electrically conductive ceramic material which contains titanium diboride and boron nitride and, if appropriate, aluminum nitride as main components, and which is produced by pressing these components.
  • the evaporator boat from 45-60 wt .-% TiB 2 , 20- 55 wt .-% BN and 0-20 wt .-% AlN, wherein further conventional additives and auxiliaries may be included.
  • the coating of the evaporator boat used according to the invention preferably has an average thickness of 1-750 ⁇ m, more preferably 15-500 ⁇ m, even more preferably 50-150 ⁇ m.
  • the evaporator boat used according to the invention has a shape known in the prior art, for example a rectangular cross-section. cut or a cross section in the form of a halved ellipse, as it is known for example from EP 0 962 546 B l.
  • the surface of the evaporator boat used according to the invention, from which the evaporation of the metal takes place, is provided with one of the following coatings:
  • Titanium, zirconium, vanadium, molybdenum and tungsten are preferred as transition metals of the 4th to 6th subgroup of the Periodic Table, in particular tungsten, and as borides in particular tungsten borides, such as WB and W 2 B 5 .
  • a coating of tungsten metal has proven to be particularly suitable for the evaporation of copper or silver, since from the beginning of use a good and uniform wetting occurs, which leads to a temporally and spatially low-spattering constant evaporation rate of the copper or silver.
  • the copper content in the coating is preferably at most 50% by volume, more preferably 20% by volume or less, to achieve a preferred first wetting behavior
  • the coating may consist of a mixture of silver and tungsten and / or tungsten borides.
  • the silver content in the coating is preferably at most 50% by volume, more preferably 20% by volume or less, in order to achieve a preferred initial wetting behavior.
  • the inventive method is not only suitable for high-vacuum strip evaporation of flexible substrates, such as paper and plastic films with copper or silver, but also for general cargo, for example of TV screens.
  • the copper and silver evaporation takes place analogously to the aluminum evaporation known in the prior art by using copper or silver wire instead of aluminum wire.
  • the copper or silver wire used may, for example, have a thickness of about 1.0-0.2 mm.
  • a coating for an evaporator boat usable in accordance with the invention takes place, for example, by applying a suspension of the coating material, such as W metal in acetone, to the surface of the evaporator boat from which the copper or silver evaporates, for example to the cavity, and subsequent drying for evaporation of the solvent.
  • the coating can also be applied by a per se known melt or plasma spraying.
  • a coating can be achieved by placing a preferably perforated metal molded part, for example a perforated metal sheet or a network of tungsten, on the evaporator boat or sprinkling a metal granulate, for example W granules, onto the surface of the evaporator boat.
  • a metal granulate for example W granules
  • Example 1 plasma-sprayed W coating for Cu evaporation
  • Evaporator boats of size 10 ⁇ 20 ⁇ 120 mm 3 made of an electrically conductive TiB 2 -BN mixed ceramic are plasma-spray-coated after appropriate preparation of the surface with a layer of metallic tungsten.
  • a W metal powder having an average particle size of 25 ⁇ m was used.
  • the layer thickness was determined on a co-coated comparative piece of 125 ⁇ m by placing a polished cut through the cross section of the reference piece.
  • the so-coated evaporators were installed in a Bandbedampfungsstrom and each occupied about 5 grams of copper wire pieces (wire diameter 2 mm). After closing the system and reaching the necessary vacuum of ⁇ 10 ⁇ 4 mbar, the heating power was set to 4.68 KW.
  • the deposited copper begins to melt, as the temperature further increases, the copper begins to wet the coated area of the evaporator.
  • the copper wire feed of the strip steaming system can be started.
  • a copper wire with a diameter of 2.0 mm was used.
  • the vaporizer boats according to the invention showed a constant evaporation rate of 2 to 6 grams of Cu per minute at 85% electrical power.
  • the uniform and constant wetting acts as a very uniform coating on the film to be vaporized.
  • Evaporator boats as described in Example 1 are coated after appropriate pretreatment on the functional surface with tungsten boride.
  • the composition of the tungsten boride is nominally WB;
  • the X-ray phase analysis of the tungsten boride used revealed that it consists essentially of WB with about 5% by volume of W 2 B 5 .
  • the layer thickness was again measured on a co-coated comparative piece. The layer thickness was 120 ⁇ m on average.
  • the evaporator boats coated in this way were installed in the strip steaming plant and, as mentioned in Example 1, brought to operating temperature with applied copper pieces.
  • the shells coated with tungsten boride show very good and uniform wetting of the coated functional surface even at lower power (corresponding to lower temperature).
  • these evaporator boats according to the invention could be maintained for 6 hours a constant evaporative power of 15 grams of copper per minute, without the performance of the evaporator has decreased.
  • Evaporation boats of size 10 ⁇ 20 ⁇ 120 mm 3 made of an electrically conductive TiB 2 -BN-AlN mixed ceramic are plasma-spray-coated after appropriate preparation of the surface with a layer consisting of a mixture of metallic tungsten and 15% by volume copper.
  • a W metal powder with an average particle size of 25 ⁇ m (manufacturer eg HC Starck in Goslar) and an electrolytic copper powder with an average particle size of 75 ⁇ m were used for this purpose.
  • the two powder components were homogenized for 12 hours dry on a roller block using hard metal balls before processing in the plasma spraying system. After homogenization of the powders, it was ensured that the powders, which tend to segregate due to the large difference in their specific gravity, do not become inhomogeneous due to vibrations or vibrations.
  • the layer thickness was determined on a co-coated control to be 132 ⁇ m by placing a polished cut through the cross section of the control.
  • the layer made in this example is easily distinguishable by the apparent reddish hue of copper from the other layers containing only W metal or tungsten boride.
  • the so coated evaporators were installed in a Bandbedampfungsstrom and each occupied about 4 grams of copper wire pieces (wire diameter 2mm). After closing the system and reaching the necessary vacuum of ⁇ 10 mbar, the heating power was set to 4.68 kW.
  • the applied copper begins to melt, and as the temperature increases further, the copper begins to wet the coated area of the evaporator very evenly. That in the layer embedded copper powder melts earlier than the applied powder because the heat transfer is better than with the laid copper wire pieces, which are heated only by thermal radiation. Due to the very early melting in the layer of copper components causes the applied copper wire pieces melt at relatively low temperature or power. By homogeneously distributed in the layer copper even more uniform initial wetting of the functional surface is effected, since the melt formed locally by the applied copper pieces does not have to be uniformed by surface forces. The effect of the copper contained in the coating is temporary because the copper from the layer, the copper of the applied wire pieces and the copper from the permanent wire feed combine.
  • the copper wire feed of the strip steaming system can be started.
  • a copper wire with a diameter of 2.0 mm was used.
  • the vaporizer boats according to the invention showed a constant evaporation rate of 18 grams of Cu per minute at 91% electrical power.
  • the relatively high evaporation rate of the evaporator boats according to the invention is probably due to the fact that the coating produced by powder mixing has a larger specific surface area than a layer which is composed only of W metal or tungsten boride.
  • the uniform and constant wetting acts as a very uniform coating on the film to be vaporized.
  • Evaporator boats as described in DE 39 35 163 Cl, are used in a Bandbedampfungsstrom. After analogous steps as in Example 1, the copper wire feed is turned on.
  • the boat shows a bad, uneven and time-varying wetting for copper.
  • there is no stable Evaporation rate which has an uneven layer thickness on the film to be vaporized.

Abstract

La présente invention concerne un procédé pour appliquer un revêtement de cuivre ou d'argent sur des substrats par vaporisation du métal, en utilisant des nacelles de vaporisation céramiques. Cette invention est caractérisée en ce que l'on utilise une nacelle de vaporisation constituée d'un matériau céramique électroconducteur dont la surface sur laquelle la vaporisation du métal a lieu présente un des revêtements suivants : a) un revêtement constitué d'au moins un métal de transition des sous-groupes 4 à 6 du tableau périodique et/ou de borures de celui-ci, b) un revêtement constitué d'un mélange du métal à vaporiser et d'au moins un métal de transition des sous-groupes 4 à 6 du tableau périodique et/ou de borures de celui-ci, c) un premier revêtement constitué d'au moins un métal de transition des sous-groupes 4 à 6 du tableau périodique et/ou de borures de celui-ci et un revêtement appliqué sur celui-ci, constitué du métal à vaporiser. Les nacelles de vaporisation utilisées présentent un bon mouillage initial pour le cuivre et l'argent, ce qui permet d'effectuer une vaporisation avec peu de projections et de manière uniforme.
PCT/EP2006/003885 2005-05-04 2006-04-26 Procede pour appliquer un revetement de cuivre ou d'argent sur des substrats WO2006117118A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200510020946 DE102005020946B4 (de) 2005-05-04 2005-05-04 Verfahren und Verdampferschiffchen zum Beschichten von Substraten mit Kupfer oder Silber
DE102005020946.7 2005-05-04

Publications (1)

Publication Number Publication Date
WO2006117118A1 true WO2006117118A1 (fr) 2006-11-09

Family

ID=36803941

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2006/003885 WO2006117118A1 (fr) 2005-05-04 2006-04-26 Procede pour appliquer un revetement de cuivre ou d'argent sur des substrats

Country Status (3)

Country Link
CN (1) CN101171359A (fr)
DE (1) DE102005020946B4 (fr)
WO (1) WO2006117118A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008025447A1 (fr) * 2006-09-01 2008-03-06 Esk Ceramics Gmbh & Co. Kg nacelle d'évaporateur en céramique, procédé pour sa fabrication et utilisation de cette nacelle

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107190241B (zh) * 2017-05-08 2019-08-27 广东工业大学 一种具有纳米层状结构的二硼化钛/钨涂层及其制备方法
CN108203314A (zh) * 2017-12-29 2018-06-26 安徽金美新材料科技有限公司 蒸发舟的高温纳米保护涂层及制备工艺及对应蒸发舟
CN109295419A (zh) * 2018-09-12 2019-02-01 山东科技大学 一种制备具有树枝状结构的超疏水表面的方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3114467A1 (de) * 1981-04-09 1982-10-28 Siemens AG, 1000 Berlin und 8000 München Verdampferschiffchen und verfahren zu seiner herstellung
EP0960956A1 (fr) * 1998-05-14 1999-12-01 Elektroschmelzwerk Kempten GmbH Nacelles d'evaporation en céramique
WO2004063419A1 (fr) * 2003-01-08 2004-07-29 Sintec Keramik Gmbh & Co. Kg Nacelle de vaporisateur chauffee par resistance
DE102004009335A1 (de) * 2004-02-26 2005-09-15 Esk Ceramics Gmbh & Co. Kg Keramische Verdampferschiffchen mit verbesserter elektrischer Leitfähigkeit

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5118941A (ja) * 1974-08-08 1976-02-14 Denki Kagaku Kogyo Kk Kinzokujohatsuyoyoki
US4446357A (en) * 1981-10-30 1984-05-01 Kennecott Corporation Resistance-heated boat for metal vaporization
US4884788A (en) * 1988-04-12 1989-12-05 Union Carbide Corporation Boron nitride containing vessel having a surface coating of titanium iron-silicon thereon
DE3935163C1 (en) * 1989-10-21 1990-10-11 Sintec Keramik Gmbh, 8959 Buching, De Polycrystalline material for resistance heat evapn. boats - comprises hot pressed electroconductive mixt. based on boron nitride
DE4100541C1 (fr) * 1991-01-10 1992-01-16 Plasco Dr. Ehrich Plasma-Coating Gmbh, 6501 Heidesheim, De

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3114467A1 (de) * 1981-04-09 1982-10-28 Siemens AG, 1000 Berlin und 8000 München Verdampferschiffchen und verfahren zu seiner herstellung
EP0960956A1 (fr) * 1998-05-14 1999-12-01 Elektroschmelzwerk Kempten GmbH Nacelles d'evaporation en céramique
WO2004063419A1 (fr) * 2003-01-08 2004-07-29 Sintec Keramik Gmbh & Co. Kg Nacelle de vaporisateur chauffee par resistance
DE102004009335A1 (de) * 2004-02-26 2005-09-15 Esk Ceramics Gmbh & Co. Kg Keramische Verdampferschiffchen mit verbesserter elektrischer Leitfähigkeit

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008025447A1 (fr) * 2006-09-01 2008-03-06 Esk Ceramics Gmbh & Co. Kg nacelle d'évaporateur en céramique, procédé pour sa fabrication et utilisation de cette nacelle

Also Published As

Publication number Publication date
CN101171359A (zh) 2008-04-30
DE102005020946A1 (de) 2006-11-09
DE102005020946B4 (de) 2007-08-02

Similar Documents

Publication Publication Date Title
DE102005020945B4 (de) Keramische Verdampferschiffchen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE3239949A1 (de) Widerstandsbeheiztes schiffchen zum verdampfen von metallen
EP1794344B1 (fr) Preparation et exploitation d'un corps de vaporisation pour installation de metallisation par depot en phase gazeuse par procede physique
DE3530106A1 (de) Aufdampfgut zum aufdampfen anorganischer verbindungen mittels einer photonen-erzeugenden strahlungsheizquelle in kontinuierlich betriebenen vakuumbedampfungsanlagen
DE102005020946B4 (de) Verfahren und Verdampferschiffchen zum Beschichten von Substraten mit Kupfer oder Silber
EP0337007B1 (fr) Couche de protection en matériau dur ayant une distribution homogène de particules
WO2002061165A1 (fr) Dispositif de revetement de type ceramique d'un substrat
DE10393947B4 (de) Widerstandsbeheiztes Schiffchen und Herstellungsverfahren dafür
EP0438627A1 (fr) Dispositif d'évaporation par décharge d'arc ayant plusieurs creusets d'évaporation
DE69634071T2 (de) Verfahren und Vorrichtung zum Beschichten eines Substrats
DE3205919C1 (de) Verfahren zur Herstellung von Festelektrolytschichten fuer galvanische Zellen
DE102015112135B4 (de) Verdampferkörper mit Titanhydridbeschichtung, Verfahren zu dessen Herstellung und Verwendung
EP1899495B1 (fr) Matiere auxiliaire de mouillage initial pour un corps de vaporisation
EP0960956B1 (fr) Procédé pour préparer des nacelles d'evaporation en céramique
DE3839745A1 (de) Verfahren zur herstellung eines anorganischen duennfilms auf einer unterlage unter verwendung eines targets
EP1161570B1 (fr) Procede pour recouvrir un corps support d'un materiau a base de se-fe-n magnetique dur, par projection au plasma
DE3935163C1 (en) Polycrystalline material for resistance heat evapn. boats - comprises hot pressed electroconductive mixt. based on boron nitride
DE2722668A1 (de) Verfahren zum herstellen duenner schichten aus hochtemperaturfesten metallen wie wolfram, molybdaen, rhenium oder osmium
DE3114467A1 (de) Verdampferschiffchen und verfahren zu seiner herstellung
DE69722619T2 (de) Vorrichtung zur Kondensationserzeugung eines Schichtes auf einem Substrat
EP3460092A1 (fr) Revêtement à faible émissivité
EP0487144A1 (fr) Anode pour tube à rayons X munie d'une couche d'oxyde
DE2346394C3 (de) Verfahren zum Herstellen dünner Schichten aus Wolfram oder Molybdän
EP0564819A2 (fr) Procédé pour déposer des couches adhérentes métalliques, céramiques ou des couches adhérantes en carbone sur les matériaux sensibles à la température
DE102022105889A1 (de) Verfahren zum Beschichten eines Substrats mit einer Metalllegierungsbeschichtung, die wenigstens zwei Metalle enthält

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
WWE Wipo information: entry into national phase

Ref document number: 200680015108.1

Country of ref document: CN

NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

NENP Non-entry into the national phase

Ref country code: RU

WWW Wipo information: withdrawn in national office

Country of ref document: RU

122 Ep: pct application non-entry in european phase

Ref document number: 06742709

Country of ref document: EP

Kind code of ref document: A1