US3403035A - Process for stabilizing autocatalytic metal plating solutions - Google Patents

Process for stabilizing autocatalytic metal plating solutions Download PDF

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Publication number
US3403035A
US3403035A US377471A US37747164A US3403035A US 3403035 A US3403035 A US 3403035A US 377471 A US377471 A US 377471A US 37747164 A US37747164 A US 37747164A US 3403035 A US3403035 A US 3403035A
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US
United States
Prior art keywords
metal
bath
autocatalytic
solution
catalytic
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Expired - Lifetime
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US377471A
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English (en)
Inventor
Jr Frederick W Schneble
Rudolph J Zeblisky
John F Mccormack
Williamson John Duff
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PROCESS RES Co
PROCESS RESEARCH Co
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PROCESS RES Co
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Priority to US377471A priority Critical patent/US3403035A/en
Priority to GB26274/65A priority patent/GB1121282A/en
Priority to CH872465A priority patent/CH467342A/de
Priority to ES0314564A priority patent/ES314564A2/es
Priority to DE19651521440 priority patent/DE1521440B2/de
Priority to SE8362/65A priority patent/SE316962B/xx
Priority to DK317365AA priority patent/DK129949B/da
Priority to AT570665A priority patent/AT270330B/de
Priority to FR22099A priority patent/FR88424E/fr
Priority to BE665911A priority patent/BE665911A/xx
Priority to NL6508142A priority patent/NL6508142A/xx
Application granted granted Critical
Publication of US3403035A publication Critical patent/US3403035A/en
Priority to NL7514608A priority patent/NL7514608A/xx
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
    • C23C18/52—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 using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
    • 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
    • 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
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • 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
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents

Definitions

  • Electroless metal deposition is also to be distinguished from displacement metal plating of the type described in Metals Finishing Guide Book, 27th Edition, 1959, pages 469 et seq., and metal mirroring procedures, wherein the metal plating desired and achieved is only a few millionths of an inch in thickness.
  • autocatalytic or electroless metal deposition solutions comprise an aqueous solution of water soluble salt of the metal or metals to be deposited, a reducing agent for the metal cations, and a complexing or sequestering agent for the metal cations.
  • the function of the complexing or sequestering agent is to form a water soluble complex with the dissolved metallic cations so as to maintain the metal in solution.
  • the function of the reducing agent is to reduce the metal cation to metal at the appropriate time, as will be made more clear hereinbelow.
  • the pH of the autocatalytic met-a1 solution will ordinarily be controlled.
  • Solution pH will depend upon the nature of the metallic salt, the sequestering agent and the reducing agent.
  • the pH may range from strongly acid to strongly alkaline, e.g., from pH 1 to 14, and usually from pH 4 to 14.
  • the goal in operating electroless metal deposition solutions is to balance the ingredients so that metallic deposition will occur only at the interface formed between the solution and a catalytic surface to be metallized.
  • the metallic precipitate constitutes a decomposition product of the plating bath, and is particularly objectionable in that it causes the desirable deposit to be coarse, rough and frequently porous. Additionally, the fine solid particles of the metallic precipitate, once formed, become suspended in the plating baths or adhere to the walls of the plating vessel, and act as nuclei to initiate the formation of additional precipitate, thereby further enhancing the tendency of the bath to decompose.
  • cyanide compound may be mentioned alkali cyanides, such as sodium and potassium cyanide, and nitriles such as alpha-hydroxy nitriles, e.g., glycolnitrile and lactonitrile.
  • alkali cyanides such as sodium and potassium cyanide
  • nitriles such as alpha-hydroxy nitriles, e.g., glycolnitrile and lactonitrile.
  • the amount of cyanide compound will ordinarily range between about 5 micrograms and 500 milligrams per liter.
  • the invention is generally applicable to autocatalytic metal deposition solutions for copper, nickel, cobalt, cadmium, tin, and similar metals.
  • the sulfates, chlorides, acetates, and nitrates of such metals are ordinarily utilized as the water soluble salts.
  • Other water soluble salts of the indicated metals may however be used, the choice being primarily a question of economics.
  • the reducing agents in such metal deposition baths include borohydrides, amine boranes, hydrazines, hypophosphites, hydrosulfites, hydroxyl amines, formaldehyde, and the like.
  • the borohydride reducing agent may consist of any water soluble borohydride having a good degree of solubility and stability in aqueous solutions. Sodium and potas sium borohydrides are preferred. In addition, substituted borohydrides in which not more than 3 hydrogen atoms of the borohydride ion have been replaced can be utilized. Sodium trimethoxy borohydride, NaB(OCH H, is illustrative of the compounds of this type.
  • ammonium borohydride and the amine boranes such as isopropylamine borane, and dimethyl amine borane.
  • hydrazines may be mentioned water soluble salts of hydrazine, such as the hydrazine sulfates, e.g., monohydrazine sulfate, di-hydrazine sulfate, hydrazine disulfate, and the like. Because of its greater solubility in Water, dihydrazine sulfate is preferred.
  • the alkali metal e.g., sodium, potassium and ammonium salts are preferred.
  • polymers of the formaldehyde e.g., paraformaldehyde
  • the reducing agent is alpha-trioxymethylene.
  • the sequestering or complexing agent will be selected to form a strong complex with the metal ions to prevent the precipitation of metal or metallic salts.
  • the complexing agent selected should also be capable of forming a metal complex which is soluble in the plating solution, and also which is sufliciently stable so that it will not react with the reducing agent in the main body of the plating solution, but only at or in the near vicinity of the catalytic surface.
  • One such material is N hydroxyethylethylenediaminetriacetate.
  • the complexing agent it is therefore preferred to first add the complexing agent to the aqueous solution of the metal salt to form the water soluble complex of the metal cations. If the reducing agent is added before the metal complex is formed, there will be a tendency for it to react instantaneously with the metal salt to precipitate the metal or a salt of the metal.
  • the pH should also be adjusted to the proper value prior to addition of the reducing agent.
  • failure to regulate the pH initially may lead to spontaneous decomposition of the reducing agent.
  • Catalytic surfaces which may be plated with the baths of this invention include metals such as nickel, cobalt, iron, steel, palladium, platinium, copper, brass, manganese, chromium, molybdenum, tungsten, titanium, tin, silver, including mixtures thereof, and oxides thereof. All such metals are catalytic to the reduction of the metal cations dissolved in the solutions described.
  • Non-metallic materials such as glass, ceramic, and various plastics are, in general, non-catalytic.
  • the surfaces of such non-catalytic materials can be rendered catalytic by producing a film or particles of one of the catalytic materialst thereon. This can be accomplished by a variety of techniques known to those skilled in the art.
  • One suitable sensitization procedure involves dipping noncatalytic materials in an acidic solution of stannous chloride, washing with water, and then contacting the treated material with an acidic solution of a precious metal salt, e.g., palladium chloride.
  • a mono-layer of precious metal is thus produced on the surface of the non-catalytic material, which mono-layer is catalytic to reduction of the metal ions in the electroless metal plating solutions described herein.
  • such materials as glass, ceramic, and plastic may be sensitized or rendered catalytic by treatment with an acidic aqueous solution containing, in combination, stannous tin ions and precious metal ions.
  • a further sensitization procedure involves adhering to the normally non-catalytic surface, finely divided particles of metals or metal oxides which are catalytic to electroless deposition.
  • catalytic surface refers to the surface of any article composed of the catalytic materials described hereinabove or covered therewith or to the surface of a non-catalytic material which has been sensitized by producing a film or particles of said catalytic materials on its surface.
  • the baths of this invention will deposit metal electrolessly on the catalytic surfaces of metals, and non-metals, such as paper, glass, ceramic, synthetic resins and plastics, including but not limited to silicones, phenolics, styrenes, acrylics, vinyl chlorides, nylon, mylar, acrylonitrilebutadiene-styrene, and the like.
  • Example 1 A bath corresponding to the following formula was prepared:
  • the control bath decomposed spontaneously after standing for /2 hour.
  • the bath containing 0.008 mole per liter of sodium cyanide had a useful copper plating life of greater than 4 hours.
  • Example 2 A bath corresponding to the following formula was prepared:
  • the control bath decomposed spontaneously after standing /2 hour,
  • the bath containing 0.0016 mole per liter of sodium cyanide had a useful copper plating life of 20 hours.
  • Example 3 A bath corresponding to the following formula was prepared:
  • the bath containing 0.0001 mole per liter of sodium cyanide did not deposit copper.
  • the bath with 0.00001 mole per liter of sodium cyanide deposited a bright copper film.
  • Water soluble metal salt 0.002 to 0.60 mole/l. Reducing agent 0.0002 to 2.5 moles/l. Complexing agent 0.7 to 10 times the moles of metal salt. Cyanide compound 0.00001 to 0.06 mole/l.
  • the amount of sequestering agent to be added to the plating solution depends upon the nature of the sequestering agent and the amount of the metal salt present in the bath. In alkaline solutions, the preferred ratio of the metal salt to complexing agent lies between about 1:1 and 1:10. A small excess of the sequestering agent, based upon the metal salt, generally is advantageous.
  • the metal salt, and the reducing agent may be replenished from time to time, and also that it may be advisable to monitor the pH, and the cyanide content of the bath, and to adjust them to their optimum value as the bath is used.
  • surfactants in an amount of less than about 5 grams per liter are added to the baths disclosed herein.
  • suitable surfactants are organic phosphate esters, and oxyethylated sodium salts.
  • Such surfactants may be obtained under the trade names Gafac RE 610 and Triton QS-lS, respectively.
  • the baths are ordinarily used at temperatures between 25 and 90 C., although they may be used at lower temperatures or at even higher temperatures. As the temperature is increased, it is usual to find that the rate of plating is increased.
  • the process of this invention permits metal to be deposited on practically any conceivable substratum and to practically any thickness desired.
  • Metallized surfaces produced by utilizing the autocatalytic metal deposition solutions of this invention are useful as ornamental designs, markings, and the like.
  • metal may be deposited in pre-determined patterns on insulating substrata and serve as electrical conductors.
  • Electrically conductive circuit patterns e.g., printed circuits, may thus be selectively plated on the activated areas of an inexpensive sheet of a wide variety of insulating material.
  • a process for increasing the useful life of autocatalytic metal plating solution used to electrolessly deposit metal onto catalytic surfaces in which the solution comprises water, a metal ion selected from the group consisting of cobalt, nickel and tin, a complexing agent and a reducing agent for said ion, said process comprising maintaining in said solution a small eflective amount of a water-soluble cyanide compound in a concentration of 5 micrograms to 500 milligrams per liter.
  • the reducing agent is a member selected from the group consisting of borohydrides, amine boranes, hydrazines, hypophosphites, hydrosulfites, hydroxyl amines and alpha-trioxymethylene.
  • a process for electrolessly depositing a metal onto a catalytic surface which comprises immersing the catalytic surface in an autocatalytic metal plating solution comprising water, a water-soluble salt of a metal selected from the group consisting of cobalt, nickel and tin, a complexing agent for said metal capable of forming a stable water-soluble complex, a reducing agent for said metal and a water-soluble cyanide compound as a stabilizing agent in a concentration of from about 5 micrograms to 500 milligrams per liter.

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  • 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)
  • Catalysts (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Paints Or Removers (AREA)
US377471A 1964-06-24 1964-06-24 Process for stabilizing autocatalytic metal plating solutions Expired - Lifetime US3403035A (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
US377471A US3403035A (en) 1964-06-24 1964-06-24 Process for stabilizing autocatalytic metal plating solutions
CH872465A CH467342A (de) 1964-06-24 1965-06-22 Verfahren zum Stabilisieren von autokatalytischen Metallabscheidungsbädern
GB26274/65A GB1121282A (en) 1964-06-24 1965-06-22 Process for stabilizing autocatalytic metal plating solutions
DE19651521440 DE1521440B2 (de) 1964-06-24 1965-06-23 Verfahren zum Stabilisieren von Bädern für die stromlose reduktive Metallabscheidung. Aren: Photocircuits Corp., Glen Cove, N.Y. (V.St.A.)
SE8362/65A SE316962B (da) 1964-06-24 1965-06-23
DK317365AA DK129949B (da) 1964-06-24 1965-06-23 Fremgangsmåde til stabilisering af et vandigt bad til strømløs afsætning af kobber, nikkel, cobalt, cadmium eller tin på overflader af bærere.
ES0314564A ES314564A2 (es) 1964-06-24 1965-06-23 Un procedimiento para el revestimiento inelectrico de cobre.
AT570665A AT270330B (de) 1964-06-24 1965-06-23 Stabilisiertes Bad zum stromlosen Abscheiden von Nickel, Kobalt, Kadmium oder Zinn
FR22099A FR88424E (fr) 1964-06-24 1965-06-24 Procédé de cuivrage non galvanique, et bains utilisés pour la mise en oeuvre de ce procédé
BE665911A BE665911A (da) 1964-06-24 1965-06-24
NL6508142A NL6508142A (da) 1964-06-24 1965-06-24
NL7514608A NL7514608A (nl) 1964-06-24 1975-12-15 Werkwijze voor het bereiden van een bad voor het stroomloos neerslaan van een metaal en werkwijze voor het stroomloos neerslaan onder toepassing van dit bad, alsmede aldus beklede voortbrengse- len.

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US377471A US3403035A (en) 1964-06-24 1964-06-24 Process for stabilizing autocatalytic metal plating solutions

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AT (1) AT270330B (da)
BE (1) BE665911A (da)
CH (1) CH467342A (da)
DE (1) DE1521440B2 (da)
DK (1) DK129949B (da)
ES (1) ES314564A2 (da)
GB (1) GB1121282A (da)
NL (1) NL6508142A (da)
SE (1) SE316962B (da)

Cited By (58)

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US3507681A (en) * 1967-06-02 1970-04-21 Mine Safety Appliances Co Metal plating of plastics
US3547818A (en) * 1969-04-07 1970-12-15 Ventron Corp Alcoholic ionic compositions containing a metal selected from hg (ii),cu (ii),ag (i),cd (ii),ni (ii),zn (ii),and co (ii)
US3637472A (en) * 1970-03-16 1972-01-25 Ventron Corp Chemical plating baths containing an alkali metal cyanoborohydride
US3645749A (en) * 1970-06-04 1972-02-29 Kollmorgen Corp Electroless plating baths with improved deposition rates
US3650708A (en) * 1970-03-30 1972-03-21 Hooker Chemical Corp Metal plating of substrates
US3653953A (en) * 1970-01-26 1972-04-04 North American Rockwell Nonaqueous electroless plating
US3663242A (en) * 1970-09-25 1972-05-16 Shipley Co Stabilized electroless plating solutions
US3717482A (en) * 1970-06-12 1973-02-20 Shipley Co Stabilized electroless plating solutions
US3798050A (en) * 1971-05-28 1974-03-19 Ppg Industries Inc Catalytic sensitization of substrates for metallization
US3870526A (en) * 1973-09-20 1975-03-11 Us Army Electroless deposition of copper and copper-tin alloys
US3881049A (en) * 1971-12-08 1975-04-29 Kalle Ag Process for depositing copper layers on shaped articles of a polyimide
US3893865A (en) * 1971-02-02 1975-07-08 Ppg Industries Inc Method for stabilizing a chemical filming composition
US3899617A (en) * 1973-07-19 1975-08-12 Enthone Process for conditioning ABS resin surface
US3915716A (en) * 1969-04-17 1975-10-28 Schering Ag Chemical nickel plating bath
DE2527096A1 (de) * 1974-06-20 1976-01-08 London Laboratories Verfahren zum abschneiden von metallischem kupfer an einer flaeche
US3946126A (en) * 1968-11-22 1976-03-23 Rca Corporation Method of electroless nickel plating
US3961109A (en) * 1973-08-01 1976-06-01 Photocircuits Division Of Kollmorgen Corporation Sensitizers and process for electroless metal deposition
US3992211A (en) * 1968-07-15 1976-11-16 Trans-Metals Corporation Electroless plating composition
US4036651A (en) * 1974-02-26 1977-07-19 Rca Corporation Electroless copper plating bath
DE2715850A1 (de) * 1976-04-08 1977-10-13 Kollmorgen Tech Corp Verfahren zum abscheiden von kupfer oder kupferlegierungen aus stromlos arbeitenden baedern
US4175146A (en) * 1977-10-06 1979-11-20 Obata Industry & Commerce Co., Ltd. Method for improving the properties of natural products composed mainly of calcium carbonate
DE2920766A1 (de) * 1978-05-25 1979-11-29 Macdermid Inc Loesung und verfahren zur stromlosen kupferabscheidung unter verwendung eines hypophosphit-reduktionsmittels
US4269625A (en) * 1978-12-04 1981-05-26 U.S. Philips Corporation Bath for electroless depositing tin on substrates
US4279951A (en) * 1979-01-15 1981-07-21 Mine Safety Appliances Company Method for the electroless deposition of palladium
US4305997A (en) * 1977-06-06 1981-12-15 Surface Technology, Inc. Electrolessly metallized product of non-catalytic metal or alloy
US4328266A (en) * 1977-06-06 1982-05-04 Surface Technology, Inc. Method for rendering non-platable substrates platable
US4355083A (en) * 1977-06-06 1982-10-19 Nathan Feldstein Electrolessly metallized silver coated article
US4481035A (en) * 1982-10-08 1984-11-06 Siemens Aktiengesellschaft Chemical gilding bath
US4482596A (en) * 1980-09-15 1984-11-13 Shipley Company Inc. Electroless alloy plating
USH325H (en) 1980-07-30 1987-09-01 Richardson Chemical Company Electroless deposition of transition metals
DE3622090C1 (da) * 1986-07-02 1990-02-15 Blasberg-Oberflaechentechnik Gmbh, 5650 Solingen, De
US5091223A (en) * 1989-06-27 1992-02-25 Henkel Corporation Process for forming a blackened layer on a zinciferous surface by contacting the surface with an aqueous solution containing nickel and cobalt ions
US5298092A (en) * 1990-05-17 1994-03-29 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5378293A (en) * 1990-05-17 1995-01-03 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5411606A (en) * 1990-05-17 1995-05-02 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5419926A (en) * 1993-11-22 1995-05-30 Lilly London, Inc. Ammonia-free deposition of copper by disproportionation
US5468307A (en) * 1990-05-17 1995-11-21 Schriever; Matthias P. Non-chromated oxide coating for aluminum substrates
US5472524A (en) * 1990-05-17 1995-12-05 The Boeing Company Non-chromated cobalt conversion coating method and coated articles
US5551994A (en) * 1990-05-17 1996-09-03 The Boeing Company Non-chromated oxide coating for aluminum substrates
US5873953A (en) * 1996-12-26 1999-02-23 The Boeing Company Non-chromated oxide coating for aluminum substrates
US6183546B1 (en) 1998-11-02 2001-02-06 Mccomas Industries International Coating compositions containing nickel and boron
US6432225B1 (en) 1999-11-02 2002-08-13 The Boeing Company Non-chromated oxide coating for aluminum substrates
US20030190426A1 (en) * 2002-04-03 2003-10-09 Deenesh Padhi Electroless deposition method
US20040217005A1 (en) * 2002-07-24 2004-11-04 Aron Rosenfeld Method for electroplating bath chemistry control
US20050124158A1 (en) * 2003-10-15 2005-06-09 Lopatin Sergey D. Silver under-layers for electroless cobalt alloys
US20050136185A1 (en) * 2002-10-30 2005-06-23 Sivakami Ramanathan Post rinse to improve selective deposition of electroless cobalt on copper for ULSI application
US20050136193A1 (en) * 2003-10-17 2005-06-23 Applied Materials, Inc. Selective self-initiating electroless capping of copper with cobalt-containing alloys
US20050164497A1 (en) * 2004-01-26 2005-07-28 Sergey Lopatin Pretreatment for electroless deposition
US20060280872A1 (en) * 2005-06-10 2006-12-14 Enthone Inc. Method for direct metallization of non-conducting substrates
US7205233B2 (en) 2003-11-07 2007-04-17 Applied Materials, Inc. Method for forming CoWRe alloys by electroless deposition
US20070108424A1 (en) * 2003-04-24 2007-05-17 Konica Minolta Holdings, Inc. Conductive pattern forming composition, formation method of conductive pattern and production method of conductive pattern forming composition
US20070261594A1 (en) * 2006-05-11 2007-11-15 Lam Research Corporation Plating solution for electroless deposition of copper
US7297190B1 (en) * 2006-06-28 2007-11-20 Lam Research Corporation Plating solutions for electroless deposition of copper
US20080206474A1 (en) * 2004-12-14 2008-08-28 Polymer Kompositer I Goteborg Ab Stabilization and Performance of Autocatalytic Electroless Processes
US7514353B2 (en) 2005-03-18 2009-04-07 Applied Materials, Inc. Contact metallization scheme using a barrier layer over a silicide layer
US7651934B2 (en) 2005-03-18 2010-01-26 Applied Materials, Inc. Process for electroless copper deposition
US7659203B2 (en) 2005-03-18 2010-02-09 Applied Materials, Inc. Electroless deposition process on a silicon contact
US20160097128A1 (en) * 2013-08-06 2016-04-07 Earthone Circuit Technologies Corporation Method of forming a conductive image using high speed electroless plating

Citations (5)

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Also Published As

Publication number Publication date
GB1121282A (en) 1968-07-24
AT270330B (de) 1969-04-25
DE1521440B2 (de) 1970-11-26
ES314564A2 (es) 1967-07-01
DE1521440A1 (de) 1970-01-08
DK129949C (da) 1975-06-30
SE316962B (da) 1969-11-03
BE665911A (da) 1965-10-18
NL6508142A (da) 1965-12-27
DK129949B (da) 1974-12-02
CH467342A (de) 1969-01-15

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