EP0251302A2 - Bain alcalin de dépôt chimique de cuivre - Google Patents

Bain alcalin de dépôt chimique de cuivre Download PDF

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Publication number
EP0251302A2
EP0251302A2 EP87109422A EP87109422A EP0251302A2 EP 0251302 A2 EP0251302 A2 EP 0251302A2 EP 87109422 A EP87109422 A EP 87109422A EP 87109422 A EP87109422 A EP 87109422A EP 0251302 A2 EP0251302 A2 EP 0251302A2
Authority
EP
European Patent Office
Prior art keywords
copper
tetrakis
ethylenediamine
hydroxypropyl
acid
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.)
Withdrawn
Application number
EP87109422A
Other languages
German (de)
English (en)
Other versions
EP0251302A3 (fr
Inventor
Walter Dr. Kronenberg
Herbert Breidenbach
Jürgen Dr. Hupe
Eberhard Knaak
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.)
Blasberg-Oberflachentechnik GmbH
Original Assignee
Blasberg-Oberflachentechnik 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 Blasberg-Oberflachentechnik GmbH filed Critical Blasberg-Oberflachentechnik GmbH
Publication of EP0251302A2 publication Critical patent/EP0251302A2/fr
Publication of EP0251302A3 publication Critical patent/EP0251302A3/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/38Coating with copper
    • C23C18/40Coating with copper using reducing agents

Definitions

  • the present invention relates to an alkaline external electroless copper bath containing copper salt, reducing agent, wetting agent, alkali hydroxide and complexing agent.
  • Such alkaline copper baths without external current are known in a wide variety of compositions. However, they all tend to more or less uncontrolled precipitation of copper by disproportionation of the copper (I) compounds formed during the reduction to copper and copper (II) compounds.
  • the object of the invention is therefore to develop an alkaline copper bath without external current, which is cyanide-free in all cases and, moreover, preferably also contains no formaldehyde.
  • This new copper bath can therefore be used free of formaldehyde or with formaldehyde. In any case, it contains no cyanide. It is crucial that it contains the N, N, N ⁇ , N ⁇ -tetrakis (2-hydroxypropyl) ethylenediamine as a complexing agent, a small amount of a gallium, indium and / or thallium salt and a thioalcohol or a thiocarboxylic acid.
  • thioalcohol or thiocarboxylic acid 2,2-thiodiethanol, thioglycolic acid, mercaptosuccinic acid, thioacetic acid, thiodiglycolic acid, 3,3-thiodipropionic acid, 2-mercaptopropionic acid and 2-mercaptobenzoic acid.
  • the thiocarboxylic acids can also be used in the form of their esters, since under the alkaline conditions the esters are rapidly saponified to give the acids.
  • An easy to handle and therefore easy to use ester is e.g. the thioglycolic acid ethyl ester.
  • the amount of copper salt is not particularly critical. It is preferably selected in the range from 4 to 6 g / l.
  • the amount of reducing agent is also not critical. Quantities between 100 and 500 mg / l are preferably used.
  • the amount of wetting agent is also not critical. However, fluorinated wetting agents such as perfluorocarboxylic acids, perfluorosulfonic acids and perfluorinated amines are preferably used. They are effective and stable even at high pH values.
  • N, N, N ⁇ , N ⁇ -tetrakis (2-hydroxypropyl) ethylenediamine is therefore essential to the invention.
  • the amount should in particular be in the range between 6 and 50 g / l.
  • 0.1 to 200 mg of a gallium, indium and / or thallium salt is also essential to the invention.
  • the improvement effect does not yet occur below the limit of 0.1 mg. Amounts greater than 200 mg are unnecessary and also undesirable for reasons of cost and toxicity.
  • the third component essential to the invention are the thioalcohols or thiocarboxylic acids. They contribute significantly to the effectiveness and stabilization of the new copper bath.
  • the copper deposits deposited from the baths according to the invention have a light copper color. They are particularly suitable for metallizing holes in printed circuit boards.
  • the non-conductive base material is usually activated with palladium chloride.
  • the surface germinated with palladium is covered with copper so densely in 15 to 20 minutes that the so-called transmitted light test is fully fulfilled. It is crucial that the copper layers obtained with the copper bath according to the invention have optimal adhesive strength and functionality for the subsequently applied metallic reinforcements.
  • An alkaline copper bath without external current contains the following components: Copper sulfate 4 g / l Mercaptosuccinic acid 250 mg / l N, N, N ⁇ , N ⁇ -tetrakis (2-hydroxypropyl) ethylenediamine 6 g / l Sodium borohydride 300 mg / l Thallium nitrate 10 mg / l fluorinated wetting agent 10 mg / l
  • Another copper bath consists of: Copper sulfate 4 g / l Thioacetic acid 150 mg / l N, N, N ⁇ , N ⁇ -tetrakis (2-hydroxypropyl) ethylenediamine 8 g / l Sodium borohydride 150 mg / l Thallium nitrate 2 mg / l fluorinated wetting agent 5 mg / l
  • Another copper bath consists of: Copper sulfate 6 g / l Thioglycolic acid 500 mg / l N, N, N ⁇ , N ⁇ -tetrakis (2-hydroxypropyl) ethylenediamine 18 g / l Thallium nitrate 5 mg / l fluorinated wetting agent 25 mg / l Sodium borohydride 500 mg / l
  • Another copper bath consists of: Copper sulfate 4 g / l N, N, N ⁇ , N ⁇ -tetrakis (2-hydroxypropyl) ethylenediamine 12 g / l fluorinated wetting agent 20 mg / l Indium (as indium sulfamate) 50 mg / l Thioglycolic acid ethyl ester 350 mg / l Sodium borohydride 700 mg / l

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
EP87109422A 1986-07-02 1987-06-30 Bain alcalin de dépôt chimique de cuivre Withdrawn EP0251302A3 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3622090 1986-07-02
DE19863622090 DE3622090C1 (fr) 1986-07-02 1986-07-02

Publications (2)

Publication Number Publication Date
EP0251302A2 true EP0251302A2 (fr) 1988-01-07
EP0251302A3 EP0251302A3 (fr) 1988-07-27

Family

ID=6304162

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87109422A Withdrawn EP0251302A3 (fr) 1986-07-02 1987-06-30 Bain alcalin de dépôt chimique de cuivre

Country Status (2)

Country Link
EP (1) EP0251302A3 (fr)
DE (1) DE3622090C1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1411147A1 (fr) * 2002-10-18 2004-04-21 Shipley Co. L.L.C. Procédé et solution de placage sans courant de cuivre exempt de formaldehyde
EP1286576A3 (fr) * 2001-08-21 2004-12-29 Shipley Company LLC Procédé de fabrication d'un matériau composite de cuivre-résine
CN100402700C (zh) * 2002-11-20 2008-07-16 希普雷公司 无甲醛化学镀铜方法及该方法中使用的溶液
US7892413B2 (en) 2006-09-27 2011-02-22 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films
US8425753B2 (en) 2008-05-19 2013-04-23 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5419926A (en) * 1993-11-22 1995-05-30 Lilly London, Inc. Ammonia-free deposition of copper by disproportionation

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1254935B (de) * 1960-12-31 1967-11-23 Bayer Ag Waessriges Bad zur chemischen Abscheidung von borhaltigen Metallueberzuegen
DE1243493B (de) * 1961-02-04 1967-06-29 Bayer Ag Waessriges Bad zur chemischen Abscheidung von borhaltigen Metallueberzuegen
US3361580A (en) * 1963-06-18 1968-01-02 Day Company Electroless copper plating
US3377174A (en) * 1963-10-24 1968-04-09 Torigai Eiichi Method and bath for chemically plating copper
US3403035A (en) * 1964-06-24 1968-09-24 Process Res Company Process for stabilizing autocatalytic metal plating solutions
US3607317A (en) * 1969-02-04 1971-09-21 Photocircuits Corp Ductility promoter and stabilizer for electroless copper plating baths
US3649308A (en) * 1970-05-21 1972-03-14 Shipley Co Stabilized electroless plating solutions
US3959531A (en) * 1971-04-23 1976-05-25 Photocircuits Corporation Improvements in electroless metal plating
US3902907A (en) * 1973-08-17 1975-09-02 Kazutaka Kishita System for electroless plating of copper and composition
NL7402422A (nl) * 1974-02-22 1975-08-26 Philips Nv Universele verkoperingsoplossing.
US4124399A (en) * 1977-09-13 1978-11-07 Shipley Company Inc. Stabilized electroless plating solutions
US4189324A (en) * 1978-06-02 1980-02-19 Michael Gulla Stabilized electroless plating solutions
US4301196A (en) * 1978-09-13 1981-11-17 Kollmorgen Technologies Corp. Electroless copper deposition process having faster plating rates
IT1157006B (it) * 1982-03-09 1987-02-11 Alfachimici Spa Miscela stabilizzante per un bagno di rame chimico

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1286576A3 (fr) * 2001-08-21 2004-12-29 Shipley Company LLC Procédé de fabrication d'un matériau composite de cuivre-résine
EP1411147A1 (fr) * 2002-10-18 2004-04-21 Shipley Co. L.L.C. Procédé et solution de placage sans courant de cuivre exempt de formaldehyde
CN100402700C (zh) * 2002-11-20 2008-07-16 希普雷公司 无甲醛化学镀铜方法及该方法中使用的溶液
US7892413B2 (en) 2006-09-27 2011-02-22 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films
US8425753B2 (en) 2008-05-19 2013-04-23 Solopower, Inc. Electroplating methods and chemistries for deposition of copper-indium-gallium containing thin films

Also Published As

Publication number Publication date
DE3622090C1 (fr) 1990-02-15
EP0251302A3 (fr) 1988-07-27

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Inventor name: BREIDENBACH, HERBERT

Inventor name: HUPE, JUERGEN, DR.

Inventor name: KRONENBERG, WALTER, DR.

Inventor name: KNAAK, EBERHARD