US3485643A - Electroless copper plating - Google Patents

Electroless copper plating Download PDF

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Publication number
US3485643A
US3485643A US548071A US3485643DA US3485643A US 3485643 A US3485643 A US 3485643A US 548071 A US548071 A US 548071A US 3485643D A US3485643D A US 3485643DA US 3485643 A US3485643 A US 3485643A
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metal
copper
solution
electroless
deposition
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US548071A
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Rudolph J Zeblisky
Frederick W Schneble Jr
John F Mccormack
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Kollmorgen Corp
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Photocircuits Corp
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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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde
    • 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
    • C23C18/48—Coating with alloys
    • 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

Definitions

  • An autocatalytic metal deposition solution which comprises water; an ion of a metal to be deposited; a complexing agent for the ion to be deposited; at reducing agent for the ion to be deposited; an agent capable of adjusting pH; and a compound containing a cyanide radical (CN) complexed with a metal selected from Group VIII of the Periodic Table of Elements in an amount sufiicient to effect acceleration of the deposition of the metal.
  • the present invention relates to electroless or auto-catalytic plating of metals, and more particularly to accelerating the rate of deposition fromautocatalytic metal plating baths.
  • Electroless or autocatalytic metal deposition solutions are characterized by a capacity to deposit metal on a wide variety of conducting and non-conducting or insulating surfaces without the assistance of an external supply of electrons.
  • such solutions comprise a solvent, a supply of ions of a metal to be deposited, an agent capable of reducing the ions of the metal to be deposited, a complexing agent for the ions of the metal to be deposited and a pH regulator.
  • sensitization techniques include the well known treatment with an acidic aqueous solution of stannous chloride (SnCl followed by treatment with a dilute aqueous acidic solution of palladium chloride (PdCl
  • sensitization may be achieved by treating the insuating substrata with an acidic solution containing a mixture of stannous chloride and precious metal chloride, such as palladium chloride, the stannous chloride being present in stoichiometric excess, based on the amount of precious metal chloride.
  • electroless metal deposition solutions of the type described have been hampered by the fact that electroless metal deposition solutions which are stable over relatively long periods of time have a tendency to deposit copper at a relatively slow rate. As a result whenever thick deposits are required, a relatively long contact time is required.
  • One object of the present invention is to accelerate the deposition rate of autocatalytic or electroless metal baths.
  • a further object of the present invention is to enhance the deposition rate of electroless metal solutions Without adversely affecting the stability or the physical properties of the electroless metal produced therefrom.
  • Another object of the present invention is to increase the rate of deposition for electroless metal solutions which contain relatively low concentrations of the basic ingredients described hereinabove.
  • Another object of this invention is to provide means for monitoring autocatalytic copper solutions soas to maintain an accelerated rate of deposition therefrom.
  • a further object of the invention is to provide autocatalytic metal deposition solutions which are capable of depositing bright, ductile electroless metal at enhanced rates over relatively long periods of time.
  • Still a further object of this invention is to provide new and useful addition agents for controlling the rate of deposition and stability of electroless copper solutions.
  • Electroless copper solutions are capable of depositing copper without the assistance of an external supply of electrons.
  • such solutions comprise water, a small amount of copper ions, e.g. a water soluble copper salt, a reducing agent for copper ions, a complexing agent for copper ions, and a pH regulator.
  • Rochelle salts the sodium mono-, di-, tri-, and tetrasodium) salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid and its alkali salts, gluconic acid, gluconates, and triethanolamine are preferred as copper ion complexing agents, but commercially available glucono-ylactone and modified ethylenediamineacetates are also useful, and in certain instances give even better results than the pure sodium ethylenediaminetetraacetates.
  • One such material is N hydroxyethylethylenediaminetriacetate.
  • Other materials suitable for use as cupric complexing agents are disclosed in US. Patent Nos. 2,996,408, 3,075,- 856, 3,075,855 and 2,938,805.
  • Copper reducing agents which have been used in alkaline electroless metal baths include formaldehyde, and formaldehyde precursors or derivatives, such as paraformaldehyde, dimethyl hydantoin, glyoxal, and the like.
  • borohydrides such as alkali metal borohydrides, e.g., sodium and potassium borohydride, as well as substituted borohydrides, e.g., sodium trimethoxyborohydride.
  • borohydrides such as alkali metal borohydrides, e.g., sodium and potassium borohydride
  • substituted borohydrides e.g., sodium trimethoxyborohydride.
  • reducing agents in such baths may also be used boranes, such as amine borane, e.g., isopropylamine borane, morpholine borane, and the like.
  • hypophosphites such as sodium and potassium hypophosphite and'the like.
  • the pH adjustor or regulator may consist of any acid or base, and here again the selection will depend primari- 1y on economics. For this reason, the pH adjustor on the alkaline side will ordinarily be sodium hydroxide. On the acid side, pH will usually be adjusted with an acid having a common anion with the copper salt. Since the preferred copper salt is the sulfate, the preferred pH adjustor on the acid side is sulfuric acid.
  • the copper salt serves as a source of copper ions
  • the reducing. agent reduces the copper ions to metallic form.
  • the reducing agent is itself oxidized to provide electrons for the reduction of the copper ions.
  • the complexing agent serves to complex the copper ion so that it will not be precipitated, e.g., by hydroxyl ions and the like, and at the same time makes the copper available as needed to the reducing action of the reducing agent.
  • the pH adjustor serves chiefly to regulate the internal plating potential of the bath.
  • the accelerating agents of this invention also appear to render electroless copper solutions less sensitive to changes of temperature and concentration, and therefore permit greater variation in operating conditions, ingredient concentration, temperature and types of ingredients than have heretofore been considered possible.
  • the present invention and the agents described herein although applicable to electroless metal deposition solutions generally, are particularly suitable for use in electroless copper deposition solutions which have high plating potential under the conditions of use.
  • the accelerating agents of this invention are water soluble complex cyano-metallo compounds in which the cyanide radical (CN) is complexed with certain metals of ,Group VIII of the Periodic Table of Elements, including mixtures of such compounds.
  • Typical of such compounds are those in which the cyanide radical (CN) is complexed with iron, iridium and rhenium, including mixtures of such compounds.
  • Preferred for use are the water soluble complex cyanoiron compounds, i.e., hexacyanoferrate (II) and hexacyanoferrate (III) compounds, as well as mixtures of such compounds.
  • Typical of such compounds are the ferricyanides and ferrocyanides of the metals of Groups IA (alkali metal) and IIA (alkaline earth metal) of the Periodic Table of Elements, and ammonium.
  • Preferred for use are the sodium, potassium and ammonium ferricyanides and ferrocyanides. It will be appreciated that in alkaline solutions the ferricyanides will be reduced to ferrocyanides, so that in such solutions the ferrocyanides will function as the accelerator, even though the accelerator is added as a ferricyanide.
  • the accelerators should be added in amounts of between about .0075 and 50 grams per liter, preferably between about 0.150 and 2.50 grams per liter. Ordinarily, the accelerator will be added in amounts of about 1 to 300 parts per million, preferably between 1 and 50 parts per million, based upon the metal which is complexed with the cyanide (CN) ion, e.g., iron (Fe).
  • CN cyanide
  • Fe iron
  • a typical electroless metal deposition bath made according to the present invention will comprise:
  • Metal salt 0.01 to 1.0 moles. Reducing agent 0.01 to 4 moles. Electroless metal complexing agent 0.7 to 40 times the moles of Accelerating agent measured metal salt.
  • pH adjustor Sufiicient to give desired Water Suflicient to make 1 liter.
  • the electroless metal salt will be a copper salt.
  • Specific embodiments of a high plating potential electroless copper solution comprise:
  • Copper salt 0.01 to 1.0 moles.
  • Formaldehyde 0.01 to 4 moles.
  • C o p p e r ion complexing agent 0.7 to 40 times the moles of metal salt.
  • Accelerating agent measured as metal complexed with cyanide 1 to 300 parts per million. Alkali metal hydroxide pH 10-14. Water Suflicient to make 1 liter.
  • a soluble cupric salt preferably cupric sulfate Alkali metal hydroxide, preferably soduim hydroxide,
  • surfactants include organic phosphate esters, and oxyethylated sodium salts, and mixtures thereof.
  • Preferred surfactants are alkylphenoxy polyethoxy phosphate esters. Typical examples of such esters are nonylphenoxy polyethoxy phosphate esters having molecular weights of between about 800 and 1000, preferably about 900. Typical of the oxyethylated sodium salts is the product sold under the tradename Triton QS-15.
  • the electroless copper solutions will ordinarily contain small effective amounts of simp e Hex'acyanoferrate (II) 6 water soluble organic and inorganic cyanide compounds, Grams/liter e.g., 0.00001 to 0.06 mole per liter.
  • Typical of such simple cyanides are the alkali metal, Tetrasodiumethylenediamine tetraacetate 5O alkaline earth metal and ammonium cyanides, such as HCHO (37% solution) 12 sodium, potassium, calcium and ammonium cyanide; and Potassium ferrocyanide 0.25 nitriles, preferably alpha-hydroxynitriles, e.g., glycoloni- 5 Phenyl polyethylene ether phosphate 0.1 trile and lactonitrile. Lactonitrile 0.02
  • the copper solutions may also contain small effective Water to make 1 liter. amounts, e. less than about 100 arts er million of sulfur coinpounds capable of formi iig sta lole but dis In room temperature Solutlons type described It sociabla Chelates with cuprous ion. 1S.
  • alphahydroxynitriles such as glycolo-
  • organic sulfur compounds may be meng as Slmp 1e cyanide l l tioned the following: thio derivatives of alkyl glycols, f l ess .metal soliltlong contalpmg the accelfalators such as 2,2'-thiodiethanol, dithiodiglycol, aliphatic sulfur- 3 mventlon are 3 actenzed PP f nitrogen compounds Such as thiocarbamates, e.g., thio eposit on surfaces of relatively low catalytic activity.
  • TlllS urea S-membered heterocyclics containing SN in the g 1S lnlustrated g the.fonOWu.]g example 5-membered ring, such as thiazoles and isothiazoles, and t g; f ess meta 591mm havmg the formula thioglycolic acid; e.g., thiazole, Z-mercaptobenzothiazole ca e e OW was prepared and the like; dithiols, e.g., 1,2-ethanedithiol and the like; CuSO -5H O grams/liter 5 G-membered heterocyclics containing SN in the ring, Rochelle salts do 40 such as thiazones, e.g., 1,2-benzisothiazine, benzothiazine, HCHO (37%) ml./l 6 and the like; thioamino acids, such as methionine, cystine, Na
  • alkali sulfides e.g., sodium Phenyl polyethylene ether phosphate ml./l l sulfide, potassium sulfide, sodium polysulfide, potassium NaOH to give pH 12-122 at C. polysulfide
  • alkali thiocyanates such as sodium-potassium 25 As a control was used the identical bath Without thlocyanatesa h H d tassium ferrocyanide.
  • Two panels similarly sensitized and of equal cross-secnolivn an may e use as e cuprou?
  • the solutions were maintained at a pH of have a relatively low sensitivity to electroless metal deposiabout 12 and at about C. throughout use. In all intion, are particularly useful for metallizing clear, readily stances about 1 ml./l. of the specific organic phosphate available plastic impregnated laminates and plastic sheet ester described above was used as a surfactant.
  • 60 stock including those prepared from ABS (acrylonitrile- In Table I, ductility is measured by bending the copper deposit through 180, in one direction, creasing, then returning it to its original position, with pressing along the crease to flatten it, this cycle constituting one bend.
  • butadiene-styrene acetal resins
  • acrylic resins such as methyl methacrylate and methylmethacrylate styrene copolymers
  • allyl resins and monomers such as diallyl phthalate
  • cellulosic resins such as ethyl cellulose, cellulose acetate, cellulose acetate butyrate, cellulose propionate and the like
  • chlorinated polyethers epoxy resins, fluoroplastics, furanes, melamine-formaldehyde resins, nylon, polyacrylic esters, phenol-formaldehyde and phenol-furfuryl resins, phenolic cast resins, aromatic polyimide resins, polyphenylene oxide resins, polyethylene, polypropylene, polystyrene, silicones, urea-formaldehyde, urethanes, vinyl polymers and copolymers and the like.
  • the surface to be plated In using the autocatalytic or electroless copper solutions to plate metal, the surface to be plated must be free of grease and other contaminating material.
  • the surface area to receive the deposit must first be sensitized to render it catalytic to the reception of electroless copper, as has been brought out hereinabove.
  • metal surface is to be plated, it should be degreased, and then treated with an acid, such as hydrochloric or phosphoric acid, to free the surface of oxides.
  • an acid such as hydrochloric or phosphoric acid
  • the sur face to be metallized is immersed in the autocatalytic copper baths, and permitted to remain in the bath until a copper deposit of the desired thickness has been built up.
  • portions of the surface of an insulating substratum in the form of a desired circuit pattern may be sensitized for the reception of electroless metal.
  • the substratum is immersed in or otherwise contacted with the electroless metal solution of the type described and permitted to remain therein until a metal deposit of the desired thickness has been built up.
  • the circuit may be formed on One or more surfaces of the substratum. If desired, interconnections between the surfaces may be provided by drilling or punching holes and sensitizing the lateral walls thereof prior to exposure of the substratum to the electroless meta-l solution.
  • electroless metal builds up on the circuit pattern and on the walls surrounding the holes.
  • Solution 1 2 3 4 Copper sulfate (moles/liter)-.. 0. 1 0. 1 0. 1 O. 1 E.D T A (moles/liter) 0.1 0.1 0.1 O. 1
  • Formaldehyde (moles/liter) 0.12 0.12 0.12 0.12 0.12 Surfactant 2 (percent) 0. 01 0.01 0.01 0. 01 Lactonitrile (mg/liter) 40 40 40 40 Potassium cyanorhenate (mg/liter) 0 1.8 18 180 pH 12.8 12.8 12.3 128 Operating ,temp 1 R.T. 1 R.I. 1 R.T. 1R31. Copper deposit in 1 hr. (mg./c 0.43 0.47 0.48 0.51
  • an autocatalytic copper plating solution comprising water, copper ions, a complexing agent for the copper ions, a reducing agent for said copper ions and an agent capable of rendering the solution alkaline; the improvemerit in which the solution comprises a water-soluble 4 compound containing a cyanide radical (CN complexed with a metal selected from Group VIII of the Periodic Table of Elements, said compound being present in an amount which is suificient to accelerate the deposition rate of the copper ions.
  • a cyanide radical CN complexed with a metal selected from Group VIII of the Periodic Table of Elements
  • the autocatalytic copper plating solution comprises a compound in which the cyanide radical is selected from the group consisting of hexacyanoferrate (II), hexacyanoferrate (III) and mixtures thereof.
  • the autocatalytic plating solution comprises formaldehyde as a reducing agent for copper.
  • the solution of claim 1 comprising from about 0.002 to 1 mole per liter of a Water soluble copper salt, a complexing agent for the copper ion in a concentration of from about 0.7 to 40 times the moles of the copper salt, from about 0.01 to 4 moles per liter of formaldehyde, a suflicient amount of an alkali metal hydroxide to render the pH of the solution from 10 to 14 and from 1 to 300 parts per million, based on iron, of a member selected from the group consisting of hexacyanoferrate (II), hexacyanoferrate (III) and mixtures thereof.
  • a method of accelerating the rate of deposition of an autocatalytic copper plating solution which comprises l0 maintaining in said solution a member selected from the group consisting of hexacyanoferrate (II), hexacyanoferrate (III) and mixtures thereof, in an amount which is suflicient to accelerate the deposition rate of copper ions.

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  • Mechanical Engineering (AREA)
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  • Organic Chemistry (AREA)
  • Chemically Coating (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US548071A 1966-05-06 1966-05-06 Electroless copper plating Expired - Lifetime US3485643A (en)

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Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647402A (en) * 1967-10-13 1972-03-07 Dynamit Nobel Ag Galvanically metallized objects having a post-chlorinated polyethylene substrate and process of producing same
US3804638A (en) * 1969-10-16 1974-04-16 Philips Corp Electroless deposition of ductile copper
US3902907A (en) * 1973-08-17 1975-09-02 Kazutaka Kishita System for electroless plating of copper and composition
FR2393683A1 (fr) * 1977-06-07 1979-01-05 M & T Chemicals Inc Revetement de substrats par impression par projection
US4133908A (en) * 1977-11-03 1979-01-09 Western Electric Company, Inc. Method for depositing a metal on a surface
US4167601A (en) * 1976-11-15 1979-09-11 Western Electric Company, Inc. Method of depositing a stress-free electroless copper deposit
US4170461A (en) * 1976-12-29 1979-10-09 Ppg Industries, Inc. Heat treatment of electrolessly deposited cuprous oxide coating
US4192764A (en) * 1977-11-03 1980-03-11 Western Electric Company, Inc. Stabilizing composition for a metal deposition process
US4228213A (en) * 1979-08-13 1980-10-14 Western Electric Company, Inc. Method of depositing a stress-free electroless copper deposit
US4443257A (en) * 1982-03-09 1984-04-17 Alfachimici S.P.A. Stabilizing mixture for a chemical copper plating bath
US4464231A (en) * 1980-10-22 1984-08-07 Dover Findings Inc. Process for fabricating miniature hollow gold spheres
US4525390A (en) * 1984-03-09 1985-06-25 International Business Machines Corporation Deposition of copper from electroless plating compositions
US4666858A (en) * 1984-10-22 1987-05-19 International Business Machines Corporation Determination of amount of anionic material in a liquid sample
EP0343816A1 (en) * 1988-05-25 1989-11-29 Engelhard Corporation Electroless deposition
US4908242A (en) * 1986-10-31 1990-03-13 Kollmorgen Corporation Method of consistently producing a copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
US5256441A (en) * 1992-08-04 1993-10-26 Amp-Akzo Corporation Ductile copper
US5258200A (en) * 1992-08-04 1993-11-02 Amp-Akzo Corporation Electroless copper deposition
US5562760A (en) * 1994-02-28 1996-10-08 International Business Machines Corp. Plating bath, and corresponding method, for electrolessly depositing a metal onto a substrate, and resulting metallized substrate
US5965211A (en) * 1989-12-29 1999-10-12 Nippondenso Co., Ltd. Electroless copper plating solution and process for formation of copper film
US20090255824A1 (en) * 2008-04-11 2009-10-15 Shenzhen Futaihong Precision Industry Co., Ltd. Method for surface treating a substrate
EP2672520A1 (en) 2012-06-06 2013-12-11 SEMIKRON Elektronik GmbH & Co. KG Method for electroless deposition of a copper layer, electroless deposited copper layer and semiconductor component comprising said electroless deposited copper layer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3259559A (en) * 1962-08-22 1966-07-05 Day Company Method for electroless copper plating
US3310430A (en) * 1965-06-30 1967-03-21 Day Company Electroless copper plating
US3326700A (en) * 1963-06-12 1967-06-20 Rudolph J Zeblisky Electroless copper plating

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3259559A (en) * 1962-08-22 1966-07-05 Day Company Method for electroless copper plating
US3326700A (en) * 1963-06-12 1967-06-20 Rudolph J Zeblisky Electroless copper plating
US3310430A (en) * 1965-06-30 1967-03-21 Day Company Electroless copper plating

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3647402A (en) * 1967-10-13 1972-03-07 Dynamit Nobel Ag Galvanically metallized objects having a post-chlorinated polyethylene substrate and process of producing same
US3804638A (en) * 1969-10-16 1974-04-16 Philips Corp Electroless deposition of ductile copper
US3902907A (en) * 1973-08-17 1975-09-02 Kazutaka Kishita System for electroless plating of copper and composition
US4167601A (en) * 1976-11-15 1979-09-11 Western Electric Company, Inc. Method of depositing a stress-free electroless copper deposit
US4170461A (en) * 1976-12-29 1979-10-09 Ppg Industries, Inc. Heat treatment of electrolessly deposited cuprous oxide coating
FR2393683A1 (fr) * 1977-06-07 1979-01-05 M & T Chemicals Inc Revetement de substrats par impression par projection
US4133908A (en) * 1977-11-03 1979-01-09 Western Electric Company, Inc. Method for depositing a metal on a surface
US4192764A (en) * 1977-11-03 1980-03-11 Western Electric Company, Inc. Stabilizing composition for a metal deposition process
US4228213A (en) * 1979-08-13 1980-10-14 Western Electric Company, Inc. Method of depositing a stress-free electroless copper deposit
US4464231A (en) * 1980-10-22 1984-08-07 Dover Findings Inc. Process for fabricating miniature hollow gold spheres
US4443257A (en) * 1982-03-09 1984-04-17 Alfachimici S.P.A. Stabilizing mixture for a chemical copper plating bath
US4525390A (en) * 1984-03-09 1985-06-25 International Business Machines Corporation Deposition of copper from electroless plating compositions
US4666858A (en) * 1984-10-22 1987-05-19 International Business Machines Corporation Determination of amount of anionic material in a liquid sample
US4908242A (en) * 1986-10-31 1990-03-13 Kollmorgen Corporation Method of consistently producing a copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
EP0343816A1 (en) * 1988-05-25 1989-11-29 Engelhard Corporation Electroless deposition
US5965211A (en) * 1989-12-29 1999-10-12 Nippondenso Co., Ltd. Electroless copper plating solution and process for formation of copper film
US5258200A (en) * 1992-08-04 1993-11-02 Amp-Akzo Corporation Electroless copper deposition
US5429861A (en) * 1992-08-04 1995-07-04 Amp-Akzo Corporation Electroless copper deposited on a printed circuit board capable of withstanding thermal cycling
US5256441A (en) * 1992-08-04 1993-10-26 Amp-Akzo Corporation Ductile copper
US5562760A (en) * 1994-02-28 1996-10-08 International Business Machines Corp. Plating bath, and corresponding method, for electrolessly depositing a metal onto a substrate, and resulting metallized substrate
US6042889A (en) * 1994-02-28 2000-03-28 International Business Machines Corporation Method for electrolessly depositing a metal onto a substrate using mediator ions
US20090255824A1 (en) * 2008-04-11 2009-10-15 Shenzhen Futaihong Precision Industry Co., Ltd. Method for surface treating a substrate
EP2672520A1 (en) 2012-06-06 2013-12-11 SEMIKRON Elektronik GmbH & Co. KG Method for electroless deposition of a copper layer, electroless deposited copper layer and semiconductor component comprising said electroless deposited copper layer

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Publication number Publication date
ES340230A1 (es) 1968-06-01
DE1621311C3 (de) 1974-10-31
SE340738B (enrdf_load_stackoverflow) 1971-11-29
DE1621311A1 (de) 1970-07-23
JPS5113734B1 (enrdf_load_stackoverflow) 1976-05-01
AT268811B (de) 1969-02-25
NL152299B (nl) 1977-02-15
GB1145578A (en) 1969-03-19
CH497541A (de) 1970-10-15
DE1621311B2 (de) 1972-06-29
NL6706434A (enrdf_load_stackoverflow) 1967-11-07

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