DE4210400C1 - Local copper@ deposition from organo:metallic film on substrate - by forming film from mixt. of copper acetate and copper formate in specified ratio and depositing film by laser irradiation - Google Patents

Local copper@ deposition from organo:metallic film on substrate - by forming film from mixt. of copper acetate and copper formate in specified ratio and depositing film by laser irradiation

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Publication number
DE4210400C1
DE4210400C1 DE4210400A DE4210400A DE4210400C1 DE 4210400 C1 DE4210400 C1 DE 4210400C1 DE 4210400 A DE4210400 A DE 4210400A DE 4210400 A DE4210400 A DE 4210400A DE 4210400 C1 DE4210400 C1 DE 4210400C1
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Germany
Prior art keywords
copper
film
deposition
acetate
formate
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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 - Fee Related
Application number
DE4210400A
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German (de)
Inventor
Friedrich Dipl.-Phys. 8000 Muenchen De Lupp
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Siemens AG
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Siemens AG
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Publication date
Application filed by Siemens AG filed Critical Siemens AG
Priority to DE4210400A priority Critical patent/DE4210400C1/en
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Publication of DE4210400C1 publication Critical patent/DE4210400C1/en
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Classifications

    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00Apparatus or processes for manufacturing printed circuits
    • H05K3/10Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
    • H05K3/105Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern by conversion of non-conductive material on or in the support into conductive material, e.g. by using an energy beam
    • CCHEMISTRY; METALLURGY
    • 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/14Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143Radiation by light, e.g. photolysis or pyrolysis
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/10Using electric, magnetic and electromagnetic fields; Using laser light
    • H05K2203/107Using laser light
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12Using specific substances
    • H05K2203/121Metallo-organic compounds

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Toxicology (AREA)
  • Health & Medical Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemically Coating (AREA)

Abstract

For local Cu deposition from an organo-metallic film on a substrate, the film is formed from a mixt. of Cu acetate and Cu formate in a ratio of 1:5 acetate:formate. The mixt. forms an amorphous film. Deposition is caused by laser beam irradiation. USE/ADVANTAGE - Used partic. for forming conductor tracks on printed circuit boards to electronic units. Film is easily applied, retains amorphous state over long periods.

Description

Die Erfindung betrifft ein Verfahren zur lokalen Abscheidung von Kupfer aus einem metallorganischen Film, wobei unter loka­ ler Erhitzung durch einen Laser das Kupfer auf der Oberfläche des mit dem Film belegten Substrates erzeugt wird.The invention relates to a method for local deposition of copper from an organometallic film, with loka Laser heating the copper on the surface of the substrate covered with the film is generated.

Für die Herstellung von Leiterbahnen, beispielsweise auf Lei­ terplatten, ist eine Vielzahl von Verfahren bekannt. Insbeson­ dere für die Reparatur von Leiterbahnen, z. B. auch auf bereits bestückten Leiterplatten wird sehr häufig ein Verfahren verwendet, bei dem Kupfer aus einem auf die Leiterplatte aufgebrachten metallorganischen Film abgeschieden wird. Der dabei erzeugte feste Film wird lokal mit einem Laser derart erhitzt, daß sich entsprechend einer vorbestimmten Struktur, die vom Laser abgefahren wird, Kupfer abscheidet. In einem nachgeschalteten Verfahrensschritt kann diese Kupferabscheidung nachträglich galvanisch oder stromlos verstärkt werden.For the production of conductor tracks, for example on Lei terplatten, a variety of methods are known. In particular for the repair of conductor tracks, e.g. B. also on PCBs that have already been populated are very common Process used in the copper from one to the Printed circuit board deposited organometallic film becomes. The solid film produced in this way is localized with a laser heated in such a way that according to a predetermined Structure that is scanned by the laser deposits copper. In a subsequent process step can Copper deposition afterwards galvanically or without current be reinforced.

Als metallorganische Stoffe zur Erzeugung des entsprechenden Filmes werden hauptsächlich Kupferformiat oder Kupferacetat eingesetzt. Beide Substanzen werden jeweils auf ein Substrat, beispielsweise einen Kunststoff, aufgebracht und getrocknet. Dabei ist es notwendig, daß die jeweilige, den Film bildende Substanz amorph vorliegt. Um dies in der Praxis zu erreichen, sind jedoch teilweise sehr aufwendige Vorgehensweisen notwen­ dig.As organometallic substances to produce the corresponding Films are mainly copper formate or copper acetate used. Both substances are each on a substrate, for example a plastic, applied and dried. It is necessary that the respective one that forms the film Substance is amorphous. To achieve this in practice, however, very complex procedures are sometimes necessary dig.

Kupferformiat kristallisiert in der Regel beim Trocknen aus. Kupferacetatschichten weisen nach dem Trocknen eine unten lie­ gende dünne, amorphe Schicht auf und eine darüberliegende kri­ stalline Schicht. In der Literatur beschriebene Methoden zur Erzeugung eines insgesamt amorphen Filmes verwenden entweder bestimmte Hilfssubstanzen und/oder eine sehr genaue Temperaturregelung für die Zeit der Abscheidung bzw. Trocknung. In diesem Zusammenhang ist zu erwähnen, daß der amorphe Zustand möglichst über längere Zeit beibehalten werden muß, damit ein zeitlicher Spielraum für die nach­ folgende Laserbearbeitung existiert. Die bisher bekannten Methoden zur amorphen Abscheidung der genannten Substanzen sind jedoch sehr aufwendig.Copper formate usually crystallizes out on drying. Copper acetate layers have a bottom after drying thin, amorphous layer and a layer above it stalline layer. Methods described in the literature for Use generation of an overall amorphous film either certain auxiliary substances and / or a very precise one  Temperature control for the time of deposition or Drying. In this context it should be mentioned that the Maintain amorphous state for a long time if possible must be, so that a time margin for the after following laser processing exists. The previously known Methods for the amorphous deposition of the substances mentioned are however very expensive.

Aus der DE-A-38 26 046 ist ein Verfahren zur Herstellung von metallischen Schichten bekannt. Es wird eine Schicht aus Palladiumacetat durch die Einwirkung von Laser­ strahlung thermisch zersetzt, wobei sich eine metallische Schicht aus Palladium ausbildet. Es wird erwähnt, daß eine flächenhafte Ausbildung der Schicht möglich ist, sowie eine strukturierte Ausbildung mittels einer Maske oder mittels gelenkter Laserstrahlung.DE-A-38 26 046 describes a process for the production known from metallic layers. It's going to be a shift from palladium acetate by the action of laser radiation thermally decomposed, forming a metallic Forms layer of palladium. It is mentioned that a areal formation of the layer is possible, as well structured training using a mask or by means of directed laser radiation.

Die DE-A-38 40 201 beschreibt ein Kontaktierverfahren zur Beschichtung von Begrenzungsflächen unter Einsatz von metallorganischen Verbindungen. Die Kontaktierschicht kann beispielsweise durch ein Metall dargestellt werden.DE-A-38 40 201 describes a contacting method for Coating of boundary surfaces using organometallic compounds. The contact layer can for example represented by a metal.

Spezielle Hineise auf den Einsatz bzw. die Handhabung von Kupferacetat oder Kupferformiat sind den folgenden beiden Literaturstellen zu entnehmen: -′Fast laser writing of copper and iridium lines from thin solid surface layers of metalorganic compounds′; P. Hoffmann, B. Lecohier, S. Goldoni, H. van den Bergh; Applied Surface Science 43 (1989) 54-60; Elsevier Science Publishers B.V. (North- Holland) und -′Laser writing of copper lines from metal­ organic films′; A. Gupta, R. Jagannathan; Appl. Phys. Lett. 51 (26), 28.12.1987, S. 2254-2256; American Institute of Physics.Special information on the use or handling of copper acetate or copper formate can be found in the following two references: -'Fast laser writing of copper and iridium lines from thin solid surface layers of metalorganic compounds'; P. Hoffmann, B. Lecohier, S. Goldoni, H. van den Bergh; Applied Surface Science 43 (1989) 54-60; Elsevier Science Publishers BV (North Holland) and Laser laser of copper lines from metal organic films; A. Gupta, R. Jagannathan; Appl. Phys. Lett. 51 (26), Dec. 28, 1987, pp. 2254-2256; American Institute of Physics.

Beide Literaturstellen befassen sich mit der Metallisierung durch Laserstrahlung aus metallorganischen Filmen. Dabei wird im Artikel von Hoffmann et al auf der Seite 55 unter Punkt 3.1. vermerkt, daß Kupferformiat nach dem Aufsprühen auch auskristallisierte, jedoch nicht so schnell wie andere Substanzen. Der Artikel von Gupta et al vermerkt auf der Seite 2254, daß eine Lösung aus Kupferformiat beim Trocknen Kristallisationserscheinungen zeigt und daß der Film kristallin und rauh wirkt. Eine metallorganische Substanz bzw. ein Gemisch das beim Trocknen über längere Zeit im amorphen Zustand ist, ist aus der Literatur nicht bekannt.Both references deal with metallization  by laser radiation from organometallic films. Here is described in the article by Hoffmann et al on page 55 under Point 3.1. noted that copper formate after spraying also crystallized out, but not as quickly as other substances. The article by Gupta et al noted on page 2254 that a solution of copper formate at Drying shows signs of crystallization and that the Film looks crystalline and rough. An organometallic Substance or mixture that dries over a longer period of time Time in the amorphous state is not from the literature known.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur lokalen Kupferabscheidung aus metallorganischen Filmen bereitzustellen, wobei der metallorganische Film sich leicht aufbringen läßt, in amorphem Zustand vorliegt und diesen Zustand über längere Zeit hält.The invention has for its object a method for local copper deposition from organometallic films to provide, the organometallic film itself can be easily applied, is in an amorphous state and maintains this condition for a long time.

Die Lösung dieser Aufgabe geschieht durch den Einsatz eines metallorganischen Filmes, der aus einem Gemisch von Kupferacetat und Kupferformiat hergestellt wird und einen amorphen Film auf einem Substrat bildet.This task is solved through the application of an organometallic film made from a mixture of Copper acetate and copper formate is produced and a forms amorphous film on a substrate.

Der Erfindung liegt die Erkenntnis zugrunde, daß sich ein Gemisch aus Kupferacetat und Kupferformiat leichter auf ein Substrat aufbringen läßt, als die einzelnen Substanzen für sich. Das Gemisch dieser beiden Substanzen bildet einen amorphen Film. Ein Substrat mit einem derartigen Film läßt sich zumindest mehrere Tage lang lagern, ohne daß Kristallisationsvorgänge im Film auftreten.The invention is based on the knowledge that a Mixture of copper acetate and copper formate more easily a substrate can be applied as the individual substances for themselves. The mixture of these two substances forms an amorphous film. A substrate with such a Film can be stored for at least several days without that crystallization processes occur in the film.

Neben der Notwendigkeit eines amorphen metallorganischen Filmes für lokalen Kupferabscheidungen, die mittels Laser erzeugt werden, ergibt sich somit auch der Vorteil einer variableren Weiterverarbeitungszeit. In addition to the need for an amorphous organometallic Film for local copper deposits using laser generated, there is also the advantage of a variable processing time.  

Die bisher gängige Meinung besagte, daß beim Trocknen einer Schicht aus einem Gemisch von Kupferformiat und Kupferacetat eine Entmischung stattfindet und als Folge davon zumindest eine Substanz ausfällt bzw. über längere Zeit separiert wird und in kristallinem Zustand vorliegt. Infolge dessen würde der Einsatz einer entsprechenden Mischung als nicht sinnvoll Die Erfindung verwendet entgegen der bisher gängigen Meinung ein Gemisch aus Kupferformiat und Kupferacetat und erzielt da­ mit eine nicht vorhersehbare Wirkung. Es tritt weder beim Trocknen bzw. bei der Herstellung des Filmes noch in einer ab­ sehbaren Zeit danach eine Entmischung bzw. eine Kristallisation auf.The current opinion was that when drying a layer of a mixture of copper formate and Copper acetate segregation takes place and as a result at least one substance fails or longer Time is separated and is in the crystalline state. As a result, the use of an appropriate Mixing does not make sense  Contrary to the current opinion, the invention uses a mixture of copper formate and copper acetate and achieved there with an unpredictable effect. It neither occurs Drying or still in one during the production of the film visible time thereafter a segregation or a Crystallization on.

Eine vorteilhafte Ausgestaltung der Erfindung sieht ein Mi­ schungsverhältnis zwischen Kupferacetat und Kupferformiat von 1 : 5 vor. Bei Versuchen, in denen der metallorganische Film in einem Heizschrank durch entsprechendes Eintrocknen einer je­ weilig wäßrigen Lösung erzeugt wurde, hat sich dieses Mi­ schungsverhaltnis als besonders vorteilhaft erwiesen.An advantageous embodiment of the invention sees a Mi ratio between copper acetate and copper formate of 1: 5 before. In experiments in which the organometallic film in a heating cabinet by drying each one because aqueous solution was generated, this Mi proved to be particularly advantageous.

Claims (2)

1. Verfahren zur lokalen Kupferabscheidung aus metallorgani­ schen Filmen auf einem Substrat mittels eines Lasers, wobei der metallorganische Film im amorphen Zustand vor­ liegt, insbesondere zur Ausbildung von Leiterbahnen an elektronischen Einheiten, dadurch gekennzeichnet daß der metallorganische Film aus einem Gemisch von Kup­ feracetat und Kupferformiat hergestellt wird.1. Process for local copper deposition from organometallic films on a substrate by means of a laser, the organometallic film being in the amorphous state, in particular for the formation of conductor tracks on electronic units, characterized in that the organometallic film consists of a mixture of copper and acetate and copper formate will be produced. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet daß das Mischungsverhältnis zwischen Kupferacetat und Kup­ ferformiat 1 : 5 beträgt.2. The method according to claim 1, characterized that the mixing ratio between copper acetate and cup ferformate is 1: 5.
DE4210400A 1992-03-30 1992-03-30 Local copper@ deposition from organo:metallic film on substrate - by forming film from mixt. of copper acetate and copper formate in specified ratio and depositing film by laser irradiation Expired - Fee Related DE4210400C1 (en)

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DE4210400A DE4210400C1 (en) 1992-03-30 1992-03-30 Local copper@ deposition from organo:metallic film on substrate - by forming film from mixt. of copper acetate and copper formate in specified ratio and depositing film by laser irradiation

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015289A1 (en) * 1994-11-14 1996-05-23 Simon Fraser University Method for directly depositing metal containing patterned films
DE19517625A1 (en) * 1995-05-13 1996-11-14 Budenheim Rud A Oetker Chemie Laser printing esp. on glass or plastic substrate
DE19723734A1 (en) * 1997-06-06 1998-12-10 Gerhard Prof Dr Naundorf Conductor structures on a non-conductive carrier material, in particular fine conductor structures, and methods for their production
EP0979029A2 (en) * 1998-08-04 2000-02-09 Wolfgang Anger Process for manufacturing printed circuit boards
NL1021245C2 (en) * 2002-08-09 2004-02-10 Tno Carrier for at least one IC and systems comprising such a carrier and an IC and / or such carrier and a connecting plate.
US6777036B2 (en) 2001-06-06 2004-08-17 Simon Fraser University Method for the deposition of materials from mesomorphous films
EP2826885A4 (en) * 2012-03-16 2015-10-21 Adeka Corp Copper film-forming composition, and method for producing copper film by using the composition

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3826046A1 (en) * 1987-08-17 1989-03-02 Asea Brown Boveri METHOD FOR PRODUCING METAL LAYERS
DE3840201A1 (en) * 1988-11-29 1990-05-31 Asea Brown Boveri Contact-making method

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3826046A1 (en) * 1987-08-17 1989-03-02 Asea Brown Boveri METHOD FOR PRODUCING METAL LAYERS
DE3840201A1 (en) * 1988-11-29 1990-05-31 Asea Brown Boveri Contact-making method

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996015289A1 (en) * 1994-11-14 1996-05-23 Simon Fraser University Method for directly depositing metal containing patterned films
CN1092244C (en) * 1994-11-14 2002-10-09 西蒙·弗雷泽大学 Method for directly depositing metal containing patterned films
DE19517625A1 (en) * 1995-05-13 1996-11-14 Budenheim Rud A Oetker Chemie Laser printing esp. on glass or plastic substrate
US6319564B1 (en) 1997-06-06 2001-11-20 Gerhard Naundorf Conductor track structures arranged on a nonconductive support material, especially fine conductor track structures, and method for producing the same
DE19723734A1 (en) * 1997-06-06 1998-12-10 Gerhard Prof Dr Naundorf Conductor structures on a non-conductive carrier material, in particular fine conductor structures, and methods for their production
DE19723734C2 (en) * 1997-06-06 2002-02-07 Gerhard Naundorf Conductor structures on a non-conductive carrier material and method for their production
EP0979029A2 (en) * 1998-08-04 2000-02-09 Wolfgang Anger Process for manufacturing printed circuit boards
EP0979029A3 (en) * 1998-08-04 2001-08-29 Wolfgang Anger Process for manufacturing printed circuit boards
DE19835158A1 (en) * 1998-08-04 2000-02-10 Wolfgang Anger Process for the production of printed circuit boards
US6777036B2 (en) 2001-06-06 2004-08-17 Simon Fraser University Method for the deposition of materials from mesomorphous films
NL1021245C2 (en) * 2002-08-09 2004-02-10 Tno Carrier for at least one IC and systems comprising such a carrier and an IC and / or such carrier and a connecting plate.
WO2004015775A1 (en) * 2002-08-09 2004-02-19 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Stacking substrate for at least one ic and system comprising such a substrate
EP2826885A4 (en) * 2012-03-16 2015-10-21 Adeka Corp Copper film-forming composition, and method for producing copper film by using the composition

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