WO1993020263A1 - Procede de metallisation de non-conducteurs, notamment de cartes de circuits imprimes - Google Patents

Procede de metallisation de non-conducteurs, notamment de cartes de circuits imprimes Download PDF

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Publication number
WO1993020263A1
WO1993020263A1 PCT/DE1993/000309 DE9300309W WO9320263A1 WO 1993020263 A1 WO1993020263 A1 WO 1993020263A1 DE 9300309 W DE9300309 W DE 9300309W WO 9320263 A1 WO9320263 A1 WO 9320263A1
Authority
WO
WIPO (PCT)
Prior art keywords
solution
treatment
noble metal
colloidal
metallization
Prior art date
Application number
PCT/DE1993/000309
Other languages
German (de)
English (en)
Inventor
Reinhard Deboer
Hans-Joachim Grapentin
Original Assignee
Atotech Deutschland 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 Atotech Deutschland Gmbh filed Critical Atotech Deutschland Gmbh
Publication of WO1993020263A1 publication Critical patent/WO1993020263A1/fr

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/423—Plated through-holes or plated via connections characterised by electroplating method
    • H05K3/424—Plated through-holes or plated via connections characterised by electroplating method by direct electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/032—Materials
    • H05K2201/0329—Intrinsically conductive polymer [ICP]; Semiconductive polymer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0716—Metallic plating catalysts, e.g. for direct electroplating of through holes; Sensitising or activating metallic plating catalysts
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0779—Treatments involving liquids, e.g. plating, rinsing characterised by the specific liquids involved
    • H05K2203/0786—Using an aqueous solution, e.g. for cleaning or during drilling of holes
    • H05K2203/0796—Oxidant in aqueous solution, e.g. permanganate
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/12—Using specific substances
    • H05K2203/122—Organic non-polymeric compounds, e.g. oil, wax, thiol
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
    • H05K3/42—Plated through-holes or plated via connections
    • H05K3/425—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern
    • H05K3/427—Plated through-holes or plated via connections characterised by the sequence of steps for plating the through-holes or via connections in relation to the conductive pattern initial plating of through-holes in metal-clad substrates

Definitions

  • the invention relates to a method for metallizing non-conductors.
  • Newer processes for the metallization of non-conductors are based on the fact that polypyrrole is a conductive polymer.
  • This polypyrrole can be applied as a first layer to a non-conductor instead of "chemical copper", followed by the galvanic metallization processes, for example galvanic copper plating.
  • EP-AI 0 206 133, DE-OS 39 31 003, DE-PS 38 06 884 and PCT / DE 00920 (WO 91/08324) methods for the direct metallization of non-conductor surfaces by the application of a treatment with oxidizing agents, for example potassium permanganate, and a heterocycle solution, for example pyrrole solution.
  • oxidizing agents for example potassium permanganate
  • a heterocycle solution for example pyrrole solution.
  • a conductive organic polymer for example polypyrrole
  • This polymeric conductive layer adheres firmly to the surface of the non-conductor and can be galvanized immediately.
  • a conductive polymer layer on non-conductors can only be produced if an adhesive layer of oxidizing agents has been applied beforehand.
  • the method is used that the non-conductor is treated with an alkaline permanganate solution, in particular when an epoxide is used as the non-conductor, this is oxidized and a manganese dioxide layer is formed on the surface, which in turn serves as an oxidizing agent for the formation of conductive polymers (when contacting) with heterocycles).
  • cyanate esters such as cyanate esters, higher crosslinked epoxides with a Tg higher than 140 ° C, epoxies with BT additives, Teflon, certain polyimides and polyamides, polystyrenes, polyethylenes, polycarbonates, block merisates made of acrylonitrile butadiene Styrrole (ABS), polyester or polysulfones, or also fillers such as glass, ceramic, aluminum oxide, titanium dioxide or barium sulfate form a layer of manganese dioxide directly and easily with the permanganate solution.
  • ABS acrylonitrile butadiene Styrrole
  • fillers such as glass, ceramic, aluminum oxide, titanium dioxide or barium sulfate form a layer of manganese dioxide directly and easily with the permanganate solution.
  • the object of the invention is to provide a method in which a uniform and homogeneous metallization can be achieved in the shortest time, in particular in the drill sleeves, and which is suitable for processing almost all conventional non-conductor materials. This problem is solved according to the teaching of the claims.
  • a noble metal-containing solution in particular palladium-containing solution, optionally contain one or more reducing agents,
  • the invention includes the use of a noble metal-containing solution, in particular a palladium-containing solution, as a process step together with the steps of a manganate and / or permanganate and pyrrole treatment in the metalization of non-conductors, in particular printed circuit boards.
  • a noble metal-containing solution in particular a palladium-containing solution
  • cleaners and / or etching cleaners all commercially available products can be used as cleaners and / or etching cleaners.
  • solutions which contain persulfate and / or acid, in particular sodium persulfate and mi mineral acid, such as sulfuric acid.
  • the treatment of the non-conductor with a chelating agent or an ionogenic organic compound generally takes place with nitrogen-containing derivatives.
  • These derivatives can be used with advantage, which are already described as conditioning agents for the treatment of base materials in the documents DE-OS 35 30 617 and DE-OS 41 12 462.
  • These are quaternary organic nitrogen compounds that can contain a vinyl or allyl group.
  • the corresponding polymeric compounds can also be used (polymerized via the respective vinyl or allyl groupings).
  • N-methyl-N * -vinyl-imidazolinium metosulfate N-methyl-N'-vinyl-pyrrolidonium chloride, N-allylimidazolium iodide, N-methyl-N'-vinyl- ⁇ -caprolactam quarter salt, N-butyl-N'-allylbenzimidazolinium methosulfate, the copolymer of N-methyl-N'-vinylimidazolinium methochloride and vinylpyrrolidone, and the homopolymers of the listed types of compounds or other salts.
  • Suitable chelating agents are, for example, ethanolamine, triethanolamine, amino acids (e.g. glycine) or hard complexing agents, such as EDTA.
  • a noble metal-containing solution in particular a palladium-containing solution, optionally containing one or more reducing agents, is carried out after the treatment with an ionogenic organic compound.
  • All commercially available products can likewise be used as noble metal-containing solutions, it being irrelevant whether the respective noble metal is in colloidal form, is stabilized with tin or organic polymer or is ionic, for example described in EP-A-0317 092, PCT / DE 90/00845 and DE-Al 16 18 299.
  • These activations by means of catalysts containing noble metals can be carried out in one or more stages.
  • the noble metal-containing solution may be sensitive to oxidation, so it can be used to redissolve the palladium, e.g. B. come as palladium chloride.
  • the introduction of oxidizing agents is prevented by treating the non-conductor with a dilute solution of a reducing agent before the treatment with the metal colloid.
  • the embodiment in which the reduction potential in the metal colloid solution is permanently monitored by means of an electrode and is kept at a constant value by the reducing agent by means of automatic replenishment.
  • treatment with a manganate and / or an ananate solution follows.
  • a solution which contains manganate in the concentration 10-75 g / 1, permanganate in a concentration 30-150 g / 1, and sodium hydroxide in a concentration of 40-70 g / 1.
  • solutions which contain only manganate or only permanganate.
  • the treatment with manganate / permanganate solution can also take place in an acidic medium, in particular a weakly acidic medium.
  • the next step in the process is treatment with a weakly acidic pyrrole solution.
  • the pH of such a solution is usually between pH 1.5 - 4.00.
  • this step can also be carried out in two stages. Either treatment is carried out first with a pyrrole solution and then with an acid solution (described in DE-PS 38 06 884) or first with an acid solution and then with a pyrrole solution.
  • the one-step method has given the best results.
  • the subsequent galvanic metal deposition is carried out using known galvanic baths.
  • all metals or alloys that can be deposited by electroplating can be deposited.
  • copper electrolytes are preferably used.
  • Sulfuric acid copper baths with a content of 50-300 g / 1 sulfuric acid and a metal content of 5-50 g / 1 are particularly preferred.
  • fluoroboric acid, hydrochloric acid thiosulfate- or pyrophosphate-containing or cyanide electrolytes, as well as electrolytes based on sulfonamides and organic sulfonic acids have proven to be well suited.
  • Electrolytes are operated under the usual conditions, namely in the temperature range between 20 and 70 ° C., with current densities between 0.1 and 20 A / dm 2 .
  • the time of the galvanic deposition can be shortened considerably, namely in particularly favorable cases to ⁇ 2 min. This gives uniform, closed and, moreover, firmly adhering metal layers which have no defects either in the so-called transmitted light test.
  • the plated-through circuits produced according to the invention can be processed in a known manner. For example, a further build-up of metallic layers can be carried out galvanically, so that copper layers of 25-40 ⁇ m are formed, which are then covered with further metallic layers which are applied to the printed circuit boards as etching resists .
  • the etch-back is independent of whether it is a plasma, permanganate-sulfuric acid, chromic acid process or a corresponding combination process.
  • the bores of the circuit board pretreated in this way, in which epoxy was etched back and the filler glass was exposed, are metallized using the following methods.
  • Etching cleaning e.g. based on 0.5 min 30 sodium persulfate / sulfuric acid
  • the current density was kept constant at 2 A / dm 2 for simplification.
  • a conventional cleaner suitable for epoxy but not containing any of the compounds described with conditioning properties was used as the cleaner.
  • Example 1 was repeated, 2 g / 1 Basotronic PVI R (product from BASF AG) being added to the cleaner.
  • Example 3 was repeated using an acidic potassium permanganate solution (pH 4) which was stabilized with phosphoric acid.
  • Epoxy with Tg> 130 ° C special epoxy (CEM 3), polyimide (glass), polyamide, acrylonitrite-butadiene-styrene block polymer (ABS), ceramic, Teflon and cyanate ester.
  • Examples 3-6 were carried out both in diving, gushing and flooding.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Chemically Coating (AREA)

Abstract

Procédé de métallisation de non-conducteurs caractérisé par les étapes suivantes: a) traitement du non-conducteur avec un agent chélatant et/ou un composé organique ionogène; b) traitement avec une solution contenant un métal noble et renfermant éventuellement un ou plusieurs réducteur(s); c) traitement avec une solution contenant du manganate et/ou du permanganate; d) traitement avec une solution pyrrolique acide, monomère et/ou oligomère; e) métallisation électrolytique.
PCT/DE1993/000309 1992-03-31 1993-03-27 Procede de metallisation de non-conducteurs, notamment de cartes de circuits imprimes WO1993020263A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4211152.8 1992-03-31
DE19924211152 DE4211152C1 (de) 1992-03-31 1992-03-31 Verfahren zur Metallisierung von Nichtleitern und Anwendung des Verfahrens

Publications (1)

Publication Number Publication Date
WO1993020263A1 true WO1993020263A1 (fr) 1993-10-14

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1993/000309 WO1993020263A1 (fr) 1992-03-31 1993-03-27 Procede de metallisation de non-conducteurs, notamment de cartes de circuits imprimes

Country Status (2)

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DE (1) DE4211152C1 (fr)
WO (1) WO1993020263A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4412463C3 (de) * 1994-04-08 2000-02-10 Atotech Deutschland Gmbh Verfahren zur Herstellung einer Palladium-Kolloid-Lösung und ihre Verwendung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0457180A2 (fr) * 1990-05-09 1991-11-21 LeaRonal (UK) plc Procédé de métallisation d'un circuit à transtraversants

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3680592D1 (de) * 1985-06-12 1991-09-05 Basf Ag Verwendung von polypyrrol zur abscheidung von metallischem kupfer auf elektrisch nichtleitende materialen.
DE3806884C1 (en) * 1988-03-03 1989-09-21 Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De Through-plated contact printed circuit and method for fabricating it
US4969979A (en) * 1989-05-08 1990-11-13 International Business Machines Corporation Direct electroplating of through holes
DE3931003A1 (de) * 1989-09-14 1991-03-28 Schering Ag Verfahren zur direkten metallisierung von leiterplatten
US4919768A (en) * 1989-09-22 1990-04-24 Shipley Company Inc. Electroplating process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0457180A2 (fr) * 1990-05-09 1991-11-21 LeaRonal (UK) plc Procédé de métallisation d'un circuit à transtraversants

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Publication number Publication date
DE4211152C1 (de) 1993-11-25

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