EP0374505B1 - Procédé de métallisation - Google Patents

Procédé de métallisation Download PDF

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Publication number
EP0374505B1
EP0374505B1 EP89121600A EP89121600A EP0374505B1 EP 0374505 B1 EP0374505 B1 EP 0374505B1 EP 89121600 A EP89121600 A EP 89121600A EP 89121600 A EP89121600 A EP 89121600A EP 0374505 B1 EP0374505 B1 EP 0374505B1
Authority
EP
European Patent Office
Prior art keywords
layer
metal
catalyst layer
radiation
substrate
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
EP89121600A
Other languages
German (de)
English (en)
Other versions
EP0374505A3 (en
EP0374505A2 (fr
Inventor
Hilmar Dr. Esrom
Ulrich Dr. Kogelschatz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Heraeus Noblelight GmbH
Original Assignee
Heraeus Noblelight GmbH
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 Heraeus Noblelight GmbH filed Critical Heraeus Noblelight GmbH
Publication of EP0374505A2 publication Critical patent/EP0374505A2/fr
Publication of EP0374505A3 publication Critical patent/EP0374505A3/de
Application granted granted Critical
Publication of EP0374505B1 publication Critical patent/EP0374505B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1608—Process or apparatus coating on selected surface areas by direct patterning from pretreatment step, i.e. selective pre-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1603—Process or apparatus coating on selected surface areas
    • C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
    • C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/02—Electroplating of selected surface areas

Definitions

  • the invention relates to a method for metallizing substrates by means of UV radiation according to the preamble of patent claim 1.
  • Such a method is preferably used to form circuits on a substrate, for which the generation of structured metallic layers on the substrate is required.
  • circuits have been made by physical vapor deposition using masks.
  • Such methods are complex since they have to be carried out in a vacuum and only allow structures with a thickness of less than 5 ⁇ m.
  • structured metal layers for circuits can also be produced by means of chemical processes. For this, closed metallic layers are applied to the substrate. The parts of the layer that are not required for switching are then removed by chemical etching. However, this is associated with environmentally harmful process steps.
  • EP 0 349 946 discloses a method for metallizing substrate surfaces made of organic or inorganic materials.
  • the substrate surface is coated with a solution of palladium chloride, cyclopentadienylpalladium allyl or cyclopentadienylpalladium chloride and then irradiated with UV radiation which has a wavelength between 60 and 320 nm (inventor: Dr.Esrom, published on January 10, 1990).
  • EP-A 349 882 describes a process for the metallization of substrates made of organic or inorganic materials. For this purpose, a powder of a metal acetate, a metal acetyl acetonate or metal formate is applied to the substrate surface. This layer is then irradiated with UV radiation with a wavelength between 100 and 360 nm. The powder is converted into a metallic layer (inventor: Dr.Esrom et al, published on January 10, 1990).
  • the object of the invention is to demonstrate a method with which metal oxide layers on substrates can be partially or completely converted into metal layers, and which is also suitable for converting metal layers completely or partially into metal oxide layers.
  • the layer applied to the substrate can be formed from a metal or a metal oxide.
  • a metal or a metal oxide For the formation of structured metal layers, depending on whether the layer consists of a metal or a metal oxide, the same is passivated or activated in some areas. If the layer is made of a metal, it is passivated at the points where no further metal layers are to be applied. This is done by means of UV radiation in a gas atmosphere, the irradiated areas being oxidized, nitrided or carbonated. If the layer on the substrate is a metal oxide layer, it is activated at the points at which a metal layer is to be applied.
  • FIG. 1 shows a flat substrate 1 with a rectangular cross section, on the surface of which a metallic catalyst layer 2 is to be deposited.
  • the substrate 1 is made of aluminum oxide (Al2O3) in the embodiment shown here.
  • the metallic catalyst layer 2 can also be applied to other substrates (not shown here) made of an organic or inorganic material.
  • the substrates used can have any geometric shape, but preferably thin plates are used which are made of aluminum nitride, borosilicate glass, Polyamide, rubber, paper or cardboard as well as made of ceramic-filled or glass-fiber reinforced fluoroplastics.
  • a powdered organometallic compound or salt-like metal compound or a solution which contains one of these compounds is applied to the cleaned surface of the substrate 1 . Then the applied layer 2 is irradiated with a UV high-power lamp.
  • the catalyst layer 2 can also be applied by vapor deposition, sputtering, by using the CVD method or by means of laser CVD. Instead of a catalyst layer 2 made of metal, a catalyst layer 2 made of a metal oxide can also be applied. Platinum, palladium, copper, gold, cobalt, silver, nickel and erbium are preferably used as metals. If the catalyst layer 2 is formed by a metal oxide, oxides of the above are preferred.
  • the catalyst layer 2 is passivated or activated. If the catalyst layer 2 is formed by a metal, the areas on which no further layer is to be applied are passivated.
  • This passivation is carried out by irradiating the catalyst layer 2 with UV photons.
  • the passivation can be carried out by oxidation, nitration or carbonation of the catalyst layer 2 in the desired areas.
  • the radiation is carried out in an oxygen atmosphere or a carbon or nitrogen atmosphere.
  • a mask 5 is arranged between the latter and a UV source 4 arranged at a defined distance above the catalyst surface 2S. If necessary, the mask 5 can also be placed directly on the catalyst surface 2S.
  • the mask 5 is arranged approximately in the middle between the UV source 4 and the catalyst layer 2.
  • the mask 5 is provided with passages 5D. These are arranged exactly where the catalyst layer 2 is to be passivated.
  • the targeted irradiation of the catalyst layer 2 means that the catalyst layer 2 is completely passivated in the regions 2P after a defined time.
  • the region 2A of the catalyst layer 2 to which at least one further layer is to be applied must be activated.
  • a UV source 4 is also arranged above the catalyst layer 2 for activation.
  • the catalyst layer 2 is irradiated exactly where the active regions 2A are to be formed. The radiation takes place in the vicinity of a hydrogen-containing gas. Ammonia (NH3), hydrogen chloride (HCl), hydrogen fluoride (HF) or other hydrogen-containing gas mixtures are suitable for this.
  • a high-power radiator as described in EP-OS 0 254 111 can be used as the UV source 4.
  • the UV high-performance lamp is provided with an inert gas filling made of argon, it is able to generate UV radiation in the wavelength range between 107 and 165 nm. With the help of suitable gas mixtures of noble gases and halogens, UV radiation with a wavelength between 170 and 360 nm be generated.
  • a high-power UV lamp with a xenon filling is preferably used, which generates a wavelength of 172 nm. It is also possible to use a frequency-multiplied laser, for example an argoion laser, a dye laser or conventional UV lamps.
  • UV high-power lamp described in EP-OS 0 254 111
  • a suitable choice of the wavelength of the UV emitter which is achieved by a suitable gas filling, it is possible to photolytically cleave molecules such as oxygen, ammonia, chlorine, fluorine, hydrogen chloride, hydrogen fluoride and the extremely reactive radicals O, NH2, H, To produce Cl, F, which bring about the activation or passivation of the catalyst layer 2.
  • this UV high-power radiator can also be cylindrical, so that a catalyst layer (not shown here), which is applied to the inner surface of a cylinder (not shown here), can be irradiated through a likewise cylindrical mask (not shown here) .
  • a catalyst layer (not shown here)
  • the catalyst layer is applied to the outer surface of a cylinder, irradiation by a cylindrical UV high-power lamp is also possible.
  • the cylindrical substrate with the catalyst layer on its surface is arranged concentrically in the cylindrical high-power radiator.
  • the high-power radiator can be moved along the catalyst layer in both cases. The same applies to a flat substrate. This enables the assembly line production of substrates with metallized surfaces without any problems.
  • the coating of the activated regions 2A of the catalyst layer 2 can be carried out. This is possible, for example, by electroless metallization in wet chemical baths. By immersing the catalyst layer 2 in such baths, it is possible to apply a further metal layer to the active areas of the catalyst layer 2. Metallic layers made of platinum, copper, palladium, nickel, iron or silver can be applied with the help of wet chemical baths. Furthermore, there is the possibility of applying resistance layers made of nickel or nickel phosphide to the active regions 2A of the catalyst layer 2.
  • Magnetic layers in the form of cobalt, cobalt-nickel-iron and phosphorus compounds (CoNiFeP), copper-nickel-phosphorus compounds (CuNiP), and cobalt-phosphorus-silver compounds (CoPAg ) are applied to the catalyst layer.
  • the above layers can be applied as thin films with a thickness between 10 Dicke2 and 1 ⁇ m. It is also possible to apply much thicker layers between 1 and 30 ⁇ m.
  • galvanic coating of the catalyst layer 2 is also possible.
  • the metallic catalyst layer 2 is applied as shown in FIG. 1 and explained in the associated description. Then, by irradiating areas 2P of the catalyst layer 2 passivated them. The passivation takes place in the same way as the passivation of the catalyst layer 2 shown in FIG. 1, but not over the entire thickness, but only in the surface area.
  • the catalyst layer is preferably applied to a thickness of 10-2 to 1.0 ⁇ m, but only 0.1 ⁇ m of this layer is passivated.
  • the catalyst layer 2 is then used as an electrode and connected to the negative pole of a voltage source (not shown here).
  • the metallic layers 3 applied to the catalyst layer 2 can be passivated in regions and further coated in the same way as described above.

Claims (5)

  1. Procédé pour structurer des couches métalliques en matériau organique ou inorganique au moyen de rayonnement UV, caractérisé en ce que l'on active localement une couche (2) constituée par un oxyde métallique, par réduction locale en métal au moyen de rayonnements UV sous l'environnement d'un gaz qui contient de l'hydrogène, sous la forme d'ammoniac, d'acide chlorhydrique gazeux ou d'acide fluorhydrique gazeux, ou en ce que l'on passive localement une couche (2), constituée d'un métal, par oxydation, nitruration ou carbonation localisée du métal au moyen de rayonnements UV dans une atmosphère contenant de l'oxygène, de l'azote ou du carbone, et en ce que l'on applique ensuite un revêtement sur les régions activées (2A) de la couche (2) avec une couche supplémentaire (3) en métal, en matériau se comportant comme une résistance électrique, ou un matériau magnétique.
  2. Procédé pour structurer des couches métalliques en matériau organique ou inorganique au moyen de rayonnements UV, selon la revendication 1, caractérisé en ce que la couche (2) appliquée sur le substrat (1) a une épaisseur entre 10⁻² et 1 µm et est formée de platine, palladium, or, cobalt, argent, nickel ou erbium, ou d'oxydes de ces métaux.
  3. Procédé selon l'une ou l'autre des revendications 1 et 2, caractérisé en ce que l'activation ou la passivation localisée de la couche (2) est effectuée à l'aide de moyens annexes optiques, ou par disposition d'un masque (5) avec des passages (5D) entre la source UV (4) et la couche (2).
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on applique sur les régions activées (2A) de la couche (2) une couche (3) en palladium, cuivre, platine, nickel, fer, or, phosphure de nickel, CuNiFeP, CuNiP ou CuPAg.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que la couche appliquée (3) est également transformée partiellement en une couche de métal ou une couche d'oxyde métallique.
EP89121600A 1988-11-29 1989-11-23 Procédé de métallisation Expired - Lifetime EP0374505B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3840199A DE3840199C2 (de) 1988-11-29 1988-11-29 Verfahren zur Strukturierung von bei der stromlosen Metallisierung katalytisch aktiven Metallschichten mittels UV-Strahlung
DE3840199 1988-11-29

Publications (3)

Publication Number Publication Date
EP0374505A2 EP0374505A2 (fr) 1990-06-27
EP0374505A3 EP0374505A3 (en) 1990-07-04
EP0374505B1 true EP0374505B1 (fr) 1994-04-06

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Family Applications (1)

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EP89121600A Expired - Lifetime EP0374505B1 (fr) 1988-11-29 1989-11-23 Procédé de métallisation

Country Status (3)

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EP (1) EP0374505B1 (fr)
JP (1) JPH03122287A (fr)
DE (2) DE3840199C2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101507769B1 (ko) 2013-10-10 2015-04-07 경기대학교 산학협력단 산화물 환원 방법 및 이를 이용하는 산화물 환원 장치

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4035080A1 (de) * 1990-11-05 1992-05-07 Abb Patent Gmbh Verfahren und einrichtung zur herstellung von partiellen metallischen schichten
JP3259310B2 (ja) 1992-02-25 2002-02-25 株式会社デンソー めっき方法及びこのめっき方法により得られる筒状コイル
JP3153682B2 (ja) * 1993-08-26 2001-04-09 松下電工株式会社 回路板の製造方法
US6602653B1 (en) * 2000-08-25 2003-08-05 Micron Technology, Inc. Conductive material patterning methods
US6451685B1 (en) 2001-02-05 2002-09-17 Micron Technology, Inc. Method for multilevel copper interconnects for ultra large scale integration
CN110091069B (zh) * 2019-04-09 2021-09-24 大族激光科技产业集团股份有限公司 激光退镀方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0349882A1 (fr) * 1988-07-02 1990-01-10 Heraeus Noblelight GmbH Procédé de fabrication de couches métalliques

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3993491A (en) * 1973-12-07 1976-11-23 Surface Technology, Inc. Electroless plating
US4241105A (en) * 1979-12-17 1980-12-23 Western Electric Company, Inc. Method of plating the surface of a substrate
DE3008434A1 (de) * 1980-03-03 1981-09-17 Schering Ag Berlin Und Bergkamen, 1000 Berlin Verfahren zur selektiven chemischen und/oder galvanischen abscheidung von metallueberzuegen, insbesondere zur herstellung von gedruckten schaltungen
US4304849A (en) * 1980-05-16 1981-12-08 Western Electric Co., Inc. Methods of depositing metallic copper on substrates
US4410569A (en) * 1980-06-13 1983-10-18 Minnesota Mining And Manufacturing Company Palladium (II) bis(hexafluoroacetylacetonate), adducts derived therefrom and uses thereof
DE3337856A1 (de) * 1983-10-18 1985-04-25 Bayer Ag, 5090 Leverkusen Verfahren zur aktivierung von substraten fuer die stromlose metallisierung
EP0167326B1 (fr) * 1984-06-29 1989-11-15 Hitachi Chemical Co., Ltd. Procédé de sensibilisation d'un substrat pour le dépôt chimique d'un métal et solution utilisée à cet effet

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0349882A1 (fr) * 1988-07-02 1990-01-10 Heraeus Noblelight GmbH Procédé de fabrication de couches métalliques
EP0349946A1 (fr) * 1988-07-02 1990-01-10 Heraeus Noblelight GmbH Procédé de fabrication de couches métalliques

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101507769B1 (ko) 2013-10-10 2015-04-07 경기대학교 산학협력단 산화물 환원 방법 및 이를 이용하는 산화물 환원 장치

Also Published As

Publication number Publication date
EP0374505A3 (en) 1990-07-04
JPH03122287A (ja) 1991-05-24
DE58907402D1 (de) 1994-05-11
EP0374505A2 (fr) 1990-06-27
DE3840199A1 (de) 1990-05-31
DE3840199C2 (de) 1994-12-01

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