US3660251A - Method for the electrolytical deposition of highly ductile copper - Google Patents

Method for the electrolytical deposition of highly ductile copper Download PDF

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Publication number
US3660251A
US3660251A US52730A US3660251DA US3660251A US 3660251 A US3660251 A US 3660251A US 52730 A US52730 A US 52730A US 3660251D A US3660251D A US 3660251DA US 3660251 A US3660251 A US 3660251A
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United States
Prior art keywords
electrolytic bath
electrolytic
microns
copper
deposition
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Expired - Lifetime
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US52730A
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English (en)
Inventor
Werner Fluhmann
Walter Saxer
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WERNER FLUHMANN AND GALVANISCH
WERNER FLUHMANN AND GALVANISCHE
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WERNER FLUHMANN AND GALVANISCH
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/06—Filtering particles other than ions
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper

Definitions

  • Kleeman ABSTRACT A homogenous, brittle-free, pore-free and dense copper layer of high ductility and having a content of included gases and/or organic impurities of less than 100 ppm is electrolytically deposited on electrically conducting surfaces from a bath comprising the copper ion and the pyrophosphate ion by maintaining the electrolytic bath constantly free from particles having a size substantially exceeding 3 microns.
  • the article to be electrolytically coated is immersed in an electrolyte bath containing ions of the metal to be deposited.
  • This electrolyte may further contain organic and/or inorganic additives capable of influencing the metal coating during its deposition, the electric conductivity, the current density etc..
  • the article is then connected as a cathode, and electrolytic (galvanic)deposition is effected by direct current. This current may be interrupted from time to time and/or reversed for short periods of time in'order to modify the coating thickness. Temperatures, pH values and agitation of the bath are controlled.
  • the article is withdrawn from the bath, thoroughly rinsed, and dried.
  • Nonmetallic articles may be made electrically conductive on the surface by one of the known techniques; see, e.g., K. Heymann et al. in “Angewandte Chemie,” Vol. 82(l970), pages 412-421.
  • metallic coatings produced by electro-deposition contain a higher quantity of gas than metals produced by metallurgical means. This disadvantage appears especially at soldering, since heating liberates the enclosed gas, by which the soldering process is hampered.
  • low ductility as used herein means a ductility of l to 6 generally 1 to 3 measured as ultimate linear elon gation at normal temperature.
  • high ductility as used herein and as achieved by the present method, means ductilitiesof more than 6 generally 10 to 30%, particularly to It is important that this high ductility is obtained without proportional decrease in ultimate tensile strength and hardness.
  • theprincipal object ot this invention to provide a method for producing high ductile, dense andpore-free copper electrodeposits of high purity having a bright surface and having a content of organic matter and/or gases of less than ppm.
  • This object of the invention is accomplished by the present method which comprises the use of an extremely pure electrolytic deposition bath containing at least one member comprising copper pyrophosphate and the combination of copper sulfate and potassium pyrophosphate, said electrolyte being free from particles having a size greater than about 3 microns.
  • the method of the invention supplies copper deposits of high ductility, Le. 10 to 30% ultimate elongation, having an ultimate tensile strength of about 27 to 29 kg/mm, under a load of 50 g (KHN).
  • KHN A more outstanding feature is the excellent toughness of the coatings of the invention. Toughness is to be understood as the product of ultimate tensile strength and ductility (ultimate elongation), and the coatings of the inventions have been found to have toughnesses of about 400 to 650 kg/mm, particularly about 5 60 kg/mm.
  • the content of organic matter and/or gases included in the coatings of the invention is measured by vacuum extraction at 1,300 C. in high vacuum. Both organic matter and gases, the former by its pyrolysis products in gaseous form, may be assayed according to this method.
  • the method according to the invention is especially applicable for the electrodeposition of copper on plastic materials and on printed circuits in electrotechniques. Because of its high ductility and since it does not fissurate during compression and elongation, the deposited copper can be pressed level with the matrix material. In order to continuously maintain the conditions of the process according to the invention, it is not only necessary to start with an electrolyte which is free of particles over 3 pm in size, but which must be continuously cleaned during the deposition. This is best carried out by a circulation whereby the. electrolyte is purified outside the bath. The electrolyte can either be filtered through a microfilter or first purified with an adsorption agent and then filtered through a microfilter.
  • the microfilters have preferably a pore diameter between 0.1 and 1.5 pm, in particular 0.5 gm; therefore the use of molecular sieves is recommended.
  • Adsorption agents which are suitable are active carbon, silicagel or alumina.
  • the electrolyte should preferably have a temperature between 30 and 75 C, in particular 55 C. A pH-value of the electrolyte between 7 and 9, in particular of 8, is indicated.
  • the printed circuits Before the eiectrolytic copper deposits can be applied on printed circuits, these have to be clad with copper either on one side or on both sides, or, the printed circuits can also be built up according to the multi-layer technique. in order to achieve a homogeneous deposition of copper on the walls of the holes of the printed circuits, it is recommended that these be previously made conductive, for example by treatment with chemical agents.
  • the following examples should illustrate more specifically the process according to the invention and its application, but are not to be construed as limiting the invention in any aspect.
  • the electrolyte is first purified over active carbon and afterwards filtered in three successive steps through microfilters, i.e. through filters with pore diameters of 3 pm, l.2 um, and 0.6 pm respectively.
  • This bath was operated by switching the polarity in cycles of 10 seconds cathodically and 1 second anodically at a cathodic current density of 2 Amp/dm and an anodic current density of l Amp/dm
  • the bath temperature was 55 C. It was continuously filtered through a microfilter, pore size 0.8 pm and in addition agitated by moving the cathode shaft.
  • EXAMPLE 2 A bath which contains g/l copper in form of copper 3o pyrophosphate and 250 g/l potassium pyrophosphate is purified over active carbon and then filtered in steps through microfilters of decreasing pore size diameter. The filtration is then continued at a pore size diameter of 0.1 pm until no residues can be detected on the filter under the light microscope.
  • Example 1 and 2 The properties of the coatings of Example 1 and 2 are compiled in the following table.
  • micropore filters having a pore size in a range between 0.1 and 1.5 microns, and wherein the last micropore filter through which the electrolytic bath passes has a pore size which does not exceed 0.8 microns.
  • micropores filters having a pore size of approximately 0.5 microns.
  • a method for the electrolytic deposition of pore-free metallic copper of high ductility and purity, containing at least less than 100 ppm of one of the ingredients comprising organic matter and gaseous inclusions, from an electrolytic bath containing at least copper ions and pyrophosphate ions comprising the steps of continuously initially passing the electrolytic bath through an adsorption agent to purify the electrolytic bath and then stepwise continuously filtering the electrolytic bath by successively passing such electrolytic bath through a number of non-ceramic microfilters of progressively decreasing pore size, the pore size of the last microfilter at most amounting to 1.5 microns, the electrolytic bath thus being freed of particles of a size exceeding 3 microns.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Electroplating Methods And Accessories (AREA)
US52730A 1969-07-10 1970-07-06 Method for the electrolytical deposition of highly ductile copper Expired - Lifetime US3660251A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1056369A CH494824A (de) 1969-07-10 1969-07-10 Verfahren zur elektrolytischen Abscheidung von Kupfer hoher Duktilität

Publications (1)

Publication Number Publication Date
US3660251A true US3660251A (en) 1972-05-02

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US52730A Expired - Lifetime US3660251A (en) 1969-07-10 1970-07-06 Method for the electrolytical deposition of highly ductile copper

Country Status (7)

Country Link
US (1) US3660251A (de)
AT (1) AT302763B (de)
CH (1) CH494824A (de)
DE (1) DE2034144A1 (de)
FR (1) FR2051660B3 (de)
GB (1) GB1316846A (de)
NL (1) NL7010237A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4956053A (en) * 1988-05-26 1990-09-11 Olin Corporation Apparatus and process for the production of micro-pore free high ductility metal foil
US6127205A (en) * 1996-07-26 2000-10-03 Nec Corporation Process for manufacturing a molded electronic component having pre-plated lead terminals
CN109210081A (zh) * 2017-07-05 2019-01-15 斯凯孚公司 滚动轴承的电镀组成部件

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2558423B2 (de) * 1975-12-23 1978-09-07 Messerschmitt-Boelkow-Blohm Gmbh, 8000 Muenchen Verfahren zum galvanischen Abscheiden von Nickel aus einem Nickelsulfamatbad
FR2531458A1 (fr) * 1982-08-04 1984-02-10 Stephanois Rech Mec Procede de traitement superficiel de surfaces ferreuses pour ameliorer leurs qualites de frottement et de resistance a l'usure et au grippage
US4568431A (en) * 1984-11-13 1986-02-04 Olin Corporation Process for producing electroplated and/or treated metal foil
US4549950A (en) * 1984-11-13 1985-10-29 Olin Corporation Systems for producing electroplated and/or treated metal foil
US4532014A (en) * 1984-11-13 1985-07-30 Olin Corporation Laser alignment system
ATE82333T1 (de) * 1985-07-05 1992-11-15 Mitsui Mining & Smelting Co Kupferfolie, durch elektrolytische abscheidung hergestellt.
DE3870685D1 (de) * 1987-02-23 1992-06-11 Siemens Ag Galvanisiereinrichtung zur erzeugung von hoeckern auf chip-bauelementen.

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1798994A (en) * 1929-01-04 1931-03-31 Gen Electric Electroplating apparatus
US3186932A (en) * 1962-12-10 1965-06-01 Audio Matrix Inc Apparatus for forming phonograph record masters, mothers, and stampers
CA715549A (en) * 1965-08-10 Martin Rudolf Electro-deposition assemblies
US3208921A (en) * 1962-01-02 1965-09-28 Sperry Rand Corp Method for making printed circuit boards
US3222268A (en) * 1961-07-13 1965-12-07 Udylite Corp Particle separator device for plating baths
US3245886A (en) * 1961-08-10 1966-04-12 Dehydag Gmbh Electroplating process and self-regulating electroplating baths therefor
US3532801A (en) * 1965-02-23 1970-10-06 Burroughs Corp Method and apparatus for fabricating laminated circuit boards

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA715549A (en) * 1965-08-10 Martin Rudolf Electro-deposition assemblies
US1798994A (en) * 1929-01-04 1931-03-31 Gen Electric Electroplating apparatus
US3222268A (en) * 1961-07-13 1965-12-07 Udylite Corp Particle separator device for plating baths
US3245886A (en) * 1961-08-10 1966-04-12 Dehydag Gmbh Electroplating process and self-regulating electroplating baths therefor
US3208921A (en) * 1962-01-02 1965-09-28 Sperry Rand Corp Method for making printed circuit boards
US3186932A (en) * 1962-12-10 1965-06-01 Audio Matrix Inc Apparatus for forming phonograph record masters, mothers, and stampers
US3532801A (en) * 1965-02-23 1970-10-06 Burroughs Corp Method and apparatus for fabricating laminated circuit boards

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4956053A (en) * 1988-05-26 1990-09-11 Olin Corporation Apparatus and process for the production of micro-pore free high ductility metal foil
US6127205A (en) * 1996-07-26 2000-10-03 Nec Corporation Process for manufacturing a molded electronic component having pre-plated lead terminals
CN109210081A (zh) * 2017-07-05 2019-01-15 斯凯孚公司 滚动轴承的电镀组成部件
US10995797B2 (en) * 2017-07-05 2021-05-04 Aktiebolaget Skf Electroplated component of a rolling element bearing

Also Published As

Publication number Publication date
FR2051660B3 (de) 1973-04-27
NL7010237A (de) 1971-01-12
DE2034144A1 (de) 1971-02-11
FR2051660A7 (de) 1971-04-09
AT302763B (de) 1972-10-25
CH494824A (de) 1970-08-15
GB1316846A (en) 1973-05-16

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