US3095309A - Electroless copper plating - Google Patents

Electroless copper plating Download PDF

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Publication number
US3095309A
US3095309A US26401A US2640160A US3095309A US 3095309 A US3095309 A US 3095309A US 26401 A US26401 A US 26401A US 2640160 A US2640160 A US 2640160A US 3095309 A US3095309 A US 3095309A
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US
United States
Prior art keywords
copper
bath
per liter
cyanide
water
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.)
Expired - Lifetime
Application number
US26401A
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English (en)
Inventor
Zeblisky Rudolph John
Mccormack John Francis
Williamson John Duff
Jr Frederick W Schneble
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.)
Day Co
Original Assignee
Day Co
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 Day Co filed Critical Day Co
Priority to US26401A priority Critical patent/US3095309A/en
Priority to DE1696312A priority patent/DE1696312C2/de
Priority to CH345361A priority patent/CH413540A/de
Priority to ES266074A priority patent/ES266074A1/es
Priority to DK152861AA priority patent/DK105901C/da
Application granted granted Critical
Publication of US3095309A publication Critical patent/US3095309A/en
Priority to CH757364A priority patent/CH445247A/de
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
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • C23C18/40—Coating with copper using reducing agents
    • C23C18/405—Formaldehyde

Definitions

  • the present invention has for its object the provision of a novel and improved process for the electroless plating or deposition of a ductile, bright layer of copper on various surfaces such as insulating members, metal, ceramic and other supporting surfaces.
  • a further object of the invention is the provision of a novel and improved electroless plating bath which is simple to use, operates with certainty and which is economical in use.
  • the invention provides an improved elect-roless copper depositing bath and process which produces a copper de posit of better color than has heretofore been realized, and which may exhibit substantially the same ductility as good electrodeposited copper.
  • the invention consists in the novel steps, processes, compositions and improvements herein shown and de scribed.
  • the deposits produced by most prior electroless copper depositing baths do not produce copper deposits which are bright, but they usually exhibit a dull surface, of poor color, often yielding a smutty layer of copper.
  • the baths of the prior processes are often subject to instability and as impurities accumulate in the bath, the bath finally reaches a condition in which it spontaneously decomposes, throwing down the copper as a useless sludge or precipitate.
  • the baths of the present invention may be used until substantially exhausted, and may be replenished from time to time so that the remaining useful ingredients in the bath are more efficiently used, thereby reducing the over-all cost of the operation.
  • the electroless plating baths of the present invention consist essentially of a soluble copper salt, such as copper sulfate, cupric chloride, cupric nitrate, copper gluconate and cupric acetate; a complexing agent for the copper ions, such as Rochelle salts, ethylenediaminetetraacetic acid and its sodium salt, triethanolamine, sugar (sucrose, dextrose, lactose, levulose or maltose), mannitol, sorbitol, or gluconic acid; sodium or potassium hydroxide; an active reducing agent such as formaldehyde; and a small amount of a complexing agent for the cuprous ions, such as a soluble cyanide, such as sodium or potassium cyanide.
  • a soluble copper salt such as copper sulfate, cupric chloride, cupric nitrate, copper gluconate and cupric acetate
  • a complexing agent for the copper ions such as Rochelle
  • Copper sulfate from 0.5 g. to saturated solution 0.002 to :15 mol or more.
  • a soluble inorganic cyanide 0.001 g. to 3.0 g., 0.00002 M.
  • the ratio of the cupric salt to the complexing agent is such that there are from 0.5 to 2.5 as many moles of complexing agent as of cupric salt; e.g. 5 grams of CuSO 5H O requires from 2.5 to 8.5 grams of Rochelle salts.
  • the amount of formaldehyde may be 0.4 to 3.4 moles per liter.
  • Sodium hydroxide and sodium cyanide are preferred over the corresponding more costly potassium and other alkali metal salts and the thiocyanates, which are of greater molecular weight.
  • Rochelle salts the sodium salts (mono-, di-, triand tetra-sodium salts) of ethylenediaminetetraacetic acid, gluconic acid, gluconates, and triethanolamine are preferred as complexing agents, but commercially available glucono 'y lactone and modified-ethylenediaminetetraacetates are also useful, and in certain instances give even better results than the pure sodium ethylenediaminetetraacetate.
  • One such material is Glyco Products Tetrine M.
  • Cupric sulfate is preferred but other soluble copper salts may be used, such as the nitrate, chloride and acetate.
  • the plating baths of the present invention are compounded within narrower limits than set forth immediately above, and they consist essentially of:
  • a soluble cupri-c salt preferably cupric sulfate 0.002 to 0.04 mole.
  • Alkali metal hydroxide preferably Sodium hydroxide to give-" pH 13.5.
  • the cupric salt, and the formaldehyde reducing agent may be replenished from time to time, and also that it may be advisable to monitor the pH and cyanide content of the bath, and to adjust it to its optimum value as the bath is used.
  • the baths are ordinarily used at slightly elevated temperatures, such as from 35 to 65 C. although many of them may be used at lower temperatures, and others may be used at even higher temperatures.
  • slightly elevated temperatures such as from 35 to 65 C. although many of them may be used at lower temperatures, and others may be used at even higher temperatures.
  • the temperature is increased, it is usual to find that the rate of plating is increased, and that the ductility of the deposit is increased to a slight extent, but the temperature is not highly critical, and within the usual operating range, excellent deposits are produced which exhibit greatly improved properties over those obtained with conventional baths and processes.
  • the efficiency of the copper recovery by electroless deposition from the bath often exceeds which is much greater than has heretofore been observed in working with conventional baths.
  • the enprous complexing agent in the bath serves to prevent or minimize the formation of cuprous oxide in the bath and also appears to inhibit the formation of resultant hydrogen in the electroless deposited metal.
  • the surface to be plated must be free of grease and other contaminating material.
  • the surface areas to receive the deposit should first be treated, as in conventional processes, with conventional sensitizing and seeding solutions, such as stannous chloride (SnCl followed by treatment with a dilute solution of palladium chloride (PdCl
  • metal surface such as stainless steel
  • it should be degreased, and then treated with acid, such as hydrochloric or phosphoric acid to free the surface of any oxide.
  • acid such as hydrochloric or phosphoric acid
  • Example 1 Cupric sulfate (CuSO -H O) 7.5 grams.
  • Example 2 A bath for similar use, but which gives even better ductility of the deposited copper, when used at a temperature of about 25 to 40 C., is as follows:
  • Cupric sulfate (CuSO -5H O) 1.0 g. 0.004 M.
  • Example 3 For use in the electroless plating of copper on a sheet of stainless steel which has been degreased and acid dipped, and which will deposit a bright ductile layer of copper about 0.001 thick in a period of 24 hours at an operating temperature of about 50 C., the following bath is preferred:
  • the complexing agents may be used as mixtures and additional amounts of the complexing agent may be added, but such excess additions beyond 2.5 times the molal concentration of the copper content of the bath do not result in any improvement and are merely wasteful under ordinary circumstances.
  • Example 5 Another bath which operates somewhat more rapidly at 40 C. than those specified above for the electroless plating of copper on insulating bases of plastic materials, such as phenolformaldehyde resins, polyester resins, nylon, polystyrene and epoxy resins, and has a greater life, but does not produce as ductile a deposit of copper as is produced by the bath of Example 1, is as follows:
  • Example 6 A bath having still higher concentration of ingredients is, as follows:
  • Cupric chloride (CuCl 2H O) g Rochelle salts g 85 to 100 Sodium hydroxide g 60 Formaldehyde, ml 35 Sodium cyanide -2 0.01 to 0.1
  • Cupric sulfate g 7.5 60 which are comprised within the scope of the present Ethylenedlamine tetracetieacidtetrasodlum salt g 15.0 invention, and which are especially useful for the deposi' Sodium hydroxide g 2 l n of bright, ductile metallic layers of copper on suit- Sodrum cyanide "g" 0. ably prepared sheets or moldings of plastic materials, Formaldehyde 40% ml 20.0 Such as the melamine or phenol-formaldehyde sheet-stock Water enough to make 1000 ml. used in the making of printed circuits.
  • Example No 7 8 0 10 11 12 13 i 14 15 CuSO;5HgO grnrns 0.5 0.5 0.5 0. 10 10 Tetrasodium E.D.'I.. do 1. 0 1. O 1. 0 1.; 25 20 NaOH to give pH. 13 14 13.5 12.5 13.5 13.0 13 K011 to give pH l2. 0 13.5 Formaldehyde 10% millilitcrs 10 10 5 10 40 5t) 500 Sodium cyanide "grams" 0.002 0. 000 0. 01 1. 5 3. 0 Potassium cyanide tlo 0.003 0.02 0.5 3.0 Water enough to make one liter.
  • Baths which give an excellent deposit but which are always easily controlled throughout their entire life because of the low copper concentration and the necessity of replenishing the copper content of the bath may be prepared according to the following formulae:
  • These baths are preferably operated at a temperature of from 40 to 50 C. and the copper content may be replenished to a limited extent by additions of cuprous chloride.
  • the surface of the sheet is first Wetted with a detergent, such as a 1% water solution of Triton X-l00 (Rohm & Haas Co.) or is roughened slightly by rubbing with an abrasive. T he surface is then thoroughly cleaned with an alkaline cleaner, such as a hot solution of trisodium phosphate in water, rinsed with water and is sensitized with a solution containing about 70 grams of stannous chloride (SnCl 2H O) and 40 ml.
  • a detergent such as a 1% water solution of Triton X-l00 (Rohm & Haas Co.) or is roughened slightly by rubbing with an abrasive.
  • an alkaline cleaner such as a hot solution of trisodium phosphate in water, rinsed with water and is sensitized with a solution containing about 70 grams of stannous chloride (SnCl 2H O) and 40 ml.
  • a similar sensitizing and seeding treatment may be used as a preliminary treatment in connection with the use of any of the other examples given above, although when a metal surface is to be plated it is seldom necessary to do more than treat the metal surface, as by a solvent or a hot solution of an alkaline cleanser (e.g. trisodium phosphate), to insure that it is grease-free and With an acid, such as hydrochloric acid if the surface has any oxide coating thereon.
  • an alkaline cleanser e.g. trisodium phosphate
  • the present invention is not limited to the use of the foregoing specific sensitizing and seeder solutions, and in many instances it is only necessary to roughen the surface of the insulating base material, or to thoroughly clean the metal surface.
  • the process and baths may be used for the electroless deposition of copper on a base material which comprises a thermoplastic or thermosetting resin, such as an epoxy resin which contains from 30% to 50% of cuprous oxide, and which have been subjected to light abrasion in those areas where the copper is to be selectively deposited.
  • a bath for the electroless plating of copper consisting essentially of: water, and a water-soluble copper salt, from 0.002 to 0.15 mole per liter; a copper complexing agent, from 0.5 to 2.5 times the moles of the copper salt; an alkali metal hydroxide, to give a pH of from 10.5 to 14; formaldehyde, from 0.06 to 3.4 moles per liter;
  • a bath for the electroless plating of copper consisting essentially of: water, and a water-soluble copper salt, from 0.002 to 0.15 mole per liter; a complexing agent for cupric ion, from 0.5 to 2.5 times the moles of the copper salt; an alkali metal hydroxide, to give a pH of from 10.5 to 14; formaldehyde, from 0.06 to 3.4 moles per liter; and, as a complexing agent for cuprous ion a water soluble cyanide salt.
  • a process of electroless copper plating which comprises immersing the receptive surface to be plated in a bath consisting essentially of: water, and a water-soluble copper salt, from 0.002 to 0.15 mole per liter; a copper complexing agent, from 1 to 2.5 times the moles of the copper salt; an alkali metal hydroxide, to give a pH of from 10.5 to 14; formaldehyde, from 0.06 to 3.4 m'oles per liter; and -a soluble inorganic cyanide from 0.00002 to 0.06 mole per liter.
  • a process of electroless copper plating which comprises immersing the receptive surface to be plated in a bath consisting essentially of water, :and a water-soluble copper salt, from 0.002 to 0.15 mole per liter; a cupric ion complexin-g agent, from 1 to 2.5 times the moles of the copper salt; an alkali metal hydroxide, to give a pH of from 10.5 to 14; formaldehyde, from 0.06 to 3.4 m'oles per liter; and, as a complexing agent for cuprous ion a water soluble cyanide salt.
  • a process of electroless copper plating which includes immersing a receptive surface to be placed in an alkaline aqueous bath having a pH of between about 10.5 and 14 and comprising water, a water soluble copper salt, a complexing agent for cupric ion, and formaldehyde, the improvement which comprises maintaining in the bath a water soluble cyanide salt in the amount of between about 0.00002 and 0.06 mole per liter.
  • an alkaline electroless copper plating bath having 'a pH of between about 10.5 and 14 and comprising water, a water soluble copper salt, a complexing agent for cupric ion, and formaldehyde, the improvement which comprises a water soluble cyanide salt which is present in the bath in an amount of between about 0.00002 and 0.06 mole 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)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
US26401A 1960-05-03 1960-05-03 Electroless copper plating Expired - Lifetime US3095309A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US26401A US3095309A (en) 1960-05-03 1960-05-03 Electroless copper plating
DE1696312A DE1696312C2 (de) 1960-05-03 1961-01-27 Bad zum stromlosen Abscheiden von Kupferüberzügen
CH345361A CH413540A (de) 1960-05-03 1961-03-23 Bad und Verfahren zum stromlosen Abscheiden von Kupferschichten
ES266074A ES266074A1 (es) 1960-05-03 1961-03-25 Un procedimiento para el revestimiento ineléctrico de cobre
DK152861AA DK105901C (da) 1960-05-03 1961-04-13 Bad til strømløs udskillelse af kobberovertræk på overflader af bærere.
CH757364A CH445247A (de) 1960-05-03 1964-06-10 Verfahren zum Abscheiden von Kupferschichten und Badflüssigkeit zu seiner Durchführung

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US26401A US3095309A (en) 1960-05-03 1960-05-03 Electroless copper plating

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US26401A Expired - Lifetime US3095309A (en) 1960-05-03 1960-05-03 Electroless copper plating

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DE (1) DE1696312C2 (en)van)
DK (1) DK105901C (en)van)
ES (1) ES266074A1 (en)van)

Cited By (31)

* 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
US3269861A (en) * 1963-06-21 1966-08-30 Day Company Method for electroless copper plating
US3296012A (en) * 1965-04-30 1967-01-03 Corning Glass Works Electroless copper plating on ceramic material
US3306830A (en) * 1963-06-13 1967-02-28 Bell Telephone Labor Inc Printed circuit boards and their fabrication
US3321328A (en) * 1962-11-15 1967-05-23 Ibm Coating of aluminum substrates with a magnetic material
US3322881A (en) * 1964-08-19 1967-05-30 Jr Frederick W Schneble Multilayer printed circuit assemblies
US3326700A (en) * 1963-06-12 1967-06-20 Rudolph J Zeblisky Electroless copper plating
US3332860A (en) * 1963-09-19 1967-07-25 Basf Ag Metallizing plastic surfaces
US3340164A (en) * 1963-12-26 1967-09-05 Sperry Rand Corp Method of copper plating anodized aluminum
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
US3853590A (en) * 1969-08-20 1974-12-10 Crown City Plating Co Electroless plating solution and process
US4036651A (en) * 1974-02-26 1977-07-19 Rca Corporation Electroless copper plating bath
FR2527833A1 (fr) * 1982-05-28 1983-12-02 Europ Composants Electron Procede de depot de terminaisons metalliques sur un condensateur ceramique multicouches et condensateur ainsi obtenu
US4460427A (en) * 1981-09-21 1984-07-17 E. I. Dupont De Nemours And Company Process for the preparation of flexible circuits
EP0152601A1 (de) * 1984-02-04 1985-08-28 Schering Aktiengesellschaft Wässriges alkalisches Bad zur Chemischen Abscheidung von Kupfer oder Nickel
US4548644A (en) * 1982-09-28 1985-10-22 Hitachi Chemical Company, Ltd. Electroless copper deposition solution
US4557762A (en) * 1983-08-04 1985-12-10 Hitachi Chemical Company Electroless copper plating solution
WO1988003181A1 (en) * 1986-10-31 1988-05-05 Kollmorgen Technologies Corporation Method of consistently producing copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
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
US5786030A (en) * 1996-11-12 1998-07-28 Henkel Corporation Spotting resistant gloss enhancement of autodeposition coating
US20090032144A1 (en) * 2007-08-03 2009-02-05 Mcmillen Mark W Pretreatment compositions and methods for coating a metal substrate
US20090084682A1 (en) * 2007-09-28 2009-04-02 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated metal substrates
US20090238979A1 (en) * 2008-03-21 2009-09-24 William Decesare Method of Applying Catalytic Solution for Use in Electroless Deposition
US20100159258A1 (en) * 2008-12-18 2010-06-24 Ppg Industries Ohio, Inc. Methods for passivating a metal substrate and related coated metal substrates
US20130071680A1 (en) * 2011-09-21 2013-03-21 Fih (Hong Kong) Limited Coated article and method for making same
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
CN106823469A (zh) * 2017-01-10 2017-06-13 华南理工大学 无需低表面能物质修饰的超疏水超亲油铜网及其制备方法
US9942982B2 (en) 1997-08-04 2018-04-10 Continental Circuits, Llc Electrical device with teeth joining layers and method for making the same
EP3351657A1 (en) 2017-01-23 2018-07-25 Rohm and Haas Electronic Materials LLC Electroless copper plating compositions

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8103174A (nl) * 1981-07-02 1983-02-01 Philips Nv Werkwijze voor de vervaardiging van lagen en patronen van goud en van goudlegeringen op substraten, aldus vervaardigde produkten en de hiervoor toe te passen oplossingen.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
US2874072A (en) * 1956-09-17 1959-02-17 Gen Electric Autocatalytic copper plating process and solution
US2938805A (en) * 1958-03-31 1960-05-31 Gen Electric Process of stabilizing autocatalytic copper plating solutions
US2956901A (en) * 1958-08-06 1960-10-18 Alpha Metal Lab Inc Copper coating composition and method of coating

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2391289A (en) * 1941-09-15 1945-12-18 Jr John F Beaver Bright copper plating
US2874072A (en) * 1956-09-17 1959-02-17 Gen Electric Autocatalytic copper plating process and solution
US2938805A (en) * 1958-03-31 1960-05-31 Gen Electric Process of stabilizing autocatalytic copper plating solutions
US2956901A (en) * 1958-08-06 1960-10-18 Alpha Metal Lab Inc Copper coating composition and method of coating

Cited By (37)

* 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
US3321328A (en) * 1962-11-15 1967-05-23 Ibm Coating of aluminum substrates with a magnetic material
US3326700A (en) * 1963-06-12 1967-06-20 Rudolph J Zeblisky Electroless copper plating
US3306830A (en) * 1963-06-13 1967-02-28 Bell Telephone Labor Inc Printed circuit boards and their fabrication
US3269861A (en) * 1963-06-21 1966-08-30 Day Company Method for electroless copper plating
US3332860A (en) * 1963-09-19 1967-07-25 Basf Ag Metallizing plastic surfaces
US3377174A (en) * 1963-10-24 1968-04-09 Torigai Eiichi Method and bath for chemically plating copper
US3340164A (en) * 1963-12-26 1967-09-05 Sperry Rand Corp Method of copper plating anodized aluminum
US3403035A (en) * 1964-06-24 1968-09-24 Process Res Company Process for stabilizing autocatalytic metal plating solutions
US3322881A (en) * 1964-08-19 1967-05-30 Jr Frederick W Schneble Multilayer printed circuit assemblies
US3296012A (en) * 1965-04-30 1967-01-03 Corning Glass Works Electroless copper plating on ceramic material
US3607317A (en) * 1969-02-04 1971-09-21 Photocircuits Corp Ductility promoter and stabilizer for electroless copper plating baths
US3853590A (en) * 1969-08-20 1974-12-10 Crown City Plating Co Electroless plating solution and process
US4036651A (en) * 1974-02-26 1977-07-19 Rca Corporation Electroless copper plating bath
US4460427A (en) * 1981-09-21 1984-07-17 E. I. Dupont De Nemours And Company Process for the preparation of flexible circuits
FR2527833A1 (fr) * 1982-05-28 1983-12-02 Europ Composants Electron Procede de depot de terminaisons metalliques sur un condensateur ceramique multicouches et condensateur ainsi obtenu
US4548644A (en) * 1982-09-28 1985-10-22 Hitachi Chemical Company, Ltd. Electroless copper deposition solution
US4557762A (en) * 1983-08-04 1985-12-10 Hitachi Chemical Company Electroless copper plating solution
EP0152601A1 (de) * 1984-02-04 1985-08-28 Schering Aktiengesellschaft Wässriges alkalisches Bad zur Chemischen Abscheidung von Kupfer oder Nickel
US4720404A (en) * 1984-02-04 1988-01-19 Josif Culjkovic Aqueous alkaline bath for the chemical deposition of copper, nickel, cobalt and their alloys
WO1988003181A1 (en) * 1986-10-31 1988-05-05 Kollmorgen Technologies Corporation Method of consistently producing copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
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
AU604284B2 (en) * 1986-10-31 1990-12-13 Amp-Akzo Corporation Method of consistently producing copper deposit on a substrate by electroless deposition which deposit is essentially free of fissures
US5786030A (en) * 1996-11-12 1998-07-28 Henkel Corporation Spotting resistant gloss enhancement of autodeposition coating
US9942982B2 (en) 1997-08-04 2018-04-10 Continental Circuits, Llc Electrical device with teeth joining layers and method for making the same
US8673091B2 (en) 2007-08-03 2014-03-18 Ppg Industries Ohio, Inc Pretreatment compositions and methods for coating a metal substrate
US20090032144A1 (en) * 2007-08-03 2009-02-05 Mcmillen Mark W Pretreatment compositions and methods for coating a metal substrate
US20090084682A1 (en) * 2007-09-28 2009-04-02 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated metal substrates
US9574093B2 (en) 2007-09-28 2017-02-21 Ppg Industries Ohio, Inc. Methods for coating a metal substrate and related coated metal substrates
US20090238979A1 (en) * 2008-03-21 2009-09-24 William Decesare Method of Applying Catalytic Solution for Use in Electroless Deposition
US20100159258A1 (en) * 2008-12-18 2010-06-24 Ppg Industries Ohio, Inc. Methods for passivating a metal substrate and related coated metal substrates
US8282801B2 (en) 2008-12-18 2012-10-09 Ppg Industries Ohio, Inc. Methods for passivating a metal substrate and related coated metal substrates
US20130071680A1 (en) * 2011-09-21 2013-03-21 Fih (Hong Kong) Limited Coated article and method for making same
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
CN106823469A (zh) * 2017-01-10 2017-06-13 华南理工大学 无需低表面能物质修饰的超疏水超亲油铜网及其制备方法
EP3351657A1 (en) 2017-01-23 2018-07-25 Rohm and Haas Electronic Materials LLC Electroless copper plating compositions
US10060034B2 (en) 2017-01-23 2018-08-28 Rohm And Haas Electronic Materials Llc Electroless copper plating compositions

Also Published As

Publication number Publication date
DE1696312C2 (de) 1979-08-16
DE1696312B2 (de) 1971-07-15
DE1696312A1 (en)van) 1971-07-15
CH413540A (de) 1966-05-15
ES266074A1 (es) 1961-06-16
DK105901C (da) 1966-11-21

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